Alkylphenol free - liquid polymeric phosphite polymer stabilizers

0001The present invention described herein generally comprises, as an antioxidant additive, at least one liquid polymeric phosphite additive selected from the group of all alkyl polymeric phosphites. The present invention relates to a molecular composition and a method for producing the same.

0002Cross-reference of related applications This application claims the priority of pending US Patent Application No. 61 / 306,014 filed on February 19, 2010 and incorporates it by citation.

0003At least one purpose related to the addition of stabilizers to the polymeric resin is to prevent degradation of the resin-derived polymers during processing at high temperatures and at least during their intended use. One reason is that by increasing the resistance to pyrolysis and photodegradation, it is possible to produce products with high inherent quality.

0004Many organic phosphites are used as stabilizers, most of which are alkylphenols. Among them, the commercially important phosphites are tris (nonylphenyl) phosphite (TNPP) and tris (2,4-di-t-butylphenyl) phosphite. Historically, TNPP has been the leading low-cost liquid phosphite stabilizer in the plastics and rubber industry. However, recently, plastic and rubber manufacturers have been reluctant to use TNPP in their formulations due to the possibility that one of the degradation products of TNPP (nonylphenol) is an exogenous estrogen.

0005U.S. Pat. No. 6,541,549 B2 and U.S. Pat. No. 7,199,170 B2 disclose phosphite compounds having general structure I as non-exogenous estrogenic stabilizers of polymers, which are also alkylphenolic.<chemistry num="1"><img id="000002" he="82" wi="159" file="JP5771630B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>

0006U.S. Pat. No. 7,186,853 B2 discloses a phosphite containing a substituted or unsubstituted tricyclodecylmethyl group. The disclosed phosphite also includes certain alcohols, which can be aliphatic, arylalkyl and alkylaryl.

0007U.S. Pat. Nos. 7,468,410 B2 and WO 07 009,916 disclose tris- (monoalkyl) phenylphosphite of General Structure II or a mixture thereof, wherein each R is an alkyl group having the same or different carbon atoms 1-8. Is. This is also an alkylphenol-based low molecular weight monophosphite.

0008The problem with monophosphite or lower molecular weight phosphite described in the patent is that these phosphites are of some alkylphenol type and the lower molecular weight phosphite can be easily extracted from the polymer. .. There is concern that alkylphenols may be skin irritants and have exogenous estrogenic activity. Easily extracted from the polymer means that phosphite or its degradation products can be easily transferred into foods in contact with the polymer that may have been stabilized by low molecular weight phosphite or monophosphite. means.

0009<chemistry num="2"><img id="000003" he="64" wi="159" file="JP5771630B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>

0010WO 08 028,858 discloses the liquid polymer phosphite of general structure III, where L is the crosslink between the repeating units n and C.₁-C₂₄Alkylene, C₂-C₂₄Alkenylene, and C interrupted with oxygen, sulfur or substituted nitrogen (NR)₂-C₂₄Contains alkenylene. The integers m are 0 and 1.<chemistry num="3"><img id="000004" he="61" wi="159" file="JP5771630B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry> The problem with the polymeric phosphites in this disclosure is that all polymeric phosphites are of some alkylphenol type. It is preferable to have a polymer phosphite containing no alkylphenol.

<p num="0011"> The present invention relates to novel liquid polymer phosphite of general structure IV as a polymer stabilizer during processing.<chemistry num="4"><img id="000005" he="46" wi="159" file="JP5771630B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>During the ceremony R¹, R², R³And R⁴Are the same or different, independent of each other, C_1-20Alkyl, C_3-22Alkenyl, C_6-40Cycloalkyl, C_7-40Cycloalkylene, C_1-20Methoxyalkyl glycol ether, C_1-20It can be selected from the group consisting of alkyl glycol ethers or it can be Y-OH (acting as a terminal capping moiety); Y is C_2-40Alkylene, C_2-40Alkyl lactones (eg ethylene, propylene, caprilactone), -R⁷-N (R)⁸)-R⁹-(For example, C_2-40Alkyldiamines and C_2-40Selected from the group consisting of alkyltriamines) Here R⁷, R⁸And R⁹Independently, R¹, R², R³And R⁴Of the group defined above, here selected from the group further containing H; m is an integer value in the range from 2 to 100 including the beginning and end; and x is an integer value in the range 1 to 1,000.</p><p num="0012"> Depending on the reaction conditions and components, it is also possible to synthesize structure V, which may be within the scope of the present invention:<chemistry num="5"><img id="000006" he="35" wi="159" file="JP5771630B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>During the ceremony R¹, R², R³And R⁴Are, respectively, as defined above; Y is as defined above; and m is as defined above.</p><p num="0013"> The novel polymeric phosphite of general structure IV or V is suitable for stabilizing organic materials against oxidative, thermal or photodegradation.</p><p num="0014"> The most preferred polymeric diphosphite or polymeric phosphite is one that has or does not contain an aromatic or alkylphenol group.</p><p num="0015"> The advantages of the liquid high molecular weight dimer phosphite and high molecular weight phosphite are that they are very low in volatility, there is no migration from the stabilized polymer, and extraction from the stabilized polymer is very difficult. Is to be. These advantages can be read as no plate-out during polymer extrusion (no dilip construction) and no transfer from the polymer used in food packaging into food. It is very advantageous to have a liquid polymer phosphite which is excellent in hydrolysis stability and is not an alkylphenol type.</p><p num="0016"> These and other objects of the invention will be apparent in the light of the drawings, detailed description and the appended claims.</p>

0017The best mode for carrying out the invention is described herein for the purpose of explaining the best form known to the applicant at the time of filing the invention. The examples and drawings are illustrative only and are not intended to limit the invention as measured by the claims and spirit.

0018As used herein, unless otherwise specified, the term "alkyl" means a monovalent group of linear and branched saturated acyclic hydrocarbons; said alkyl. The group may optionally further comprise one or more suitable substituents independently selected from the group consisting of amino, halogen, hydroxy, sulfhydryl, haloalkyl, alkoxy and the like. Specific non-limiting examples of linear and branched alkyl groups are C_1-20It is alkyl and is, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecylic, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl and stearyl groups. Alkyl may be interrupted with oxygen, sulfur or nitrogen, for example CH₃-O-CH₂CH₂-, CH₃-S-CH₂CH₂-, CH₃-N (CH₃)-CH₂CH₂-, CH₃-O-CH₂CH₂-O-CH₂CH₂-, CH₃-(O-CH₂CH₂-)₂O-CH₂CH₂-, CH₃-(O-CH₂CH₂-)₃O-CH₂CH₂-Or CH₃-(O-CH₂CH₂-)₄O-CH₂CH₂-Can be mentioned.

0019As used herein, unless otherwise specified, the term "alkoxy" means a monovalent group of linear and branched unsaturated acyclic hydrocarbons; The alkenyl group may optionally further comprise one or more suitable substituents independently selected from the group consisting of amino, halogen, hydroxy, sulfhydryl, haloalkyl, alkoxy and the like. Specific non-limiting examples of straight and branched alkenyl groups are those having 2 to 30 carbon atoms, where the position of the double bond may vary, buttenyl, pentenyl. , Hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl and the like. It has also been found that alkenyl may be interrupted with oxygen, sulfur or nitrogen, for example -CH.₂-O-CH₂-, -CH₂-S-CH₂-, -CH₂-N (CH₃)-CH₂-, -CH₂-O-CH₂CH₂-, -CH₂CH₂-O-CH₂CH₂-, -CH₂CH₂-O-CH₂CH₂-O-CH₂CH₂-, -CH₂CH₂-(O-CH₂CH₂-)₂O-CH₂CH₂-, -CH₂CH₂-(O-CH₂CH₂-)₃O-CH₂CH₂-, -CH₂CH₂-(O-CH₂CH₂-)₄O-CH₂CH₂-, -CH₂CH₂-S-CH₂CH₂-Or-CH₂CH₂-N (CH₃)-CH₂CH₂-Can be mentioned.

0020As used herein, unless otherwise specified, the term "cyclic aliphatic" is a monovalent mono- or polycyclic saturated hydrocarbon having 3 to 10 carbon atoms. Group, or C with 7-10 carbon atoms_7-10Refers to the monovalent group of polycyclic saturated hydrocarbons. Specific non-limiting examples of cyclic aliphatic or cyclic alkyl groups, which may have substituents, are rings with 5-7 carbon atoms, such as cyclopentyl, cyclohexyl and cycloheptyl groups. Formula alkyl groups and alkylcycloalkyl groups having 6 to 11 carbon atoms, the positions of the alkyl groups may vary, such as methylcyclopentyl, dimethylcyclopentyl, methylethylcyclopentyl, dimethylcyclopentyl, Methylcyclohexyl, dimethylcyclohexyl, methylethylcyclohexyl, diethylcyclohexyl, methylcycloheptyl, dimethylcycloheptyl, methylcycloheptyl, diethylcycloheptyl group and the like. It is also accepted that in the case of cyclic aliphatics, it may be interrupted by oxygen, sulfur or nitrogen.

0021As used herein, unless otherwise specified, the term "heteroatom" has 2 to 15 carbon atoms and one or more heteroatoms in one or more rings. Means a mono- or polycyclic, saturated or mono-unsaturated or poly-unsaturated monovalent hydrocarbon group containing, each ring having 3 to 10 atoms (and optionally the ring described above). Further comprises one or more heteroatoms attached to one or more carbon atoms of, eg, in the form of a carbonyl or thiocarbonyl or selenocarbonyl group, and / or to one or more heteroatoms of the ring above. It further comprises one or more heteroatoms to be attached, each of which is independently selected from the group consisting of nitrogen, oxygen, sulfur, selenium and phosphorus. Heteroatoms are all possible of which. Each carbon atom of the hetero ring contains an isomer form, independently of halogen, nitro, and C._1-7Alkyl (as defined above, especially methyl), C_3-7Alkenyl, trifluoromethyl, C_3-10Cycloalkyl, hydroxyl, sulfhydryl, C_1-7Alkoxy (as defined above, especially methoxy), thio C_1-7Alkyl, thio C_3-10It may be substituted with a substituent selected from the group consisting of cycloalkyl, cyano, carboxylic acid or ester. Depending on the number of unsaturated rings in each of the above rings, the heterocyclic group may be subdivided into heteroaromatic (or "heteroaryl") groups and non-aromatic heterocyclic groups; If the heteroatom of the ring group is nitrogen, the latter is C_1-7Alkyl, C_3-10It may be substituted with a substituent selected from the group consisting of cycloalkyl, aryl, arylalkyl and alkylaryl (each of which is as defined herein).

0022As used herein, unless otherwise specified, the term "alkoxy" refers to a substituent in which an alkyl group is single bonded to an oxygen atom.

0023As used herein, unless otherwise specified, the term "halo" or "halogen" refers to any atom selected from the group consisting of fluorine, chlorine, bromine and iodine. means.

0024As used herein, unless otherwise specified, the term "acyl" corresponds to an organic monocarboxylic acid, carbonic acid, carbamic acid (which serves as a carbamoyl substituent) or the acid described above. It refers to a substituent derived from an acid such as thioic acid or imidic acid (which becomes a carbamic acid substituent), and the above-mentioned acid contains an aliphatic, aromatic or heterocyclic group in the molecule. More specific species of "acyl" groups within the above definition are alkyl, cycloalkyl, aryl, arylalkyl or carbonyl (oxo) groups flanking the heterocyclic group, all of which are herein. It is as specified in.

0025The present invention relates to novel liquid polymer phosphite of general structure IV as a polymer stabilizer during processing.<chemistry num="6"><img id="000007" he="47" wi="159" file="JP5771630B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>During the ceremony R¹, R², R³And R⁴Are the same or different, independent of each other, C_1-20Alkyl, C_3-22Alkenyl, C_6-40Cycloalkyl, C_7-40Cycloalkylene, C_1-20Methoxyalkyl glycol ether, C_1-20It can be selected from the group consisting of alkyl glycol ethers or it can be Y-OH (acting as a terminal capping moiety); Y is C_2-40Alkylene, C_2-40Alkyl lactones (eg ethylene, propylene, caprilactone), -R⁷-N (R)⁸)-R⁹-(For example, C_2-40Alkyldiamines and C_2-40Selected from the group consisting of alkyltriamines) Here R⁷, R⁸And R⁹Independently, R¹, R², R³And R⁴Of the group defined above, here selected from the group further containing H; m is an integer value containing the beginning and end of the range 2-100; and x is an integer value in the range 1 to 1,000.

0026Depending on the reaction conditions and components, it is also possible to synthesize structure V, which can be within the scope of the present invention:<chemistry num="7"><img id="000008" he="35" wi="159" file="JP5771630B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>During the ceremony R¹, R², R³And R⁴Are, respectively, as defined above; Y is as defined above; and m is as defined above.

0027Synthesis of compositions typically involves transesterification, where triphenylphosphite (or any other suitable alkyl or arylphosphite) is an alkyl or alkenyl alcohol or polyethylene or polypropylene glycol ether, and a diol or High molecular weight diol H (OY)_mOH, where Y and m are as defined above, and with suitable base catalysts, temperatures between 20 ° C and 250 ° C, more preferably between 50 ° C and 185 ° C. You may react at the temperature of. Non-limiting examples of monoalkyl or alkenyl alcohols include decyl, isodecyl, lauryl, tridecylic, isotridecyl, myristyl, pentadecyl, palmyl, stearyl, isostearyl, oleyl alcohol, monohydroxyglycol ethers and the like.

0028Suitable base catalysts include sodium hydroxide, sodium methoxide, sodium phenolate, potassium hydroxide, and potassium carbonate. The amount of base catalyst used is in the range of 0.01 to 10% by weight based on the total amount of the loaded reactants. In a preferred embodiment, the amount is within 0.1-1.0% by weight of the reactants.

0029For thiophenylphosphite, the molar ratio of alkyl alcohols or glycol ethers (without alkylphenols) to high molecular weight diols used to form diphosphite of general structure IV or V is phenol per mole of triphenylphosphite. Alternatively, alcohol or glycol ether is about 1.9 to 2.2 mol and diol is 0.3 to 0.6 mol per mol of triphenylphosphite. In a preferred embodiment, the molar ratio is 2.0 to 1.0 for alkyl or alkenyl alcohol or glycol ether per mole of triphenylphosphine, and the molar ratio of diol to triphenylphosphine is 0.5 to 1.0.

0030The structural composition of the polymeric phosphite of Structure IV is, for example, the temperature, the order in which the reactants are added, the alkyl or alkenyl alcohol or glycol ether used, or a mixture of alkyl or alkenyl alcohol or glycol ether, or some or all. It depends on the reaction conditions such as the combination of alkyl or alkenyl alcohol or glycol ether and the molar ratio and concentration of the high molecular weight diol, and the molecular weight of the high molecular weight diol selected. For example, the phosphorus content of the polymeric phosphite can be adjusted by the molecular weight of the selected diol and alkyl or alkenyl alcohol or glycol ether. Again, the viscosity of polyphosphite depends on the molecular weight, length and structure of the linear or branched diol used, as well as the phenol alkyl or alkenyl alcohol or glycol ether used. It can be adjusted by the molecular weight of.

0031The preferred alkyl alcohol used is C₁₂~ C₁₈Is. The preferred alkenyl alcohol used is C₁₆~ C₁₈Is. Also preferred glycol ethers used are Carbowax 350 (polyethylene glycol monomethyl ether, MW 350), and tripropylene glycol monobutyl ether.

0032The polymeric diols used in the process are commercially available, known as polyglycols. Preferred polyglycols are polyethylene or polypropylene glycols, which have a molecular weight in the range of 200 to 3000 and are present as a liquid at room temperature. Most preferred are polyethylene glycols with a molecular weight of 300-400 and polypropylene glycols with a molecular weight of 300-1000.

0033Polymer diphosphite of general structure IV and polymer phosphite of general structure V are suitable for stabilizing organic materials against oxidative, thermal or photodegradation.

0034The organic material is preferably a synthetic polymer. Non-limiting examples of such polymers include:

0035Monoolefin and Diolefin Polymers: For example, polypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyvinylcyclohexane, polyisoprene or polybutadiene, and cycloolefins such as cyclopentene or norbornene. Polymers such as high density polyethylene (HDPE), high density and high density polyethylene (HDPE-HMW), high density and ultra high density polyethylene (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), chains A mixture of low density polyethylene (LLDPE), polyethylene (VLDPE) and (ULDPE) (which can be optionally crosslinked), and the polymers described above, regardless of production method.

0036Mixtures of the above polymers: for example, a mixture of polypropylene and polyisobutylene, a mixture of polypropylene and polyethylene (eg PP / HDPE, PP / LDPE) and a mixture of various types of polyethylene (eg LDPE / HDPE).

0037Copolymers of monoolefins and diolefins with each other or with other vinyl monomers: eg, ethylene / propylene copolymers, chains of low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene / pig-1- Encopolymer, propylene / isobutylene copolymer, ethylene / buta-1-ene copolymer, ethylene / hexene copolymer, ethylene / methylpentene copolymer, ethylene / heptene copolymer, ethylene / octene copolymer, ethylene / vinylcyclohexane copolymer, ethylene / cycloolefin copolymer (For example, norbornene such as ethylene / COC), ethylene / 1-olefin copolymers in which 1-olefin is produced in-situ; propylene / butadiene copolymer, isobutylene / isoprene copolymer, ethylene / vinylcyclohexene copolymer, ethylene / Alkyl acrylate copolymers, ethylene / alkyl methacrylate copolymers, ethylene / vinyl acetate copolymers or ethylene / acrylic acid copolymers and salts thereof (ionomers), and ethylene and propylene with diene such as hexadiene, dicyclopentadiene or ethylidene-norbornene. Tarpolymers; and mixtures of such copolymers with each other and with the above-mentioned polymers, such as polypropylene / ethylene-propylene copolymers, LDPE / ethylene-vinyl acetate copolymers (EVA), LDPE / ethylene-acrylic acid copolymers (LDPE / ethylene-acrylic acid copolymers). EAA), LLDPE / EVA, LLDPE / EAA, and alternating or random polyalkylene / carbon monooxide copolymers, and mixtures with other polymers such as polyamide.

0038Hydrocarbon resin: (eg C₅-C₉), Its hydrogenated modifiers (eg, tackifiers) and mixtures of polyalkylenes and starch.

0039Homopolymers and copolymers: As described above, they may have any conformation, including syndiotactics, isotactics, hemiisotactics or atactics. Stereo block polymers are also included.

0040Polystyrene and poly (p-methylstyrene) and poly (α-methylstyrene).

0041Aromatic homopolymers and copolymers derived from vinyl aromatic monomers: All isomeres of styrene, α-methylstyrene, vinyltoluene, especially all of p-vinyltoluene, ethylstyrene, propylstyrene, vinylbiphenyl, vinylnaphthalene and vinylanthracene. Includes isomers, and mixtures thereof. Homopolymers and copolymers may have any conformation, including syndiotactics, isotactics, hemiisotactics or atactics. Stereo block polymers are also included. Copolymers include, for example, vinyl aromatic monomers and comonomer selected from ethylene, propylene, diene, nitrile, acid, maleic anhydride, maleimide, vinyl acetate and vinyl chloride or acrylic derivatives and mixtures thereof, eg, Styrene / butadiene, styrene / acrylonitrile, styrene / ethylene (interpolymer), styrene / alkyl methacrylate, styrene / butadiene / alkyl acrylate, styrene / butadiene / acrylic methacrylate, styrene / maleic anhydride, styrene / acrylonitrile / acrylic Methyl Acid Acid; A High Impact High Mixture of Styrene Copolymers with Other Polymers, eg Polyacrylate, Diene Polymer or Ethylene / Propylene / Dienter Polymer; And styrene block copolymers such as styrene / butadiene / styrene, styrene / isoprene / styrene, styrene / ethylene / butylene / styrene or styrene / ethylene / propylene / styrene. Includes hydrogenated aromatic polymers derived from the hydrogenation of the above polymers, especially polycyclohexylethylene (PCHE) produced by hydrogenating atactic polystyrene, which is often polyvinylcyclohexane (PVCH). ) Is also called. Further included are hydrogenated aromatic polymers induced by hydrogenation of the above polymers. Homopolymers and copolymers may have any conformation, including syndiotactics, isotactics, hemiisotactics or atactics. Stereo block polymers are also included.

0042Graft copolymers of vinyl aromatic monomers: styrene or α-methylstyrene, for example, styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-alicronitrile copolymers; styrene on polybutadiene and acrylonitrile (or methacrylonitrile) ); Styrene on polybutadiene, acrylonitrile and methyl methacrylate; Styrene on polybutadiene and maleic anhydride; Styrene on polybutadiene, acrylonitrile and maleic anhydride or maleimide; Styrene and maleimide on polybutadiene; Styrene on polybutadiene and alkyl acrylate Or alkyl methacrylate; styrene and acrylonitrile on ethylene / propylene / dienter polymer; styrene and acrylonitrile on alkyl polyacrylate or alkyl methacrylate, styrene and acrylonitrile on acrylate / butadiene copolymer, and listed above. Mixtures with styrenes, eg, copolymer blends known as ABS, MBS, ASA or AES polymers.

0043Halogen-containing polymers: eg polychloroprene, rubber chloride, chlorinated and brominated copolymers of isobutylene-isoprene (halobutyl rubber), chlorinated or sulfo-polyethylene chloride, copolymers of ethylene and ethylene chloride, homo and copolymers of epichlorohydrin, especially Polymers of halogen-containing vinyl compounds such as polyvinyl chloride, polyvinylidene chloride, vinyl fluoride, vinylidene fluoride, and copolymers thereof such as vinyl chloride / vinylidene chloride, vinyl chloride / vinyl acetate or vinylidene chloride / vinyl acetate copolymer. For example, styrene on polybutadiene, styrene and alkyl acrylate or alkyl methacrylate on butadiene, styrene and acrylonitrile on ethylene / propylene / dienterpolymer, styrene and acrylonitrile on polyacrylate or polymethacrylate, on acrylate / butadiene copolymers. A blend of styrene and acrylonitrile, and copolymers known as ABS, MBS, and AES polymers.

0044Polymers derived from α, β-unsaturated acids and their derivatives: for example, polymethylmethacrylate, polyacrylamide and polyacrylonitrile modified with butyl acrylate for impact resistance; polyacrylate and polymethacrylate.

0045Copolymers of the monomers described in the previous paragraph with each other or with other unsaturated monomers: eg, acrylonitrile / butadiene copolymer, acrylonitrile / alkyl acrylate copolymer, acrylonitrile / alkoxyalkyl acrylate or acrylonitrile / vinyl halide copolymer or acrylonitrile / alkyl Methacrylate / butadiene terpolymer.

0046Polymers derived from unsaturated alcohols and amines or acyl derivatives thereof or acetals: for example, polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine; and the above olefins. Those copolymers with.

0047Homopolymers and copolymers of cyclic ethers: eg, copolymers with polyalkylene glycols, polyethylene oxides, polypropylene oxides or their bisglycidyl ethers.

0048Polyacetal: For example, polyoxymethylene and polyoxymethylene containing ethylene oxide as a comonomer; polyacetal modified with thermoplastic polyurethane, acrylate or MBS.

0049A mixture of polyphenylene oxide and sulfide, and polyphenylene oxide with a styrene polymer or polyamide.

0050Polyurethanes, one of which is a hydroxyl-terminated polyether, polyester or polybutadiene, and the other of which is derived from an aliphatic or aromatic polyisocyanate, and precursors thereof.

0051Polyamides and copolyamides derived from diamines and dicarboxylic acids and / or aminocarboxylic acids or corresponding lactams: eg, polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6 / 12, 4/6, 12/12, Polyamide 11, Polyamide 12, m-Xylenideamine and aromatic polyamide starting from adipic acid; polyamide prepared from hexamethylenediamine and isophthal and / and terephthalic acid, Polyamides, olefin copolymers, ionomers, or those with or without elastomers as polymerization modifiers, such as poly-2,4,4-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide; and the above polyamides. Block copolymers with chemically bonded or grafted elastomers; or block copolymers with polyamide polyethers, such as polyamides with polyethylene glycol, polypropylene glycol or polytetramethylene glycol; and EPDM or ABS modified polyamides or Copolyamide; and polyamide (RIM polyamide type) that is condensed during processing.

0052Polyurea, polyimide, polyamide-imide, polyetherimide, polyesterimide, polyhydantoin and polybenzimidazole.

0053Polyesters derived from dicarboxylic acids and diols and / or hydroxycarboxylic acids or corresponding lactones: eg polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylolcyclohexane terephthalate, polyalkylene naphthalate (PAN) and polyhydroxybenzoate. , And a block copolyether ester derived from a hydroxyl-terminated polyether; and a polyester modified with polycarbonate or MBS.

0054Polycarbonate and polyester carbonate.

0055Polysulfone, polyethersulfone and polyetherketone.

0056Crosslinked polymers: One is derived from aldehydes and the other is derived from phenols, urea and melamines, such as phenol / formaldehyde resins, urea / formaldehyde resins and melamine / formaldehyde resins.

0057Dry and non-dry alkyd resins.

0058Unsaturated polyester resin: Derived from saturated and unsaturated dicarboxylic acid copolyesters with polyhydric alcohols and vinyl compounds as cross-linking agents, and low flammability halogen-containing modifications thereof.

0059Crosslinkable Acrylate Resin: Derived from substituted acrylates, such as epoxy acrylates, urethane acrylates or polyester acrylates.

0060Alkyd resins, polyester resins and acrylate resins crosslinked with melamine resins, urea resins, isocyanates, isocyanurates, polyisocyanates or epoxy resins.

0061Crosslinked epoxy resins from aliphatic, cyclic aliphatic, heterocyclic or aromatic glycidyl compounds: products of diglycidyl ethers of, for example, bisphenol A and bisphenol F, conventional hardeners such as anhydrides or amines. And those that are crosslinked with or without an accelerator.

0062Natural Polymers: Cellulose, rubber, gelatin and cellulosic ethers such as uniform derivatives thereof, eg, cellulose acetate, cellulose propionate and cellulose acetate, or methyl cellulose; and rosin derivatives thereof.

0063Blends and alloys (polyblends) of the above polymers: eg PP / EPDM, polyamide / EPDM or ABS, PVC / EVA, PVC / ABS, PVC / MBS, PC / ABS, PC / polyester, PBTP / ABS, PC / ASA, PC / PBT, PVC / CPE, PVC / acrylate, POM / thermoplastic PUR, PC / thermoplastic PUR, POM / acrylate, POM / MBS, PPO / HIPS, PPO / PA 6.6 and copolymers, PA / HDPE, PA / PP, PA / PPO, PBT / PC / ABS or PBT / PET / PC.

0064Naturally occurring and synthetic organic materials that are pure monomeric compounds or mixtures of such compounds: eg mineral oils, animal and vegetable fats, fats and waxes, or synthetic ester oils, fats and waxes (eg, Mixtures of phthalates, adipates, phosphates or trimellites) and synthetic esters in any weight ratio of mineral oils, typically used as spinning compositions, as well as aqueous emulsions of such materials.

0065Aqueous emulsions of natural or synthetic rubber: For example, latexes of carboxylated styrene / butadiene copolymers, or natural latex.

0066Generally, the polymeric diphosphite and polymeric phosphite of the present invention are added to the organic material to be stabilized in an amount of about 0.001% to about 5% by weight of the weight of the organic material to be stabilized. .. A more preferred range is from about 0.01% to 2.0%. The most preferred range is 0.025% to 1%.

0067The stabilizers of the present invention may be incorporated into the organic material at any convenient stage prior to the manufacture of the molding, using techniques known in the art.

0068The stabilized polymer composition of the present invention may also contain about 0.001% to 5%, preferably 0.01% to 2%, most preferably 0.025% to 1% of other conventional stabilizers, but is not limited. A representative list is provided below.

0069Hindered Phenol Antioxidants: For example, 2,6-di-t-butyl-4-methylphenol; octadecyl-3,5-di-t-butyl-4-hydroxy-hydrocinnamate; tetrakismethylene (3, 5-Di-t-Butyl-4-hydroxyhydrosinamate) methane; and Tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanate.

0070Thioester: A non-limiting representative list includes dilauryl thiodipropionate and distearyl thiodipropionate.

0071Aromatic amine stabilizers: A non-limiting representative list includes N, N'-diphenyl-p-phenylene-diamine.

0072Hindered Amine Light Stabilizer: Known as HALS, on a non-limiting representative list, bis- (2,2,6,6-tetramethylpiperidyl) sebacate, N, N'-(2,2,6.6-) Tetramethylpiperidyl) -condensation product of hexamethylenediamine and 4,4-octylamino-2,6-dichloro-s-triazine, and N, N'-(2,2,6.6-tetramethylpiperidyl) -hexamethylene Condensation products of diamine with 4-N-morpholinyl-2,6-dichloro-s-triazine.

0073UV Absorbents: 2-Hydroxy-4-n-octyloxybenzophenone, 2 (2'-hydroxy-5'-methylphenyl) -benzotriazole, and 2 (2'-hydroxy- 5-t-octylphenyl) -benzotriazole can be mentioned.

0074Phosphite: A non-limiting representative list includes tris (2,4-di-t-butylphenyl) phosphite, distearylpentaerythritol diphosphite, and 2,4-dicumylphenylpentaerythritol diphosphite. Can be mentioned.

0075Acid Neutralizers: A non-limiting representative list includes calcium stearate, zinc stearate, calcium lactate, calcium stearyl lactate, epoxidized soybean oil, and hydrotalcite (natural and synthetic).

0076Other additives such as lubricants, antistatics, antiblocking agents, lubricants, flame retardants, nucleating agents, impact modifiers, foaming agents, plasticizers, bulking agents, dyes and dyes in suitable amounts. , The polymer diphosphite of the present invention may be used in combination to modify selected properties of the polymer, the additive being, for example, an alkanolamine, and a non-limiting representative list is triethanol. Examples include amines and triisopropanolamines.

0077The novel polymeric phosphite of structures IV and V can be used, in particular, in combination with phenolic antioxidants, light stabilizers and / or processing stabilizers.

0078In addition to the liquid polymeric compounds of formulas IV and V, the novel compositions may further include, for example, the following additives:

0079Antioxidants:

0080Alkylated monophenols: for example, 2,6-di-t-butyl-4-methylphenol, 2-t-butyl-4,6-di-methylphenol, 2,6-di-t-butyl-4-ethyl Phenol, 2,6-di-t-butyl-4-n-butylphenol, 2,6-di-t-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2- (α-) Methylcyclohexyl) -4,6-dimethyl-phenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-t-butyl-4-methoxymethylphenol, Nonylphenol with chain or branched side chains, such as 2,6-di-nonyl-4-methoxyphenol, 2,4-dimethyl-6- (1'-methylundeca-1'-yl) phenol, 2,4 -Dimethyl-6- (1'-methylheptadeca-1'-yl) phenol, 2,4-dimethyl-6- (1'-methyltrideca-1'-yl) phenol and mixtures thereof.

0081Alkylthiomethylphenols: For example, 2,4-dioctylthiomethyl-6-t-butylphenol, 2,4-dioctyl-thiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6- Di-dodecylthiomethyl-4-nonylphenol.

0082Hydroquinone and Alkylated Hydroquinone: For example, 2,6-di-t-butyl-4-methoxy-phenol, 2,5-di-t-butylhydroquinone, 2,5-di-t-amylhydroquinone, 2,6- Diphenyl-4-octadecyloxyphenol, 2,6-di-t-butylhydroquinone, 2,5-di-t-butyl-4-hydroxyanisole, 3,5-di-t-butyl-4-hydroxyanisole, 3 , 5-Di-t-butyl-4-hydroxyphenyl stearate, bis (3,5-di-t-butyl-4-hydroxyphenyl) adipate.

0083Tocopherols: eg α-tocopherols, β-tocopherols, γ-tocopherols, δ-tocopherols and mixtures thereof (vitamin E).

0084Hydrolated thiodiphenyl ethers: for example, 2,2'-thiobis (6-t-butyl-4-methylphenol), 2,2'-thiobis (4-octylphenol), 4,4'-thiobis (6-t-butyl) -3-Methylphenol), 4,4'-thiobis (6-t-butyl-2-methylphenol), 4,4'-thiobis (3,6-di-sec-amylphenol), 4,4'- Bis (2,6-dimethyl-4-hydroxyphenyl) -disulfide.

0085Alkylidenebisphenols: For example, 2,2'-methylenebis (6-t-butyl-4-methylphenol), 2,2'-methylenebis (6-t-butyl-4-ethylphenol), 2,2'-methylenebis [ 4-Methyl-6- (α-Methylcyclohexyl) -phenol], 2,2'-methylenebis (4-methyl-6-cyclohexylphenol), 2,2'-methylenebis (6-nonyl-4-methylphenol), 2,2'-Methylenebis (4,6-di-t-Butylphenol), 2,2'-Echilidenebis (4,6-di-t-Butylphenol), 2,2'-Echilidenbis (6-t-Butylphenol) -4-isobutylphenol), 2,2'-methylenebis [6- (α-methylbenzyl) -4-nonylphenol], 2,2'-methylenebis [6- (α, α-dimethylbenzyl) -4-nonylphenol] , 4,4'-methylenebis (2,6-di-t-butylphenol), 4,4'-methylenebis (6-t-butyl-2-methylphenol), 1,1-bis (5-t-butyl-butyl-) 4-Hydroxy-2-methylphenyl) butane, 2,6-bis (3-t-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol, 1,1,3-tris (5-t- Butyl-4-hydroxy-2-methylphenyl) butane, 1,1-bis (5-t-butyl-4-hydroxy-2-methylphenyl) -3-n-dodecyl mercaptobutane, ethylene glycol bis [3,3 -Bis (3'-t-butyl-4'-hydroxyphenyl) butyrate], bis (3-t-butyl-4-hydroxy-5-methyl-phenyl) dicyclopentadiene, bis [2- (3'-t) -Butyl-2'-Hydroxy-5'-Methylbenzyl) -6-t-Butyl-4-methylphenyl] terephthalate, 1,1-bis- (3,5-dimethyl-2-hydroxyphenyl) butane, 2, 2-Bistyl (3,5-di-t-butyl-4-hydroxyphenyl) propane, 2,2-bis- (5-t-butyl-4-hydroxy2-methylphenyl) -4-n-dodecyl mercaptobutane, 1,1,5 , 5-Tetra (5-t-butyl-4-hydroxy-2-methylphenyl) pentane.

0086O-, N- and S-benzyl compounds: for example, 3,5,3', 5'-tetra-t-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethyl Benzyl mercaptoacetate, tridecyl-4-hydroxy-3,5-di-t-butyl benzyl mercaptoacetate, tris (3,5-di-t-butyl-4-hydroxybenzyl) amine, bis (4-t-butyl- 3-Hydroxy-2,6-dimethylbenzyl) dithioterephthalate, bis (3,5-di-t-butyl-4-hydroxybenzyl) sulfide, isooctyl-3,5-di-t-butyl-4-hydroxybenzyl mercapto acetate.

0087Hydroxybenzylated malonate: for example, dioctadecyl-2,2-bis (3,5-di-t-butyl-2-hydroxybenzyl) malonate, di-octadecyl-2- (3-t-butyl-4-hydroxy-) 5-Methylbenzyl) malonate, di-dodecyl mercaptoethyl-2,2-bis (3,5-di-t-butyl-4-hydroxybenzyl) malonate, bis [4- (1,1,3,3-tetra) Methylbutyl) phenyl] -2,2-bis (3,5-di-t-butyl-4-hydroxybenzyl) malonate.

0088Aromatic hydroxybenzyl compounds: for example, 1,3,5-tris (3,5-di-t-butyl-4-hydroxy-benzyl) -2,4,6-trimethylbenzene, 1,4-bis (3, 5-di-t-butyl-4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene, 2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) phenol ..

0089Triazine compounds: For example, 2,4-bis (octyl mercapto) -6- (3,5-di-t-butyl-4-hydroxy-anilino) -1,3,5-triazine, 2-octyl mercapto-4, 6-bis (3,5-di-t-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octyl mercapto-4,6-bis (3,5-di-t-butyl- 4-Hydroxyphenoxy) -1,3,5-triazine, 2,4,6-Tris (3,5-di-t-butyl-4-hydroxyphenoxy) -1,2,3-triazine, 1,3, 5-Tris (3,5-di-t-Butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-Tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 2,4,6-Tris (3,5-di-t-butyl-4-hydroxyphenylethyl) -1,3,5-triazine, 1,3,5-Tris (3,5-di-t-butyl) -4-Hydroxyphenylpropionyl) -hexahydro-1,3,5-triazine, 1,3,5-tris (3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate.

0090Benzylphosphonates: for example, dimethyl-2,5-di-t-butyl-4-hydroxybenzylphosphonate, diethyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate, dioctadecyl-3,5-di- Monoethyl ester of t-butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-t-butyl-4-hydroxy-3-methylbenzylphosphonate, 3,5-di-t-butyl-4-hydroxybenzylphosphonic acid Benzyl salt.

0091Acylaminophenols: for example 4-hydroxyraulanilide, 4-hydroxystealanilide, octyl N- (3,5-di-t-butyl-4-hydroxyphenyl) carbamate.

0092Esters of β- (3,5-di-t-butyl-4-hydroxyphenyl) propionic acid with monohydric or polyhydric alcohols: eg methanol, ethanol, n-octanol, i-octanol, octadecanol, 1 , 6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N '-Bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [ 2.2.2] Ester with octane.

0093Esters of β- (5-t-butyl-4-hydroxy-3-methylphenyl) propionic acid with monohydric or polyhydric alcohols: eg, methanol, ethanol, n-octanol, i-octanol, octadecanol, 1 , 6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N '-Bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [ 2.2.2] Ester with octane; 3,9-bis [2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2, 4,8,10-Tetraoxaspiro [5.5] Undecane.

0094Esters with monohydric or polyhydric alcohols of β- (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid: eg methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9- Nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3 -Ester with thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane.

0095Esters with monohydric or polyhydric alcohols of 3,5-di-t-butyl-4-hydroxyphenylacetic acid: eg methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonane Diol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3- Esters with thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane.

0096Amido of β- (3,5-di-t-butyl-4-hydroxyphenyl) propionic acid: For example, N, N'-bis (3,5-di-t-butyl-4-hydroxyphenylpropionyl) hexamethylene Diamide, N, N'-bis (3,5-di-t-butyl-4-hydroxy-phenylpropionyl) Trimethylenediamide, N, N'-bis (3,5-di-t-butyl-4-hydroxy) Phenylpropionyl) hydrazide, N, N'-bis [2- (3- [3,5-di-t-butyl-4-hydroxyphenyl] propionyloxy) ethyl] oxamide.

0097Ascorbic acid (vitamin C).

0098Amine-based antioxidants: For example, N, N'-di-isopropyl-p-phenylenediamine, N, N'-di-sec-butyl-p-phenylenediamine, N, N'-bis (1,4-dimethyl) Pentyl) -p-phenylenediamine, N, N'-bis (1-ethyl-3-methylpentyl) -p-phenylenediamine, N, N'-bis (1-methylheptyl) -p-phenylenediamine, N, N'-dicyclohexyl-p-phenylenediamine, N, N'-diphenyl-p-phenylenediamine, N, N'-bis (2-naphthyl) -p-phenylenediamine, N-isopropyl-N'-phenyl-p- Phenylene diamine, N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, N- (1-methylheptyl) -N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'- Phenyl-p-phenylenediamine, 4- (p-toluene sulfamoyl) diphenylamine, N, N'-dimethyl-N, N'-di-sec-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4 -Isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N- (4-t-octylphenyl) -1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, eg p, p'-di-t -Octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol, bis (4-methoxyphenyl) amine, 2,6-di-t-butyl-4-dimethylaminomethylphenol, 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, N, N, N', N'-tetramethyl-4,4'-Diaminodiphenylmethane, 1,2-bis [(2-methylphenyl) amino] ethane, 1,2-bis (phenylamino) propane, (o-tolyl) biguanide, bis [4- (1', 3'-dimethyl) Butyl) phenyl] amines, t-octylated N-phenyl-1-naphthylamines, mono and dialkylated t-butyl / t-octyldiphenylamine mixtures, mono and dialkylated nonyldiphenylamine mixtures, mono and dialkylated dodecyldiphenylamine mixtures. , Mono and dialkylated isopropyl / isohexyldiphenylamine mixture, mono and dialkylated t-butyldiphenylamine mixture, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, mono and dialkylated Mix of t-butyl / t-octylphenothiazine, mono and dialkylated mixture of t-octylphenothiazine, N-allylphenothiazine, N, N, N', N'-tetraphenyl-1,4-diaminobut-2-ene, N, N-bis (2,2,6,6-tetramethylpiperidi-4-yl-hexamethylenediamine, bis (2,2,6,6-tetramethylpiperid-4-yl) sebacate, 2, 2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol.-Dimethylbutyl) phenyl] amine, t-octylated N-phenyl-1-naphthylamine, mono and dialkylated t-butyl / t-octyldiphenylamine mixture, mono and dialkylated nonyldiphenylamine mixture, mono and dialkylated dodecyldiphenylamine , Mono and dialkylated isopropyl / isohexyldiphenylamine mixture, mono and dialkylated t-butyldiphenylamine mixture, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, mono and Dialkylated t-butyl / t-octylphenothiazine mixture, mono and dialkylated t-octylphenothiazine mixture, N-allylphenothiazine, N, N, N', N'-tetraphenyl-1,4-diaminobut-2- En, N, N-bis (2,2,6,6-tetramethylpiperidi-4-yl-hexamethylenediamine, bis (2,2,6,6-tetramethylpiperid-4-yl) sebacate, 2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol.-Dimethylbutyl) phenyl] amine, t-octylated N-phenyl-1-naphthylamine, mono and dialkylated t-butyl / t-octyldiphenylamine mixture, mono and dialkylated nonyldiphenylamine mixture, mono and dialkylated dodecyldiphenylamine , Mono and dialkylated isopropyl / isohexyldiphenylamine mixture, mono and dialkylated t-butyldiphenylamine mixture, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, mono and Dialkylated t-butyl / t-octylphenothiazine mixture, mono and dialkylated t-octylphenothiazine mixture, N-allylphenothiazine, N, N, N', N'-tetraphenyl-1,4-diaminobut-2- En, N, N-bis (2,2,6,6-tetramethylpiperidi-4-yl-hexamethylenediamine, bis (2,2,6,6-tetramethylpiperid-4-yl) sebacate, 2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol.

0099UV absorbers and light stabilizers

01002- (2'-Hydroxyphenyl) benzotriazole: For example, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3', 5'-di-t-butyl-2'-hydroxy Phenyl) benzotriazole, 2- (5'-t-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-(1,1,3,3-tetramethylbutyl) phenyl) Benzotriazole, 2- (3', 5'-di-t-butyl-2'-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'-t-butyl-2'-hydroxy-5'-methyl Phenyl) -5-chlorobenzotriazole, 2- (3'-sec-butyl-5'-t-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-4'-octyloxyphenyl) Bentotriazole, 2- (3', 5'-di-t-amyl-2'-hydroxyphenyl) Bentriazole, 2- (3', 5'-bis (α, α-dimethylbenzyl) -2'-hydroxy Phenyl) benzotriazole, 2- (3'-t-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl) phenyl) -5-chlorobenzotriazole, 2- (3'-t-butyl- 5'-[2- (2-Ethylhexyloxy) carbonyl ethyl] -2'-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'-t-butyl-2'-hydroxy-5'-(2-) Methoxycarbonylethyl) phenyl) -5-chlorobenzotriazole, 2- (3'-t-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl) phenyl) benzotriazole, 2- (3'-t-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl) phenyl) benzotriazole, 2- (3'- t-Butyl-5'-[2- (2-ethylhexyloxy) carbonyl ethyl] -2'-hydroxyphenyl) benzotriazole, 2- (3'-dodecyl-2'-hydroxy-5'-methylphenyl) benzotriazole , 2- (3'-t-Butyl-2'-Hydroxy-5'-(2-isooctyloxycarbonylethyl) phenylbenzotriazole, 2,2'-methylenebis [4- (1,1,3,3-) Tetramethylbutyl) -6-benzotriazole-2-ylphenol]; 2- [3'-t-butyl-5'-(2-methoxycarbonylethyl) -2'-hydroxyphenyl] -2H-benzotriazole, Ester exchange product with polyethylene glycol 300;-[R-CH-Hydroxyphenyl] -2H-benzotriazole, transesterified product with polyethylene glycol 300;-[R-CH-Hydroxyphenyl] -2H-benzotriazole, transesterified product with polyethylene glycol 300;-[R-CH₂CH₂-COO-CH₂CH₂]₂-, Where R = 3'-t-butyl-4'-hydroxy-5'-2H-benzotriazole-2-ylphenyl, 2- [2'-hydroxy-3'-(α, α-dimethylbenzyl) -5'-(1,1,3,3-tetramethylbutyl) phenyl] -benzotriazole; 2- [2'-hydroxy-3'-(1,1,3,3-tetramethylbutyl) -5' -(Α, α-Dimethylbenzyl) phenyl] benzotriazole.

01012-Hydroxybenzophenone: for example 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2', 4'-trihydroxy and 2'-hydroxy- 4,4'-dimethoxy derivative.

0102Esters of substituted and unsubstituted benzoic acid: for example, 4-t-butylphenyl salicylate, phenylsalicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis (4-t-butylbenzoyl) resorcinol, benzoyl resorcinol, 2,4-di-t-butylphenyl, 3,5-di-t-butyl-4-hydroxybenzoate, hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate, octadecyl-3,5-di -t-Butyl-4-hydroxybenzoate, 2-methyl-4,6-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate.

0103Nitriles: For example, ethyl α-cyano-β, β-diphenyl acrylate, isooctyl-α-cyano-β, β-diphenyl acrylate, methyl α-carbomethoxycinnamate, methyl α-cyano-β-methyl-p-methoxycinna Methyl, butyl α-cyano-β-methyl-p-methoxycinnamate, methyl α-carbomethoxy-p-methoxysinname and N- (β-carbomethoxy β-cyanovinyl) -2-methylindrin.

0104Nickel compound: For example, a nickel complex such as a 1: 1 or 1: 2 complex of 2,2'-thiobis [4- (1,1,3,3-tetramethyl-butyl) phenol], n- Those with or without additional ligands such as butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of monoalkyl esters, eg 4-hydroxy-3,5-di-t-butylbenzylphosphones. Methyl or ethyl ester of acid, nickel complex of ketooxime, eg, nickel complex of 2-hydroxy-4-methylphenylundecyl ketooxime, nickel complex of 1-phenyl-4-lauroyl-5-hydroxypyrazole, with additional ligands. Those that do not have.

0105Three-dimensional disorders Amin: For example, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, bis (1,2, 2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6- Pentamethyl-4-piperidyl) n-butyl-3,5-di-t-butyl-4-hydroxybenzylmalonate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-hydroxy Condensation of piperidine and succinic acid, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-t-octylamino-2,6-dichloro-1, Linear or cyclic condensate with 3,5-triazine, tris (2,2,6,6-tetramethyl-4-piperidyl) nitrilotriacetate, tetrakis (2,2,6,6-tetramethyl-4) -Piperidyl) -1,2,3,4-butanetetracarboxylate, 1,1'-(1,2-ethanediyl) -bis (3,3,5,5-tetramethylpiperazinone), 4-benzoyl -2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethyl-piperidine, bis (1,2,2,6,6-pentamethylpiperidyl) -2- n-Butyl-2- (2-hydroxy-3,5-di-t-butylbenzyl) malonate, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4.5 ] Decane-2,4-dione, bis (1-octyloxy-2,2,6,6-tetramethylpiperidyl) sebacate, bis (1-octyloxy-2,2,6,6-tetramethylpiperidyl) succinate , N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine linear or Cyclic condensate, 2-chloro-4,A condensate of 6-bis (4-n-butylamino-2,2,6,6-tetramethylpiperidyl) -1,3,5-triazine and 1,2-bis (3-aminopropylamino) ethane, 2-Chloro-4,6-di- (4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl) -1,3,5-triazine and 1,2-bis (3-amino) Condensate with propylamino) ethane, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4.5] decane-2,4-dione, 3-dodecyl- 1- (2,2,6,6-tetramethyl-4-piperidyl) pyrridine-2,5-dione, 3-dodecyl-1- (1,2,2,6,6-pentamethyl-4-piperidyl) piperidine A mixture of -2,5-dione, 4-hexadecyloxy- and 4-stearyloxy-2,2,6,6-tetramethylpiperidine, N, N'-bis (2,2,6,6-tetramethyl) -4-piperidyl) A condensate of hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, 1,2-bis (3-aminopropylamino) ethane and 2,4, Condensate of 6-trichloro-1,3,5-triazine and 4-butylamino-2,2,6,6-tetramethylpiperidine, 1,6-hexanediamine and 2,4,6-trichloro-1, A condensate of 3,5-triazine, N, N-dibutylamine and 4-butylamino-2,2,6,6-tetramethylpiperidine, N- (2,2,6,6-tetramethyl-4-) Piperidine) -n-dodecyl succinimide, N- (1,2,2,6,6-pentamethyl-4-piperidyl) -n-dodecyl succinimide, 2-undecyl-7,7,9,9-tetramethyl-1- Oxa-3,8-di-aza-4-oxo-spiro [4,5] decane, 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4 -Oxospiro- [4,5] Reaction product of decane and epichlorohydrin, 1,1-bis (1,2,2,6,6-Pentamethyl-4-piperidyloxycarbonyl) -2- (4-methoxyphenyl) ethene, N, N'-bis-formyl-N, N'-bis (2,2,6,6-tetramethyl-4- Piperidil) Hexamethylenediamine, diester of 4-methoxymethylenemalonic acid with 1,2,2,6,6-pentamethyl-4-hydroxypiperidine, poly [methylpropyl-3-oxy-4- (2,2,6) , 6-Tetramethyl-4-piperidyl)] siloxane, maleic anhydride-α-olefin copolymer 2,2,6,6-tetramethyl-4-aminopiperidine or 1,2,2,6,6-pentamethyl -4-Reaction product with aminopiperidine.

0106Oxamide: For example, 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-di-t-butoxanilide, 2,2'- Didodecyloxy-5,5'-di-t-butoxanilide, 2-ethoxy-2'-ethyloxanilide, N, N'-bis (3-dimethylaminopropyl) oxamide, 2-ethoxy-5-t- Butyl-2'-etoxanilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-t-butoxanilide, mixture of o- and p-methoxy-disubstituted oxamide and o- and p- A mixture of ethoxy-disubstituted oxanilides.

01072- (2-Hydroxyphenyl) -1,3,5-triazine: For example, 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2- (2) -Hydroxy-4-octyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2) , 4-Dimethylphenyl) -1,3,5-Triazine, 2,4-Bis (2-Hydroxy-4-propyloxyphenyl) -6- (2,4-Dimethylphenyl) -1,3,5-Triazine , 2- (2-Hydroxy-4-octyloxyphenyl) -4,6-bis (4-methylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -4 , 6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-tridecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl)- 1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-butyloxypropoxy) phenyl] -4,6-bis (2,4-dimethyl) -1,3,5- Triazine, 2- [2-hydroxy-4- (2-hydroxy-3-octyloxypropyloxy) phenyl] -4,6-bis (2,4-dimethyl) -1,3,5-triazine, 2-[ 4- (Dodecyloxy / Tridecyloxy-2-hydroxypropoxy) -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy -4- (2-Hydroxy-3-dodecyloxypropoxy) phenyl] -4,6-bis (2,4-dimethyl-phenyl) -1,3,5-triazine, 2- (2-hydroxy-4-hexyl) Oxy) Phenyl-4,6-diphenyl-1,3,5-triazine, 2- (2-Hydroxy-4-methoxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2,4,6-Tris [2-hydroxy-4- (3-butoxy-2-hydroxypropoxy) phenyl] -1,3,5-triazine, 2- (2-hydroxyphenyl) -4- (4-methoxyphenyl) -6 -Phenyl-1,3,5-triazine, 2- [2-hydroxy-4- [3- (2-ethylhexyl-1-oxy) -2-hydroxypropyloxy] phenyl] -4,6-bis (2, 4-Dimethylphenyl) -1,3,5-triazine, 2- [2-Hydroxy-4- (2-ethylethoxy) phenyl] -4,6-diphenyl-1,3,5-triazine.

0108Metal Inactivating Agents: For example, N, N'-diphenyloxamide, N-salicyral-N'-salicyloyl hydrazine, N, N'-bis (salicyloyl) hydrazine, N, N'-bis (3,5) -Di-t-butyl-4-hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1,2,4-triazol, bis (benzylidene) oxalyldihydrazide, oxanilide, isophthaloyldihydrazide, sebacyl bisphenylhydrazide, N, N'-diacetylazipoyl dihydrazide, N, N'-bis (salicyloyl) oxalyl dihydrazine, N, N'-bis (salicyloyl) thiopropionyl dihydrazine.

0109Phosphite and phosphonite: for example, triphenylphosphite, diphenylalkylphosphite, phenyldialkylphosphite, tris (nonylphenyl) phosphite, trilaurylphosphite, trioctadecylphosphite, distearylpentaerythritol diphosphite, tris ( 2,4-di-t-butylphenyl) phosphite, diisodecylpentaerythritol diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,4-di-cumylphenyl) Pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis (2,4-di-t-butyl-6) -Methylphenyl) -pentaerythritol diphosphite, bis (2,4,6-tris (t-butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis (2,4-di-t-butylphenyl) ) 4,4'-Biphenylenediphosphonite, 6-isooctyloxy-2,4,8,10-tetra-t-butyl-12H-dibenz [d, g] -1,3,2-dioxaphosphocin , Bis (2,4-di-t-butyl-6-methylphenyl) methylphosphite, Bis (2,4-di-t-butyl-6-methylphenyl) ethylphosphite, 6-fluoro-2,4 , 8,10-Tetra-t-Butyl-12-Methyl-dibenz [d, g] -1,3,2-dioxaphosphocin, 2,2', 2''-Nitrilo- [Triethyltris (3,,) 3', 5,5'-tetra-t-butyl-1, r-bi [rho] henyl-2,2'-diyl) phosphite], 2-ethylhexyl (3,3', 5,5'-tetra -t-Butyl-1,1'-biphenyl-2,2'-Diyl) phosphite, 5-butyl-5-ethyl-2- (2,4,6-tri-t-butylphenoxy) -1,3,2-dioxaphosphyran.

0110Phosphine: For example, 1,3-bis (diphenylphosphino) -2,2-dimethyl-propane.

0111Hydroxylamine: For example, N, N-dibenzylhydroxylamine, N, N-diethylhydroxylamine, N, N-dioctylhydroxylamine, N, N-dilaurylhydroxylamine, N, N-ditetradecylhydroxylamine, N , N-Dihexadecyl Hydroxylamine, N, N-Dioctadecyl Hydroxylamine, N-Hexadecyl-N-Octadecyl Hydroxylamine, N-Heptadecyl-N-Octadecyl Hydroxylamine, N, N-Dialkyl Hydroxylamine Derived from Hydroxylamine Amin.

0112Nitrones: For example, N-benzyl-α-phenylnitrone, N-ethyl-α-methylnitrone, N-octyl-α-heptyl nitrone, N-lauryl-α-undecyl nitrone, N-tetradecyl-α-tridecyl nitrone , N-hexadecyl-α-pentadecyl nitrone, N-octadecyl-α-heptadecylnitrone, N-hexadecyl-α-heptadecylnitrone, N-octadecyl-α-pentadecylnitrone, N-heptadecyl-α-heptadecylnitrone , N-Octadecyl-α-Hexadecyl nitrone, Nitrone derived from N, N-dialkylhydroxylamine derived from hydride tallow amine.

0113Sulfur synergists (thiosynerqists): For example, dilauryl thiodipropionate or distearyl thiodipropionate.

0114Peroxide scavengers: eg esters of β-thiodipropionic acid, eg lauryl, stearyl, myristyl or tridecyl ester esters, mercaptobenzimidazole or zinc salts of 2-mercapto-benzimidazole, zinc dibutyldithiocarbamate, di Octadecyl disulfide, pentaerythritol tetrakis (β-dodecyl mercapto) propionate.

0115Polyamide stabilizers: for example, copper salts in combination with iodides and / or phosphorus compounds, and divalent manganese salts.

0116Basic auxiliary stabilizers: for example, melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkyl metal salts of higher fatty acids and alkaline earth metal salts, such as calcium stearate, Zinc stearate, magnesium behenate, magnesium stearate, sodium ricinolate and potassium palmitate, antimony pyrocatecholate or zinc pyrocatecholate.

0117Nucleating agents: for example, inorganic substances such as talcum, metal oxides such as titanium dioxide or magnesium oxide, preferably alkali earth metal phosphates, carbonates or sulfates; mono or polycarboxylic acids and salts thereof, etc. Organic compounds such as 4-t-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; high molecular weight compounds such as ionic copolymers (ionomers), eg 1,3: 2,4-bis ( 3', 4'-dimethylbenzylidene) sorbitol, 1,3: 2,4-di (paramethyldibenziliden) sorbitol, and 1,3: 2,4-di (benziliden) sorbitol.

0118Bulking and strengthening agents: for example, calcium carbonate, silicates, fiberglass, glass spheres, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood flour and others. Natural powder or fiber, synthetic fiber.

0119Other Additives: For example, plasticizers, lubricants, emulsifiers, pigments, rheology additives, catalysts, flow controllers, optical brighteners, flame retardants, antistatic agents, foaming agents, and infrared (IR) absorbers. .. Preferred IR absorbers are, for example, dyes, dyes or organometallic compounds.

0120Benzofuranones and indolinones, such as 3- [4- (2-acetoxyethoxy) phenyl] -5,7-di-t-butylbenzofuran-2-one, 5,7-di-t-butyl-3- [4-] (2-Stearoyl-oxyethoxy) phenyl] benzofuran-2-one, 3,3'-bis [5,7-di-t-butyl-3- (4- [2-hydroxyethoxy] phenyl) -benzofuran-2 -On], 5,7-di-t-butyl-3- (4-ethoxyphenyl) benzofuran-2-one, 3- (4-acetoxy-3,5-dimethylphenyl) -5,7-di-t -Butylbenzofuran-2-one, 3- (3,5-dimethyl-4-pivaloyloxyphenyl) -5,7-di-t-butylbenzofuran-2-one, 3- (3,4-dimethylphenyl) )-5,7-di-t-butylbenzofuran-2-one, 3- (2,3-dimethylphenyl) -5,7-di-t-butylbenzofuran-2-one or 3- (2-acetyl- 5-isooctylphenyl) -5-isooctylbenzofuran-2-one.

0121Synthetic polymers prepared in this way can be applied in a wide range of forms, for example as foams, films, fibers, tapes, molding materials, as outer frames or binders of coating materials, especially powder coatings, adhesives. It can be applied as a binder for agents, putty, or in particular as a thick layer of polyolefin molded article in long-term contact with the extraction medium, examples of molded article being pipes, films, fibers, geo for liquids or gases. A membrane, tape, outer frame or tank, etc.

0122In one non-limiting aspect, the layer thickness of the preferred thick layer of polyolefin molding is 1-50 mm, particularly 1-30 mm, eg 2-10 mm.

0123The compositions according to the invention can be advantageously used in the production of articles of various shapes. A representative and non-limiting list of end applications is not limited to: Floating equipment, marine applications, taillights, buoys, plastic deck decks, piers, boats, kayaks, oars, and coastal reinforcements; automotive applications, Especially bumpers, dashboards, batteries, rear and front linings, molded parts under the bonnet, hat shelves, trunk linings, internal linings, airbag covers, molded parts for electronic parts for accessories (lights), frames for dashboards, Headlight glass, instrument panel, external lining, chair material, automobile lighting, headlight, parking light, tail lamp, brake lamp, internal and external trim; door panel; gasoline tank; front glass; rear window; seat backing, external panel, electric wire Insulations, deformed extruded products for sealing, cladding, stanchions, chassis parts, exhaust systems, fuel filters / refueling parts, fuel pumps, fuel tanks, body-side molded products, open car roofs, external mirrors, exterior trims, fixtures / Accessories, tip modules, glass, hinges, locking systems, luggage racks / roof racks, stamped / stamped parts, seals, side collision protection, anti-vibration materials / insulators and sun roofs; road traffic equipment, especially signs, Road sign pillars, car accessories, triangular display boards, medical case, helmets, tires; equipment for aircraft, railroads, automobiles (cars, motorcycles), including fixtures; space application equipment, especially rockets and satellites, For example, re-entry shields; building and design equipment, mining applications, silent systems, safe zones, and shelters.

0124The present invention also has the applicability of: electrical appliances, general electrical / electronic device cases and covers (computers, telephones, mobile phones, printers, televisions, audio and video devices), flower ware, satellite televisions, And panel equipment; jackets for other materials such as steel or fabrics; equipment for the electronic industry, especially plug insulation, especially computer plug insulation, cases for electrical and electronic components, printed boards, and chips, check cards. Or materials for storing electronic data such as credit cards; appliances, especially washing machines, tumblers, ovens (microscopes), dishwashers, mixers, and irons; lighting covers (eg street lights, lamp shades); wires and Applications in cables (semiconductors, insulation and cable jackets); and foils for capacitors, refrigerators, heating devices, air conditioners, electronic encapsulation, semiconductors, coffee machines, and vacuum cleaners.

0125The present invention further has the applicability of: Specialized products such as gears, slide fittings, spacers, screws, bolts, handles, and knobs; rotary wings, ventilators and windmill wings, solar devices, swimming. Pools, swimming pool covers, pool linings, pond linings, closets, wardrobes, bulkheads, slat walls, folding doors, roofs, shutters (eg roller shutters), fittings, joints between pipes, sleeves, and conveyors. Belts; sanitary supplies, especially shower rooms, toilet seats, lids, and sinks; sanitary supplies, especially omelets (baby, adult incontinence), women's sanitary goods, shower curtains, brushes, mats, bathtubs, movable toilets, toothbrushes, and beds. Pan; pipes for water, drainage and chemicals (interlinked or unlinked), pipes for wire and cable protection, pipes for gas, oil and sewage, gutters, verticals, and drainage systems; Frames of all shapes (window frames) and siding; glass substitutes, especially extruded or co-extruded plates, building polish (single, double or multi-layer), aircraft, schools, extruded sheets, windows for architectural polish Films, trains, transportation, sanitary goods, and greenhouses; plates (walls, cutting boards), extruded coatings (printing paper, tetrapacks and pipe coatings), silos, wood substitutes, plastics, wood composites, walls, surfaces , Furniture, decorative foils, floor coverings (indoor and outdoor adaptation), flooring, canvas boards, and tiles; intake and exhaust pipes; and cement, concrete, composite materials applications and covers, siding and cladding, Handrails, stair railings, kitchen worktops, roof wipes, roof boards, tiles, and waterproof cloth.

0126Further adaptations include: plates (walls and cutting boards), trays, artificial turf, astroturf, artificial coverings for stadium rings (athletic), artificial floors for stadium rings (athletic): , And tapes; continuous and major textiles, fibers (carpets / sanitary goods / geotextiles / monofilaments; filters; wiping fibers / curtains (shades) / medical uses), bulk fibers (gowns / protective cloths, etc.), nets , Rope, cable, string, cord, thread, safety seat belt, clothes, underwear, gloves; boots; rubber boots, underwear, clothing, swimwear, sportswear, umbrellas (rain umbrellas, sun umbrellas), parachutes, paraglide, sails, "airballs" Clothes, camping equipment, tents, air beds, sunbathing beds, bulk bags, and bags; and roofs, tunnels, trash dumps, ponds, trash dumps, wall membranes, insulators, covers and seals, roof wipes. Membranes, geomembranes, swimming pools, curtains (shades) / sunshields, awnings, eaves, wallpaper, food packaging and wrapping (plastic and solid), pharmaceutical packaging (plastic and solid), airbags / safety belts, arms and headrests , Carpets, center consoles, dashboards, cockpits, doors, ceiling console modules, door trims, headliners, interior lighting, interior mirrors, luggage racks, rear luggage covers, seats, steering columns, handles, fabrics, and trunks. trim.

0127Further indications include: films (packing, trash cans, stacking, agriculture and gardening, greenhouses, mulch, tunnels, silage), bale packing, swimming pools, trash cans, wallpapers, stretched films, raffia, de-scraping. Salt film, batteries, and connectors; food packaging and wrapping (plastic and solid), bottles; boxes (frame boxes), travel bags, storage bins, household boxes, carriers, shelves, rails, screw-cap boxes, packs , And storage systems such as cans; and cartridges, syringes, medical applications, containers for all kinds of transportation, waste baskets and trash cans, trash bags, trash cans, trash cans, inner bags of trash cans, wheely bins, general containers , Water / drainage / chemicals / gas / oil / gasoline / diesel tanks; tank linings, frame boxes, battery cases, bait bins, medical equipment such as pistons, ophthalmic applications, diagnostic equipment, and pharmaceutical blister Packaging.

0128Further indications may include: Extruded coatings (printing paper, tetrapacks, pipe coatings), household items of all kinds (eg appliances, magic bottles / clothes hangers), plugs, wire and cable clamps, zippers. Fastening systems such as seals, locks, and snap stoppers; for leisure such as assistive devices, sports and fitness equipment, gym mats, ski boots, inline skates, skis, bigfoot, athletic surfaces (eg tennis courts), etc. Articles; Containers with screw caps, lids and stoppers for bottles, and cans; General furniture, foam articles (cushions, shock absorbers), foams, sponges, tableware cloths, mats, garden chairs, stadium seats, Tables, couches, toys, construction kits (composite boards / figures / balls), playhouses, slides, and riding toys; materials for optical and magnetic data storage; kitchen utensils (for food, drinks, cooking) , For storage); Boxes for CDs, cassettes and video tapes; DVD electronic supplies, office supplies of all kinds (ball pens, stamps and ink pads, mice, shelves, rails), bottles of all capacities and contents (beverages, detergents) , Cosmetics containing perfume), and adhesive tape; footwear (shoes / soles), inlays, spats, adhesives, structural adhesives, food containers (fruits, vegetables, meat, fish), synthetic paper, bottle labels, Couch, Artificial Joint (Human), Printing Plate (Flexo Printing), Printed Substrate, and Display Technology; and Filled Polymers (Tark, Chalk, Ceramic (Kaolin), Silica, Dye, Carbon Black, TiO2, Mica, Nanocomposite, Dolomite, silicate, glass, asbestos) equipment.

0129Further indications may include: Ingredients, compositions containing fibers and fabrics used in medical non-woven fabrics and related clothing (surgical gowns, curtains, bandings), building materials (house packaging, roofing materials). , Swimming pool packaging) and household goods (roof, table linen, shower curtains).

0130As described above, a further aspect of the present invention relates to a molded product, particularly a film, a pipe, a frame, a bottle, a tank or a container, and a fiber containing the above-mentioned composition.

0131As is clear from the above, the organic material to be protected is preferably an organic polymer, especially a synthetic polymer. Thermoplastic materials, especially polyolefins, are protected particularly advantageously. In particular, the excellent effectiveness of the polymeric compound of formula IV as a processing stabilizer (heat stabilizer) should be emphasized. For this purpose, they are added favorably to the polymer before or during its processing. However, other polymers (eg elastomers) or lubricants or hydraulic oils can also be stabilized against degradation, such as photodegradation or thermal oxidative degradation.

0132Thus, at least one aspect of the invention is contained in a liquid polymeric compound of formula IV or V, or in formulas IV and / or V, to protect the organic material against oxidation, thermal or photodegradation. Is the use of a mixture of compositions obtained by synthesizing the compositions. The novel liquid polymeric compounds are identified, at least in part, by their apparent hydrolysis stability and favorable coloring behavior, i.e., less discoloration of the organic material during processing.

0133The present invention will be described herein by a series of examples.

<p num="0134">Example # 1 The device of Example # 1 was used. PPG 425 (55 g, 0.129 mol), triphenylphosphite (45 g, 0.145 mol), Carbowax 350 (monomethyl ether polyethylene glycol with average molecular weight (MW) 350) (63 g, 0.189 mol), and 0.8 g of potassium hydroxide was added. The mixture was mixed well, heated to 160-162 ° C under nitrogen and kept at that temperature for 1 hour. After that, the pressure was gradually reduced to 0.3 mmHg, and the temperature was raised to 170 to 172 ° C for 1 hour. The reaction contents were kept under vacuum at 170-172 ° C for 2 hours, at which time no more phenol was distilled off. The vacuum was then interrupted with nitrogen and the crude product was cooled to 50 ° C. The product was a clear, colorless liquid.</p><p num="0135">Example # 2 The device of Example # 1 was used. PPG 400 (95 g, 0.237 mol), triphenylphosphine (73 g, 0.235 mol), a mixture of lauryl and myristyl alcohols with a hydroxyl value of about 280 (47 g, 0.235 mol), and 0.8 g potassium hydroxide. Added. The mixture was mixed well, heated to 160-162 ° C under nitrogen and kept at that temperature for 1 hour. After that, the pressure was gradually reduced to 0.3 mmHg, and the temperature was raised to 170 to 172 ° C for 1 hour. The reaction contents were kept under vacuum at 170-172 ° C for 2 hours, at which time no more phenol was distilled off. The vacuum was then interrupted with nitrogen and the crude product was cooled to 50 ° C. The product was a clear, colorless liquid.</p><p num="0136">Example # 3 The device of Example # 1 was used. PPG 400 (48 g, 0.12 mol), triphenylphosphite (73 g, 0.235 mol), lauryl alcohol (47 g, 0.235 mol), dipropylene glycol (16 g, 0.12 mol) and 0.8 g potassium hydroxide Added. The mixture was mixed well, heated to 160-162 ° C under nitrogen and kept at that temperature for 1 hour. After that, the pressure was gradually reduced to 0.3 mmHg, and the temperature was raised to 170 to 172 ° C for 1 hour. The reaction contents were kept under vacuum at 170-172 ° C for 2 hours, at which time no more phenol was distilled off. The vacuum was then interrupted with nitrogen and the crude product cooled to 50 ° C. The product was a clear, colorless liquid.</p><p num="0137">Example # 4 The device of Example # 1 was used. PPG 400 (50.22 g, 0.1256 mol), triphenylphosphite (40 g, 0.129 mol), Carbowax 350 (monomethyl ether polyethylene glycol with average molecular weight (MW) 350) (26 g, 0.074 mol), tri Isopropanolamine (4.5 g, 0.023 mol) and 0.8 g potassium hydroxide were added. The mixture was mixed well, heated to 160-162 ° C under nitrogen and kept at that temperature for 1 hour. After that, the pressure was gradually reduced to 0.3 mmHg, and the temperature was raised to 170 to 172 ° C for 1 hour. The reaction contents were kept under vacuum at 170-172 ° C for 2 hours, at which time no more phenol was distilled off. The vacuum was then interrupted with nitrogen and the crude product cooled to 50 ° C. The product was a clear, colorless liquid.</p><p num="0138">Example # 5 The device of Example # 1 was used. PPG 400 (100 g, 0.25 mol), triphenylphosphite (78 g, 0.2516 mol), a mixture of cetyl and stearyl alcohol with a hydroxyl value of about 211 (34 g, 0.1285 mol), tripropylene glycol butyl ether (32 g, 0.129 mol) and 0.8 g of potassium carbonate were added. The mixture was mixed well, heated to 160-162 ° C under nitrogen and kept at that temperature for 1 hour. After that, the pressure was gradually reduced to 0.3 mmHg, and the temperature was raised to 170 to 172 ° C for 1 hour. The reaction contents were kept under vacuum at 170-172 ° C for 2 hours, at which time no more phenol was distilled off. The vacuum was then interrupted with nitrogen and the crude product cooled to 50 ° C. The product was a clear, colorless liquid.</p><p num="0139">Example # 6 The device of Example # 1 was used. PPG 400 (100 g, 0.25 mol), triphenylphosphite (78 g, 0.2516 mol), a mixture of cetyl and stearyl alcohol with a hydroxyl value of about 211 (34 g, 0.1285 mol), oleyl alcohol (34 g, 0.126 mol) ) And 0.8 g of potassium carbonate were added. The mixture was mixed well, heated to 160-162 ° C under nitrogen and kept at that temperature for 1 hour. After that, the pressure was gradually reduced to 0.3 mmHg, and the temperature was raised to 170 to 172 ° C for 1 hour. The reaction contents were kept under vacuum at 170-172 ° C for 2 hours, at which time no more phenol was distilled off. The vacuum was then interrupted with nitrogen and the crude product cooled to 50 ° C. The product was a clear, colorless liquid.</p><p num="0140">Example # 7 The device of Example # 1 was used. PPG 400 (95 g, 0.237 mol), triphenylphosphine (73 g, 0.235 mol), Neodol 23 (C₁₂And C₁₃Alcohol formulation) (57 g, 0.266 mol) and 0.8 g potassium hydroxide were added. The mixture was mixed well, heated to 160-162 ° C under nitrogen and kept at that temperature for 1 hour. After that, the pressure was gradually reduced to 0.3 mmHg, and the temperature was raised to 170 to 172 ° C for 1 hour. The reaction contents were kept under vacuum at 170-172 ° C for 2 hours, at which time no more phenol was distilled off. The vacuum was then interrupted with nitrogen and the crude product cooled to 50 ° C. The product was a cloudy, colorless liquid.</p><p num="0141">Example # 8 The device of Example # 1 was used. PPG 400 (100 g, 0.25 mol), triphenylphosphine (155 g, 0.5 mol), a mixture of lauryl and myristyl alcohols with a hydroxyl value of about 280 (200 g, 1.0 mol), and 0.8 g potassium hydroxide. Added. The mixture was mixed well, heated to 160-162 ° C under nitrogen and kept at that temperature for 1 hour. After that, the pressure was gradually reduced to 0.3 mmHg, and the temperature was raised to 170 to 172 ° C for 1 hour. The reaction contents were kept under vacuum at 170-172 ° C for 2 hours, at which time no more phenol was distilled off. The vacuum was then interrupted with nitrogen and the crude product cooled to 50 ° C. The product was a clear, colorless liquid.</p><p num="0142">Example # 9 The device of Example # 1 was used. 1,6-Hexanediol (57 g, 0.48 mol), triphenylphosphine (150 g, 0.48 mol), a mixture of lauryl and myristyl alcohols with a hydroxyl value of about 280 (97 g, 0.48 mol), and 0.8 g. Potassium hydroxide was added. The mixture was mixed well, heated to 160-162 ° C under nitrogen and kept at that temperature for 1 hour. After that, the pressure was gradually reduced to 0.3 mmHg, and the temperature was raised to 170 to 172 ° C for 1 hour. The reaction contents were kept under vacuum at 170-172 ° C for 2 hours, at which time no more phenol was distilled off. The vacuum was then interrupted with nitrogen and the crude product cooled to 50 ° C. The product was a cloudy, colorless liquid.</p><p num="0143">Example # 10 The device of Example # 1 was used. Poly-THF 250 MW (121 g, 0.48 mol), triphenylphosphine (150 g, 0.48 mol), a mixture of lauryl and myristyl alcohols with a hydroxyl value of about 280 (97 g, 0.48 mol), and 0.8 g potassium hydroxide. Was added. The mixture was mixed well, heated to 160-162 ° C under nitrogen and kept at that temperature for 1 hour. After that, the pressure was gradually reduced to 0.3 mmHg, and the temperature was raised to 170 to 172 ° C for 1 hour. The reaction contents were kept under vacuum at 170-172 ° C for 2 hours, at which time no more phenol was distilled off. The vacuum was then interrupted with nitrogen and the crude product was cooled to 50 ° C. The product was a cloudy, colorless liquid.</p><p num="0144">Example # 11 The device of Example # 1 was used. Methyldiethanolamine (58 g, 0.48 mol), triphenylphosphite (150 g, 0.48 mol), a mixture of lauryl and myristyl alcohols with a hydroxyl value of about 280 (97 g, 0.48 mol), and 0.8 g potassium hydroxide. Added. The mixture was mixed well, heated to 160-162 ° C under nitrogen and kept at that temperature for 1 hour. After that, the pressure was gradually reduced to 0.3 mmHg, and the temperature was raised to 170 to 172 ° C for 1 hour. The reaction contents were kept under vacuum at 170-172 ° C for 2 hours, at which time no more phenol was distilled off. The vacuum was then interrupted with nitrogen and the crude product was cooled to 50 ° C. The product was a cloudy, colorless liquid.</p><p num="0145"> The characteristics of various synthetic additives can have, at least in part, the properties according to the table below.<tables num="1"><img id="000009" he="91" wi="159" file="JP5771630B2_D0001.tif" img-format="tif" img-content="drawing" /></tables><tables num="2"><img id="000010" he="78" wi="159" file="JP5771630B2_D0001.tif" img-format="tif" img-content="drawing" /></tables></p><p num="0146"> The polymer phosphite of Examples 1 to 11 is very interesting because it is not an alkylphenol type.</p><p num="0147"> The table below details the properties of some polymeric phosphite stabilizers 1-18 in polyolefins (using linear low density polyethylene, Exxon or Nova LLDPE). As plastic stabilizers, these compounds exhibit properties equal to or better than TNPP. For melt flow velocity (MFR), a good plastic stabilizer has a low initial MFR and then maintains that low MFR. The hunter color measurement performance b shows that a good plastic stabilizer has less initial coloration and then maintains that less coloration. Sample preparation</p><p num="0148"> Polyolefin powders (polyethylene, LLDPE) (high density polyethylene, HDPE) and (polypropylene, PP) are dry mixed with stabilizer formulations using a walling blender. Run the mixer for 30 seconds, shaking the mixer every 5 seconds, at approximately 60 rpm or at a speed at which the ingredients do not pop out of the bowl. The masterbatch is then added to a preheated co-rotating twin-screw extruder where the plastics are uniformly mixed. Extrusion is typically carried out at 260 ° C. The extruded plastic is cooled in a cold water batch, completely dried and pelletized. The recovered polymer pellets are the result of first pass extrusion and are the starting material for all subsequent test protocols. The isolated pellets are placed in a repeat extruder to produce material that has passed 3 and 5 times. Melt flow velocity analysis</p><p num="0149"> Melting flow rates were measured at 21.6 Kg / 190 ° C using the ASTM 1238-90b test method. Melting flow rates were measured with a Tinius Olsen extrusion plasticizer. Colorimetric analysis</p><p num="0150"> Colorimetric analysis was performed on compression molded films or plaques using a Hunter Lab Ulstrascan XE machine. Observations were made with a D65 light source and a 10 ° observation device. Yellowness index measurements were performed according to ASTM D1925-70. The lower the YI (Yellowness Index), the better the color. Gas fade aging</p><p num="0151"> Gas fade aging was performed using a NOx gas oven based on the method of ASTM 1925. The analysis was performed on compression molded plaques placed in a nitrogen oven at 60 ° C. Color progression during exposure to nitrogen oxides was observed by measuring the yellowness index.</p><p num="0152"> Neutralizers include 900 ppm phosphite and 500 ppm primary antioxidant Dovernox 76, or 1800 ppm phosphite, 300 ppm dovernox 76, 200 ppm zinc stearate and 100 ppm DHT4A. Was used to test the LLPE formulation.</p><p num="0153"> HDPR formulations were tested using 900 ppm phosphite, 500 ppm Dovernox 76 and 500 pp calcium stearate.</p><p num="0154"> PP formulations were tested using 500 ppm phosphite, 500 ppm Dovernox 10 and 500 pp calcium stearate.<tables num="3"><img id="000011" he="117" wi="159" file="JP5771630B2_D0001.tif" img-format="tif" img-content="drawing" /></tables></p><p num="0155"> The data show that TNPP gives good MFI stability and so does polymeric phosphite. Polymer phosphite is comparable to or outperforms TNPP in some cases.<tables num="4"><img id="000012" he="91" wi="159" file="JP5771630B2_D0001.tif" img-format="tif" img-content="drawing" /></tables></p><p num="0156"> Polymer phosphite is about as good as or superior to TNPP in color stability (the lower the YI, the better the color).<tables num="5"><img id="000013" he="52" wi="159" file="JP5771630B2_D0001.tif" img-format="tif" img-content="drawing" /></tables></p><p num="0157"> The gas fade results are better with polymeric phosphite.<tables num="6"><img id="000014" he="89" wi="159" file="JP5771630B2_D0001.tif" img-format="tif" img-content="drawing" /></tables><tables num="7"><img id="000015" he="61" wi="159" file="JP5771630B2_D0001.tif" img-format="tif" img-content="drawing" /></tables></p><p num="0158"> Polymer phosphite exhibits good performance as a stabilizer for HDPE, especially for color.<tables num="8"><img id="000016" he="109" wi="159" file="JP5771630B2_D0001.tif" img-format="tif" img-content="drawing" /></tables><tables num="9"><img id="000017" he="109" wi="159" file="JP5771630B2_D0001.tif" img-format="tif" img-content="drawing" /></tables></p><p num="0159"> Polymer phosphite exhibits good performance as a stabilizer in PP. The use of vitamin E instead of Dovernox 10 as the primary antioxidant significantly improves MFI.</p><p num="0160"> These data indicate that some of the polymeric phosphites are as effective as or superior to TNPP. In addition to providing good melt flow stability and color stability during processing and in gas fade tests, polymeric diphosphite and polymeric polyphosphite have excellent compatibility with LLDPE and do not migrate. Non-migration is especially important for additives used in polymer films or plastics used in contact with food. Also, the non-migration can reduce or eliminate plate-out or die assembly with volatile additives as the roll cools. The polymeric polyphosphite described in Examples 1, 2, 3, 4, 6, 7 and 8 does not contain any alkylphenols and is basically all made from biodegradable raw materials and is therefore a food product. It is a polymer stabilizer that is particularly good for plastics that come into contact with.</p><p num="0161"> What has been described is the ability to synthesize liquid polymeric phosphite in which the substituents are substantially all aliphatic. The liquid phosphite is preferably polyphosphite, in which the segments between the phosphite moieties are preferably polyalkylene glycol, more preferably polyethylene or polypropylene glycol.</p><p num="0162"> The present invention has been described with reference to preferred and alternative embodiments. Obviously, other modifications and changes arise from the interpretation and understanding of the specification. All such modifications and modifications are intended to be included, as long as they are within the appended claims or their equivalents.</p>