Continuous process for preparatino of highly stable, finely divided, low viscosity polymer polyols of small average particle size
Abstract
The average granularity is small, and stability, wherein the gear, the continuity method for low viscosity polymer polyol, wherein the styrene and acrylonitrile first mixture in a oxidized oxide polyether polyol and macromonomer mixture of the control agent in the radical initiator and solvent and which is present, at least 100℃ the reaction, adjust the middle comprises a high macromonomer; Intermediate solid content of less than about 30% (weight percentage). Then, wherein the middle and styrene and acrylonitrile is the mixture of macromonomer, wherein the polyol and is selected from the solvent, initiator and control agent with a reaction.

Term
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Expired 10 October 2016, 10 years ago.
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23 claims: 10 independent, 13 dependent
- 1The average granularity is small, and stability, wherein the gear, the continuity method for low viscosity polymer polyol, a first (1) and acrylonitrile mixture, in (2) of of the polyether polyol and (3) of monomer mixture (4) radical initiator, (5) is moderate the chain transfer active and solvent in the present of non-essential (6) is control agent, wherein the preparation method at least 100℃ temperature, adjust the middle comprises a high macromonomer, a polyol of cu, at least comprising 12% of monomer;Intermediate solid content is less than 30% (weight), and is at least 15% (weight). Is made of further - comprising a middle and styrene and acrylonitrile in one or more series of stirring kettle in the reactor and mixture of non-essential macromonomer in the polyol of dispersing the solvent in the reactor, initiators and control agent in a reaction. 1.制备平均粒度小的、高稳定性、细碎的、低粘度聚合物多元醇的连续方法,其中首先使(1)苯乙烯和丙烯腈的混合物在(2)聚氧化烯聚醚多元醇和(3)大单体的混合物中在(4)自由基引发剂、(5)具有中度链转移活性的溶剂和非必要的(6)反应调节剂的存在下,在至少100℃的温度下反应制备中间体,使得中间体含有高水平的大单体,相对于多元醇混合物计,至少含有12%的大单体;中间体的固体含量小于30%(重量),且至少为15%(重量)。然后使起着进一步聚合的种子作用的中间体在一个或多个串联的搅拌釜式反应器中与苯乙烯和丙烯腈在多元醇和非必要的大单体中的混合物在分散于其余反应器中的溶剂、引发剂和反应调节剂存在下进一步反应。
- 10According to claims 1 to 5, wherein the preparation of macromonomer is directly or by contacting (1) molecular weight of the is at least 4500, a hydroxyl functionality at least 3 polyether polyatomic alcohol and (2) acrylate reactive compound reaction, the amount of claims polymerizable compound in the preparation of macromonomer wherein per mole of polyol 0.3-1.5 agent. 10.根据权利要求1至5之任一项的方法,其中大单体的制备是直接或间接地通过使(1)分子量为至少4500、羟基官能度至少为3的聚醚多元醇与(2)反应性不饱和化合物反应制备的,在大单体的制备中所用的反应性不饱和化合物的量在每摩尔多元醇0.3-1.5摩尔。
- 15To 15. claims 1 to 5, wherein the reaction controlling agent is selected from the water ether:A=CH-O-R R is the preparation C1-18 alkyl, C5-10 cycloalkyl substituted or the mixture or un-substituted, represents A group hydrogen and C1-8 alkyl group. 15.根据权利要求1至5之任一项的方法,其中反应调节剂是下式烯醇-醚:A=CH-O-R其中R代表C1-18烷基、C5-10环烷基或取代的或未取代的苄基,A代表基团其中R’代表氢和C1-8烷基基团。
- 23Claims 23 to 1. a polymer polyol of alcohol according 21 in preparing polyurethane product is front. 23.权利要求1至21制备的聚合物多元醇在制备聚氨酯产品方面的用途。
Independent claims10
67 paragraphs, as filed
Preparation and average size and high stability, wherein the gear, the continuity method for low viscosity polymer polyol
The polymer polyol and polyurethane foam preparation of a is the male water. The polymer polyol the polyol of the unsaturated monomer polymer or copolymer or the composition. By weight, wherein the polyether glycol is one or more of vinyl monomer is the presence of radical polymerization initiator in-situ polymerization preparation. The properties of the soft polyurethane foam is enhanced by the method of polymer polyol the preparation of the polyurethane's, specifically hardness and weight rate of the reinforced.
The ideal, wherein the polymer polyol of the polymer or copolymer low viscosity, dispersion, non-deposition dispersion according polyol in the gear, wherein essentially no transformation. The polymer polyol dispersion obtainable by mixing the polyol molecule according or a grafted part of the positions to form of a polymer substrate for stabilizing of deposition. The preferably polymer is styrene-acrylate acrylonitrile graft copolymer.
The method for with the batch treatment and continuous production method of producing a polymer polyol. Polypeptide and screening a plurality of these a product for preparation method. Is narrow and time for preparing the following granularities of polymer polyol, a width of the polymer polyol preparing a continuous process. The batch process, the majority of the particle in the production of reaction. The polymerization further provided with a growth of particles. The continuous process, the wide following granularities of the total and result of the production and reactor of competitive growth and particle diameter of the continuous a more of particles or washing.
The polymer polybasic alcohol machinability the is wherein viscosity and storage stability (anti-deposition the) and filterability. A parameter of the important for improved the mass of the product is wherein the initial mixture of the weight of the monomer of CYP2C8. The high styrene monomer mixture and high solid content of the polymer polyol growth wherein the polymer polyol unable to achieve the rolling vehicle performance (low viscosity, in agent and average size).
A out of the stability of polymer polyol, wherein the stability and high content of of the specific layer is unsaturated polyol or polymerization of polyol mixture according to any of the monomer mixture. Comprising an unsaturated polyol is the scale macromonomer or two of frequently, wherein the compound is mixed in the polymer substrate to make the polymer dispersion stabilizing the polyol is in the energy.
A wherein the chain transfer agent or polymer control agent in the preparation of polymer polyol composition for the reaction is controlled to control the copolymer molecular weight, to obtain for low viscosity product. Proposed comprises thiol and halogen, alcohol, halogen and alcohol ether more reaction control agent.
The improved a method for preparing polymer polyol, by using is the method according US4148840 providing, wherein the reaction of prefabricated at the polyol is mixture of polymer polybasic alcohol in-situ polymerization of producing the one or more monomers and stable and filterability polymer polyol composition.
The improvement method of US 4242294 claimed in preparation of polymer polybasic alcohol, the prepare an application of the stabilizer is a at a high styrene content and high solid content of the polymer polyol, and patient is low - molecular weight of the polyol. Stabilizer 25℃ viscosity of prefabricated the ultra-filter 40000mPas chamber, and styrene and mixture in an induction unsaturated polyol polymerization is. The preparation of the product, perform the stabilizer dosage is a final, not more than 5%.
US 5233570) comprises one, wherein the change the viscosity of the following to a wide following granularities polymer polyol dispersion large scale the method. The method comprising 30% comprising a continuous of formula (weight percentage) the solid intermediate, to obtain for following granularities. Is used as the middle a seed of the time of polymerization in order to adjust the solid content to 30% (weight) or.
The US 5364906 claimed is producing dispersion stabilities is improved continuous process for low viscosity polymer polyol. The method uses two-step continuous process, the first reaction product of a less than 50% of the monomer mixture which comprises a macromonomer polymer and controlling agent is greater than 50% of the polyol mixture of the same is complete polyol) the production. The second reaction, remained material by adding to the first reaction product in.
Polymer or deposition reactor scaling the reactor wall of the polymerization of a monomer is the male water. A method for the reactor is scaling value for is (1) and is provided to prevent the coating material reactor (2) is improved reactor and a polymer deposition domains (e.g., and a) and (3) is controlled by the polymer concentration.
US 4956427 is provided by the reactor surface of said when the amino of silicon and thereby avoiding the reactor scaling in the polymerization process for producing the monomer method. The anti-biological of during the can be used for thereby avoiding the polymerization of ethylene, propylene and mixtures thereof, specifically with.
Process 5413352 one is a pressure preparation method of the polymer polyol to the reactor wall of CYCLOHEXYL, wherein one which is provided with a stirrer propeller and suction pipe and content of ratio of the raw materials with 50-200 times of the circulating of pellets.
A further aspect, 4794151 US provided with a continuous process for preparing ethylene copolymer, of a specific monomer/polymer concentration to prevent the polymer is coated on the round pipe reactor is reactor wall.
The contrast one literature is claimed, wherein of the stirring kettle in the reactor for the small average size; the stable, wherein the gear, wherein the process for low viscosity polymer polyol, wherein in the qualify of wherein the average size of polymerization, wherein the middle and optionally is importance. The literature related to the field normal industrial reconstituted with human with the suggested one or more or significantly of the reactor scaling through the invention claims a preparation method of (named as polymer. the deposition reactor wall).
Indeed, comprising a polymer polyol the method is in to further improve. The method of the dispersing stability of reinforcing and HNO3 much (especially of polyethylene content of the polymer polyol and average size of the gear (absence of producing a polymer polyol. The method according hope to develop capable of the abroad and a diplomatic mission reactor is factor is maximal and a as a result of the fermenting time shortest osmosis method of the reactor is scaling. The polymer polyol and preparation method of the invention description connected with the or.
The invention devotes to the use of the stirring kettle in the reactor the average granularity is small, wherein the stability, wherein the gear, the continuous process for low viscosity polymer polyol. A a preferably an embodiment, wherein the generated in qualify further replaced by. A method of making the styrene and acrylonitrile mixture and a polyol mixture of the conventional polyether glycol is the unsaturated polyol is composed of the so-called macromonomer the reaction product, macromonomer is polyol at least about 12% (weight), preferably at least about 15% (weight); the middle solid content of less than about 30% (weight), preferably of less than about 25% (weight), at least one of about 15% (weight). Is further playing a role the middle and styrene and acrylonitrile in one or more of a connection the reaction mixture is macromonomer in the polyol and a, is in a water solvent in the reactor, initiators and control agent in a reaction. The other preferably an embodiment of the invention, the concentration of the distribution of raw material, and centigrade in the polymerization reactor is minimum, wherein is added to the reactor amount of monomer is less than about wherein the reactor (30%) weight, preferably in the polymerization reactor is equal. According to the part content of the invention, further preferably with the chain transfer active solvent. Method of the invention is removed or a large scale reduction reactor scaling, namely polymer is deposition reactor wall. The invention further relates to the high stability for preparing method, wherein the gear, low-viscosity polymer polyol and application thereof in preparing polyurethane.
According to the invention, is a small average size and is suitable improved is a polymerization method for preparing to the: The first (1) and acrylonitrile mixture, in (2) of of the polyether polyol and (3) of monomer mixture (4) radical initiator, (5) is presence of (6) and controlling agent moderate chain transfer active and solvent is selected from the reaction, adjust the middle comprises a high macromonomer, at least comprising about 12%, preferably at least comprising about 15% to (polyol mixture of) of monomer; Intermediate solid content of less than about 30%, preferably of less than about 25%, and at least one of about 15% (weight).
A and a polymerization in the middle and styrene in one or more series of stirring kettle in the reactor and acrylonitrile, wherein the polyol is the mixture of the monomer and a is the dispersing the solvent in the reactor, initiators and control agent with the reaction. The other preferably an embodiment of the invention, raw material is the polymerization reactors wherein the monomer is concentrated to achieve is minimum, therefore of adding amount in any reactor is less than the reactor of about 30%, preferably of each adding the monomer reactor and equal.
The organic stirring kettle in the reaction mixture reactor are generally is further being is a mixture of adding monomer is the polymer and reactor for converting.
The temperature of the polymer is performed for at least a 100℃, preferably 100-140℃, wherein the preferred 120-130℃. The intensive mixed in the reactor, the retention time at least one of about 20 minutes, preferably at 30-90 min in. Wherein the reaction can in the pressure at the outer pressure at the working temperature is isolates, and performing or performing the system under normal pressure. Such as nitrogen or argon and normal oxygen from the whole device with inert gas. The process, which is the inert atmosphere in the system. Is (is a is a conventional method of vacuum distillation, wherein film or FORMULA employs the evaporator) and residual to the volatile component of the exits from the product.
Is suitable for monomer in-situ grafting polymerization of the styrene and acrylonitrile, wherein the ratio of 100/0 to 20/80, wherein the content is max 50% in. A for at surface of the unsaturated monomer and styrols of the acrylonitrile together, or used as the styrene of the acrylonitrile wherein. A, comprises but not limit follows: Methyl vinyl cyanide, d- methyl styrene, methyl styrene and vinyltoluene, unsaturated monocarboxylic acid (e.g. acrylic acid, methacrylic acid, maleic acid, fumaric acid or itaconic acid) and an unsaturated carboxyl monomer of substituted (e.g. methyl acrylate and (2) propyl acrylate, methyl methacrylate and methacrylic acid 2 ppm methyl ester and methacrylic acid and propyl ester) and so on.
Can be used as the invention claims a polyol comprising the ether is known the product. As a ethylene, propylene oxide, oxidized succinate, tetrahydrofuran and raw material compound mixture, wherein the raw material compound that has at least two active hydrogen atoms, these compounds of such as a Polyurethane: Chemical and Technology, wherein the mixture obtained by ), the class I), the 32-44th print (J.H.Saunders and K.C.Frish, Robert E.Krieger Publishing Co.Malabar, FL, 1983) is said. Raw material compound is suitable for the polyhydroxylated compound such as alkylene glycol, glycerol, trimethylolpropane, pentaerythritol, sucralose, glucose and cane. The other of examples precursor compound is suitable for comprising a water, ammonia aminoalcohol and (e.g. ethanolamine, diethanol amine and triethanolamine) and primary amine and secondary amine catalyst or (e.g. quadrol, aniline and tolylene) comprising. The invention is used for preparing the polymer polyol is polyether polyol and molecular weight of 500-12000, preferably of 2000-8000, a hydroxyl functionality of claims. The polyether chain are generally is composed of propylene oxide and ethylene device. The oxide with a through the addition, or can be added to form the block or terminated separatedly. The obtained polyatomic alcohol can be according to the corresponding oxide the sequence and dosage of which is a tert-butyl group that is mainly And in the range is.
The invention can of monomers, but not limit to the polyol and reactive compound contains reaction product: The maleic anhydrides, fumaric acid and 1,1 of the dimethyl pseudoallyl isopropenyl with isocyanate and methacrylic acid and acids of the methyl ester and 2 - 3-butene-1-alcohol (1,4) glycol and 1 - 3-butene-1-alcohol (3,4) and acrylic acid hydroxyethyl acrylate propyl ester, methyl methacrylate, acrylic acid or methacrylic acid, methyl acryloyl chloride, methacrylic acid and prepared and glycidyl ether. That of the polycarboxylic acid or anhydride, wherein easiest uses unsaturated polyol and alkylene oxide reaction in order to for the invention by using the substitution carboxyl reducing acid value. A polyol wherein the same of the molecule weight of the manufacture of a is at least 4500, a hydroxyl functionality at least 3 and antioxidant is polyether polyatomic alcohol. The preparation method of the monomer; and dosage of the reactive compound contains the same in per mole of polyol 0.3-1.5 mole of range, preferably in per mole of polyol 0.5-1.2 mole of range. The dosage of macromonomer is the polymer has an amount of which is not using to a fully. Generally speaking, macromonomer total amount of the finished product of polyol mixture (2%) weight to 10% by weight) in the range, and possibly a at a circumstances more of the stable dispersions.
Initiation of polymerization is conducted with a free radical initiator. The method for initiator comprises such as follows: Organic peroxide (e.g. dibenzoyl peroxide and peroxidation decanoyl), carboxylic ester (e.g. is tertiary Butyl Ester and 2 to ethylhexoic acid tertiary amyl ester) and an aliphatic azo compound (e.g. 2,2 ' - azo of (a) with and 2,2 ' - azo two (2 - 2-bromomethyl-2-phenyl methyl)). Heat initiator decomposition's is 110-250 of the polymerization conditions as far as a low, preferably for about 1 minute; a to the monomer is the fast according of polymer. The dosage of the initiator and preferably of the total amount of 0.5-5% (weight).
The polymerization the same, and is soluble polymer in the organic solvent. The declarative as follows: The benzene, methylbenzene, methyl benzene, xylols, hexanes, iso-propanol, n-butanol, 2 - butyl alcohol, ethyl acetate, butyl acetate and so on, known is suitable for the field is the organic solvent of vinyl monomer and. Preferably uses normal boiling point solvent in the range 100-140℃. Use of the normal boiling point is lower than 100℃ solvent, and reaction is performed on the container and. The alcohol solvent and preferably a moderate chain transfer thereof. The ethyl benzene and n-butyl alcohol in qualify used as the invention the solvent. The general dosage of the solvent is about 2-20% (weight), and is used for producing wherein the solvent the polymer polyol of the mixture of the polyurethane foam.
Amplifying reaction control agent or the chain transfer agent or polymer control agent during polymerization is arranged. The use of such a reaction is controlled at least when the preparation method for intermediate, and further comprises polymerizing in the solid layer is greater than 30% (weight) is necessary. As of of the control agent comprising: A thiol, an alkyl, halogen compound and water ether. The reaction preferably controlling agent is selected from the water ether: A=CH-O-R R is the preparation C1-18 alkyl, C5-10 cycloalkyl substituted or the mixture or un-substituted, 98 ' he=' and 49' file= C9611275900111.tif "” " img-format= tif'/>r ' represents hydrogen and C1-8 alkyl group and salts of group <img wi=.
Water preferably of the ether according to Vulkazon is AFD (Bayer the product AG), or (to generate - 3 according to one of methyl) acrylic. The dosage of the control agent is the total amount of about 0.5% (weight) to about 5% (weight).
The invention claims a process to the reactor is scaling remove or greater at least reducing, wherein the method is a step of more of weeks, but not intermittent.
Polymer polyol of the invention method for preparing for producing all of the polyurethane resin, specifically the soft) and hard polyurethane foam. The polymer polyol comprises is deposited the coarse particle is a filter, and a low viscosity, or at least comprising industrial product of unknown preparation method has a first of the same and a small average size.
Producing polyurethane foam a polymer polyol the known method. The of the application of the polymer polyol which is a soft the molding and brick and hard polyurethane foam, and which can with improved hardness and a) by weight and. The material according such as soft is adhered foam the opening of the other of the foam plastic and contractility a synchronous improved.
The invention further relates to a and shapes method for non-vesicular polyurethane resin, comprising contacting heads (1) diisocyanate, molecular weight according (2) polymer polyol and which is the compound in 40-10000 of can be selected and (3) comprises isocyanate reactive hydrogen atoms in (4) catalyst (5), the foaming agent (6) and other known additive with a reaction.
Wherein isocyanate comprising group, an aliphatic ring and an aliphatic polyisocyanate and combinations thereof. The polyisocyanate composition according claim comprising diisocyanate, for example 2,4 of toluene isocyanate and 2,6 of toluene isocyanate, and phenylene diisocyanate, the hexamethylene diisocyanate, the methylene diisocyanate and dose 1,4 - diisocyanate, the hydrogenation toluene diisocyanate and naphthalene - 1,5 - diisocyanate, 4,4 ' - diphenyl methane diisocyanate and 3,3 ' - dimethyl Ditan-4,4 ' - diisocyanate; Three diisocyanate, for example) - 2,4,6 - or diisocyanate and 4,4 ' 4” - triphenyl methane the isocyanate. Compound is further arranged is 2,4 of toluene isocyanate,Of 2,4 of toluene isocyanate and 2,6 of toluene isocyanate mixture of the concentrated diamine's tolylene phosgenation is obtained; 4,4 ' - Diphenyl methane diisocyanate and a thick diphenyl-methane-diisocyanate is thick diphenylmethane diamidogen's phosgenation is obtained.
The foam plastic is comprising according to polymer polyol of the invention, preparation and can further comprises a molecular weight is 400-10000/having at least two isocyanate reactive hydrogen at compound. The compound according to one hydroxyl, amino, sulfydryl or carboxyl groups. The preferably compound is the molecular weight of 400-10000, preferably is 1000-8000 comprises combusting the organic compound. The following compound and is preferably by the polyurethane the surface of the polyester or polyether.
The invention can chain growth agent or crosslinking agent, comprises but not limit to water, hydrazinium atoms, and an aliphatic or (of the xenylamines quadrol, diethylenetriamine and a, 2,4 and 2,6 of the hydrogen tolylene diamines), aminoalcohol (e.g., and methyldiethanolamines, triethanolamine and 3) amino) 2-propanol, amino acid, organic acid and PIBSA (e.g. glycol, propanediol, glycerol, 1,4 - butanediol, 1,6 - onto sorbitol and) and molecular weight comprises as high as 400 wt% of polyethylene glycol or mixtures or a propylene glycol or poly of Claim.
Use of the catalyst is suitable for preparing the polyurethane foam, comprising a tertiary amine is the triethylamine, combination, N- methyl morpholine and N, N, N ", N ' - tetramethyl, 2-ethylene the 1,4 of the [2.2.2] octane, N, N'- the benzylamines and n, n-dimethyl cyclohexylamine. A further of the triethanolamine, the For removing and N, N ' - middle and an oxide of the product. The catalyst according the is capable of containing carboxylic acid and (II) - (e.g. acetic acid and (II), and is (II), ethylhexoic acid and (II) and lauric acid and (II))A device (II) compound (e.g. the organic group, and dichlorized the dibutyltin tin, the acetic acid and tin and dibutyltin dilaurate and maleic acid and tin and acetic acid dioctyl) and. Can be further of the catalyst to the mixture.
Can be selected uses the foaming agent, for example water and/or organic volatile or dead substance. The foaming agent is suitable for comprising such as acetone, ethyl acetate, and can halohydrocarbon (e.g. dichloromethane, trichloromethane, f11 trichlorofluoromethane, f22 difluoromonochloromethane and dichloro-difluro-methane), butane, hexanes or two ethyl ether. A for the foaming agent, wherein the air, CO2 or N2O. The foaming agent and obtainable by adding that the stripping gas the compound according to any one of high - temperature.
Root according to the invention, wherein in the amplification agent, comprising surface of active agent, foam stabilizer and inhibitor, stabilizer, flame-retardancy material, plasticizer, dye, filler and anti-fungus and antimicrobial material. The detail for and function of the addition of agent into a further G.Oertel the Polyurethane Handbook, wherein the acrylate having volume; the 104-127th print (CarlHanser Publishers, Munich, 1993) carrying.
Polyol B: A is trimethylol propane and propylene oxide and polyether amine and preparation method. An ethylene content of 17.5% by weight). The method comprising 80-90% or hydroxyl group, a hydroxyl value is 35.
Polyol as follows: A is trimethylol propane and propylene oxide and polyether amine and preparation method. An ethylene content of 17.7% by weight). The polyether to about 90% (hydroxyl group, a hydroxyl value is 28. Polyol D: A wherein the glycerol and propylene oxide and polyether amine and preparation method. The ethylene content of polyether is 10% (weight), comprising And hydroxyl group, a hydroxyl value is 56.
Macromonomer I: By reacting polyol B and maleic anhydride the reaction comprises an unsaturated polyether and addition reaction. The non-degree of the saturated of macromonomer is 0.050meq/g, and hydroxyl value is 33.9.
Macromonomer II: A through the polyol IS the acrylic acid to the toluenesulfonic acid in the reaction is comprising an unsaturated polyether. The non-degree of the saturated of macromonomer is 0.065meq/g, and hydroxyl value is 25.9.
: Initiator2,2 ' - Azo two (2 - 2-bromomethyl-2-phenyl methyl), Vazo_67, a is of DuPont. moderator: The sub-nanometre to generate - 3 according to one of methyl) benzene, Vulkazon_AFD, a is from BayerAG. A: Of: ATEthylbenzene BUOH: 1 - butanol: stabilizerOS22 stabilizer, a is from Bayer AG. Catalyst is 1: The middle, Desmorapid_DMEA, a is from Rhein Chemie.
Catalyst is 2: The dipropylene glycol is (2 to the amino ethyl) ether, RC-PUR Activator108 a is from Rhein Chemie.
Catalyst is 3: The stannous octoate, Desmorapid_SO, a is from Rhein Chemie. : TDIToluene diisocyanate (80%2,4-; 20%2,6- Toluene isocyanate), Desmodur_T80, a is from Bayer AG.
The preparation of polymer polyol preparing the substantially as a series of stirring kettle in the reactor of the polymer polyol. The material component and pumped into the said reactor. The intensive content of mixing the reactor, the temperature is controlled at 125℃. The reaction are performed with the overflow reactor is normal pressure inert atmosphere. The overflow from the first reactor body of the raw material secondary reactor. Alcohol, wherein a necessary - of the reactor similarly, wherein the raw material dispensing of each reactor. Series of the reaction mixture reactor served as a and reactor, adding initiating agent and solvent to the reactor, technique amplification monomer is selected from the group of the polymer. Is less than the main product of 1 millibars and 125℃ vacuum distillation several hours, wherein removing the solvent and residual monomer, then, a use of the polymer polyol of the polyurethane foam. A preparation of the polyurethane foam is a center for type group to the first polyurethane foam the prescription. Use of the preceding and an embodiment from polymer polyol preparing is selected from the lather plastic. Is selected from the lather plastic is
<img id="idf0001" file="CN1069654CD00151.tif" img-content="drawing" img-format="tif" />
A wherein the polyisocyanate) is put in the container and fierce is prepared from from the group to the first polyurethane foam. Added into the polyisocyanate under stirring and water into the content of the opening the mould. Wherein the polyurethane foam get in an initiator and reacting under room temperature. The analysis and detecting conversion monomer is considered and distillate to the conversion of polymer. The viscosity of viscosity polymer polyol is provided with The weigh Wherein the rotation of viscosimeter. The average grain size (method for determining 3nm and light scattering method to 3 μ m particle size technology of). A reporting the value of the average value of 6 times determining.
The acid residue of evaluates the polymer polyol the mass percentage of storage stability method. The experimental is performed to the: First is more 10ml a detection tube wall of the 2-3ml polymer polyol. Under room temperature settles for 24 hours after 1-3, wherein the wall, the root according to the limpid and diameter is about 5-30 μ the polymer particles or agent film polymer particles of evaluates.
0= Resistance and good 1= the 2= medium/3= the medium 4= medium/miss to the difference 5= hardness foam plastic the hardness of the polyester the DIN 53577 be method determinations.
The break elongation of extending rate foam plastic according to DIN 53571 be method determinations.
The tensile strength of a foam plastic according to DIN 53571 be method determinations.
The substantially as following of such treatment is (listed in Table I) explain to the power of the invention clearly.
, And substantially as to is a claim more of the invention have the used is covered.
The substantially as to with an overflow reactor preparation, wherein of the average size of (than 1000nm), the viscosity (25℃ viscosity is more than 5000mPas). Through the method for preparing the residue of the material usual performance of pest, wherein in the material comprising quite part of the polymer particles or the removal of polymer particles, and a novel of the continuous phase of based polyol. 4-6 Hours, 1 and 2 of an anti-biological reactor in substantially as the early of the polymer having a reactor wall). The pharmaceutical composition according to claim 3 and ethylbenzene of the toluene, scaling is improved, wherein the viscosity of the product is 10-20, - into the I.
The pharmaceutical composition according to claim 4, wherein the added to the reaction mixture in series in the reaction stills, each reactor is 50% reaction mixture. The viscosity and average size of the obtained product and. The pharmaceutical composition according to claim 5, light and monomer dispensing in the reactor, and total polyol and macromonomer is added to the first reactor. The compulsive, 7 hours after 1-3, the aggregated of polymer in the second reactor. The viscosity and compulsive of the product 1, wherein the average granularity of the quite of residue, the display with the polymer particles or agent polymer particles.
The cleaning of producing a bond process parameter of with the stirring kettle in the reactor and average size, and; the low viscosity polymer polyol entire. The of 6-16 as a expounded the power of the invention.
The substantially as from the expounded or preparing the intermediate in the macromonomer concentration and solid content is the final polymer polyol dispersion is performance. A kept in the first reactor and macromonomer concentration and solid content, a form suitable for a polymerization, and average size, middle and. The pharmaceutical composition according to claim 6,7 or 9, wherein the macromonomer concentration is fixed on the polyol is about 15%, wherein the first reactor solid layer of (a) is 20,30 and 25% (weight))A wherein the average granularity is 430,550 and 505nm intermediate. The solid content is greater than 40% of the product has low viscosity and average size (- into the I). The pharmaceutical composition according to claim 8, wherein the macromonomer concentration in the first reactor and is 12% to (polyol of), the solid content of 15% by weight), wherein the average granularity of the intermediate 390nm. , And then added to a secondary reaction to the amount of monomer is this high, wherein the reactor wall of the degree of the aggregated.
The substantially as a 10-16 expounded using the polymerization reactors of the invention, wherein a monomer is further produced to make the reactor scaling minimum the functional. Use of the material of the preparation method, comprising are generally and at least one of polymer particles and agent polymer particles. The pharmaceutical composition according to claim 10 or 11 is further expounded macromonomer in the principal the preparation method for intermediate and final the physical and performance. The pharmaceutical composition according to claim 12, wherein the macromonomer in distributed on one of polymerization reactor, to substantially does not contain of the polymer or agent polymer particles polymer dispersions. With 13 of the second component of macromonomer in the substantially as. The pharmaceutical composition according to claim 14 expounded with the use of the solvent 1 is butyl alcohol. The pharmaceutical composition according to claim 15, wherein the styrene/vinyl cyanide ratio of preparing the intermediate, with low styrene/vinyl cyanide ratio is that the small average size intermediate. A for high concentration thereof in the preparation of substantially as intermediates 16, wherein the furthermore by the small average size intermediate.
The 1
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The (1) continued
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The (1) continued
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The examples and as a sticking the carrier books invention, wherein not according to claim the invention, this invention claims a is - comprising the following claim device.
6 sheets
Sheet 1 Sheet 2 Sheet 3 Sheet 4 Sheet 5 Sheet 6
Every citation, both ways
| Document | Relation | Office | Cited during |
|---|---|---|---|
| CN104053692A | Cited by | China | Search report |
| CN108570130A | Cited by | China | Search report |
| CN108559033A | Cited by | China | Search report |
| US4960956A | Cites | United States of America | Search report |
| US5364906A | Cites | United States of America | Search report |
| US496095619870901 | Cites | United States of America | – |
| US536490619941115 | Cites | United States of America | – |
34 members in 13 offices
Priority claims4
| Document | Office | Kind | Date |
|---|---|---|---|
| 95115940 | European Patent Office (EPO) | A | |
| 951159409 | European Patent Office (EPO) | – | |
| 951159409 | – | – | – |
| EP19950115940 | – | – | – |
Members34
| Document | Office | Kind | |
|---|---|---|---|
| CA2187125A1 | Canada | A1 | |
| EP0768324A1 | European Patent Office (EPO) | A1 | |
| CA2188890A1 | Canada | A1 | |
| JPH09124750A | Japan | A | |
| KR970021113A | Republic of Korea | A | |
| KR970021114A | Republic of Korea | A | |
| EP0776915A2 | European Patent Office (EPO) | A2 | |
| JPH09216967A | Japan | A | |
| CN1160061A | China | A | |
| EP0776915A3 | European Patent Office (EPO) | A3 | |
| MX9604686A | Mexico | A | |
| BR9605032A | Brazil | A | |
| US5773520A | United States of America | A | |
| US5814699A | United States of America | A | |
| TW360665B | Taiwan Province of China | B | |
| TW375618B | Taiwan Province of China | B | |
| JP2992236B2 | Japan | B2 | |
| CA2188890C | Canada | C | |
| EP0768324B1 | European Patent Office (EPO) | B1 | |
| DE69518423D1 | Germany | D1 | |
| ES2148397T3 | Spain | T3 | |
| DE69518423T2 | Germany | T2 | |
| KR100277053B1 | Republic of Korea | B1 | |
| CN1069654CThis record | China | C | |
| USRE37851E | United States of America | E | |
| EP0776915B1 | European Patent Office (EPO) | B1 | |
| AT233285T | Austria | T | |
| ATE233285T1 | Austria | T1 | |
| DE69626361D1 | Germany | D1 | |
| DK0776915T3 | Denmark | T3 | |
| ES2192600T3 | Spain | T3 | |
| DE69626361T2 | Germany | T2 | |
| KR100433147B1 | Republic of Korea | B1 | |
| US7015282B1 | United States of America | B1 |
4 legal events, as the office reported them to INPADOC
Over the term
Point at a mark for the eventEvents
| Event | Code | |
|---|---|---|
| Lapse of patent right due to non-payment of the annual feeLapsedC19 | C19 | |
| Grant of patent or utility modelGrantedC14 | C14 | |
| Entry into substantive examinationC10 | C10 | |
| PublicationC06 | C06 |
Numbers
- Publication
- 1069654
- Publication, DOCDB
- 1069654
- Publication, EPODOC
- CN1069654C
- Application
- 96112759
- Application, DOCDB
- 96112759
- Application, EPODOC
- CN19961002759
Titles2
- Chinese
- 制备小平均粒度、高稳定性、细碎的、低粘度聚合物多元醇的连续方法
- English
- Continuous process for preparatino of highly stable, finely divided, low viscosity polymer polyols of small average particle size
Classification
- CPC, 4
- C08G18/635
- C08F290/02
- C08G2101/0008
- C08G2101/0016
- IPC, 7
- C08F212 10
- C08F220 42
- C08F220 44
- C08F283 06
- C08F285 00
- C08F290 02
- C08G18 63