Epichlorohydrin, manufacturing process and use

0001Cross-reference of related applications This patent application is a French patent application FR07 / 55696 filed on June 12, 2007, FR07 / 57751 filed on September 21, 2007, and US provisional patent application No. 61/013672 filed on December 14, 2007. Claims the interests of the specification and US Provisional Patent Application No. 61/007661 filed December 14, 2007, all of which are incorporated herein by reference.

0002[Technical field] The present invention relates to epichlorohydrin-based products, methods of their production and purification, and their use in various manufacturing industries.

0003Epichlorohydrin is a reaction intermediate in the production of epoxy resins, synthetic elastomers, glycidyl ethers, polyamide resins and the like ((Non-Patent Document 1)). Epichlorohydrin can be produced, for example, by dehydrochlorination of dichloropropanol derived from the treatment of allyl chloride with hypochlorous acid. The epichlorohydrin thus obtained is not suitable for certain applications.

<p num="0004"><nplcit num="1"><text>Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Volume A9, p. 539</text></nplcit></p>

<p num="0005"> An object of the present invention is to provide a product containing epichlorohydrin that does not have these drawbacks.</p>

<p num="0006"> The present invention therefore relates to products containing epichlorohydrin and trichloropropane, wherein the amount of trichloropropane per kg of product is less than 0.01 g.</p><p num="0007"> One of the basic features of the present invention is the small amount of trichloropropane present in the epichlorohydrin product. Of the other halogenated hydrocarbons, the presence of trichloropropane in epichlorohydrin is actually a nuisance in some applications, such as the production of epoxy resins intended for the electrical components and printing circuit industries. Has been proven in. Of some halogenated hydrocarbons, trichloropropane is, for example, carcinogenic or suspected to be carcinogenic, developmental toxicity, reproductive toxicity, cardiotoxicity, endocrine toxicity, immunotoxicity, and liver. Suspected to be toxic to the liver, nerves, airways and skin. These can remain in the final product and can decompose as the properties of the final product deteriorate. They are either toxic or can be degraded in compounds that are somewhat toxic, raising safety issues, especially if the final product is intended to come into contact with food and beverages. To do. Moreover, they can accumulate and contaminate, for example, wastewater or industrial water such as water containing pulp that is recycled in the pulp and paper industry. In the latter case, these higher concentrations can increase the contamination of the paper formed with recycled water.</p><p num="0008"> The epichlorohydrin content in the product is generally greater than 900 g of epichlorohydrin / product 1 kg, preferably at least 950 g / kg, more preferably at least 990 g / kg and most preferably at least 999 g / kg. ..</p><p num="0009"> Trichloropropane in the product according to the invention is generally 0.008 g / product 1 kg or less, often 0.006 g / kg or less, frequently 0.004 g / kg or less, usually 0.002 g / kg or less, often 0.001 g / kg. It is present below, and especially in amounts of 0.0005 g / kg or less. This content is typically at least 0.001 mg / kg.</p><p num="0010"> Trichloropropane can be selected from any of the isomers of trichloropropane alone or in combination, and the TCPa content of the product according to the invention refers to the sum of all isomers.</p><p num="0011"> Trichloropropane is 1,2,3-trichloropropane, 1,1,1-trichloropropane, 1,1,3-trichloropropane, 1,1,2-trichloropropane and a mixture of at least two of them. It is possible to select from. Trichloropropane is often 1,1,1-trichloropropane.</p><p num="0012"> The product according to the invention may contain at least one halogenated hydrocarbon different from trichloropropane in addition to trichloropropane and epichlorohydrin. This halogenated hydrocarbon is chloropropene, trichloropropene, chloropropanol, chloropropanol, dichloropropene, dichloropropane, dichloropropanol, monochloropropanediol, chloroether, monochlorobenzene, and a mixture of at least two of them. It is possible to select from.</p><p num="0013"> The content of this halogenated hydrocarbon in the product is usually less than 1 g / product 1 kg, usually 0.8 g / product 1 kg or less, usually 0.6 g / kg or less, often 0.5 g / kg or less, often 0.4 g / kg or less, often 0.2 g / kg or less, often 0.1 g / kg or less, more often 0.05 g / kg or less, especially 0.01 g / kg or less, and especially 0.001 g / kg or less. This content is generally 0.001 mg / kg or more.</p><p num="0014"> Halogenated hydrocarbons: Chloropropene, often 2-chloro-1-propene, often 1-chloro-1-propenesis, usually 1-chloro-1-propene trans, especially 3-chloro-1-propene and at least two of these. Either mixture Chloropropane, often 2-chloropropane, often 1-chloropropane and mixtures of at least two of these -Methyl chloride, often dichloromethane, often trichloromethane, usually tetrachloromethane, and a mixture of at least two of these. Dichloroethane, often 1,2-dichloroethane, Chloroethanol, often 2-chloroethanol, Trichloropropene, often 1,3,3-trichloro-1-propene-cis, often 1,3,3-trichloro-1-propene-trans, usually 1,2,3-trichloropropene-cis, especially more 1,2,3-Trichloropropene-trans, and a mixture of at least two of these Chloropropanol, often 3-chloro-1-propanol, Chloropropenol, often 2-chloro-2-propen-1-ol, often 3-chloro-2-propen-1-olsis and especially 3-chloro-2-propen-1-oltrans, and these A mixture of at least one of the two Dichloropropene, often cis-1,3-dichloropropene, often trans-1,3-dichloropropene, usually 3,3-dichloro-1-propene, often 2,3-dichloro-1-propene, usually Is 1,3-dichloro-1-propene-cis, especially 1,3-dichloro-1-propene-trans, and a mixture of at least two of these, Dichloropropane, preferably 1,3-dichloropropane, 1,2-dichloropropane, 2,2-dichloropropane, and mixtures thereof. Dichloropropanol, often 1,3-dichloropropane-2-ol, 2,3-dichloropropane-1-ol, and mixtures thereof Monochloropropanediol, often 3-chloro-1,2-propanediol, often 2-chloro-1,3-propanediol, and mixtures thereof, and -Chloro ether, preferably composition formula: C₆H₁₀Cl₂O₂, C₆H₁₂Cl₂O, C₆H₉Cl₃O₂, C₆H₁₁Cl₃O₂Chloro ether and a mixture of at least two of these Composition formula C₄H₇ClO₂, C₆H₉Cl₃, C₆H₉Cl₃O₂, C₉H₁₇Cl₃O₄, C₉H₁₅Cl₅O, C₃H₃Cl₃And a mixture of at least two of these Dichloroepoxy propane It can be an aliphatic or aromatic halogenated hydrocarbon containing oxygen, preferably an aliphatic halogenated hydrocarbon, and the like.</p><p num="0015"> Haloketones and epichlorohydrins are not considered halogenated hydrocarbons.</p><p num="0016"> Aromatic halogenated hydrocarbons contain at least one aromatic ring and halogen atom. The halogen atom is preferably bonded directly to the aromatic ring. Halogen can be selected from fluorine, chlorine, bromine, iodine and mixtures thereof. Chlorine is preferred. The aromatic ring can be mononuclear or polynuclear, preferably mononuclear. Aromatic halogenated hydrocarbons can be selected from mono-, di-, tri-, tetra-, penta- and hexachloro-benzene and / or naphthalene. Monochlorobenzene is particularly preferred.</p><p num="0017"> Although not bound by one theoretical explanation, monochlorobenzene is believed to be derived from the process of producing epichlorohydrin, especially when it is obtained by dehydrochlorination of dichloropropanol. More specifically, it is believed that monochlorobenzene can be present in dichloropropanol, especially if it is obtained by the process of chlorinating glycerol with a chlorinating agent containing hydrogen chloride. More specifically, chlorobenzene is an isocyanate, diisocyanate or poly, especially one such as 4,4-methylene diphenyl diisocyanate (MDI) or toluene diisocyanate (TDI) or hexamethylene-1,6-diisocyanate (HDI). It is believed that it may be present in hydrogen chloride if it is derived from other production processes such as the production of isocyanates.</p><p num="0018"> The product according to the invention is chloropropene, usually 0.8 g / product 1 kg or less, generally 0.6 g / kg or less, often 0.5 g / kg or less, often 0.4 g / kg or less, usually 0.2 g / kg or less. Advantageously, it can be contained in a content of 0.1 g / kg or less, particularly 0.05 g / kg or less, and more particularly 0.01 g / kg or less. Values below 0.001 g / kg give good results. This content is typically at least 0.001 mg / kg. Chloropropene is selected from 2-chloro-1-propene, 1-chloro-1-propenesis, 1-chloro-1-propene trance, 3-chloro-1-propene, and mixtures of at least two of these. Can be done.</p><p num="0019"> The product according to the invention is trichloropropene, usually 0.8 g / product 1 kg or less, generally 0.6 g / kg or less, usually 0.5 g / kg or less, often 0.4 g / kg or less, often 0.2 g / kg or less. , Frequently, it can be contained in a content of 0.1 g / kg or less, particularly 0.05 g / kg or less, particularly 0.01 g / kg or less. A content of 0.001 g / kg or less gives good results. This content is typically at least 0.001 mg / kg. Trichloropropene is 1,3,3-trichloro-1-propene-cis, 1,3,3-trichloro-1-propene-trans, 1,2,3-trichloropropene-cis, especially 1,2,3. -Trichloropropene-can be selected from trans and a mixture of at least two of these.</p><p num="0020"> The product according to the invention contains chloropropenol, usually 0.8 g / product 1 kg or less, generally 0.6 g / kg or less, often 0.5 g / kg or less, often 0.4 g / kg or less, usually 0.2 g / kg. Hereinafter, it is possible to preferably contain the content in an amount of 0.1 g / kg or less, particularly 0.05 g / kg or less, and further 0.01 g / kg or less. Values below 0.001 g / kg give good results. This content is typically at least 0.001 mg / kg. Chloropropenol is 2-chloro-2-propen-1-ol, 3-chloro-2-propen-1-olsis, 3-chloro-2-propen-1-oltrans and at least one of these two species. Can be selected from a mixture of.</p><p num="0021"> The product according to the invention is dichloropropene, usually 0.8 g / product 1 kg or less, generally 0.6 g / kg or less, often 0.5 g / kg or less, often 0.4 g / kg or less, usually 0.2 g / kg or less. Advantageously, it can be contained in a content of 0.1 g / kg or less, particularly 0.05 g / kg or less, and more particularly 0.01 g / kg or less. Values below 0.001 g / kg give good results. This content is typically at least 0.001 mg / kg. Dichloropropene includes 3,3-dichloro-1-propene, 2,3-dichloro-1-propene, 1,3-dichloro-1-propene-cis, 1,3-dichloro-1-propene-trans and theirs. It can be selected from at least one mixture of two types.</p><p num="0022"> The product according to the invention is dichloropropane, usually 0.8 g / product 1 kg or less, generally 0.6 g / kg or less, often 0.5 g / kg or less, often 0.4 g / kg or less, usually 0.2 g / kg or less. Advantageously, it can be contained in a content of 0.1 g / kg or less, particularly 0.05 g / kg or less, and more particularly 0.01 g / kg or less. Values below 0.001 g / kg give good results. This content is typically at least 0.001 mg / kg. Dichloropropane can be selected from 1,3-dichloropropane, 1,2-dichloropropane, 2,2-dichloropropane, and mixtures of at least two of these.</p><p num="0023"> The product according to the invention contains dichloropropanol, usually 0.8 g / product 1 kg or less, generally 0.6 g / kg or less, often 0.5 g / kg or less, often 0.4 g / kg or less, usually 0.2 g / kg or less. Advantageously, it can be contained in a content of 0.1 g / kg or less, particularly 0.05 g / kg or less, and more particularly 0.01 g / kg or less. Values below 0.001 g / kg give good results. This content is typically at least 0.001 mg / kg. Dichloropropanol can be selected from 1,3-dichloropropane-2-ol, 2,3-dichloropropane-1-ol and mixtures thereof.</p><p num="0024"> The product according to the invention is monochloropropanediol, usually 0.8 g / product 1 kg or less, generally 0.6 g / kg or less, often 0.5 g / kg or less, often 0.4 g / kg or less, usually 0.2 g / kg. Hereinafter, it is possible to preferably contain the content in an amount of 0.1 g / kg or less, particularly 0.05 g / kg or less, and further 0.01 g / kg or less. Values below 0.001 g / kg give good results. This content is typically at least 0.001 mg / kg. Monochloropropanediol can be selected from 3-chloro-1,2-propanediol, 2-chloro-1,3-propanediol and mixtures thereof.</p><p num="0025"> The product according to the invention is usually chloroether, usually 0.8 g / product 1 kg or less, generally 0.6 g / kg or less, often 0.5 g / kg or less, often 0.4 g / kg or less, usually 0.2 g / kg. It can be contained in a content of kg or less, preferably 0.1 g / kg or less, particularly 0.05 g / kg or less, and particularly 0.01 g / kg or less. Values below 0.001 g / kg give good results. This content is typically at least 0.001 mg / kg. Chloro ether has a composition formula C₆H₁₀Cl₂O₂, C₆H₁₂Cl₂O, C₆H₉Cl₃O₂, C₆H₁₁Cl₃O₂Chloro ether, and any mixture of these can be selected.</p><p num="0026"> The product according to the invention usually contains chlorobenzene, often monochlorobenzene, usually 0.8 g / product 1 kg or less, generally 0.6 g / kg or less, often 0.5 g / kg or less, often 0.4 g / It is contained in an amount of kg or less, usually 0.2 g / kg or less, preferably 0.1 g / kg or less, particularly 0.05 g / kg or less, and particularly 0.01 g / kg or less. Values below 0.001 g / kg give good results. This content is typically at least 0.001 mg / kg.</p><p num="0027"> The products according to the invention are, in addition, for example: Aldehydes such as acetaldehyde, acrolein, isobutanal and isopentanal, Alkylating glycidyl ethers such as methyl glycidyl ethers, -Acetone, chloroacetone, cyclopentanone, 2-butanone, cyclohexanone, 2-methyl-2-cyclopenten-1-one, 3,5-dimethyl-2-cyclohexen-1-one; Composition formula C₅H₁₀O, C₆H₁₂Ketones like O's Ketone Aliphatic alcohols such as isopropanol, allyl alcohol, glycerol, Aromatic alcohols such as phenol -Hydroxyketones such as hydroxyacetone, and Epoxides different from epichlorohydrin, such as propylene oxide, 1,2-epoxyhexene, glycidol, -Methylcyclopentane, hydrocarbons such as ethylbenzene, Composition formula C₆H₁₀O, C₇H₁₀O, C₇H₁₄O₂, C₆H₈O₂, C₉H₁₀O₂Compounds It may also contain compounds that are not halogenated hydrocarbons, such as those defined above.</p><p num="0028"> The product according to the invention contains at least one aldehyde, usually 0.8 g / product 1 kg or less, generally 0.6 g / kg or less, often 0.5 g / kg or less, often 0.4 g / kg or less, usually 0.2 g. It can be contained in a content of / kg or less, preferably 0.1 g / kg or less, particularly 0.05 g / kg or less, and particularly 0.01 g / kg or less. Values below 0.001 g / kg give good results. This content is typically at least 0.001 mg / kg. The aldehyde can be selected from acetaldehyde, acrolein, isobutanal, isopentanal and a mixture of at least two of these.</p><p num="0029"> The product according to the invention can contain acrolein in an amount usually less than 0.07 g / product 1 kg, generally 0.01 g / kg or less, usually 0.005 g / kg or less. This content is usually at least 0.001 g / kg.</p><p num="0030"> The product according to the invention contains at least one alkylglycidyl ether, usually 0.8 g / product 1 kg or less, generally 0.6 g / kg or less, often 0.5 g / kg or less, often 0.4 g / kg or less, usually It can be contained in a content of 0.2 g / kg or less, preferably 0.1 g / kg or less, particularly 0.05 g / kg or less, and particularly 0.01 g / kg or less. Values below 0.001 g / kg give good results. This content is typically at least 0.001 mg / kg. Alkyl glycidyl ethers can be selected from methyl-, ethyl-, propyl-, butyl glycidyl ethers, and mixtures of at least two of these.</p><p num="0031"> The product according to the invention can contain methylglycidyl ether in an amount of usually 0.5 g / product 1 kg or less, generally 0.1 g / kg or less and usually 0.05 g / kg or less. This content is typically at least 0.001 g / kg.</p><p num="0032"> The product according to the invention contains ketones, usually 0.8 g / product 1 kg or less, generally 0.6 g / kg or less, often 0.5 g / kg or less, often 0.4 g / kg or less, usually 0.2 g / kg or less, Advantageously, it can be contained in a content of 0.1 g / kg or less, particularly 0.05 g / kg or less, and more particularly 0.01 g / kg or less. Values below 0.001 g / kg give good results. This content is typically at least 0.001 mg / kg. Ketones are acetone, chloroacetone, 2-butanone, cyclopentanone, cyclohexanone, 2-methyl-2-cyclopenten-1-one, 3,5-dimethyl-2-cyclohexen-1-one, composition formula C.₅H₁₀O, C₆H₁₂It can be selected from ketones of O, and mixtures of at least two of these.</p><p num="0033"> The product according to the invention can contain cyclopentanone in an amount of at least 0.001 mg / kg, generally at least 0.01 mg / kg, usually at least 0.1 mg / kg and often at least 0.001 g / kg. Is. This content is usually 0.5 g / kg or less, generally 0.3 g / kg or less, usually 0.1 g / kg or less, often 0.05 g / kg or less, often 0.01 g / kg or less and especially 0.005 g / kg or less. Is. This content is usually at least 0.001 mg / kg, generally at least 0.01 mg / kg, usually at least 0.1 mg / kg, often at least 0.5 mg / kg and especially at least 1 mg / kg.</p><p num="0034"> The product according to the invention can contain chloroacetone in an amount of usually less than 0.05 g / 1 kg of product, generally 0.03 g / kg or less and typically 0.01 g / kg or less. This content is typically at least 0.001 g / kg.</p><p num="0035"> The product according to the invention is an aliphatic alcohol, usually 0.8 g / product 1 kg or less, generally 0.6 g / kg or less, often 0.5 g / kg or less, often 0.4 g / kg or less, usually 0.2 g / kg. Hereinafter, it is possible to preferably contain the content in an amount of 0.1 g / kg or less, particularly 0.05 g / kg or less, particularly 0.01 g / kg or less. Values below 0.001 g / kg give good results. This content is typically at least 0.001 mg / kg. The aliphatic alcohol can be selected from isopropanol, allyl alcohol, glycerol, and a mixture of at least two of these.</p><p num="0036"> The product according to the invention contains hydroxyketone, usually 0.8 g / product 1 kg or less, generally 0.6 g / kg or less, often 0.5 g / kg or less, often 0.4 g / kg or less, usually 0.2 g. It can be contained in a content of / kg or less, preferably 0.1 g / kg or less, particularly 0.05 g / kg or less, and particularly 0.01 g / kg or less. Values below 0.001 g / kg give good results. This content is typically at least 0.001 mg / kg. Hydroxyketone is often hydroxyacetone.</p><p num="0037"> The product according to the invention contains an epoxide different from epichlorohydrin, usually 0.8 g / product 1 kg or less, generally 0.6 g / kg or less, often 0.5 g / kg or less, often 0.4 g / kg or less, It can be contained in a content of usually 0.2 g / kg or less, preferably 0.1 g / kg or less, particularly 0.05 g / kg or less, and particularly further 0.01 g / kg or less. Values below 0.001 g / kg give good results. This content is typically at least 0.001 mg / kg. The epoxide can be selected from propylene oxide, 1,2-epoxy-hexane, glycidol, and a mixture of at least two of these.</p><p num="0038"> The product according to the invention is glycidol, usually 0.5 g / product 1 kg or less, generally 0.2 g / kg or less, frequently 0.10 g / product 1 kg or less, usually 0.05 g / product 1 kg or less, often 0.01 g. It can be contained in amounts of / kg or less and frequently 0.005 g / kg or less.</p><p num="0039"> The product according to the invention usually contains glycerol, hydroxyacetone and glycidol, the sum of these contents is usually less than 0.1 g / product 1 kg, typically 0.01 g / kg or less and generally 0.005 g / kg. It is as follows. This content is usually at least 0.001 g / kg.</p><p num="0040"> The present invention is also a method for producing a product containing epichlorohydrin, wherein the amount of trichloropropane per 1 kg of the product is less than 0.01 g, as follows. a) 1,3-Dichloro-2-propanol having a content of 1,3-dichloro-2-propanol of 10% by weight or more in the liquid reaction medium to form epichlorohydrin and at least one salt. A step of reacting a mixture of propanol and 2,3-dichloro-1-propanol with at least one basic compound, and b) The first fraction containing at least part of the liquid reaction medium from step a) and most of the epichlorohydrin contained in part of the reaction medium from step a) prior to the precipitation operation. Prior to the precipitation operation, the steps to be subjected to the precipitation operation separated from the second fraction containing most of the salts contained in a part of the reaction medium from step a), and. c) The first fraction separated in step b) is subjected to at least one supplementary treatment selected alone or in combination from dilution, concentration, evaporation, distillation, stripping, liquid / liquid extraction and adsorption operations. With the steps to serve Regarding methods including.</p><p num="0041"> In the rest of this document, the term "dichloropropanol" will be used to refer to the dichloropropanol mixture.</p><p num="0042"> The notation "almost" is understood to mean "half and more than half", that is, 50% by weight or more than 50% by weight.</p><p num="0043"> Halogenated hydrocarbons can be produced, in particular, during the various steps of the dichloropropanol production process.</p><p num="0044"> The dichloropropanol from step a) of the method according to the invention can be produced, for example, by chlorochlorination of glycerol and / or by treatment of allyl chloride with hypochlorous acid, and allyl chloride itself is produced by chlorolysis of propylene. To. Glycerol can be obtained from oils or greases of plant or animal origin. Oil-producing plants or crops include, for example, corn, cashew nuts, crow wheat, palm, lupinus, rubber seeds, kenaf, kinsenka, cotton, asa, soybeans, coffee, flaxseed, hazelnuts, euphorbia, pumpkin seeds, coriander, caracina, camelina, sesame. , Hamana, Benibana, Buffalo Goad, Rice, Vernicia, Sunflower, Cacao, Peanuts, Keshi, Rapeseed, Olive, Piassaba, Holt Saw, Sunflower, Bacuri, Pekan, Hojoba, Babasuu Palm, for example Jatropha Curcas Jatropha genus such as L.), Jatropha curcas or Jatropha curcas (Triadica Sebifera) L.), macadamia nuts, brazil nuts, avocados, coconuts, oysters, british palms, peki, macauba palms and oil palms. Oil-producing algae include, for example, Neochloris oleoabundans, Scenedesmus dimorphus, Euglena gracilis, Phaeodactylum tricornutum, and Pleurochrysis carterae. ), Prymnesium parvum, Tetraselmis chui, Tetraselmis suecica, Isochrysis galbana, Nannochloropsis salina, Nanochloropsis butcher (Nannochloris) atomus Butcher), Nanochloris makurata butcher (Nannochloris) maculata Butcher), Nanochloropsis gaditana Lubian, and Nannochloropsis oculata; Botryococcus braunii, Botryococcus, Dunariella teruiolecta It is an algae strain species such as (Dunaliella tertiolecta), Nannochloris sp., Spirulina species, Chlorophycean (Chlorophycean) and Bacilliarophy (Silk algae). Methyl glycidyl ether is Solvay Glycerol impurities obtained by transesterification of fats or oils derived from animals or plants, as described in FR06 / 05325 and FR07 / 53863, the contents of which are filed by SA, incorporated herein by reference. It can be derived from glycerol methyl ether. Haloketones, such as chloroacetone, can be produced in the method for producing dichloropropanol by chlorochlorination of glycerol and / or in step a) of the method according to the invention.</p><p num="0045"> Steps a) and b) of the method used to produce the product according to the invention may be carried out under conditions such as those described in FR07 / 53375 and FR07 / 54548 of the Solvay SA application. The liquid reaction medium from step a) may particularly contain an organic solvent such as trichloropropane.</p><p num="0046"> The dichloropropanol used in step a) can be supplied to step a) as an organic composition or a mixture thereof as an aqueous composition.</p><p num="0047"> The dichloropropanol content of the aqueous composition is usually at least 1 g / kg, often at least 10 g / kg, often at least 50 g / kg and especially at least 90 g / kg. This content is generally 500 g / kg or less, usually 200 g / kg or less, often 150 g / kg or less, often 120 g / kg or less, and especially 110 g / kg or less. The content of 100g / kg is convenient.</p><p num="0048"> The dichloropropanol content of the organic composition is usually at least 500 g / kg, often at least 750 g / kg, often at least 800 g / kg and especially at least 850 g / kg. This content is usually 999 g / kg or less, often 950 g / kg or less, often 900 g / kg or less, and especially 880 g / kg or less. The content of 870 g / kg is convenient.</p><p num="0049"> In certain embodiments, the mixture of dichloropropanol used in step a) of the method according to the invention is at least one chloroalkoxy as described in SOLVAY SA, US Provisional Patent Application No. 61 / 007,661. It is possible to contain propanol. The content of chloroalkoxypropanol in dichloropropanol is usually 0.2 g / kg or less, generally 0.1 g / kg or less, often 0.06 g / kg or less, and frequently 0.04 g / kg or less. This content is usually 0.001 g / kg or more.</p><p num="0050"> Chloroalkoxypropanol is often chloromethoxypropanol. Chloromethoxypropanol is 2-chloro-3-methoxy-1-propanol, 1-chloro-3-methoxy-2-propanol, 3-chloro-2-methoxy-1-propanol, and at least one of two of these. It is possible to choose from a mixture of.</p><p num="0051"> Steps a) to c) of the method for obtaining a product according to the present invention can be independently carried out in continuous mode or batch mode. It is preferable to carry out steps a) to c) in continuous mode.</p><p num="0052"> In the method according to the invention, the reaction from step a) is in one or more reaction zones, preferably in at least two reaction zones, more preferably in at least three reaction zones, and even more preferably in at least four reaction zones. Can be carried out at. These reaction zones can consist of volumes assembled in a single jacket or volumes in individual jackets. If the capacitances are assembled in a single jacket, the reaction zones may be located horizontally or perpendicular to each other. When these zones are located horizontally to each other, movement from one zone to another can be done by gravity or by forced circulation. In the case of gravitational circulation, movement can be performed with or without precipitation in one or more channels. Movement in a single flow path without precipitation is preferred. When these zones are assembled vertically, movement from one zone to another can be done by gravity or by forced circulation. Movement by gravity is preferred. It is particularly preferred to perform step a) on a mechanically agitated column subdivided by a perforated split plate. Stirring may be performed by any known means, for example by rotation of the spindle in a liquid medium or by pulsing the flow. A column that is agitated by rotation of the spindle is particularly preferred. These reaction zones may be arranged in series, in parallel, or in any configuration, some in series and others in parallel.</p><p num="0053"> In the method according to the invention, the reaction zones may be supplied with at least two of dichloropropanol, basic compounds, water or compounds thereof independently of each other. When a number of reaction zones are in series, it is preferred to supply most of the basic compounds to a series of first reaction zones.</p><p num="0054"> The notation "reaction zone" is understood to mean the zone in which all of the compounds required for the reaction from step a) are found, namely dichloropropanol, basic compounds and any reaction solvent.</p><p num="0055"> In the method for producing epichlorohydrin-based products according to the invention, dichloropropanol is related to the method according to the invention, such as that defined in FR07 / 53375 and FR07 / 54548 filed by Solvay SA. It can be without dichloropropanol, recycled dichloropropanol or a mixture of the two. The notation "recycled (recycled) dichloropropanol" is understood to mean dichloropropanol that was separated in a step after step b) in the method according to the invention and then regenerated in step a) of the method. The term "exogenous dichloropropanol" is understood to mean dichloropropanol that has not been recycled in the process according to the invention.</p><p num="0056"> Temperature, pressure, reaction time and residence time may have different values in different reaction zones, such as those defined in FR07 / 53375 and FR07 / 54548 filed by Solvay SA.</p><p num="0057"> The ratio of 2,3-dichloro-1-propanol content to 1,3-dichloro-2-propanol content in dichloropropanol can vary depending on the reaction zone to which dichloropropanol is supplied. This ratio may be as described in FR07 / 53375 and FR07 / 54548 filed by Solvay SA.</p><p num="0058"> The molar ratio of dichloropropanol to basic compounds can vary depending on the reaction zone to which these compounds are supplied. This ratio may be as described in FR07 / 53375 and FR07 / 54548 filed by Solvay SA.</p><p num="0059"> The basic compound can be an organic or inorganic basic compound. Organic basic compounds are, for example, amines, phosphines and ammonium, phosphonium salts or alsonium hydroxides. Inorganic basic compounds are preferred. The notation "inorganic compound" is understood to mean a compound that does not contain a carbon-hydrogen bond. Inorganic basic compounds can be selected from alkaline and alkaline earth metal oxides, hydroxides, carbonates, bicarbonates, phosphates, hydrogen phosphates and borates, and mixtures thereof. Alkaline and alkaline earth metal oxides, as well as hydroxides are preferred. Different basic compounds may be used in the various reaction zones where the reaction of step a) is carried out.</p><p num="0060"> In general, the temperature, reaction time or residence time and the molar ratio of dichloropropanol to basic compound are higher in the reaction zone where the 2,3-dichloro-1-propanol / 1,3-dichloro-2-propanol ratio is high.</p><p num="0061"> Step a) may be followed by an operation to neutralize the excess basic compound.</p><p num="0062"> It is possible to combine step a) or part of step a) with step b) in common devices partitioned into various reaction and precipitation zones.</p><p num="0063"> The first fraction separated in step b) is in step b) of the epichlorohydrin production method, which is the subject of FR07 / 53375 and 075/55448 by Solvay SA, the content of which is incorporated herein by reference. It may have a composition such as that described for the separated first fraction.</p><p num="0064"> In addition to epichlorohydrin and trichloropropane, the first fraction separated in step b) includes, for example, halogenated hydrocarbons other than trichloropropane, chloroacetone and methylglycidyl ether, glycerol, hydroxyacetone, glycidol, etc. It may contain other organic compounds such as acetaldehyde, achlorine, acetone, ethylene oxide, propylene oxide and 2-butanone. These compounds can be derived from the method for producing dichloropropanol and / or can be formed during the reaction of dichloropropanol with a basic compound during step a) of the method according to the invention.</p><p num="0065"> The first fraction separated in step b) is generally at least 100 g of epichlorohydrin / 1 kg / kg of the first fraction, preferably 200 g / kg or more, even more preferably 300 g / kg or more. Even more preferably 400 g / kg or more, still more preferably 500 g / kg or more, even more preferably 600 g / kg or more, even more preferably 700 g / kg or more, most preferably 800 g / kg or more, and just the most. It preferably contains 850 g / kg or more. The epichlorohydrin content of the separated first fraction is generally 900 g / kg or less. The epichlorohydrin content of the separated first fraction is, for example, the use of organic solvents and / or imperfections in the mixture of 1,3-dichloro-2-propanol and 2,3-dichloro-1-propanol. Respond to conversion.</p><p num="0066"> The first fraction separated in step b) is generally the first fraction of 2 g or less of chloroacetone / 1 kg / kg and usually 0.3 g / kg or less, typically 0.1 g / kg or less, and particularly preferably. Contains 0.05 g / kg or less. The chloroacetone content is generally 0.005 g / kg or more.</p><p num="0067"> The first fraction separated in step b) generally contains less than 5 g of acrolein / 1 kg / kg of the first fraction, usually less than 0.3 g / kg and typically less than 0.1 g / kg. The acrolein content is generally 0.07 g / kg or more.</p><p num="0068"> The first fraction separated in step b) is generally 20 g or less of chloroether / 1 kg / kg of the first fraction, usually 5 g / kg or less, usually 2 g / kg or less, and particularly preferably 1 g. Contains less than / kg. The content of chloro ether is generally 0.5 g / kg or more.</p><p num="0069"> Chloro ether is a compound in which the molecule contains at least one chlorine atom and at least one oxygen atom, and the oxygen atom is bonded to two carbon atoms. Epichlorohydrin is not considered here as chloroether. These chloro ethers preferably contain 6 carbon atoms. These chloro ethers preferably contain 2 and sometimes 3 chlorine atoms. These chloro ethers preferably contain two oxygen atoms. These chloro ethers have a composition formula: C₆H₁₀Cl₂O₂, C₆H₁₂Cl₂O, C₆H₉Cl₃O₂, C₆H₁₁Cl₃O₂It is preferable to select from the compounds of the above and at least two mixtures thereof.</p><p num="0070"> The first fraction separated in step b) is generally the composition formula C of the first fraction of 10 g or less.₆H₁₀Cl₂O₂It contains / kg of chloro ether, usually 5 g / kg or less, usually 0.5 g / kg or less, and most preferably 0.1 g / kg or less. The content of this chloro ether is generally 0.05 g / kg or more.</p><p num="0071"> The first fraction separated in step b) is generally the composition formula C of the first fraction of 5 g or less.₆H₁₂Cl₂It contains O / kg of chloro ether, usually 2 g / kg or less, usually 0.5 g / kg or less, and most preferably 0.1 g / kg or less. The content of this chloro ether is generally 0.05 g / kg or more.</p><p num="0072"> The first fraction separated in step b) is generally the composition formula C of the first fraction of 5 g or less.₆H₉Cl₃O₂It contains / kg of chloro ether, usually 2 g / kg or less, usually 0.5 g / kg or less, and most preferably 0.1 g / kg or less. The content of this chloro ether is generally 0.02 g / kg or more.</p><p num="0073"> The first fraction separated in step b) is generally the composition formula C of the first fraction of 5 g or less.₆H₁₁Cl₃O₂It contains / kg of chloro ether, usually 2 g / kg or less, usually 1 g / kg or less, and most preferably 0.6 g / kg or less. The content of this chloro ether is generally 0.5 g / kg or more.</p><p num="0074"> The first fraction separated in step b) generally contains other organic compounds such as, for example, 1,3-dichloro-2-propanol, 2,3-dichloro-1-propanol and mixtures thereof. .. The sum of the contents of these dichloropropanols is generally 900 g / first fraction 1 kg or less, usually 800 g / kg or less, usually 700 g / kg or less, often 500 g / kg or less, often 300 g / kg or less and often. It is less than 200 g / kg. The sum of the contents of these dichloropropanols is generally at least 90 g / kg.</p><p num="0075"> The first fraction separated in step b) generally contains other organic compounds in addition to epichlorohydrin, chloroacetone, acrolein, chloroether and dichloropropanol.</p><p num="0076"> The latter can be derived from the dichloropropanol production process and / or can be formed during the reaction of dichloropropanol with a basic compound during step a) of the method according to the invention. Examples of these compounds are glycerol, 3-chloro-1,2-propanediol, 2-chloro-1,3-propanediol and mixtures thereof, hydroxyacetone, glycidol, methylglycidyl ether, 1,2,3- Trichloropropane, cis and trans 1,3-dichloropropene, 1,3-dichloropropane, and 2-chloro-2-propen-1-ol.</p><p num="0077"> The sum of the contents of glycerol, hydroxyacetone and glycidol is generally 100 g / kg or less per first fraction, usually 50 g / kg or less, usually 30 g / kg or less, especially 10 g / kg or less, and more specifically. It is 1 g / kg or less. The sum of these contents is generally 0.1 g / kg or more.</p><p num="0078"> The sum of the contents of 3-chloro-1,2-propanediol and 2-chloro-1,3-propanediol is generally 5 g / kg or less per first fraction, usually 3 g / kg or less, and usually 1 g. It is less than / kg. This sum is generally 0.5 g / kg or more.</p><p num="0079"> The methylglycidyl ether content is generally 5 g / kg or less per first fraction, usually 3 g / kg or less, and typically 1 g / kg or less. This content is generally 0.005 g / kg or more.</p><p num="0080"> The content of 1,2,3-trichloropropane is generally 10 g / kg or less per first fraction, usually 5 g / kg or less, usually 3 g / kg or less, and most preferably 1 g / kg or less. This content is generally 0.0001 g / kg or more.</p><p num="0081"> The sum of the contents of cis and trans 1,3-dichloropropene is generally 2 g / kg or less per first fraction, usually 1 g / kg or less, and typically 0.1 g / kg or less. This sum is generally 0.01 g / kg or more.</p><p num="0082"> The 1,3-dichloropropane content is generally 2 g / kg or less per first fraction, usually 1 g / kg or less, and typically 0.5 g / kg or less. This content is generally 0.001 g / kg or more.</p><p num="0083"> The content of 2-chloro-2-propen-1-ol is generally 2 g / kg or less per first fraction, usually 1 g / kg or less, and typically 0.5 g / kg or less. This content is generally 0.01 g / kg or more.</p><p num="0084"> The first fraction separated in step b) generally contains water as well as inorganic compounds such as basic compounds and salts.</p><p num="0085"> The water content is generally 90 g / kg or less per first fraction, usually 80 g / kg or less, usually 50 g / kg or less, often 30 g / kg or less and often 15 g / kg or less. The water content is generally 1 g / kg or more per first fraction.</p><p num="0086"> The salt content is generally 10 g / first fraction 1 kg or less, usually 5 g / kg or less, usually 2 g / kg or less, often 0.1 g / kg or less and often 0.015 g / kg or less. This salt content is generally at least 0.01 g / kg.</p><p num="0087"> The proportion of salt present in a portion of the liquid reaction medium from the precipitation step b) previous step a) found in the first fraction separated in step b) is generally 25% or less, preferably 10 % Or less and more preferably 5% or less.</p><p num="0088"> Salts can be selected from alkali or alkaline earth metal chlorides, sulfates, hydrogensulfates, hydroxides, carbonates, bicarbonates, phosphates, hydrogen phosphates and borates, and mixtures thereof. It is preferable to be done. Alkaline and alkaline earth metal chlorides are preferred. Calcium chloride and sodium chloride are more preferred. Sodium chloride is the most preferred salt.</p><p num="0089"> The first fraction separated in step b) may also contain an acid compound. Acid compounds can be selected from monobasic and polybasic acids, organic and inorganic acids, and mixtures thereof. Polybasic acids can be found in a variety of protonated forms. Inorganic acids are preferred. The notation "inorganic acid" refers to hydrogen chloride, carbonic acid and its acid salts, sulfuric acid and its acid salts, phosphoric acid and its acid salts, and boric acid and its acid salts, whose molecules do not contain carbon-hydrogen bonds. It is understood to mean acid. Hydrogen chloride is preferred. This acid can be added as part of the reaction medium from step a) as described in FR07 / 53375 filed by Solvay SA.</p><p num="0090"> The second fraction separated in step b) is the subject of FR07 / 53375 and 07/55448 by Solvay SA, the content of which is incorporated herein by reference, in step b) of the method for producing epichlorohydrin. It may have a composition such as that described for the second fraction separated in.</p><p num="0091"> Of the supplementary treatments from step c), liquid / liquid extraction, adsorption and distillation operations are preferred alone or in combination, and liquid / liquid extraction and distillation operations are particularly preferred alone or in combination.</p><p num="0092"> In the first embodiment of step c) of the method for producing a product according to the invention, the treatment from step c) is at least one for the first fraction separated in step b). Includes liquid / liquid extraction operations.</p><p num="0093"> The extraction operation can be performed in parallel or countercurrent.</p><p num="0094"> The parallel flow operation is generally performed in at least one stirring reactor, followed by a settling tank. The countercurrent operation is generally performed in at least one extraction tower. Various types of reactors, settling tanks and extraction towers can be used, such as those described in the "Perry's Chemical Engineers' Handbook", 6th Edition, Chapter 21, pages 21, pages 55 and beyond.</p><p num="0095"> The extraction solvent may be an organic composition or an aqueous composition.</p><p num="0096"> The extraction solvent is often an aqueous composition. In addition to water, the aqueous composition may contain salts and / or basic compounds and / or acid compounds such as those described above and / or other compounds such as dichloropropanol. Frequently, aqueous compositions are essentially composed of water, especially desalinated water.</p><p num="0097"> After the extraction, the first portion containing most of the epichlorohydrin contained in the first fraction before the extraction operation and the second portion containing most of the extraction solvent are separated.</p><p num="0098"> Precipitation of the method according to the invention found in the first portion separated in step c), prior to the liquid / liquid extraction operation from step c), during the last separated first fraction of step b). The proportion of epichlorohydrin present is preferably at least 80%, more preferably at least 90% and even more preferably at least 95%. These proportions are more specifically obtained when the extraction solvent is an aqueous composition.</p><p num="0099"> The epichlorohydrin content of the first portion separated in step c) is generally greater than 900 g of epichlorohydrin / first portion of 1 kg, preferably 950 g / kg or more, more preferably 990 g / kg or more and Most preferably, it is 999 g / kg or more. These contents are more specifically obtained when the extraction solvent is an aqueous composition.</p><p num="0100"> The water content of the first portion is generally 150 g or less of water per 1 kg of the first portion, usually 100 g / kg or less, usually 10 g / kg or less and particularly less than 1 g / kg.</p><p num="0101"> These contents are more particularly obtained when the extraction solvent is an aqueous composition.</p><p num="0102"> The content of the organic extraction solvent from the first moiety separated in step c) is generally 100 g / first moiety 1 kg or less, usually 50 g / kg or less and especially 1 g / kg or less.</p><p num="0103"> The first portion obtained at the end of the liquid / liquid extraction process from step c) may constitute the product according to the invention, especially if the extraction solvent is water. It is preferred that this first portion constitutes the product according to the invention.</p><p num="0104"> The first portion separated in step c) may be subjected to subsequent processing such as, for example, distillation, evaporation or stripping operations.</p><p num="0105"> The second moiety separated in step c) is generally added prior to the basic compound and / or precipitation step b) used in step a) of the method, especially if the extraction solvent is an aqueous composition. Contains the acid compounds to be added and / or the salts used and / or formed in step a) of the method.</p><p num="0106"> Precipitation of the method according to the invention, found in the second portion separated in step c), before the liquid / liquid extraction operation from step c), during the last separated first fraction of step b). The proportion of basic compounds present is generally at least 80%, preferably at least 90% and more preferably at least 95%.</p><p num="0107"> Precipitation of the method according to the invention, found in the second portion separated in step c), before the liquid / liquid extraction operation from step c), during the last separated first fraction of step b). The proportion of salt present is generally at least 80%, preferably at least 90% and more preferably at least 95%.</p><p num="0108"> These proportions are more specifically obtained when the extraction solvent is an aqueous composition.</p><p num="0109"> The second portion separated in step c) may be partially or completely recycled to and / or after step a) of the method and before step b). This second part is often recycled after step a) and before step b) and often in operations to neutralize excess basic compounds after step a). ..</p><p num="0110"> The second portion separated in step c) may be subjected to a stripping, evaporation or distillation operation that allows recovery of epichlorohydrin dissolved in this moiety.</p><p num="0111"> In a second embodiment of step c) of the method for producing a product according to the invention, in step c), the first fraction separated in step b) is distilled at least once. , A process comprising at least two distillation operations, preferably at least two distillation operations and more preferably at least one drying operation by azeotropic distillation. This treatment preferably comprises at least 2 distillation operations and more preferably at least 4 distillation operations and most preferably at least 6 distillation operations in addition to the azeotropic distillation drying operation.</p><p num="0112"> The notation "distillation operation" means the separation of a mixture into two fractions of different composition by a series of countercurrent continuous evaporation and condensation operations performed on a particular device or part of a particular device. Then it is understood. If the separation of the mixture into N fractions of different composition is carried out in a single physical jacket, this is considered to correspond to N-1 distillation.</p><p num="0113"> A drying operation by azeotropic, preferably heteroazeotropic distillation, with the removal of the aqueous and organic phases, preferably with the removal of the aqueous phase, can be performed prior to other distillation operations. The azeotropic distillation drying operation can be performed after one or more other distillation operations.</p><p num="0114"> In this second embodiment, two quantities are obtained after the treatment from step c).</p><p num="0115"> In this second embodiment, the first separated first separated at the end of the precipitation step b) of the method according to the invention, found in the first quantity separated in step c), before the treatment from step c). The proportion of epichlorohydrin present in the fraction is generally at least 80%, preferably at least 90% and more preferably at least 95%.</p><p num="0116"> In this second embodiment, the first separated first separated at the end of the precipitation step b) of the method according to the invention, found in the second amount separated in step c) before the treatment from step c). The proportion of dichloropropanol present in the fraction is generally at least 80%, preferably at least 90% and more preferably at least 95%.</p><p num="0117"> In this second embodiment, the first quantity obtained at the end of the distillation operation of the treatment from step c) may constitute the product according to the invention. It is preferred that this first quantity constitutes the product according to the invention.</p><p num="0118"> In this second embodiment, the second amount can be partially or completely recycled in step a) of the method for obtaining the product according to the invention.</p><p num="0119"> In a third aspect of step c) of the method for producing a product according to the invention, in step c), the first fraction separated in step b) is subjected to at least one adsorption operation and It is subjected to a process comprising at least one distillation operation, and preferably at least three distillation operations and more preferably at least five distillation operations.</p><p num="0120"> The notation "distillation operation" refers to the separation of a mixture into two fractions with different compositions by a series of countercurrent continuous evaporation and condensation operations performed on a particular device or part of a particular device. It is understood to mean. If the separation of the mixture into N fractions of different composition is carried out in a single physical jacket, this is considered to correspond to N-1 distillation.</p><p num="0121"> In this third aspect, the adsorption operation can be performed prior to the distillation operation. The adsorption operation may be performed after one or more distillation operations. The purpose of the adsorption operation is generally to reduce the water content of the fraction to be treated. Commonly used adsorbents are molecular sieves such as 3A, 4A and 5A.</p><p num="0122"> In this third aspect, two fractions are obtained after the treatment from step c).</p><p num="0123"> In this third aspect, the first separated first separated at the end of the precipitation step b) of the method according to the invention found in the first fraction separated in step c) before the treatment from step c). The proportion of epichlorohydrin present in the fraction is generally at least 80%, preferably at least 90% and more preferably at least 95%.</p><p num="0124"> In this third aspect, the first separated at the end of the precipitation step b) of the method according to the invention, found in the second fraction separated in step c), before the treatment from step c). The proportion of dichloropropanol present in the fraction is generally at least 80%, preferably at least 90% and more preferably at least 95%.</p><p num="0125"> In this third aspect, it is epichlorohydrin that is separated at the end of the treatment described in the second and third aspects, the water content of which is generally 0.5 g of water / 1 kg of epichlorohydrin. Less than, usually 0.1 g / kg or less and usually 0.05 g / kg or less. In this epichlorohydrin, the content of organic compounds having a boiling point below the boiling point of epichlorohydrin under a pressure of 1 absolute bar is generally 0.3 g of these compounds / 1 kg or less of epichlorohydrin, usually 0.2 g. It is less than / kg and usually less than 0.1 g / kg. These compounds are, for example, acrolein, methylglycidyl ether and chloroacetone. In this epichlorohydrin, the content of organic compounds having a boiling point equal to or higher than the boiling point of epichlorohydrin under a pressure of 1 absolute bar is generally 0.7 g of these compounds / 1 kg or less of epichlorohydrin, usually 0.5. It is g / kg or less and usually 0.3 g / kg or less. These compounds are, for example, 2-chloro-2-propen-1-ol, dichloropropene, dichloropropane, hydroxyacetone, trichloropropane, glycidol, dichloropropanol, monochloropropanediol, glycerol and chloroethers such as those mentioned above. is there.</p><p num="0126"> In this third aspect, the first fraction obtained at the end of the treatment from step c) may constitute the product according to the invention. It is preferred that this first quantity constitutes the product according to the invention.</p><p num="0127"> In the fourth embodiment of step c) of the method for producing a preferred product according to the invention, the first and second embodiments are combined, and in one preferred variant, first. , Aqueous composition in which the first fraction separated in step b) is separated from the first portion containing most of the epichlorohydrin contained in the first fraction prior to the extraction operation. Is subjected to at least one liquid / liquid extraction operation in, and this first portion is subjected to at least one treatment including at least one drying operation by azeotropic distillation and at least one distillation operation. Will be done.</p><p num="0128"> In this fourth embodiment, two fractions are obtained after the treatment from step c).</p><p num="0129"> In this fourth embodiment, the first separated at the end of the precipitation step b) of the method according to the invention, found in the first fraction separated in step c), before the treatment from step c). The proportion of epichlorohydrin present in the fraction is generally at least 80%, preferably at least 90% and more preferably at least 95%.</p><p num="0130"> In this fourth embodiment, the first separated at the end of the precipitation step b) of the method according to the invention found in the second fraction separated in step c) before the treatment from step c). The proportion of dichloropropanol present in the fraction is generally at least 80%, preferably at least 90% and more preferably at least 95%.</p><p num="0131"> In this fourth embodiment, it is epichlorohydrin that is separated at the end of the treatment from step c), the water content of which is generally less than 0.5 g of water / 1 kg of epichlorohydrin, usually 0.1 g. It is less than / kg and usually less than 0.05 g / kg. In this epichlorohydrin, under a pressure of 1 absolute bar, the content of organic compounds having a boiling point below the boiling point of epichlorohydrin is generally 0.3 g of these compounds / 1 kg or less of epichlorohydrin, usually 0.2. It is g / kg or less and usually 0.1 g / kg or less. In this epichlorohydrin, the content of organic compounds having a boiling point equal to or higher than the boiling point of epichlorohydrin under a pressure of 1 absolute bar is generally 0.7 g of these compounds / 1 kg or less of epichlorohydrin, usually 0.5. It is g / kg or less and usually 0.3 g / kg or less.</p><p num="0132"> In this fourth embodiment, the first fraction obtained at the end of the treatment from step c) may constitute the product according to the invention. It is preferred that this first fraction constitutes the product according to the invention.</p>

0133<figref num="1">This is the first scheme of equipment used to obtain the products according to the invention.</figref><figref num="2">A second scheme of equipment used to obtain the products according to the invention.</figref><figref num="3">A third scheme of equipment used to obtain the products according to the invention.</figref><figref num="4">This is an example of the chemical formula of an epoxy resin.</figref><figref num="5">It is an example of a chemical formula of a compound having at least one aromatic hydroxyl group.</figref><figref num="6">It is an example of a chemical formula of a compound having at least one aromatic hydroxyl group or aromatic amine group per molecule.</figref><figref num="7">It is an example of the chemical formula of polycyclopentadiene polyphenols or aromatic polyamines.</figref><figref num="8">This is an example of the chemical formula of the coagulant molecule.</figref><figref num="9">This is an example of the chemical formula of a wet-reinforced resin polymer.</figref><figref num="10">This is an example of the chemical formula of a compound used as a phosphorus-containing flame retardant.</figref>

0134FIG. 1 shows a first scheme of equipment used to obtain the products according to the invention.

0135In the first variant of this first scheme, the first reactor (1) has a first stream of dichloropropanol via line (2) and is basic via line (3). A first stream of the compound is supplied. The discharge from the reactor (1) via the line (4) is a stream containing unreacted epichlorohydrin, salts, dichloropropanol and basic compounds, which in the second reactor (5). The stream is supplied. The reactor (5) is supplied with a second stream of dichloropropanol via line (6) and a second stream of basic compound via line (7). The discharge from the second reactor (5) via the line (8) is a stream containing epichlorohydrin and salt, which is fed to the first settling tank (9). In the first settling tank (9), the first fraction containing most of the epichlorohydrin contained in the stream (8) and most of the salt contained in the stream (8) are contained. The second fraction is separated. The second fraction is discharged from the settling tank (9) via the line (10) and the first fraction via the line (11). The first portion of the first fraction ejected from the line (11) is supplied to the first extractor (13) via the line (12). Water is also supplied to the first extractor (13) via the line (14). Vigorous agitation is performed in the first extractor (13). A stream is discharged from the extractor (13) through the line (15) and is supplied to the second settling tank (16). The discharge from the second settling tank (16) via the line (17) is the third fraction containing most of the epichlorohydrin contained in the stream (15), as well as the line (18). ) Is the fourth fraction containing water and salt.

0136In various aspects of this first variant of this first scheme, a portion of the fourth fraction containing water and salt discharged via line (18) is, respectively, line (19). To the first reactor (1) via and / or between the first reactor (1) and the second reactor (5) via the line (20) and / or the line ( It is recycled between the second reactor (5) and the first settling tank (9) via 21).

0137In the second variant of this first scheme, the first fraction discharged from the first settling tank (9) via the line (11) is no longer supplied to the extractor (13). The procedure from the first modification is followed except that it is supplied to the extraction tower (23) via the line (22). Water is countercurrently supplied to the extraction tower (23) via the line (24). The discharge from the column (23) via the line (25) is the fifth fraction containing most of the epichlorohydrin contained in the stream (22) and through the line (26). The discharge is the sixth fraction containing water and salt.

0138In various aspects of this second variant of this first scheme, a portion of the second fraction containing water and salt discharged via line (26) is, respectively, line (27). To the first reactor (1) via the line (1) and / or to the second reactor (5) via the line (28) and / or to the second reactor (5) via the line (29). ) And the first settling tank (9).

0139In the third and fourth variants of this first scheme, the procedure from the first variant or the procedure from the second variant is followed, respectively, in addition to the third reactor ( 30) is supplied with a third stream of dichloropropanol via the line (31) and a third stream of the basic compound via the line (32). The effluent from the reactor (30) via the line (33) is a stream containing unreacted epichlorohydrin, salts, dichloropropanol and basic compounds, which is in the fourth reactor (34). The stream is supplied. The fourth reactor (34) is supplied with a fourth stream of dichloropropanol via line (35) and a fourth stream of basic compound via line (36). The discharge from the fourth reactor (34) via the line (37) is a stream containing epichlorohydrin and salt, which is fed to the first settling tank (9).

0140In various aspects of these third and fourth variants of this embodiment, the third reactor (30) is supplied with steam via the line (38) and the line (30). Emissions from the third reactor (30) via 39) are streams containing water and epichlorohydrin, and / or to the fourth reactor (34) via line (40). Along with the supply of water vapor, the discharge from the fourth reactor (34) via the line (41) is a stream containing water and epichlorohydrin.

0141In these various variants, parts of the stream (18) and / or (26) may result in a purge through the lines (42) and (43), respectively.

0142Without being bound by any theory, 1,3-dichloro-2-propanol in a mixture of dichloropropanol containing 1,3-dichloro-2-propanol and 2,3-dichloro-1-propanol. The isomers are converted to epichlorohydrin primarily in the first reactors (1) and / or (30), while the 2,3-dichloro-1-propanol isomer is predominantly the second reaction. It is believed to be converted to epichlorohydrin in vessels (5) and / or (34).

0143FIG. 2 shows a second scheme of equipment used to obtain the products according to the invention.

0144In the first variant of this second scheme, the azeotropic drying column (50) is fed a stream containing epichlorohydrin via a line (51). This stream comes from one or more lines of the equipment shown in FIG. 1, ie, the organic fractions of lines (17), (25), and lines (39) and (41). This stream, in addition to epichlorohydrin, is a light product such as acetaldehyde and achlorine, in other words, one whose boiling point under absolute bar pressure is less than the boiling point of epichlorohydrin; water; heavy glycidol. , 2-Chloro-2-propen-1-ol, hydroxyacetone, chloroacetone, 1,3-dichloropropane, 1,3-dichloropropene, 1,2,3-trichloropropane, 2-methyl-2-cyclopentene- Products such as 1-one, cyclopentanone, 2-chloroethanol and chloropropanol, in other words, its boiling point under absolute bar pressure is above the boiling point of epichlorohydrin and below the boiling point of dichloropropanol. Those; as well as superheavy products such as monochloropropanediol and partially chlorinated and / or esterified glycerol oligomers, in other words, those whose boiling point under pressure of 1 absolute bar is greater than the boiling point of dichloropropanol.

0145The discharge from the column (50) via the line (52) is a stream containing water, epichlorohydrin, light products and heavy products forming an azeotropic product with water, the first condenser ( 53), then the first settling tank (55) is fed this stream via the line (54). The discharge from the first settling tank (55) via the line (56) is the aqueous phase, and the discharge via the line (57) is water-saturated epichlorohydrin. This aqueous phase can be further sent to the high temperature oxidation treatment unit. A first portion of the stream discharged through the line (57) is optionally fed through the line (58) to the distillation column (50). A second portion of the stream discharged through the line (57) is fed through the line (59) to the second distillation column (60). The discharge from the second column (60) through the line (61) is essentially a stream containing light products, a second capacitor (96), then a second settling tank (97). This stream is supplied to the capacitor via line (61). The discharge from the second settling tank (97) is a gas phase containing a light product via the line (99), which can be further delivered to the hot oxidation treatment unit. The discharge from the second settling tank (97) is the aqueous phase through the line (98), which can be further delivered to the hot oxidation treatment unit. The liquid contained in the settling tank (97), preferably part of the organic phase, can be returned to the top of the distillation column (60) via a line (106). The discharge from the second distillation column (60) via the line (62) is a stream containing predominantly epichlorohydrin, which is fed to the first distillation column (50).

0146The discharge from the column (50) through the line (63) is a water-free stream, which is fed to a third distillation column (64).

0147Emissions from the third column (64) via line (65) are streams containing epichlorohydrin, light and heavy products. This stream is fed to a fourth distillation column (66), and future emissions via line (67) are essentially streams containing light products. A portion of this stream can be returned to the first distillation column (50) via the line (68). The discharge from the fourth distillation column (66) via the line (69) is a stream depleted of light compounds, which is fed to the fifth distillation column (70). Emissions via line (71) from the fifth distillation column (70) are purified epichlorohydrin, and some of the emissions via line (72) are on line (73). A stream containing heavy products that can be carried via a third distillation column (64).

0148Emissions from the third column (64) via the line (74) are streams containing epichlorohydrin, heavy products, dichloropropanol and super heavy products on the sixth distillation column (75). This stream is supplied. The discharge from the sixth distillation column (75) via the line (76) is a stream containing epichlorohydrin and heavy products, which is fed to the twelfth distillation column (100). Along with this, the discharge from the sixth distillation column (75) via the line (77) is a stream containing dichloropropanol and superheavy products, which is supplied to the seventh distillation column (78). Will be done.

0149The discharge from the 12th distillation column (100) via the line (102) is a stream containing epichlorohydrin, which is returned to the 1st distillation column (50) for recycling. .. The discharge from the twelfth distillation column (100) via the line (101) is a stream containing heavy products, which stream can be further processed in the high oxidation temperature unit.

0150The discharge via line (79) from the seventh distillation column (78) is a stream of dichloropropanol, and the discharge via line (80) is a stream containing super-heavy products. The stream of dichloropropanol recovered via line (79) can be carried to one or more of the reactors (1), (5), (30) and (34) of the equipment shown in FIG. Streams containing superheavy products can be sent to the hot oxidation unit for further processing.

0151In the second variant of the second scheme, the lines and columns (74)-(80) are absent and the emissions from the third column (64) via the line (81) are epichloro. Follow the procedure from the first variant, except that it is a stream containing hydrin, heavy products, dichloropropanol and super heavy products, and that this stream is fed to the eighth distillation column (82). The effluent from the eighth distillation column (82) via the line (83) is a stream containing superheavy products that can be further processed in the hot oxidation unit along with the line (84). The mediated discharge is a stream containing epichlorohydrin, heavy products and dichloropropanol, which is fed to the ninth distillation column (85).

0152The discharge via line (86) from the ninth distillation column (85) is a stream of dichloropropanol, and the discharge via line (87) is a stream containing epichlorohydrin and heavy products. This stream is supplied to the twelfth distillation column 100. The stream of dichloropropanol recovered via line (86) can be carried to one or more of the reactors (1), (5), (30) and (34) of the equipment shown in FIG.

0153In the third variant of this second scheme, the procedure from the first variant is followed except that the lines and columns (65)-(73) do not exist.

0154Emissions from the third column (64) via line (88) are streams containing epichlorohydrin, light and heavy products. This stream is fed to the tenth distillation column (89), and the discharge through the line (90) from now on is a stream containing heavy products. A portion of this stream can be returned to the third distillation column (64) via the line (91). The discharge from the tenth distillation column (89) via the line (92) is a stream containing epichlorohydrin and light products, which is fed to the eleventh distillation column (93). .. The discharge via line (94) from the eleventh distillation column (93) is a stream of purified epichlorohydrin, and the discharge via line (95) is a stream containing a light compound. is there. A portion of this stream can be sent via the line (96) to the first distillation column (50).

0155In the fourth variant of this second scheme, the procedure from the second variant is followed except that the lines and columns (65)-(73) do not exist.

0156Emissions from the third column (64) via line (88) are streams containing epichlorohydrin, light and heavy products. This stream is fed to the tenth distillation column (89), and the discharge through the line (90) from now on is a stream containing heavy products. A portion of this stream can be returned to the third distillation column (64) via the line (91). The discharge from the tenth distillation column (89) via the line (92) is a stream containing epichlorohydrin and light products, which is fed to the eleventh distillation column (93). .. The discharge via line (94) from the eleventh distillation column (93) is a stream of purified epichlorohydrin, and the discharge via line (95) is a stream containing a light compound. is there. A portion of this stream can be sent via the line (96) to the first distillation column (50).

0157In the fifth modification of this second scheme, the procedure from the first modification is followed except that the lines and columns (69) to (73) do not exist.

0158The discharge via line (103) from the third column (66) is a stream containing epichlorohydrin, and the discharge via line (104) is partly in line (105). A stream containing a heavy product that can be recycled to a third distillation column (64) via.

0159FIG. 3 shows a third scheme of equipment used to obtain the products according to the invention.

0160In the first variant of this third scheme, the first distillation column (200) is fed a stream containing epichlorohydrin via a line (201). This stream comes from one or more lines of equipment shown in FIG. 1, ie, lines (17) and (25), as well as organic fractions of lines (39) and (41). This stream, in addition to epichlorohydrin, is a light product such as acetaldehyde and achlorine, in other words, one whose boiling point under absolute bar pressure is less than the boiling point of epichlorohydrin; water; heavy glycidol. , 2-Chloro-2-propen-1-ol, hydroxyacetone, chloroacetone, 1,3-dichloropropane, 1,3-dichloropropene, 1,2,3-trichloropropane, 2-methyl-2-cyclopentene- Products such as 1-one, cyclopentanone, 2-chloroethanol and chloropropanol, in other words, the boiling point under pressure of 1 absolute bar is above the boiling point of epichlorohydrin and below the boiling point of dichloropropanol. Contains; as well as superheavy products such as monochloropropanediol and partially chlorinated and / or esterified glycerol oligomers, in other words, those whose boiling point under absolute bar pressure is above the boiling point of dichloropropanol. To do.

0161The discharge from the distillation column (200) via the line (202) is a stream containing epichlorohydrin, water, light and heavy compounds, which is fed to the azeotropic drying column (203). To. The discharge from the drying column (203) via the line (204) is a stream containing epichlorohydrin and water carried to the settling tank (207) via the condenser (205) and line (206). .. The discharge from the settling tank (207) via the line (208) is a stream containing mainly water, and the discharge via the line (209) is mainly carried to the distillation column (200). A stream containing hydrin.

0162The effluent from the azeotropic drying column (203) via the line (210) is a stream containing epichlorohydrin, light and heavy compounds, which is on the second distillation column (211). Supplied. The discharge via line (212) from the second distillation column (211) is a stream containing the light compound, while the discharge via line (213) contains epichlorohydrin and heavy compounds. This stream is supplied to the third distillation column (214). The discharge from the column (214) via the line (215) is a stream composed of purified epichlorohydrin, and the discharge via the line (216) is the first distillation column (200). A stream containing heavy compounds that are recycled into.

0163The discharge from the first distillation column (200) via the line (217) is a stream containing dichloropropanol, heavy compounds and super-heavy compounds, which is on the fifth distillation column (218). Be supplied. The discharge from the column (218) via the line (219) is a stream containing superheavy products, while the discharge via the line (220) is a stream containing dichloropropanol and heavy products. This stream is supplied to the sixth distillation column (221). The discharge from the column (221) via the line (222) is primarily a stream containing dichloropropanol, and the discharge via the line (223) is essentially a stream containing heavy products. ..

0164The stream of dichloropropanol recovered via line (222) can be carried to one or more of the reactors (1), (5), (30) and (34) of the equipment shown in FIG.

0165In the second variant of the third scheme, the lines and columns (217)-(223) are absent and the emissions from the first column (200) via the line (224) are heavy products. , A stream containing dichloropropanol and superheavy products, which follows the procedure from the first variant, except that the stream is fed to a seventh distillation column (225). The discharge via line (226) from the seventh distillation column (225) is a stream containing heavy products, while the discharge via line (227) contains super-heavy products and dichloropropanol. It is a stream, and this stream is supplied to the eighth distillation column (228).

0166The discharge via line (229) from the eighth distillation column (228) is a stream of dichloropropanol, and the discharge via line (230) is a stream containing super-heavy products. The stream of dichloropropanol recovered via line (229) can be carried to one or more of the reactors (1), (5), (30) and (34) of the equipment shown in FIG.

0167In the third modification of the third scheme, the procedure from the first modification is followed except that the lines and columns (210) to (216) do not exist.

0168Emissions from the dry column (203) via the line (231) are streams containing epichlorohydrin, light and heavy products. This stream is fed to the ninth distillation column (232), and the discharge via the line (233) from now on is a stream containing heavy products. The discharge from the ninth distillation column (232) via the line (234) is a stream containing epichlorohydrin and light products, which is fed to the tenth distillation column (235). .. The discharge via line (236) from the tenth distillation column (235) is a stream of purified epichlorohydrin, and the discharge via line (237) is a stream containing a light compound. is there.

0169In the fourth variant of the third scheme, the procedure from the second variant is followed except that the lines and columns (210)-(216) do not exist.

0170Emissions from the dry column (203) via the line (231) are streams containing epichlorohydrin, light and heavy products. This stream is fed to the eighth distillation column (232), and the discharge via the line (233) from now on is a stream containing heavy products. The discharge from the eighth distillation column (232) via the line (234) is a stream containing epichlorohydrin and light products, which is fed to the ninth distillation column (235). .. The discharge via line (236) from the ninth distillation column (235) is a stream of purified epichlorohydrin, and the discharge via line (237) is a stream containing a light compound. is there.

0171It is possible to easily imagine other variants of the various embodiments.

0172The present invention also includes epoxy resins; synthetic glycerol; polyamide-epichlorohydrin resins; chemical formulations for water treatment such as polyacrylamides, polyamines and quaternary ammonium salts; epichlorohydrin homopolymers, epichlorohydrin. / Epichlorohydrin elastomers such as ethylene oxide copolymers and epichlorohydrin / ethylene oxide / allylglycidyl ethers Terrapolymers; glycidyl ethers such as cresylglycidyl, butyl, decyl or dodecyl ethers; surfactants; difficulties such as phosphorylation flame retardants With respect to the use of the epichlorohydrin-based products described above as reactants in the fuel agents; resins for the production of water resistant papers; and methods for producing glycidyl acrylates and methacrylates.

0173The presence of impurities in epichlorohydrin can prove awkward in some of these applications for a variety of reasons. Some halogenated hydrocarbons are, for example, carcinogenic or suspected to be carcinogenic, developmental toxicity, reproductive toxicity, cardiotoxicity, endocrine toxicity, immunotoxicity, as well as liver, kidney, nerve. Suspected to be toxic to the airway and skin. These can remain in the final product and can decompose with the accompanying deterioration of the properties of the final product. They are either toxic or can be degraded in compounds that are somewhat toxic, raising safety issues, especially if the final product is intended to come into contact with food and beverages. To do. Moreover, they can be accumulated and contaminated in industrial water, such as wastewater or water containing pulp that is recycled in the pulp and paper industry. In the latter case, these higher concentrations can increase the contamination of the paper formed with recycled water.

0174Further goals of the present invention are the production of epoxy derivatives, products that will be used in food and beverage applications, cationizing agents, flame retardants, products that will be used as cleaning ingredients, and epichlorohydrin elastomers. It is to solve these problems by providing a product containing epichlorohydrin and containing low levels of impurities, which can be used in.

0175The present invention also thus relates to the present invention in the production of epoxy resins or glycidyl esters or glycidyl ethers or glycidyl amides or glycidyl imides or flocculants or wet strengthening resins or cationizing agents or flame retardants or cleaning ingredients or epichlorohydrin elastomers. Regarding the use of products by.

01761. Epoxy derivative 1.1. General Epoxy derivatives are, for example, epoxy resins, glycidyl ethers, glycidyl esters and glycidyl amides, and imides. Examples of glycidyl esters are glycidyl acrylates and glycidyl methacrylates.

0177Epoxy resins are intended to represent polymers whose chemical formula contains at least one oxylan group, preferably one 2,3-epoxypropyloxy group.

0178Polymers are intended to refer to molecules with many units that are often repetitively bonded to each other via chemical covalent bonds, and these units are referred to as repeating units. The number of repeating units is 1 or more. The polymer contains at least one type of repeating unit. If the polymer contains only one type of repeating unit, it is called a homopolymer. When a polymer contains more than one type of repeating unit, it is called a copolymer. These copolymers can be of random, alternating or block type, such as those described in "Polymer Science Dictionary, MSM, Elsevier Applied Science (London and New York), 1989, p. 86". Is.

0179An example of the chemical formula of the epoxy resin is shown in FIG. 4, where n is not 0.

0180A glycidyl ether is intended to represent an ether whose chemical formula contains at least one glycidyl (2,3-epoxypropyl) group and is not a polymer. Examples of glycidyl ethers are N-butyl glycidyl ethers, C₁₂~ C₁₄Aliphatic glycidyl ethers, o-cresol glycidyl ethers, neopentyl glycol diglycidyl ethers and butanediol diglycidyl ethers.

0181A glycidyl ester is intended to represent an ester whose chemical formula contains at least one glycidyl (2,3-epoxypropyl) group and is not a polymer. Examples of glycidyl esters are diglycidyl ester of hexahydrophthalic acid, glycidyl ester of neodecanoic acid, glycidyl acrylate and glycidyl methacrylate.

0182The glycidyl amides and imides are intended to represent non-polymeric amides or imides whose chemical formulas contain at least one glycidyl (2,3-epoxypropyl) group. Examples of glycidylamides and imides are 1,3,5-tris (2,3-epoxypropyl) -1,3,5-perhydrotriazine-2,4,6-trione and 5,5-dimethyl-1, 3-Bis (2,3-epoxypropyl) -2,4-imidazolidinedione.

01831.2. Coreactants When the epichlorohydrin-containing product according to the present invention is used in the production of an epoxy derivative, the epichlorohydrin-containing product is usually at least one active hydrogen atom, preferably at least two. It was subjected to a reaction with at least one compound containing an active hydrogen atom, followed by dehydrochlorination as described in Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, 1987, A9, pp. 547-553. Used for hydrogen.

0184Compounds containing one active hydrogen atom are from monoalcohols, preferably 1-butanol, C.₁₂~ C₁₄It is possible to choose from primary alcohols or cresols, as well as monocarboxylic acids such as neodecanoic acid, acrylic acid, methacrylic acid or mixtures thereof.

0185Compounds containing at least two active hydrogen atoms can be selected from polyols, polyamines, aminoalcohols, polyimides and amides, polycarboxylic acids, and mixtures thereof.

0186The polyol can be aromatic or aliphatic. Aromatic polyols are preferred.

0187Preferred aliphatic polyols are aliphatic diols, more preferably butanediol, neopentyl glycol, hydride bisphenol A (4,4'-dihydroxy-2,2-dicyclohexylpropane), and aliphatic triols, preferably glycerol. It is selected from poly (oxypropylene) glycols, as well as mixtures thereof.

0188Aromatic polyols can be selected from polyhydroxybenzene, polyphenol compounds, and mixtures thereof.

0189The polyhydroxybenzene is preferably selected from dihydroxybenzene, trihydroxybenzene, and mixtures thereof. Dihydroxybenzene is more preferably selected from 1,2-, 1,3-, 1,4-dihydroxybenzene and mixtures thereof.

0190The trihydroxybenzene is preferably 1,3,5-trihydroxybenzene.

0191A polyphenol compound is generally a compound whose molecule contains at least one aromatic hydroxyl group.

0192Suitable compounds having at least one aromatic hydroxyl group that can be utilized herein include those of US Pat. No. 4,499,255, the contents of which are incorporated herein by reference. There are, for example, phenol, bisphenol, novolak resin, polyvinylphenol, related amine compounds such as those shown in formulas I to V of FIG. 5, and each A in the formula is independently 1 to about 1 to about. 12 carbon atoms, preferably 1 to about 6 carbon atoms, -O-, -S-, -SS-,-(S = O)₂A divalent hydrocarbon group having-,-(S = O)-or-(C = O)-; A'is 1 to about 12 carbon atoms, preferably 1 to about 6 carbon atoms. A trivalent hydrocarbon group with atoms; each R is independently hydrogen; a hydrocarbyl group with 1 to about 10 carbon atoms, preferably 1 to about 4 carbon atoms; preferably chlorine or Halogen atoms such as bromine; or hydroxyl or amino groups; each Z is independently -OH or NH₂P has a value of about 1 to about 100, preferably about 2 to about 50; m has a value of about 1.00 to about 6; and n has a value of 0 or 1. ..

0193As a compound having at least one aromatic hydroxyl group or aromatic amine group per molecule, those represented by the formulas VI to VIII of FIG. 6 are also suitable, and each R is 1 to about 18 in the formula. A divalent hydrocarbyl group having carbon atoms of, preferably about 2 to about 12 carbon atoms and most preferably about 2 to about 6 carbon atoms, represented by the formula IX, X, XI or XII of FIG. R is a group that forms a stable heterocycle with a nitrogen atom.¹Each A can be independently combined with 1 to about 10 carbon atoms, preferably 1 to about 4 carbon atoms, -O-, -S-, -SS-,- (S = O)₂A divalent hydrocarbyl group with-,-(S = O)-or-(C = O)-; each R¹Independently, hydrogen, 2,3-epoxypropyl group, 2-alkyl-2,3-epoxypropyl group, monovalent hydrocarbyl group or hydroxyl-substituted monovalent hydrocarbyl group (the hydrocarbyl group is 1 to about 9). It has carbon atoms, the alkyl has 1 to about 4 carbon atoms, preferably 1 to about 3 carbon atoms); each R²Are independently alkyl groups or hydrogens having 1 to about 4 carbon atoms, preferably 1 to about 3 carbon atoms; each R³Are independently alkyl groups or hydrogens with 1 to about 4 carbon atoms; each R⁴Are independently hydrocarbyl or halogen-substituted hydrocarbyl groups having 1 to about 9 carbon atoms, preferably 1 to about 2 carbon atoms, hydrogen; each R.⁸Is independently selected from the groups represented by the formula XIV, or R⁸R except that can not be hydrogen¹Selected from the same group as; each R⁹Are independently divalent hydrocarbyl groups with 2 to about 4 carbon atoms, preferably 2 carbon atoms; each Z is independently -OH or -NH2; each X Are independently hydrogen, chlorine, bromine, or hydrocarbyl or hydrocarbyloxy groups having 1 to about 9 carbon atoms, preferably 1 to about 6 carbon atoms; each m is independent. , 0 or 1; n has an average value of about 0.01 to about 6, preferably 0.1 to about 4; p has an average value of 1 to about 10, preferably 1 to about 3. Has; q has an average value of at least 1, preferably 1 to about 150, most preferably 1 to about 100, and usually 1 to about 10; and each y and z is 1 independently. Or has a value of 2.

0194Polycyclopentadiene polyphenols or aromatic polyamines represented by formula XIII in FIG. 7 are also suitable, in which Z is -OH or -NH.₂And n has a value of 1 to about 5; n'has a value of about 1 to about 10, preferably 3 to about 6; each R independently has a value of hydrogen; 1 to about. A hydrocarbyl group having 10 carbon atoms, preferably 1 to about 4 carbon atoms; preferably a halogen atom such as chlorine or bromine; or a hydroxyl or amino group.

0195Suitable such polycyclopentadiene polyphenols and methods for preparing them are incorporated herein by reference in US Pat. No. 4,390,680, issued June 28, 1983 to Donald L. Nelson. It is possible to find it in the book. By substituting aromatic amines for phenolic compounds, polycyclo-pentadiene aromatic polyamines can be prepared in a similar manner.

0196Compounds containing both at least one aromatic hydroxyl group and at least one aromatic amine group, such as hydroxyaniline, aminoxyl enol, etc., are also suitable.

0197The polyphenol compound is preferably bisphenol A (4,4'-dihydroxy-2,2-diphenylpropane, 4,4'-isopropyridendiphenol), tetrabromobisphenol A (4,4'-isopropyridenebis (2). , 6-dibromophenol)), bisphenol AF (4,4'-[2,2,2-trifluoro-1- (trifluoromethyl) ethylidene] bisphenol) = hexafluorobisphenol A (4,4'-dihydroxy- 2,2-Diphenyl-1,1,1,3,3,3-hexafluoropropane), 1,1,2,2-tetra (p-hydroxyphenyl) ethane, hexafluorobisphenol A, tetramethylbisphenol (4) , 4'-dihydroxy-3,3', 5,5'-tetramethylbisphenol), 1,5-dihydroxynaphthalene, 1,1', 7,7'-tetrahydroxy-dinaphthylmethane, 4,4'- Dihydroxy-α-methylstylben, condensate of bisphenol A with formaldehyde (bisphenol A novolak), condensate of phenol with formaldehyde, preferably bisphenol F (o, o', o, p'and p, p of dihydroxydiphenylmethane 'Mixture of isomers), condensate of cresol with formaldehyde (mixture of o, o', o, p'and p, p'isomers of methylhydroxydiphenylmethane), phenol and dicyclopentadiene (2,5-bis) Alkylated products of [(hydroxyphenyl] octahydro-4,7-methano-5H-indene), condensates of phenol and glyoxal (tetrakis (4-hydroxy-phenyl) ethane), phenol and hydroxybenzaldehyde (eg, tris (eg, tris) It is selected from a condensate of 4-hydroxyphenyl) methane), 1,1,3-tris- (p-hydroxyphenyl) -propane, and mixtures thereof.

0198Polyamines can be aliphatic or aromatic. Aromatic diamines such as 4,4'-diaminodiphenylmethane are preferred.

0199Amino alcohols can be aliphatic or aromatic. For example, aromatic amino alcohols such as p-aminophenol are preferred.

0200Imides and amides can be aliphatic or aromatic. Heterocyclic imides and amides such as 1,3,5-triazinetriol and imidazolidine-2,4-dione are preferred.

0201The polycarboxylic acid can be aliphatic or aromatic. An example of a dimeric fatty acid is linoleic acid. The polycarboxylic acid is preferably an aromatic dicarboxylic acid, such as hexahydrophthalic acid.

02021.3. Epoxy derivative formation method Methods for forming epoxy resins, glycidyl ethers and glycidyl esters are generally the reaction of a product containing epichlorohydrin and a compound containing at least one active hydrogen atom, followed by a basic agent. Including dehydrochlorination of.

0203The method for forming the epoxy resin usually involves two steps: preparation of the uncured epoxy resin, followed by a curing step.

02041.3.1. Uncured ER The reaction of a product containing epichlorohydrin with a compound containing at least one, preferably two, active hydrogen atoms is, for example, a caustic coupling method for forming a liquid epoxy resin (LER) and a caustic coupling method. It can be carried out by any method known in the art such as phase transfer catalyst method, toffee method for forming solid epoxy resin (SER) and advanced method or fusion.

0205Caustic coupling method In the caustic method, the caustic alkali acts as a catalyst for the nucleophilic ring opening (coupling reaction) of the epoxide group linked to the primary carbon atom of epichlorohydrin by the phenolic hydroxyl group, and It is used as a dechloride agent for the conversion of chlorohydrin to epoxide groups. Caustic alkali (NaOH), however, can be replaced with any basic compound.

0206Compounds with epichlorohydrin and active hydrogen atoms, preferably aromatic hydroxyl or aromatic amine compounds, have a molar ratio of about 2: 1 to about 10: 1, preferably about 2: 1 to about 6: 1, respectively. Used in.

0207The basic compound can be an organic or inorganic basic compound. Organic basic compounds are, for example, amines, phosphines and ammonium, phosphoniums or arsonium hydroxides. Inorganic basic compounds are preferred. The notation "inorganic compound" is understood to mean a compound that does not contain a carbon-hydrogen bond. Inorganic basic compounds can be selected from alkaline and alkaline earth metal oxides, hydroxides, carbonates, bicarbonates, phosphates, hydrogen phosphates and borates, and mixtures thereof. Alkaline and alkaline earth metal oxides, as well as alkaline and alkaline earth metal hydroxides are preferred. Preferred alkali metal hydroxides that can be utilized herein include, for example, sodium hydroxide, potassium hydroxide, lithium hydroxide or mixtures thereof. Sodium hydroxide is particularly preferred.

0208In the method according to the invention, the basic compound can be in the form of a liquid, a essentially anhydrous solid, a hydrated solid, an aqueous and / or organic solution, or an aqueous and / or organic suspension. The basic compound is preferably in the form of an anhydrous solid, a hydrated solid, an aqueous solution or an aqueous suspension. A solution or suspension, preferably an aqueous solution of a basic compound, preferably an aqueous solution of sodium hydroxide is used.

0209The content of the basic agent in the solution or suspension is generally at least 5% by weight, preferably at least 10% by weight, preferably at least 20% by weight, and most preferably at least 30% by weight. This content is usually 70% by weight or less, preferably 60% by weight or less, preferably 50% by weight or less, and most preferably 40% by weight or less.

0210The alkali metal hydroxide is preferably used as an aqueous solution at a concentration of usually about 20 to about 50, preferably about 40 to about 50% by weight.

0211The amount of the basic compound, preferably the alkali metal hydroxide used in the method of the present invention, is preferably about 0.80 mol to about 1.2 mol of base per aromatic, hydroxyl group and preferably aromatic, amine hydrogen, respectively. The sex agent, preferably about 0.90 to 1.0 mol.

0212Compounds containing a basic agent, epichlorohydrin and an active hydrogen atom can be mixed in any order. The basic compound is preferably added to a mixture of the other two reactants. The basic agent, preferably the alkali metal hydroxide, can be added continuously or incrementally, but not all the alkali metal hydroxides added in one increment.

0213This reaction can be carried out in a solvent. Suitable solvents that can be utilized include any solvent that does not react with any of the constituents in the reaction mixture. Preferably, such a solvent is partially or completely hydrated to form a co-distillate with epichlorohydrin and water, and the distillate reacts at the pressure utilized. It has a lower boiling point than the lowest boiling point component of the mixture. Suitable such solvents include, for example, primary and secondary alcohols such as 1-methoxy-2-hydroxypropane, 1-butoxy-2-hydroxyethane, cyclohexanol. Secondary alcohols are preferred.

0214If a solvent is used, the amount of solvent used will depend on the particular solvent used and the compound containing the active hydrogen atom. The solvent is generally in the range of about 5 to about 50 weight percent, preferably about 10 to about 40 weight percent, based on the total weight of the reactants.

0215The pressure can be equal to 1 absolute bar, less than 1 absolute bar or greater than 1 absolute bar. If a solvent is used, a suitable pressure that can be utilized will result in a co-distillate having a boiling point of about 45 ° C to about 80 ° C, preferably about 55 ° C to about 70 ° C. It will be.

0216The reaction temperature is usually 25 ° C or higher, preferably 50 ° C or higher, more preferably 90 ° C or higher, and most preferably 95 ° C or higher. The reaction temperature is usually 200 ° C. or lower, preferably 150 ° C. or lower, more preferably 125 ° C. or lower, and most preferably 120 ° C. or lower.

0217This reaction is usually carried out for a length of time such that the amount of active hydrogen atom-containing groups remaining in the reaction mixture is about 0.5 or less, preferably about 0.2 weight percent or less. This time is usually 0.5 hours or more, often 1.0 hours or more, often 2.0 hours or more, and especially 3.0 hours or more. Reaction times are usually 20 hours or less, often 10 hours or less, often 5 hours or less, and especially 4 hours or less.

0218Once the reaction is complete, the resulting epoxy resin is finished in one of the commonly used methods. Excess epichlorohydrin is usually removed by distillation, while salts are removed by filtration, centrifugation and / or washing with water.

0219Epichlorohydrin distillation is generally performed in two steps. The first step is generally atmospheric pressure (1 absolute bar), usually 100 ° C or higher, preferably 120 ° C or higher, more preferably 130 ° C or higher, and most preferably 145 ° C or higher and usually 200 ° C or higher. It is carried out at a temperature of ° C or lower, preferably 180 ° C or lower, more preferably 175 ° C or lower, and most preferably 155 ° C or lower. The second step is usually quasi-atmospheric pressure, usually 0.1 absolute bar or less, preferably 0.01 bar or less, more preferably 0.005 bar or less, and most preferably 0.002 bar or less, usually 150 ° C or higher, preferably 170 ° C or higher, more preferably 190 ° C or higher, and most preferably 195 ° C or higher and usually 300 ° C or lower, preferably 250 ° C or lower, more preferably 220 ° C or lower, and most preferably 215 ° C. It is carried out at a temperature below C.

0220The salt formed can be separated from the crude product by the addition of a solvent such as toluene, followed by filtration and distillation to remove the solvent.

0221Phase transfer catalyst method Alternatively, in the phase transfer catalyst method, the coupling reaction and dehydrochlorination are individually carried out by using a phase transfer coupling catalyst such as a quaternary ammonium salt which is not a strong base enough to promote dehydrochlorination. It is possible to carry out. Once the coupling reaction is complete, caustic alkali is added and a dehydrochlorination step is performed. Through this method, for example, higher yields (&gt; 90%) of monomeric diglycidyl ether (DGEBA) of bisphenol A can be easily achieved.

0222It is possible to use the batch method and preferably the continuous or semi-continuous method.

0223Taffy method The toffee method is used to prepare higher molecular weight solid resins. It is direct from epichlorohydrin, compounds containing active hydrogen atoms and theoretical amounts of NaOH. This method is very similar to the caustic coupling method used to prepare liquid epoxy resins. A lower ratio of compounds containing epichlorohydrin to active hydrogen atoms is used to promote the formation of high molecular weight resins. Upon completion of the polymerization, the mixture is composed of an aqueous alkaline salt solution and a water-resin emulsion. The product is recovered by separating the phases, washing the resin with water, and removing the water under reduced pressure.

0224Compounds with epichlorohydrin and active hydrogen atoms, preferably aromatic hydroxyl or aromatic amine compounds, have a molar ratio of about 1: 1 to about 2: 1, preferably about 1.3: 1 to about 1.8: 1, respectively. Used in.

0225The alkali metal hydroxide is preferably used as an aqueous solution at a concentration of about 1 to about 20, preferably about 5 to about 15 weight percent.

0226The amount of the basic compound, preferably the alkali metal hydroxide used in the method of the present invention, is preferably about 0.05 mol to about 2 mol, preferably about 0.05 mol to about 2 mol, each of an aromatic, a hydroxyl group, and preferably an aromatic, an amine hydrogen. Is a basic drug of about 0.1 mol to 0.5 mol.

0227The reaction temperature is usually 25 ° C or higher, preferably 50 ° C or higher, more preferably 90 ° C or higher, and most preferably 95 ° C or higher. The reaction temperature is usually 200 ° C. or lower, preferably 150 ° C. or lower, more preferably 125 ° C. or lower, and most preferably 120 ° C. or lower.

0228Reaction times are usually 0.1 hours or longer, often 0.5 hours or longer, often 1.0 hours or longer, and especially 1.5 hours or longer. Reaction times are usually 20 hours or less, often 10 hours or less, often 5 hours or less, and especially 4 hours or less.

0229Compounds containing basic agents, epichlorohydrin and active hydrogen atoms can be mixed in any order. It is preferred to add epichlorohydrin to the mixture of the other two reactants.

0230This reaction is usually carried out with vigorous stirring.

0231At the end of the reaction, the mixture separates into two layers. The heavier aqueous layer is removed and the molten toffee-like product is washed with hot water until the wash water is neutral. The toffee-like product is generally dried at a temperature of at least 100 ° C, preferably at least 120 ° C.

0232Alternatively, epichlorohydrin and water can be removed by distillation at a temperature below 180 ° C. under reduced pressure. The crude resin / salt mixture can then be dissolved in a secondary solvent to facilitate washing with water and salt removal. The secondary solvent can then be removed via vacuum distillation to obtain the product.

0233The advanced or fusion method is an alternative method for forming solid epoxy resins, which are based on the chain extension reaction of liquid epoxy resins (eg, crude DGEBA) with bisphenol A.

02341.3.2. Hardener Curing of the epoxy resin can be performed using a classical curing agent. Curing can be carried out with a co-reactive curing agent or can be catalytic or photoinitiating cationic.

0235Co-reactive curing agents include amine-functional curing agents, catalytically functional polyester and anhydride curing agents, phenol-sealed curing agents, melamine-, urea-, and phenol-formaldehyde resins, mercaptan (polysulfide and polymercaptan) curing. It can be selected from agents, cyclic amidin curing agents, isocyanate curing agents and cyanate ester curing agents.

0236The amine functional curing agent can be primary and secondary amines, polyamides, amidamines and dicyandiamides.

0237The amine can be aliphatic, alicyclic, aromatic amine or arylyl amine.

0238Aliphatic amines include polyethylene polyamines, hexamethylenediamines, polyetheramines (polyglycol-based polyamines), ketimines (reaction products of ketones and primary aliphatic amines), Mannig base additives (amines, phenols and It can be selected from liquid aliphatic polyamines such as (reaction products of formaldehyde), polyetheramines (reaction products of polyols and amines derived from ethylene or propylene oxide), and mixtures thereof.

0239The alicyclic amine can be selected from isophorone diamine, bis (4-amino-cyclohexyl) methane, 1,2-diamino-cyclohexane, trihexylmethylenediamine, m-xylylenediamine, and mixtures thereof. ..

0240Aromatic amines should be selected from meta-phenylenediamine, methylenedianiline, alkyl (tetraethyl-)-substituted methylenedianiline, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, diethylenetoluenediamine. Is possible.

0241Arylylamine can be selected from m-xylylenediamine, 1,3-bis (aminomethylcyclohexane).

0242Amines are diethylenetriamine, triethylenetetramine, poly (oxypropylenediamine), poly (oxypropylenetriamine), poly (glycolamine), N-aminoethylpiperazine, isophoronediamine, 1,2-diaminocyclohexane, bis (4-amino). More specific than cyclohexyl) methane, 4,4-diamino-diphenylmethane, 4,4-diaminodiphenylsulfone, m-phenylenediamine, diethyltoluenediamine, meta-xylenediamine, 1,3-bis (aminomethylcyclohexane, and mixtures thereof). Is selected from.

0243Polyamides are obtained by the reaction of dimerized and trimerized vegetable oil fatty acids with (9,12 and 9,11-linoleic acid) polyamines (diethylenetriamines) or by the reaction of polyamines with phenol-containing carboxylic acids (phenalkamines). It is possible.

0244Amidoamines can be obtained by reacting monofunctional acids such as tall oil fatty acids with polyamines such as diethylenediamine.

0245Catalytically functional polyesters can be obtained by reaction with terphthalic acid, trimellitic anhydride and neopentyl alcohol.

0246Acid anhydrides are phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, nadic methyl anhydride or methylhymic hydride. , Benzophenone tetracarboxylic dianhydride, tetrachlorophthalic anhydride, and mixtures thereof.

0247Phenol-sealed hardeners are products that can be obtained by the reaction of phenol, cresol or bisphenol A with formaldehyde.

0248Mercaptan (polysulfide and polymercaptan) hardeners generally contain terminal thiols.

0249The cyclic amidine curing agent can be, for example, 2-phenylimidazolidine.

0250The cyanate ester curing agent can be, for example, bisphenol A dicyanic acid ester.

0251Catalytic curing can be performed with a Lewis base or Lewis acid.

0252Lewis bases are tertiary amines such as 2-diethylamino-methylphenol, 2,4,6-tris (dimethylaminomethyl) phenol; and imidazoles such as 2-methylimidazole and 2-phenylimidazole; 2- Cyclic amidines such as phenylimidazolin; substituted ureas such as 3-phenyl-1,1-dimethylurea; and quaternary ammonium salts such as tetraalkyl- and alkyl-triphenylphosphonium salts.

0253Lewis acids can be selected from boron trihalides, preferably boron trifluorides.

0254Photoinitiating cationic curing can be performed with photoinitiators such as aryldiazonium salts, diallyldiazonium salts, diaryldiionium salts and onium salts of Group VIa elements such as triarylsulfonium salts, dialkylphenacil sulfonium salts. It is possible.

02551.4 Use of epoxy resin Epoxy resins can be used in coating and structural applications. Coating applications are marine and industrial maintenance (corrosion resistant coatings for transport infrastructure such as ships, shipping containers, offshore oil drilling equipment and platforms, bridges, railroad vehicle coatings: coatings for industrial storage tanks; and for light industry And agricultural appliance primers), metal containers (aluminum and steel food and beverage cans) and coil coatings (metal can edges, can bodies, building products, appliance panels, transportation, and metal fixture applications), automotive coatings (primer surfaces) It can be in the field of coatings), as well as inks and resists. The coating can be performed using a variety of techniques such as low solids solvent coatings, high solid solvent coatings, non-solvent coatings, aqueous coatings, powder coatings and radiation-curable coatings.

0256Structural applications include structural composites (glass, boron, graphite and aromatic polyaramid-based fiber reinforced materials); civil engineering, flooring (floor paints, self-leveling floors, trowelable floors, and gravel finish floors). And the field of construction; the field of electrical laminates; the field of electrical laminates (printed wiring boards and printed circuit boards); casting, potting, encapsulation (switchgear parts, transformers, insulators, high voltage cable accessories, and so on. Devices) and other fields of electrical and electronic applications such as transfer molding (encapsulation of electronic components such as semiconductor chips, passive elements and integrated circuits); adhesive fields (metals, glass, ceramics, wood, weaving) Adhesion between similar and dissimilar materials such as cloth and many types of plastics; as well as prototypes, master models, molds, and molds for the tool field (space, automobiles, foundry, boat construction and various industrial moldings, and It can be in other parts).

02571.5 Use of glycidyl ethers and esters These products are used in applications such as coatings, adhesives and reactive diluents.

02581.6 Use of glycidyl amides and imides These products are used in applications such as outdoor powder coating with polyester, or in applications where a non-yellowing epoxy resin is desired.

02592. Food-Beverage products-Flocculator 2.1. General The epichlorohydrin-containing product according to the present invention is used in the production of products that will be used in applications that come into contact with foods and beverages, and more specifically in the production of synthetic organic coagulants. It is possible.

0260Flocculation refers to the reduction or elimination of electrostatic repulsion between particles through the addition of a constant coagulant, which in technical terms, after chemical mixing and destabilization, is a coagulant. Refers to the first phase of flock formation prior to the introduction of.

0261The coagulant is generally a polymer that has a high cationic charge density that neutralizes the negative charge of the colloid and initiates the formation of flocs. They generally exhibit a relatively low molecular weight to allow good diffusion of charge around the particles and a low viscosity to allow good dispersion of the polymer in the eluate.

0262The coagulant is intended to refer to a polymer containing at least one repeating unit containing at least one 2-hydroxypropyldialkylammonium group.

0263An example of a coagulant molecule is shown in FIG.

02642.2. Coreactants In applications according to the invention, products containing epichlorohydrin are typically subjected to reactions with ammonia, amines, polyaminoamides or polyimines.

0265These amines can be mono-, di- or polyamines. Amines can be aliphatic, alicyclic or aromatic, saturated or unsaturated, linear or substituted. Amines preferably have at least one, more preferably at least two primary amino hydrogens.

0266Amine is a general formula: H- (NH-R²¹)_r-NR²²-(R²³-NH)_s-R²⁴ (XIV) Can be represented by, in the formula, R²²And R²⁴Can be equal or different except when equal to H, which are independently H, alkyl or alkenyl radicals, linear with 1-30 carbon atoms, Can be selected from branched or carbocyclic rings; R²¹And R²³Can be equivalent or different, preferably equivalent, can be a divalent aliphatic radical aromatic radical with 2-12 carbon atoms, r and Each of s is an integer from 0 to 6, and the sum of r and s is equal to 0 to 6.

0267Amines include lower alkyl and lower alkenyl primary monoamines such as methylamine, ethylamine, isopropylamine, t-butylamine, mixed amylamine, n-octylamine, branched nonylamine; dimethylamine, ethylmethylamine, diethylamine, propylmethyl. Secondary amines such as amines, propylethylamines, dipropylamines, dibutylamines, propylbutylamines, ethylbutylamines, methylbutylamines, pentylethylamines, pentylethylamines, and pentylpropylamines; tertiary amines, as well as alkylenediamines, triamines and Polyamines include ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, hexylenediamine, octylenediamine, dodecylenediamine, cyclohexylenediamine, diethylenetriamine, dipropylenetriamine, dipentylenetriamine, triethylene. Tetraamine, tributylenetetraamine, trihexylenetetraamine, tetraethylenepentamine, tetrapropylenepentamine, pentahexylenehexamine, pentapropylenehexamine, N-ethyl-1,2-ethylenediamine, N- (2-propenyl)- 1,3-Propanediamine, N-hexyl-1,4-butanediamine, N-2 ethylhexyl-1,3-propanediamine, N- (5-octenyl) -1,6-hexanediamine, N-butyltriethylene Triamine, N-hexyltripropylenetetramine, N-nonyltetrabutylenepentamine and N- (oleyl) -hexetylene heptamine, N-alkyl-1,With or without alkenyl or alkyl substituents attached to nitrogen such as 3-diaminopropane, butane and hexane, where the radical alkyl is hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl. , Tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, nonadecylic, eikosyl, hexaneeikosyl, docosyl, tricosyl, and tetracosyl.

0268The monoamine is preferably a secondary amine, more preferably a dimethylamine.

0269The diamine is more preferably 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, N-substituted diaminopropane, more preferably 1-amino-3-dimethylaminopropane, 1-. Amino-3-diethylaminopropane, 1-amino-3-cyclohexylaminopropane, N, N, N', N'-tetramethyl-1,3-propanediamine, 1,3-diaminobutane, 1,5-diaminopentane , 1,8-Diaminooctane, 1,10-diaminodecane, 1,12-diaminododecane, 2- (diethylamino) ethylamine, 1-diethylamino-4-aminopentane, 3-aminoethyl-3,5,5-trimethyl It is selected from cyclohexylamine and N, N, N', N', -tetramethyl-1,6-hexanediamine.

0270Polyaminoamides are generally obtained from polyamides, preferably polyacrylamides, formaldehyde and amines, preferably secondary amines. Poly [N- (dialkylaminoalkyl) acrylamide] is particularly preferred.

0271Polyimine is usually obtained by ring-opening polymerization of alkyleneimine, preferably ethyleneimine.

02722.3. Method The reaction between a product containing epichlorohydrin and a compound containing at least one, preferably two primary amino hydrogens, may be carried out by any method known in the art. It is possible.

0273This reaction is generally carried out in the liquid phase, optionally in the presence of a solvent. The solvent can be selected from water, preferably an organic solvent that is hydrated, or a mixture thereof. Water is preferred. Monoalcohols such as methanol, ethanol, n-propanol, isopropanol and butanol are preferred organic solvents.

0274When a solvent is used, the ammonia or amine content in the solvent-ammonia or amine mixture is usually 5% by weight (% wt) or higher, preferably 10% by weight or higher, more preferably 20% by weight or higher and most preferably. 45% by weight or more. This content is usually 90% by weight or less, preferably 75% by weight or less, more preferably 60% by weight or less, and most preferably 55% by weight or less.

0275The molar ratio between epichlorohydrin and ammonia or amines is generally 0.1 or greater, preferably 0.5 or greater, more preferably 0.75 or greater and most preferably 1 or greater. This ratio is usually 10 or less, preferably 5 or less, more preferably 3 or less, and most preferably 2 or less.

0276The temperature at which this reaction is carried out is generally 10 ° C. or higher, preferably 25 ° C. or higher, more preferably 50 ° C. or higher, and most preferably 60 ° C. or higher. This temperature is usually 120 ° C. or lower, preferably 110 ° C. or lower, more preferably 100 ° C. or lower, and most preferably 90 ° C. or lower.

0277The pressure at which the reaction is carried out is generally 0.1 absolute bar or higher, preferably 0.2 absolute bar or higher, more preferably 0.5 absolute bar or higher and most preferably 1 absolute bar or higher. This pressure is usually 20 absolute bar or less, preferably 10 absolute bar or less, more preferably 5 absolute bar or less, and most preferably 2 absolute bar or less.

0278The reaction time is generally 10 absolute minutes or more, preferably 20 absolute minutes or more, more preferably 30 absolute minutes or more, and most preferably 60 absolute minutes or more. This time is usually 10 absolute hours or less, preferably 5 absolute hours or less, more preferably 3 absolute hours or less, and most preferably 2 absolute hours or less.

0279The manufacturing procedure is usually the dissolution of amine or ammonia in a solvent, followed by the slow addition of epichlorohydrin, which is optionally itself dissolved in the solvent, with a reaction temperature of 10-50 ° C. Includes occasional cooling, often to maintain 25-40 ° C, and then raising the temperature to 60-90 ° C after the addition of epichlorohydrin is complete.

0280The reaction product can be recovered as an aqueous solution or as a solid after further treatment, such as distillation of a solvent under reduced pressure, treatment of the solution with an acid or base.

0281These reactions result in the formation of monomers. For example, the reaction of epichlorohydrin with dimethylamine results in an epichlorohydrin dimethylamine monomer. It is then homopolymerized with the corresponding quaternary ammonium compound, which is a low molecular weight cationic polymer used as a coagulant. Such polymerization is usually carried out under alkaline conditions.

0282Monomers can also be copolymerized with acrylamide to produce higher molecular weight polymers that are also used in water treatments.

02832.4. Product characteristics The resulting polymer usually exhibits a molecular weight of at least 5000, often at least 10000, and often at least 50,000. This molecular weight is usually less than 500,000, often less than 400,000, and often less than 300,000. These can be obtained as an aqueous solution containing 40 to 50% by weight of a polymer and exhibiting a viscosity of 40 to 11000 centipores.

02842.5. Use These polymers can be used for raw water treatment for conversion to drinking water, water paper recycling in the pulp and paper industry, coating stickiness prevention, brake oil emulsions, oil and grease removal, and sludge dewatering. It is possible. These can also be used for refined sugar.

02853. Food-Beverage Use Product-Wet Reinforced Resin 3.1. General The epichlorohydrin-containing product according to the present invention may be used in the production of products that will be used in applications that come into contact with foods and beverages, more specifically in the production of wet toughened resins. It is possible.

0286Wet-reinforced resins have chemical formulas of 2,3-epoxypropylamine, 2,3-epoxypropylammonium, 3-chloro-2-hydroxypropylamine, 3-chloro-2-hydroxypropylammonium, and 3-hydroxyazeti. It is intended to represent a polyaminoamide polymer containing dinium and at least one group selected from any combination of at least two of these.

0287An example of the chemical formula of such a polymer is shown in FIG.

02883.2. Coreactants In applications according to the invention, products containing epichlorohydrin are typically subjected to reactions with polyamines or polyamides.

0289The polyamines and reaction conditions are as described above for the production of the coagulant.

0290Polyamides are usually amines, preferably polyalkylene polyamines (in which case the polyamides are generally polyamine amides, as described in US Pat. No. 8,65,727, the contents of which are incorporated herein by reference. (Pointing to) and dicarboxylic acid, preferably saturated aliphatic dicarboxylic acid. This polyamide is a general formula -NH- (R²¹)_r-NR²²-(R²³-NH)_s-COR²⁴CO- (XV) Can be represented by, in the formula, R²¹, R²², R²³, R and s are as described above, and R²⁴Is preferably a divalent hydrocarbon radical of a basic carboxylic acid selected from phenylene, naphthalene, methylene, ethylene, propylene, butylene, pentylene, hexylene, octylene and nonylene.

0291Preferably, the polyamide is of the general formula -NH (C_tH_2tHN)_x-COR²⁴CO- (XVI) Can be represented by, in the equation, t and x are 2 or more each, and in the equation, -NH (C_tH_2tHN)_x-Groups are preferably derived from the above-mentioned polyamines containing 2-8 alkylene groups, more preferably diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenetriamine and N-bis (aminopropyl) methylamine. Derived from -COR²⁴The CO-group is preferably derived from a dibasic carboxylic acid containing 2-12 carbon atoms selected from phenylene, naphthalene, methylene, ethylene, propylene, butylene, pentylene, hexylene, octylene and nonylene. The acid is more preferably selected from malonic acid, succinic acid, glutaric acid, adipic acid, diglycolic acid, sebacic acid or azelaic acid, and mixtures thereof.

02923.3. Method The reaction of polyamide with epichlorohydrin is usually carried out at temperatures above 45 ° C. This temperature is usually 100 ° C. or lower, preferably 70 ° C. or lower. The temperature at which this reaction takes place is preferably selected in two stages. In the first stage, the reaction mixture is maintained at 30 ° C to 50 ° C, preferably 39 ° to 41 ° C. The reaction time for the first stage is preferably about 90-190 minutes to form the intermediate polyaminochlorohydrin. The reaction temperature is then gradually raised to 55 ° C to 75 ° C so that the intermediate polyaminochlorohydrin is then controlledly crosslinked to a determined level. The second stage is continued until the viscosity of the reaction mixture reaches the desired level (preferably levels M-N on the Gardner-Holdt viscosity scale).

0293In general, this reaction can be carried out alone or in aqueous solution of 57% by weight or less. Preferably, the polyaminoamide is placed in water in a 52-57 wt% aqueous solution, i.e. 43-48 wt% total solids (% by weight of the solution which is the solubilized solid material), more preferably about 45 wt%. React with epichlorohydrin in a solution of total solids. The reaction time varies with temperature, with lower temperatures taking longer. The typical composition of these resins is 12.5% (10-40% solids). However, due to the need to transport water, the company sought to produce higher concentrations of resin solution. At least one of the main problems in forming such concentrated solutions, which are difficult to prepare, is the high content of these dichloropropanols, thus exceeding the level of this impurity in the end application. Is considered to be.

0294The reaction is preferably carried out until all or substantially all of the available amine groups of the polyaminoamide have reacted with epichlorohydrin. In general, the reaction time varies from about 1 to 19 hours, preferably 3 to 6 hours. Since this reaction is exothermic, epichlorohydrin is slowly added to the polyaminoamide over time, allowing more effective heat transfer from the reaction medium. Heat transfer from the reaction medium can be achieved according to known procedures such as immersing the reaction vessel in a cooling environment such as an ice bath or passing a cooling coil through the reaction vessel.

0295This reaction is usually carried out in aqueous solution to mitigate the reaction. Although pH adjustments are usually not required, in some cases it may be desirable to add an alkali to combine with at least some of the acids formed, as the pH drops during the reaction.

0296In this reaction, it is preferable to use sufficient epichlorohydrin to convert all secondary amine groups to tertiary amine groups. The molar ratio of epichlorohydrin to the secondary amine group is usually 0.1 or greater, preferably 0.5 or greater, and more preferably 1 or greater. This molar ratio is usually 10 or less, preferably 5 or less, and more preferably 2 or less.

0297The reaction of the polyamide with epichlorohydrin can also be carried out in the presence of a quaternizing agent, and the conditions of the reaction and the reactants other than the inclusion of the quaternizing agent are basically described above. Same as the case. In a preferred procedure, epichlorohydrin is first added to the aqueous polyamide solution at a temperature of 45-55 ° C. The reaction mixture is then heated to a temperature of about 60-100 ° C, preferably about 50-80 ° C, depending on the desired polymerization rate. A quaternizing agent is added after a suitable time at this temperature, i.e. 0-100 minutes, after the epoxy group of epichlorohydrin has reacted with the secondary amine group of the polyamide. The reaction mixture is preferably heated at a temperature of 60 ° C to 80 ° C. The pH of this reaction mixture is then lowered to 4, preferably 2-3, with any suitable acid such as sulfuric acid, hydrochloric acid, formic acid and the like. The amount of quaternizing agent should be sufficient to convert 25% to 75%, preferably 50% of tertiary amine groups to quaternary groups.

0298The quaternizing agent can be any compound capable of quaternizing the tertiary nitrogen atom in the aqueous medium. Generally, these compounds are characterized by having, as a major part of their structure, an alkyl group or a substituted alkyl group that is readily available for alkylation under the conditions described herein. These include halides, sulfates and phosphates, as well as lower alkyl esters of mineral acids such as substituted alkyl halides. Examples of these compounds that can be used are dimethyl, diethyl and dipropyl sulfate; methyl chloride; methyl iodide; methyl bromide; ethyl bromide; propyl bromide; mono-, di- or tri-methyl, ethyl and propyl. Phosphate; 1,3-dichloropropanol-2; as well as 1-chloroglycerol. Certain aromatic compounds such as benzyl chloride and methyl p-toluenesulfonate can also be used.

0299The above products resulting from the reaction of epichlorohydrin with polyamide can be further bridge polymerized by treatment with sodium carbonate or sodium hydroxide solution at a pH of 10.5-12.

03003.4. Use These resins are used for paper towels, tea bags, coffee filters, milk cartons, meat wraps, wallpaper and other wet paper. They can also be used in the production of high fructose corn syrup and to prevent shrinkage of wool.

03014. Cationic agent 4.1. General The product containing epichlorohydrin according to the present invention can be used in the production of a cationizing agent.

0302A cationizing agent is a quaternary ammonium salt having a chemical formula of 2,3-epoxypropyl, 3-chloro-2-hydroxypropyl and at least one group selected from a combination thereof, and is a polymer. Intended to show what is not.

0303The cationizing agent is often a quaternary ammonium salt containing a glycidyl or 3-chloro-2-hydroxypropyl group attached to a nitrogen atom. The cationizing agent can be isolated as a solid or as a solution in an aqueous solution or an organic solvent.

0304Examples of cationizing agents are 3-chloro-2-hydroxypropyltrimethylammonium chloride and glycidyltrimethylammonium chloride.

03054.2. Coreactants In applications according to the invention, products containing epichlorohydrin are typically subjected to reactions with amines, amine salts, or mixtures thereof.

0306The amine is preferably a tertiary amine, and the amine salt is preferably a tertiary amine salt.

0307The tertiary amine salt is a salt obtained by treating the amine with, for example, an acid, preferably an inorganic acid such as hydrochloric acid or sulfuric acid.

0308The tertiary amine is the formula R³¹-N (R)³²)-R³³ (XVII) Can be represented by, in the formula, R³¹, R³²And R³³Are selected from the group consisting of alkyl, cycloalkyl, alkene, aryl, aralkyl, alkylaryl, where these two species optionally combine to form a ring and contain 1-25 carbon atoms. Is possible. The groups attached to the nitrogen can be linear or substituted, saturated or unsaturated.

0309R³¹, R³²And R³³If all three of are identical, they should preferably contain no more than 4 carbon atoms. R³¹, R³²And R³³If all three are not the same, and R³³If contains 18 or less carbon atoms, then R³¹And R³²Should preferably be a group composed of methyl and ethyl. R³¹And R³²If they combine to form a ring, then R³³Should preferably be derived from a group composed of methyl and ethyl.

0310Examples of suitable tertiary amines are triethylamine, N-methyl and N-ethylmorpholine, N-ethyl and N-methylpiperidin and methyldiallylamine, trimethylamine, dimethylbenzylamine, dimethyldodecylamine, dimethylstearylamine, dimethylaniline, It is tri-npropylamine.

0311It is particularly preferred that the tertiary amine has two methyl groups attached to nitrogen, such as, for example, trimethylamine, dimethylbenzylamine, dimethyldodecylamine, dimethylstearylamine and dimethylaniline.

0312The amine salt is preferably a salt obtained by reacting the above-mentioned amine with hydrochloric acid or sulfuric acid, preferably hydrochloric acid.

03134.3. Method Reactions of epichlorohydrin-containing products with amines or amine salts are known in the art, such as those described in US Pat. No. 2,876,217, the contents of which are incorporated herein by reference. It can be carried out by either method.

0314This reaction is generally carried out in the liquid phase, optionally in the presence of a solvent. The solvent can be selected from water, preferably a hydrating organic solvent such as alcohols, ketones, esters or aliphatic hydrocarbons, or mixtures thereof. Water is preferred. Monoalcohols such as methanol, ethanol, n-propanol, isopropanol and butanol are preferred organic solvents, with methanol being particularly preferred.

0315The content of epichlorohydrin in the solvent is usually 0.1 mol / l or more, often 0.5 mol / l or more, often 1.0 mol / l or more, especially 2 mol / l or more, especially 5 mol / l or more and sometimes. It is 10 mol / l or more. This epichlorohydrin content is typically less than 20 mol / l.

0316The content of amines or amine salts in the solvent is usually 0.1 mol / l or more, often 0.5 mol / l or more, often 1.0 mol / l or more, especially 2 mol / l or more, especially 5 mol / l or more and sometimes 10 mol. It is greater than / l. This amine or amine salt content is typically less than 20 mol / l.

0317The molar ratio of epichlorohydrin / amine or amine salt is usually 0.1 or greater, preferably 0.5 or greater, more preferably 1 or greater and most preferably 1.2 or greater. This ratio is usually 10 or less, more preferably 5 or less and most preferably 2 or less.

0318The temperature at which the reaction is carried out is generally 0 ° C. or higher, preferably 10 ° C. or higher, more preferably 25 ° C. or higher, and most preferably 40 ° C. or higher. This temperature is usually 100 ° C or lower, preferably 80 ° C or lower, more preferably 60 ° C or lower, and most preferably 50 ° C or lower.

0319The pressure at which the reaction is carried out is generally 0.1 absolute bar or higher, preferably 0.2 absolute bar or higher, more preferably 0.5 absolute bar or higher and most preferably 1 absolute bar or higher. This pressure is usually 20 absolute bar or less, preferably 10 absolute bar or less, more preferably 5 absolute bar or less, and most preferably 2 absolute bar or less.

0320The reaction time is generally 10 absolute minutes or more, preferably 20 absolute minutes or more, more preferably 30 absolute minutes or more, and most preferably 60 absolute minutes or more. This time is usually 72 absolute hours or less, preferably 60 absolute hours or less, more preferably 48 absolute hours or less, and most preferably 10 absolute hours or less.

0321When an amine salt or a mixture of amines and amine salts is used, the pH of the reaction is usually at least 5, and preferably at least 6. This pH is usually 9 or less, preferably 8 or less.

0322In the first embodiment, the manufacturing procedure usually involves mixing amine, epichlorohydrin and water, followed by heating at the desired temperature for the desired time. The aqueous solution is further concentrated by vacuum distillation. The distillation temperature is as described for the reaction. The distillation pressure is usually 100 absolute mbar or less, preferably 75 absolute mbar or less and most preferably 50 absolute mbar or less. This pressure is usually at least 1 absolute mbar.

0323In the second embodiment, an aqueous solution of amine is first added to hydrochloric acid until a pH of 8-9 is achieved. Epichlorohydrin is further added to the resulting solution and the mixture is stirred at the desired temperature for the desired time. The solution is further distilled under reduced pressure into solid 3-chloro-2-trialkylammonium chloride. This solid can be used as it is or after being further cyclized into a glycidyl derivative by reaction with sodium hydroxide in an aqueous solution.

0324In the third aspect, the amine hydrochloride is dispersed in water. Sufficient sodium hydroxide is added to raise the pH from about 3 to about 8. Epichlorohydrin is further added to the resulting solution and the mixture is stirred at the desired temperature for the desired time. The chlorohydrin group is further cyclized into a glycidyl derivative by reaction with sodium hydroxide in aqueous solution.

0325In various embodiments, the aqueous solution obtained at the end of the reaction is evaporated under reduced pressure or distilled at a temperature below 50 ° C. to obtain a slurry containing at least 90% by weight solid, preferably at least 95% by weight. It can be further concentrated. Isopropanol, n-propanol, and t-butanol, preferably isopropanol, etc., so as to obtain an alcohol content of 10-70% wt, preferably 25-50% wt based on the total weight of the resulting alcohol-water slurry. A hydrated alcohol with 3-4 carbon atoms is added to the slurry. The precipitated solids are then recovered by filtration or other means suitable for removing the solids from the liquid. The solid can optionally be washed with an additional amount of alcohol or other non-solvent and / or dried to remove trace amounts of water and alcohol altogether.

0326The reaction product can be recovered as an aqueous solution or as a solid after further treatment, such as distillation of a solvent under reduced pressure, treatment of the solution with an acid or base.

03274.4. Use Catabolic agents are mainly used in the cationization of starches utilized by the paper industry for the treatment of high quality paper grades or for the cationization of fabrics for dye fixation.

03285. Flame retardant 5.1. General The epichlorohydrin-containing product according to the present invention can be used in the production of flame retardant additives.

0329The epichlorohydrin-containing product according to the present invention can preferably be used in the production of phosphorus-containing flame retardant additives.

0330A phosphorus-containing flame retardant is a flame retardant whose chemical formula is at least one phosphorus atom, at least one group selected from 2,3-epoxypropyloxy, 3-chloro-2-hydroxypropyl, and at least two of these. It is intended to indicate a compound containing a combination of.

0331An example of the chemical formula of such a compound is shown in FIG.

03325.2. Coreactants In applications according to the invention, epichlorohydrin-containing products are typically subjected to reactions with phosphorus-containing inorganic or organic compounds. Such inorganic compounds are, for example, phosphoric acid (ortho, pyro and polyphosphoric acid), phosphates and phosphorus oxychloride. Examples of phosphorus-containing organic compounds include, for example, phosphate esters (of ortho, pyro and polyphosphate), phosphonic acids, esters or salts thereof, phosphinic acids, esters or salts thereof, and phosphine oxides. Is.

0333Phosphorus-containing compounds have a general formula O = P (X)¹) (X²) (X³) (XVIII) Or P (X¹) (X²) (X³) (XIX) Can be represented by, in the formula, X¹, X², X³Halogen, H, OH, OR independently⁴¹, R⁴¹, OR⁴²(OH)_nAnd R⁴²(OH)_nCan be selected from In the formula, the halogen is preferably selected from bromine and chlorine, and preferably chlorine. In the formula, R⁴¹Are alkyl, aryl, alkylaryl, arylalkyl, cycloalkyl radicals containing 1 to 20 carbon atoms, often 3 to 12 carbon atoms. In the formula, R⁴²Are alkylene, arylene, alkylarylene, arylalkylene, cycloalkylene radicals containing 1 to 20 carbon atoms, often 3 to 12 carbon atoms. In the formula, n is an integer equal to 1 or 2 and In the formula, X¹, X², X³At least two of them are capable of bonding to form a ring, preferably together with a phosphorus atom.

0334Examples of phosphorus-containing compounds are tris (1,3-dichloro-2-propyl) phosphate, tris (1-chloro-2-propyl) phosphate, tris (2,3-dichloropropyl) phosphate, isobutylbis ( Hydroxypropyl) phosphine oxide, 10- (2', 5'-dihydroxyphenyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DHQEP), 9,10-dihydro-9- Oxa-10-phosphaphenantrene-10-oxide (DOPO), DOPO and 4,4'-dihydroxybenzophenone (Liu YL, Journal of Polymer Science: Part A: Polymer Chemistry, 2002, Vol. 40, pp. 359-368) And the reaction product with DOPO 2OH and 2 DOPO-PhOH, II) described in the Journal of Applied Polymer Science, 2002, Vol. 83, pp. 1697-1701.

03355.3. Method Reactions of epichlorohydrin-containing products with phosphorus-containing compounds are known in the art, such as those described in the Journal of Applied Polymer Science, 2002, Vol. 83, pp. 1697-1701. It is carried out by either method.

0336This reaction is generally carried out in the liquid phase, optionally in the presence of a solvent. The solvent can be selected from water, an organic solvent such as alcohol, or a mixture thereof. Alcohol is preferred. Monoalcohols such as methanol, ethanol, n-propanol, isopropanol and butanol are preferred organic solvents, with ethanol being particularly preferred.

0337The content of epichlorohydrin in the reaction mixture is usually 0.1 mol / l or more, often 1.0 mol / l or more, often 2 mol / l or more, and especially 5 mol / l or more. This epichlorohydrin content is typically less than 20 mol / l.

0338The content of the phosphorus-containing compound in the reaction mixture is usually 0.1 mol / l or more, often 0.2 mol / l or more, and frequently 0.5 mol / l or more. This content is typically less than 2 mol / l.

0339The molar ratio of the epichlorohydrin / phosphorus-containing compound is usually 1 or more, preferably 2 or more, more preferably 5 or more, and most preferably 10 or more. This ratio is usually 50 or less, more preferably 30 or less and most preferably 20 or less.

0340The temperature at which the reaction is carried out is generally above 0 ° C, often above 5 ° C, often above 10 ° C, especially above 20 ° C and more specifically above 50 ° C. This temperature is usually 100 ° C. or lower, preferably 80 ° C. or lower, more preferably 60 ° C. or lower, and most preferably 30 ° C. or lower.

0341The pressure at which the reaction is carried out is generally 0.1 absolute bar or higher, preferably 0.2 absolute bar or higher, more preferably 0.5 absolute bar or higher and most preferably 1 absolute bar or higher. This pressure is usually 20 absolute bar or less, preferably 10 absolute bar or less, more preferably 5 absolute bar or less, and most preferably 2 absolute bar or less.

0342The reaction time depends on the temperature at which the reaction is carried out. This time is generally 10 absolute minutes or more, preferably 1 absolute time or more, more preferably 10 absolute minutes or more, and most preferably 24 absolute hours or more. This time is usually 72 absolute hours or less, preferably 60 absolute hours or less, more preferably 48 absolute hours or less, and most preferably 30 absolute hours or less.

0343It is possible that a basic compound such as potassium hydroxide is present in the reaction medium. This is generally the case when the phosphorus-containing compound contains an OH group in the molecule. The molar ratio of basic compound / phosphorus-containing compound is usually 0.1 or more, preferably 0.15 or more, and most preferably 0.2 or more. This ratio is usually 5 or less, more preferably 3 or less and most preferably 1 or less.

0344Onium salts, such as benzyltrimethylammonium chloride, preferably quaternary ammonium or phosphonium salts, more preferably quaternary ammonium chloride, can be present in the reaction medium. This is generally the case when the phosphorus-containing compound is a phosphine oxide. The onium / phosphorus-containing compound ratio is usually 0.01 or more, preferably 0.05 or more, and most preferably 0.1 or more. This ratio is usually 1 or less, more preferably 0.5 or less, and most preferably 0.2 or less.

0345The product of this reaction can be recovered by any means, such as filtration, and is subjected to a washing operation before being subjected to evaporation under reduced pressure.

03465.4. Use Flame retardants are typically used to prevent the generation of flammable gases, especially in various materials such as polymers such as polyurethane foam.

03476. Cleaning prescription ingredients 6.1. General The epichlorohydrin-containing product according to the invention can be used in the production of cleaning ingredients. The cleaning component is intended to refer to a compound whose chemical formula contains at least one 3-sulfonate-2-hydroxy-propyloxy group. This compound can be an oligomer or a polymer. Oligomers are polymers in which the number of repeating units in each polymer molecule is less than 20.

0348The cleaning component is intended to indicate a polymer in which at least one repeating unit contains at least one 2-hydroxypropylammonium group, preferably a 2-hydroxypropylimidazolidium group.

0349The epichlorohydrin-containing products according to the invention are preferably cationic monomers, polymers or oligomers, anionic surfactants such as sulfonate-based surfactants, preferably alkylglyceryl ether sulfonate surfactants. , Monomeric or oligomeric or cationic cyclic amine based polymers can be used.

03506.2. Coreactants In applications according to the invention, when the cleaning aid is a sulfonate-based surfactant, the product containing epichlorohydrin will typically have 10-40 carbon atoms, preferably 10-22 carbon atoms. It is subjected to a reaction with an atom, more preferably an aliphatic alcohol containing 14-18 carbon atoms and most preferably 16-18 carbon atoms. The alkyl chain can be branched or linear or ethoxylated, and if present, the side chain contains an alkyl moiety containing 1 to 4 carbon atoms such as methyl or ethyl.

0351In applications according to the invention, when the cleaning component is a cationic amine-based polymer, the epichlorohydrin-containing product is typically a linear alkylamine, a branched alkylamine, a cycloalkylamine, an alkoxyamine, an amino. It is subjected to a reaction with an alcohol selected from the group consisting of cyclic amines containing at least one nitrogen atom in the ring structure, alkylenediamines, polyether diamines and polyalkylene polyaminesamines.

0352Specific examples of said amines are given above.

0353Cyclic amines containing at least one nitrogen atom in the ring structure are, for example, monoaminoalkylpiperazine, bis (aminoalkyl) piperazine, monoaminoalkylimidazole, aminoalkylmorpholin, aminoalkylpiperazine and aminoalkylpyrrolidine. Monoaminoalkylpiperazines are, for example, 1- (2-aminoethyl) piperazine and 1- (3-aminopropyl) piperazine. Preferred monoaminoalkylimidazoles have 2-8 carbon atoms in the alkyl group. Examples of suitable compounds are 1- (2-aminoethyl) imidazole and 1- (3-aminopropyl) imidazole. Suitable bis (aminoalkyl) piperazines are, for example, 1,4-bis (2-aminoethyl) piperazine and 1,4-bis (3-aminopropyl) -piperazine. Preferred aminoalkyl morpholines are aminoethyl morpholine and 4- (3-aminopropyl) -morpholine. Other preferred compounds in this group are aminoethyl piperidine, aminopropyl piperidine and aminopropyl pyrrolidine.

0354Cyclic amines having at least two reactive nitrogen atoms in the ring include 1-25 such as imidazole; 2-methylimidazole, 2-ethyl imidazole, 2-propyl imidazole, 2-isopropyl imidazole and 2-isobutyl imidazole. C-alkyl substituted imidazoline having 1 carbon atom in the alkyl group; imidazoline; C-alkyl substituted imidazoline and aryl imidazolin having 1 to 25 carbon atoms in the alkyl group, such as 2-phenylimidazolin and 2-trilumidazoline. Piperazine; 1-ethyl piperazine, 1- (2-hydroxy-1-ethyl) piperazine, 1- (2-hydroxy-1-propyl) piperazine, 1- (2-hydroxy-1-butyl) piperazine, 1-( 2-Hydroxy-1-pentyl) piperazine, 1- (2,3-dihydroxy-1-propyl) piperazine, 1- (2-hydroxy-3-phenoxyethyl) piperazine, 1- (2-hydroxy-2-phenyl-) N-alkyl piperazine having 1 to 25 carbon atoms in the alkyl group, such as 1-ethyl) piperazine; for example, 1,4-dimethyl piperazine, 1,4-diethyl piperazine, 1,4-dipropyl piperazine, 1, 4-dibenzylpiperazin, 1,4-bis (2-hydroxy-1-ethyl) piperazine, 1,4-bis (2-hydroxy-1-propyl) piperazine, 1,4-bis (2-hydroxy-1-propyl) piperazine 1 to 25 carbon atoms such as butyl) piperazine, 1,4-bis (2-hydroxy-1-pentyl) piperazine, and 1,4-bis (2-hydroxy-2-phenyl-1-ethyl) piperazine It is N, N'-dialkylpiperazin contained in an alkyl group. Other cyclic amines with at least two reactive nitrogen atoms are melamine and benzimidazoles such as 2-hydroxybenzimidazole and 2-aminobenzimidazole.

03556.3. Method Reactions of epichlorohydrin-containing products with alcohol are described in US Pat. No. 5,567,359 and US Patent Application Publication No. 2006/0079433, the contents of which are incorporated herein by reference. It is carried out by any method known in the art such as.

0356This reaction is usually carried out at a temperature of 65-90 ° C.

0357Typical molar ratios of alcohol: epichlorohydrin range from 1: 1.24 to 1: 4.02.

0358A catalyst such as second tin chloride is usually used in carrying out the reaction. The initial alcohol: second tin chloride mass ratio is generally 100: 0.67.

0359The reaction time is usually 0.25 to 1 hour.

0360The epichlorohydrin / alcohol ratio and time can be adapted to the required degree of oligomerization.

0361Epichlorohydrin is usually added slowly to the alcohol-catalyzed mixture.

0362The product of this reaction is a monomeric or oligomeric alkylchloroglyceryl ether.

0363The alkylchloroglyceryl ether is further converted to an alkylglycidyl ether by reaction with a basic compound, preferably sodium hydroxide. This reaction is usually carried out with a 35% aqueous solution of sodium hydroxide at temperatures above 90 ° C and at an alcohol: NaOH molar ratio of 1: 1.5.

0364Alkyl glycidyl ethers are further converted to alkyl glyceryl surfactants by reaction with a mixture of sodium hydrogen sulfite and sodium sulfite, commonly obtained by combining sodium metabisulfite and sodium hydroxide.

0365The reaction of a product containing epichlorohydrin with an amine is described in US Pat. No. 6,740,633 and US Patent Application Publication No. 2006/0052272, the contents of which are incorporated herein by reference. It is carried out by any method known in the art such as.

0366This reaction is typically carried out in two steps at a temperature of 25-90 ° C, where the first step is at a temperature of 40-60 ° C and the second step is at 90-100 ° C. It is carried out at the temperature of.

0367Typical molar ratios of amines: epichlorohydrin range from 1: 1 to 1: 1.4.

0368The reaction time is usually 0.25 to 1 hour.

0369Condensations of amines and epichlorohydrin are usually alkyl halides, epoxides, chloroacetic acid, 2-chloroethanesulfonic acid, chloropropionic acid, epoxysuccinic acid, propanesulfone, 3-chloro-2-hydroxypropanesulfone. It is further quaternized with acid, dimethylsulfone and / or diethylsulfone, or oxidized to N-oxide by oxidation of the tertiary nitrogen atom of this condensate.

03706.4. Use Examples of cleaning ingredients are surfactants or surface deposition promoting materials. These are typically used as constituents of cleaning compositions such as dishwashing detergents, laundry compositions, shampoos and synbars.

03717. Epichlorohydrin elastomer 7.1. General The epichlorohydrin-containing product according to the present invention can be used in the production of epichlorohydrin elastomers.

0372Epichlorohydrin elastomers are intended to refer to polymers containing at least one type of repeating unit, at least one type of repeating unit containing at least one 2-chloromethyl ethoxy group. This polymer can be a homopolymer or a copolymer.

0373Examples of epichlorohydrin elastomers are epichlorohydrin homopolymers, epichlorohydrin alkylene or phenylene oxide copolymers, and epichlorohydrin alkylene or phenylene oxide terpolymers with glycidyl ether. ..

0374The alkylene oxide can be selected from styrene oxide, propylene oxide, ethylene oxide, butene-1 oxide and dodecene-1-oxide, and ethylene oxide is preferable.

0375The glycidyl ether can be selected from alkyl and haloalkyl glycidyl ethers such as 2-chloroethyl glycidyl ether and allyl glycidyl ether.

03767.2. Coreactants In applications according to the invention, products containing epichlorohydrin are usually subjected to reactions with alkylene or phenylene oxides, or reactions with alkylene or phenylene oxides and glycidyl ethers, or epichlorohydrin. Phyrin is homopolymerized.

03777.3. Method This reaction is incorporated herein by reference in US Pat. No. 3,135,705, US Pat. No. 3,158,580, US Pat. No. 3,158,581, US Pat. No. 3,026,270 and US Pat. It is carried out by any method known in the art, such as that described in Japanese Patent No. 3,341,491.

0378This reaction is usually carried out in a solution of aliphatic or aromatic hydrocarbons, chlorinated hydrocarbons, or ethers.

0379The weight ratio between epichlorohydrin and alkylene oxide is usually 20:80 to 90:10.

0380This reaction is R⁵¹₃A catalyst (R) formed by reacting Al and water⁵¹₂Al-O-AlR⁵¹₂It is preferable to carry out in the presence of (which is considered to be), and in the equation, R⁵¹Can be selected from alkyl, cycloalkyl, aryl or alkaline radicals. It is possible to improve the catalytic activity by adding acetylacetone. Combinations of some organozinc and organomagnesium compounds, as well as other additives and chelating agents in combination with alkylaluminum compounds, are also effective catalysts.

0381This reaction can be carried out in a continuous process using a reverse mixing reactor .

0382The temperature at which the reaction can be carried out typically comprises -80 ° C to 250 ° C, preferably -80 to 150 ° C, more preferably -30 to 100 ° C. Temperatures of 25 to 50 ° C are particularly convenient.

0383Homopolymers and copolymers of epichlorohydrin, for example with polyamines or amines in the presence of at least one drug in the group sulfur, dithiocarbamate, thiuram sulfide and thiazole, or salts of aromatic carboxylic acids, aliphatics. Carboxylic acid salts, carbonic acid salts, phosphite salts, silicic acid salts, and oxides of group IIA, IIB and IVA metals of the Periodic Table, and 2-mercaptoimidazoline and 2-mercaptopyri. Further cross-linking is possible by further reacting with a metal compound selected from the group consisting of at least one heterocyclic compound selected from the group consisting of imidine.

03847.4. Use Epichlorohydrin elastomers are generally used in specialized applications such as automotive parts (fuel pump diaphragms, exhaust gas control hoses, motor mounts, gaskets, seals and portable fuel tanks), specialized applications in the aviation industry, dedicated roof membranes. Used in applications, coated cloths, solvent storage containers, paper mills and printing rollers, as well as professional applications in a variety of oil specialty areas. -80 ° C and 250 ° C, preferably -80 to 150 ° C, more preferably -30 to 100 ° C. Temperatures of 25 to 50 ° C are particularly convenient.

0385Homopolymers and copolymers of epichlorohydrin can be further crosslinked by further reacting with polyamines or amines, for example, in the presence of at least one agent derived from the group sulfur, dithiocarbamate, thiuram sulfide. Is.

0386A further goal of the present invention is to provide epichlorohydrin obtained from a starting material different from propylene, which can be used in a variety of applications. The present invention therefore further relates to the use of epichlorohydrin obtained from glycerol in the production of glycidyl amides or glycidyl imides or coagulants or wet-strengthening resins or cationizing agents or flame retardants, or cleaning ingredients.

<p num="0387"> Five epichlorohydrin (ECH) samples were used. These compositions obtained by gas chromatographic analysis are shown in Table 1.</p><p num="0388"><tables num="1A"><img id="000002" he="178" wi="159" file="JP5877641B2_D0001.tif" img-format="tif" img-content="drawing" /></tables><tables num="1B"><img id="000003" he="148" wi="157" file="JP5877641B2_D0001.tif" img-format="tif" img-content="drawing" /></tables></p><p num="0389">Examples 1 to 10 (homopolymerization of ECH) The test was performed with epichlorohydrin samples ECH1 (Examples 1-3), ECH2 (Examples 4-6) and ECH3 (Examples 7-10) according to the following procedure. The amount of chemicals is shown in Table 2.</p><p num="0390"> Polymerization of epichlorohydrin (ECH) is a system of tetraoctylammonium bromide (Noct)₄Performed in the presence of Br) / triisobutylaluminum (TiBA).</p><p num="0391"> Epichlorohydrin was dried under reduced pressure at 25 ° C. over 24 hours with calcium hydroxide and further distilled.</p><p num="0392"> The polymerization reaction was carried out in a Pyrex® container fitted with a polytetrafluoroethylene valve. This container was exhausted under flame heating to remove residual water. After cooling to room temperature, the vessel was cooled to -30 ° C (ethanol / liquid nitrogen cooling bath) and toluene and epichlorohydrin were added under reduced pressure. After these additions, argon was introduced into the vessel and tetraoctylammonium bromide and triisobutylaluminum were added to the vessel. This addition is set to zero reaction time. After standing at -30 ° C for a given time under magnetic agitation, the reaction was stopped by adding 1-2 mL of ethanol to the vessel. Half of the volume of the reaction medium was then subjected to evaporation and then the polymer was recovered from the vessel.</p><p num="0393"> The conversion rate was obtained by comparing the weight of the recovered polymer with the weight of the added epichlorohydrin.</p><p num="0394"> The theoretical molar weight (Mn th.) Was calculated based on the amount of tetraoctyl ammonium bromide.</p><p num="0395"> The measured polymer molar weights (Mn exp) and molar weight dispersions were obtained by gel permeation chromatography.</p><p num="0396"> The stereoregularity of the polymer¹³C and¹Obtained by 1 H NMR.</p><p num="0397"> The test results are summarized in Table 3.</p><p num="0398"><tables num="2"><img id="000004" he="96" wi="144" file="JP5877641B2_D0001.tif" img-format="tif" img-content="drawing" /></tables></p><p num="0399"><tables num="3"><img id="000005" he="82" wi="159" file="JP5877641B2_D0001.tif" img-format="tif" img-content="drawing" /></tables></p><p num="0400">Examples 13 to 15 (homopolymerization of ECH) The test was performed with epichlorohydrin samples ECH1 (Example 13), ECH2 (Example 14) and ECH3 (Example 15) according to the following procedure. The amount of chemicals is shown in Table 4.</p><p num="0401"> Polymerization of epichlorohydrin (ECH) was performed in the presence of system water / triethylaluminum (TEA).</p><p num="0402"> TEA in a solution of toluene and water is first added to an evacuated and dried container under argon and 30 minutes under reduced pressure under magnetic agitation before adding ECH in toluene (zero reaction time). The procedure of Example 1 was followed except that the mixture was allowed to stand. The polymerization was carried out at a temperature of 25 ° C. for 12 hours. The results are summarized in Table 5.</p><p num="0403"><tables num="4"><img id="000006" he="53" wi="144" file="JP5877641B2_D0001.tif" img-format="tif" img-content="drawing" /></tables></p><p num="0404"><tables num="5"><img id="000007" he="59" wi="160" file="JP5877641B2_D0001.tif" img-format="tif" img-content="drawing" /></tables></p><p num="0405">Example 16 Preparation of a product predominantly composed of diglycidyl diether of bisphenol A according to U.S. Pat. No. 2,811,227 The device used was a thermostatic flask equipped with a mechanical stirrer, a jacket with a thermocouple and a Dean-Stark separator with a water-cooled condenser. An aqueous solution of caustic soda was poured into the flask at a constant rate using a pump.</p><p num="0406"> The reaction flask was initially charged with a mixture of bisphenol A (68.4 g, 0.3 mol) and epichlorohydrin sample ECH4 (277.5 g, 3.0 mol) from a propylene-chlorine plant. The analysis of epichlorohydrin is shown in Table 1. The content of trichloropropane is 0.049 g / kg. The mixture was heated to a temperature of 111 ° C. with stirring under reflux. A 40% aqueous solution of caustic soda (60.8 g, 0.6 mol) was introduced at a rate of 12 ml / h for 3.5 hours. The temperature of the mixture in the flask was maintained in the range of 100 ° C to 115 ° C to ensure constant reflux. The rich epichlorohydrin organic phase tilted during the reaction as the lower phase in the separator was periodically recycled into the reaction flask, and the rich aqueous phase recovered as the upper phase in the separator was periodically extracted. After introducing all the caustic soda solution, heating was maintained for 15 minutes to achieve recovery of the aqueous phase in the decanter. 29.7 g of an aqueous phase was recovered with the composition shown in Table 6.</p><p num="0407"> Excess epichlorohydrin was removed from the reaction mixture by distillation under reduced pressure of 30 mbar and by progressive heating of the mixture to 109 ° C. 156.1 g (1.7 mol) of epichlorohydrin was recovered in this step. The composition of the distillate is shown in Table 6.</p><p num="0408"> After the addition of 567.2 g of toluene under stirring, the salt was separated from the crude product (45.5 g) by filtration. The filtered cake was washed with 124.4 g of toluene. The toluene solution was mixed and evaporated at 185 ° C. under a pressure of 1 mbar.</p><p num="0409"> 659.4 g of toluene was recovered as a condensate of the fraction evaporated with the composition shown in Table 6. The residual product of evaporation (100.5 g) contained diglycidyl ether of bisphenol A as the main product and no unconverted bisphenol A (&lt;5 mg / kg). The residue contained 4.98 mol epoxy / kg and 1.52% hydrolyzable chlorine.</p><p num="0410">Example 17 Trials were realized in the apparatus described in Example 16.</p><p num="0411"> The reaction flask was initially charged with a mixture of bisphenol A (68.4 g, 0.3 mol) and epichlorohydrin sample ECH5 (277.5 g, 3.0 mol). The analysis of epichlorohydrin is shown in Table 1. The content of trichloropropane is 0.007 g / kg. The mixture was heated to a temperature of 119 ° C with stirring under reflux. A 40% aqueous solution of caustic soda (60.8 g, 0.6 mol) was introduced at a rate of 12 ml / h for 3.5 hours. The temperature of the mixture in the flask was maintained in the range 102 ° C to 119 ° C to ensure constant reflux. The rich epichlorohydrin organic phase tilted during the reaction as the lower phase in the separator was periodically recycled into the reaction flask, and the rich aqueous phase recovered as the upper phase in the separator was periodically extracted. After introducing all the caustic soda solution, heating was maintained for 15 minutes to achieve recovery of the aqueous phase in the decanter. 54.5 g of an aqueous phase was recovered with the composition shown in Table 6.</p><p num="0412"> Excess epichlorohydrin was removed from the reaction mixture by distillation under reduced pressure of 30 mbar and by progressive heating of the mixture to 118 ° C. 148.2 g (1.5 mol) of epichlorohydrin was recovered in this step. The composition of the distillate is shown in Table 6.</p><p num="0413"> After the addition of 228.4 g of toluene under stirring, the salt was separated from the crude product (47.8 g) by filtration. The filtered cake was washed with 97.3 g of toluene. The toluene solution was mixed and evaporated at 180 ° C. under a pressure of 1 mbar.</p><p num="0414"> 305.0 g of toluene was recovered as an evaporation condensate with the composition shown in Table 6. The residual product of evaporation (99.8 g) contained diglycidyl ether of bisphenol A as the main product and was completely free of unconverted bisphenol A (&lt;5 mg / kg). The residue contained 4.93 mol epoxy / kg and 0.49% hydrolyzable chlorine.</p><p num="0415"> High performance liquid chromatography analysis of the residual products obtained in Examples 16 and 17 was similar.</p><p num="0416"><tables num="6"><img id="000008" he="226" wi="145" file="JP5877641B2_D0001.tif" img-format="tif" img-content="drawing" /></tables></p><p num="0417"><tables num="7"><img id="000009" he="226" wi="132" file="JP5877641B2_D0001.tif" img-format="tif" img-content="drawing" /></tables></p><p num="0418">Example 18 In accordance with WO 2005/054167, filed by Solvay SA, a glass constant temperature jacket reactor with a running volume of 305 mL, 47.2 wt% sodium hydroxide, and an aqueous mixture of dichloropropanol, glycerol and concentration. The mixture prepared from hydrochloric acid was continuously fed in the presence of an organic acid. The mixture consisted of 575 g of water / kg, 404.6 g of 1,3-dichloro-2-propanol / kg, 20.1 g of 2,3-dichloro-1-propanol / kg, 0.14 g of achlorine / kg, 0.13 g. Composition formula C of epichlorohydrin / kg, 0.04 g 1,2,3-trichloropropane / kg, 0.04 g chloroacetone / kg and 0.03 g₆H₁₀O₂Cl₂It contained / kg of ether. Sodium hydroxide was introduced at a flow rate of 262 g / h and an aqueous dichloropropanol mixture was introduced at a flow rate of 1180 g / h. The reaction medium was kept constant at 25 ° C with vigorous stirring. The liquid mixture leaving the reactor by continuous overflow was recovered and then separated in batch mode in a glass funnel to obtain the first and second separated fractions. The first separated fraction (MEL1) of 3753 g was subjected to batch distillation under reduced pressure of 193 mbar. Using a round-bottom flask equipped with a magnetic stirrer bar, a thermocouple for measuring the temperature of the liquid, and a plate distillation column equipped with a device that allows the reflux of some of the distillate at the top of the column. Batch distillation was carried out. The glass plate column has an internal aperture of 10 mm diameter central hole for liquid flow, and each hole located on the side beyond three quarters of the periphery, separated by a constant interval of less than 1 mm. It contained five plates with a diameter of 30 mm, perforated with small holes with a diameter of about 0.8 mm in three rows. The separation distance between the plates was 30 mm. This column was insulating (glass jacket under vacuum). A thermocouple located at the top of the distillation column made it possible to measure the temperature of the vapor phase being distilled. The distillate was collected in a funnel equipped with a stopcock. Recovery of the first distilled fraction between 49 ° C and 67 ° C resulted in 425 g of organic phase (D1 org) and 159 g of aqueous phase (D1 aq) after separation. The organic phase (D1 org) was combined with the contents of the boiler to give a mixture (MEL2), which was then distilled at a temperature of 187 ° C. Recovery of the second distilled fraction between 66 ° C and 67 ° C resulted in 244 g of organic phase (D2 org) and 11.5 g of aqueous phase (D2 aq) after separation. Next is m main distillate 999. 2082 g of epichlorohydrin at 5 g / kg was recovered at a temperature of 67 ° C (D3). The mixture constituting the final boiler (MEL3) weighed 1226 g and contained only epichlorohydrin with a very low fraction. Organic phase D2 org and boiler MEL3 at improved values to recover epichlorohydrin and mixtures of 1,3-dichloro-2-propanol and 2,3-dichloro-1-propanol, respectively. It was possible to recycle into a distillation operation. The composition (g / kg) obtained with use in the distillation operation is shown in Table 7.</p><p num="0419"><tables num="8"><img id="000010" he="225" wi="146" file="JP5877641B2_D0001.tif" img-format="tif" img-content="drawing" /></tables></p><p num="0420"><tables num="9"><img id="000011" he="225" wi="111" file="JP5877641B2_D0001.tif" img-format="tif" img-content="drawing" /></tables></p>