CN101638463A - Preparation method for polymer polyatomic alcohol used for polyurethane soft high-resilience cold molding and application - Google Patents
Preparation method for polymer polyatomic alcohol used for polyurethane soft high-resilience cold molding and application Download PDFInfo
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- CN101638463A CN101638463A CN200810053998A CN200810053998A CN101638463A CN 101638463 A CN101638463 A CN 101638463A CN 200810053998 A CN200810053998 A CN 200810053998A CN 200810053998 A CN200810053998 A CN 200810053998A CN 101638463 A CN101638463 A CN 101638463A
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Abstract
The invention relates to a preparation method for polymer polyatomic alcohol used for polyurethane soft high-resilience cold molding. The key technology is the design and synthesis process of a molecular structure and an optimal molecular weight of a macromolecular dispersant. The method synthesizes polyether macromolecules different from the prior patent; the optimal functionality in the macromolecular synthesis of the dispersant is between 3.2 and 3.8; and the macromolecules take water and pentaerythritol as a starting agent to carry out addition polymerization of PO and EO, and the EO capsends. The EO content is between 14 and 18 percent, the molecular weight of the macromolecules is between 6,000 and 8,000, an unsaturated double-bond compound introduced to the macromolecules is maleicanhydride, and redundant carboxyl is end-capped by the EO. The components of the synthetic polymer comprise high-activity polyether polyatomic alcohol based polyether polyatomic alcohol, the macromolecular dispersant, unsaturated vinyl monomers of styrene and acrylonitrile, polymer initiator azodiisobutyronitrile, and chain transfer agents of 12 alkyl sulfhydryl and isopropanol; and the solid content of the synthesized polymer polyatomic alcohol is over 44 weight percent. The preparation method is mainly used for polyurethane soft high-resilience cold molding products.
Description
Technical field
The invention belongs to the urethane polymer polyatomic alcohol, particularly a kind of manufacturing process of polymer polyatomic alcohol of polyurethane soft high-resilience cold molding foam polymer polyatomic alcohol Preparation method and use, particularly high solids content.Manufacture and design the optimum formula that the macromole of suitable macromolecular structure dispersion agent and synthesis of high solid content polymer polyol are arranged.
Background technology
Polymer polyatomic alcohol is a main raw material of making high resilience flexible foam, adds the load that polymer polyatomic alcohol can improve foam article, foamy rebound resilience, foam hardness in making the foamy prescription.High rebound foam divides two kinds: a kind of is the bulk polyurethane foam; Another is a moulded foam.Moulded foam divides cold molding and hot-moulded foam again.In recent years, for adapting to relevant industries,, more and more higher to the solid content requirement of polymer polyatomic alcohol as the development of automobile, aviation, furniture etc.Initial polymer polyatomic alcohol solid content is about 20wt%, develops into 30wt% in succession, 40wt%, 42wt%, 43wt%.R﹠D direction in recent years is 45wt% or the polymer polyatomic alcohol that is higher than the 45wt% solid content.
The problem of producing the polymer polyatomic alcohol most critical of high solids content is the molecular structure of macromole dispersion agent in the prescription, the design of molecular weight and synthetic and definite optimum formula of making polymkeric substance.Therefore the manufacturing prescription of the synthetic and polymer polyatomic alcohol of macromole dispersion agent is all proposed about the document of polymer polyatomic alcohol.As:
Narrated two kinds of dispersion agents among the U.S.4.652.589, a kind of is to be initiator addition polymerization PO, EO with 6 functional sorbyl alcohols, carries out block polymerization, EO is at inner segment, make molecular weight and be 12000 macromole, use the EO end-blocking after introducing two keys with the cis-butenedioic anhydride reaction again, make the macromole dispersion agent; Another kind is to be initiator addition polymerization PO, EO with 3 functional glycerine, and EO end-blocking 15wt% makes the macromole of molecular weight about 5000, introduce two keys with the cis-butenedioic anhydride reaction again after, use the EO end-blocking, make the macromole dispersion agent.Utilize these two kinds of dispersion agents to make polymer polyatomic alcohol and be used for the bulk polyurethane foam.Using the polymerization control agent in polymer formulators is Virahol, and the polymer polyatomic alcohol solid content of manufacturing is 41～45wt%.
Having narrated with 3 functional TriMethylolPropane(TMP)s among the U.S.4.458.038 is initiator addition polymerization PO, EO, make molecular weight and be 6732 macromole, behind the two keys of cis-butenedioic anhydride reaction introducing, the EO end-blocking, make the macromole dispersion agent, in the manufacturing prescription of polymkeric substance, adopting the polymerization control agent is lauryl mercaptan, make about the solid content 34wt% of polymkeric substance, be used for high resilience bulk foam.
Set forth the macromole that adopts three kinds of different molecular weights in the U.S.5.594.066 patent and made dispersion agent, but having only 6 officials can sorbyl alcohol be that the macromole of initiator can be used, its molecular weight 12020, the mode of introducing two keys is that hydroxypropyl methacrylate is linked with TDI earlier, link with macromole again, make dispersion agent.Polymerization stabilizer Virahol in polymkeric substance is made contains solvent toluene in the prescription simultaneously.The polymer polyatomic alcohol solid content 44wt% that makes is used for high resilience bulk foam.
Having set forth in the U.S.2005024572 patent and having made macromolecular program is with TDI the trifunctional macromole coupling of methacrylic acid hydroxyethyl ester and 3000 molecular weight to be made dispersion agent.In the prescription of preparation polymkeric substance, add solvent: methyl alcohol or ethanol or dimethylbenzene or mixed solvent, the bulk foam polymer polyatomic alcohol of system solid content 50wt%.
Set forth several modes that adopt in the U.S.20060025492 patent, to being to introduce two keys in 12000 the molecule with sorbyl alcohol initiator addition polymerization PO, EO molecular weight, the compound of introducing two keys has cis-butenedioic anhydride, methacrylic acid hydroxyethyl ester and TMI
(Isopropenyl dimelhyl benzyl isocyanatl) Virahol dimethyl benzoyl isocyanic ester, divide two sections continuous processings to make preformed stabilizers (in the polymer polyatomic alcohol preparation, playing the dispersion agent effect) with the macromole of making then, contain 60% polymerization control agent Virahol in the preformed stabilizers, 15.9% poly-SAN particle, 24% macromole.This preformed stabilizers can be made into the bulk foam with and cold molding foam polymer polyatomic alcohol.The wherein obtained cold molding solid content 60-62wt% of polymer polyatomic alcohol, but viscosity is very high.Viscosity during polymer polyatomic alcohol solid content 60.82wt% is 93622CST, and the viscosity during solid content 62.25wt% is 251311CST, and high like this viscosity is that post-treatment causes very big difficulty, and inconvenience is used.
Having set forth in the U.S.20050245724 patent and having used TDI is that 7000 polyether glycol carries out coupling and makes dispersion agent with methacrylic acid hydroxyethyl ester and 4 functional molecule amounts.Adopt this dispersion agent to make polymer polyatomic alcohol and be used for the bulk foam.
Set forth among the U.S.20060025491 and with MDI the sorbyl alcohol initiator of 12000 molecular weight has been added polyether glycol that PO, EO make and TMI and carry out coupling and make macromole, make preformed stabilizers with two sections successive reactions then, resynthesis is used for the polymer polyatomic alcohol of cold molding.Its solid content 43wt% adopts Virahol as the polymerization control agent in the synthesizing formula.
Summary of the invention
The invention provides a kind of polymer polyatomic alcohol used for polyurethane soft high-resilience cold molding Preparation method and use: polymer polyatomic alcohol is a stable dispersion, i.e. the polymer particles of stable be scattered here and there vinylbenzene and vinyl cyanide in basic polyether glycol.Therefore in the polyurethane flexible foam goods, for improving the load of high rebound foam goods, these polymer particles play an important role.The purposes of the structure of the basic polyether glycol in the polymer polyatomic alcohol and molecular weight decision polymer polyatomic alcohol.In foam article, when the molecular weight of basic polyether glycol about 3000, proportion of primary OH groups was less than 5% o'clock, polymer polyatomic alcohol is used for the high rebound foam of production bulk; The molecular weight of the basic polyether glycol in polymer polyatomic alcohol is greater than 4800, and proportion of primary OH groups was used for the high rebound foam of cold molding greater than 70% o'clock.The main raw material of preparation polymer polyatomic alcohol has basic polyether glycol, macromole dispersion agent, polymerization control agent (or claiming chain-transfer agent), unsaturated monomer, solvent, initiator etc.
Particular content of the present invention
A kind of polymer polyatomic alcohol used for polyurethane soft high-resilience cold molding, it is characterized in that: the solid content of usefulness high solid content polymer polyol is 44wt% at least, in the 100wt% formulation weight that always feeds intake, the prescription of making polymer polyatomic alcohol comprises: A basis polyether glycol; B macromole dispersion agent; At least a unsaturated vinyl monomer of C; The D free radical polymerization initiator; At least a chain-transfer agent of E.
Wherein E is that chain-transfer agent is the mixture of mercaptan or low mass molecule alcohol or pure and mild mercaptan.
Wherein E is that chain-transfer agent is a Virahol, lauryl mercaptan and their mixture.Wherein the add-on of chain-transfer agent is counted 0.2～5wt% with the 100wt% formulation weight that feeds intake.
Wherein D is that free radical polymerization initiator is AIBN, in 100wt% feed intake the prescription add-on be 0.3～0.6wt%.
Wherein the unsaturated vinyl monomer of C adopts vinylbenzene and vinyl cyanide, and the ratio of vinylbenzene and vinyl cyanide is 80～20/20～80, monomeric add-on 40～60wt%.
Wherein B is that the macromole initiator in the said macromole dispersion agent is tetramethylolmethane and water, functionality 3.2～3.8, PO and EO block polymerization, EO end-blocking, EO content 14～18wt%, macromolecular molecular weight 6000～8000.
Wherein the unsaturated double-bond compound of macromole dispersion agent introducing is a cis-butenedioic anhydride, and the mole number that cis-butenedioic anhydride is introduced is that each macromole polyether glycol is introduced 0.6～0.95mol cis-butenedioic anhydride.
Wherein A is that basic polyether glycol is a polyether polyol with high activity, promptly is that the product grade of Tianjin Petrochemical Company polyethers portion is: TEP-330N and TEP3033; The basis polyether glycol is 40～60wt% in the add-on of the prescription that feeds intake.
The production technique of polymer polyatomic alcohol is a continuous processing, removes finished product solid content behind the monomer greater than 44wt%.
Polymer polyatomic alcohol used for polyurethane soft high-resilience cold molding is mainly used in polyurethane soft high-resilience cold molding foam article.
Embodiment
The basis polyether glycol: basic polyether glycol is an initiator with the polyvalent alcohol of 2～4 functionality generally, and alkali makees catalyzer or DMC catalysis adds poly(propylene oxide) (PO) and oxyethane (EO), makes the polyether glycol of different structure and molecular weight.But PO and EO block polymerization, but also random polymerization, available EO end-blocking in the molecular structure, also end-blocking not.Polyvalent alcohol initiator commonly used has glycerine, TriMethylolPropane(TMP), tetramethylolmethane, propylene glycol, water etc.Functionality in bulk foam usefulness polymer polyatomic alcohol is about 3, can be that full PO adds dimerization product, also can carry out random polymerization by partially mixed EO, molecular weight is generally about 3000, proportion of primary OH groups is generally less than 5%, is high reactivity at the cold molding foam with the basic polyether glycol of polymer polyatomic alcohol, and proportion of primary OH groups is generally greater than 70%.EO end-blocking, molecular weight are generally more than 4800.CASE series generally is that two sense polyvalent alcohols are initiator with the basic polyether glycol of polymer polyatomic alcohol, addition polymerization PO or by the EO end-blocking.Be mainly used in CASE series product such as elastomer precursor gum stick, sealing agent, coating.
The basic polyether glycol that the present invention adopts is a high reactivity, and proportion of primary OH groups is greater than 75%.Its molecular structure is glycerine-PO-EO, EO content 15%, i.e. and the proprietary technology product TEP330N of our department, hydroxyl value is 35mgKOH/g.
Unsaturated monomer: unsaturated ethylene thiazolinyl monomer has a variety of available, as vinylbenzene, vinyl cyanide, acrylate, vinylchlorid, vinylidene chloride, butylene, divinyl or isoprene etc.Commonly used is vinylbenzene and vinyl cyanide, and vinyl cyanide and vinylbenzene are dispersed in the external phase at the aggregated particles that carries out the SAN of autohemagglutination and copolymerization formation under the processing condition of regulation in the polyether glycol of external phase basis.The content of the polymkeric substance of vinylbenzene and vinyl cyanide in basic polyether glycol is called solid content, along with increasing of solid content, and the bad stability of polymer polyatomic alcohol, viscosity increased simultaneously.Therefore, in the manufacturing prescription of polymer polyatomic alcohol, need increase stability and the reduction viscosity of macromole dispersion agent, be convenient to the processing of polyurethane product to improve polymer polyatomic alcohol.
Polymerization control agent or chain-transfer agent: chain-transfer agent prevents that in polyreaction excessive polymer particle from producing, control lower crosslinked, the diameter that makes polymer particle and makes the smooth surface of polymer beads in the scope that is fit to, to reduce the viscosity of polymkeric substance.Common low-molecular-weight liquid can be used as chain-transfer agent, and as water, cycloalkanes, ketone, alcohol, aldehyde, halohydrocarbon, benzene etc., chain-transfer agent commonly used in the polymer polyatomic alcohol manufacturing is lauryl mercaptan and Virahol.Generally in 0.3～10wt% (in total throwing amount of filling a prescription), the present invention uses lauryl mercaptan and Virahol to usage quantity in the manufacturing of polymer polyatomic alcohol, and add-on is at 0.2～5wt%.
Initiator: the free-radical initiator that is suitable for polymerization of vinyl monomer and the two keyed jointing branch polymerization of vinyl monomers in the dispersant molecule are used for free fundamental mode polymerization, its transformation period should the following residence time of polymeric reaction condition 25% or lower.Suitable initiator has the superoxide of alkane and aromatic hydrocarbons, the over cure acid esters, the peroxyboric acid ester, peroxocarbonate, azo-compounds etc. all are the available free radical polymerization initiators, as hydrogen peroxide, ditertiary butyl peroxide, the diethyl peroxide tert-butyl acetate, the peroxidation acid tertiary butyl ester, the peroxidation butyl isobutyrate, 3,5,5-trimethylammonium peroxidation caproic acid tertiary butyl ester, peroxidation phenylformic acid tertiary butyl ester, the peroxidation trimethylacetic acid tert-butyl ester, peroxidation trimethylacetic acid tert-pentyl ester, the peroxidation 2 ethyl hexanoic acid tert-butyl ester, lauroyl peroxide, the dicumyl peroxide tert-butylhydroperoxide, Diisopropyl azodicarboxylate (AIBN), 2,2 '-azo-two (α methylbutyronitrile), 2,2 '-azo-two (2, the 4-methyl pentane nitrile), the 2-tertiary butyl-azo-2-itrile group-4 methoxyl group-4 methylpentane, the 2-tertiary butyl-azo-2-itrile group butane.The most frequently used free-radical initiator is AIBN in synthetic polymer, usage quantity 0.3-0.6% (in total throwing amount of filling a prescription).
Solvent: in some documents, introduce the manufacturing polymer polyatomic alcohol and can adopt appropriate solvent, as methyl alcohol, ethanol, the trimethyl carbinol, benzene,toluene,xylene etc.Manufacturing prescription of the present invention does not adopt solvent.
The macromole dispersion agent: the macromole dispersion agent is absolutely necessary in prescription, especially during the polymer polyatomic alcohol more than making the 25wt% solid content, suitable dispersion agent must be arranged, and it can reduce the viscosity of polymer polyatomic alcohol, the stability and the filterableness of raising dispersion.The general earlier synthetic functionality of the manufacturing process of macromole dispersion agent is greater than 3 high molecular weight polyether, in macromole, introduce two keys then, usually the compound of the unsaturated double-bond of introducing comprises the alkoxy compound of cis-butenedioic anhydride, maleic acid, FUMARIC ACID TECH GRADE, acrylate, methacrylic ester, vinyl carbinol etc., and the technology of introducing two keys generally is intermittence or semi-batch technology.In the technology of making the macromole dispersion agent, the design of macromolecular molecular structure and molecular weight is very important, macromolecular initiator functionality generally gets 3～8, molecular weight 5000-12000, macromolecular manufacturing process adopts conventional polyether glycol manufacturing process, promptly under the processing condition of regulation, addition polymerization PO and EO in initiator, available traditional potassium hydroxide is made catalyzer, also available DMC catalysis, but PO, EO addition polymerization block also can be random, the addition polymerization of EO can be in the end, also can be in the middle of segment.Initiator commonly used in the document is a sorbyl alcohol, macromolecular molecular weight about 12000.The macromole of making is under defined terms and contain unsaturated double-bond compound chemical combination, introduces two keys in macromole.The compound that contains unsaturated double-bond commonly used is a cis-butenedioic anhydride.Using the EO end-blocking, make dispersion agent behind the access cis-butenedioic anhydride.General macromole is that macromole is about 1 to 0.7～1mol than cis-butenedioic anhydride with the ingredient proportion of cis-butenedioic anhydride.
The present invention design and synthesized the polyethers macromole different with existing patent, making macromolecular initiator is tetramethylolmethane and water, PO and EO block polymerization, the EO end-blocking, EO content is 14～17wt%, molecular weight is 6000～8000, and adding of macromole and cis-butenedioic anhydride is proportional for 1mol macromole/0.6～0.95mol cis-butenedioic anhydride.After introducing two keys, use the EO end-blocking, make the macromole dispersion agent.
The synthesis technique of macromole dispersion agent: the polyethers synthesis technique is made macromole routinely earlier, and macromolecular molecular weight is 6000～8000, functionality 3.2～3.8, EO content 14～17wt%, PO and EO block polymerization.The synthetic employing batch technology of dispersion agent, carry out in autoclave, the molecule that has high input earlier adds the catalyzer potassium hydroxide aqueous solution again, the input amount of potassium hydroxide is 50～500ppm, intensification is dewatered to below the 0.02wt%, under agitation drops into cis-butenedioic anhydride, and cis-butenedioic anhydride and macromolecular molar ratio are 0.6～0.95mol, reacted 2 hours, 125 ℃ of temperature of reaction drop into EO, EO again
Mol/ cis-butenedioic anhydride=2～10mol reacted 2.5 hours, reaction pressure≤400Kpa, and isomerization reaction then, 150～200 ℃ of temperature controls were reacted 16 hours.
The synthesis technique of polymer polyatomic alcohol: adopt two still continuous reaction process, with material, basis polyether glycol TEP-330N, the macromole dispersion agent, monomer styrene and vinyl cyanide, lauryl mercaptan and Virahol, the AIBN mixing is cooled to below 30 ℃, the ratio of monomer styrene and vinyl cyanide can change as required, variation range can be at SM/AN=90/10-10/90, the total amount of SM and AN is more than 40wt% in the prescription, AIBN is at 0.3～0.6wt%, the dispersion agent add-on is at 1～10wt%, mercaptan add-on 0.2～1wt%, the add-on of basic polyether glycol is 40～60wt%.Mixed material drops into reactor continuously, and temperature of reaction is controlled at 115 ± 5 ℃, and pressure-controlling is less than 450Kpa, reaction time 1～2 hour.
Example by the polymer polyatomic alcohol of above prescription and technology manufacturing is listed in the table below:
Claims (11)
1, a kind of polymer polyatomic alcohol used for polyurethane soft high-resilience cold molding preparation method, it is characterized in that: the solid content of high solid content polymer polyol is 44wt% at least, in the 100wt% formulation weight that always feeds intake, the prescription of making polymer polyatomic alcohol comprises: A basis polyether glycol; B macromole dispersion agent; At least a unsaturated vinyl monomer of C; The D free radical polymerization initiator; At least a chain-transfer agent of E.
2, polymer polyatomic alcohol used for polyurethane soft high-resilience cold molding preparation method according to claim 1 is characterized in that: wherein E is that chain-transfer agent is the mixture of mercaptan or low mass molecule alcohol or pure and mild mercaptan.
3, polymer polyatomic alcohol used for polyurethane soft high-resilience cold molding preparation method according to claim 1 is characterized in that: wherein E is that chain-transfer agent is a Virahol, lauryl mercaptan and their mixture.
4, polymer polyatomic alcohol used for polyurethane soft high-resilience cold molding preparation method according to claim 3 is characterized in that: wherein the add-on of chain-transfer agent is counted 0.2～5wt% with the 100wt% formulation weight that feeds intake.
5, polymer polyatomic alcohol used for polyurethane soft high-resilience cold molding preparation method according to claim 1 is characterized in that: wherein D is that free radical polymerization initiator is AIBN, is 0.3～0.6wt% in the feed intake add-on of formulation weight of 100wt%.
6, the high resilience cold molding of flexible polyurethane system according to claim 1 foamed resin preparation method, it is characterized in that: wherein the unsaturated vinyl monomer of C adopts vinylbenzene and vinyl cyanide, the ratio of vinylbenzene and vinyl cyanide is 80-20/20-80, monomeric add-on 40-60wt%.
7, polymer polyatomic alcohol used for polyurethane soft high-resilience cold molding preparation method according to claim 1, it is characterized in that: wherein B is that the macromole initiator in the said macromole dispersion agent is tetramethylolmethane and water, functionality 3.2～3.8, PO and EO block polymerization, the EO end-blocking, EO content 14～18wt%, macromolecular molecular weight 6000～8000.
8, polymer polyatomic alcohol used for polyurethane soft high-resilience cold molding preparation method according to claim 7, it is characterized in that: wherein the unsaturated double-bond compound of macromole dispersion agent introducing is a cis-butenedioic anhydride, and the mole number that cis-butenedioic anhydride is introduced is that each macromole polyether glycol is introduced 0.6～0.95mol cis-butenedioic anhydride.
9, polymer polyatomic alcohol used for polyurethane soft high-resilience cold molding preparation method according to claim 1, it is characterized in that: wherein A is that basic polyether glycol is a polyether polyol with high activity, promptly is that the product grade of Tianjin Petrochemical Company polyethers portion is: TEP-330N and TEP-3033; The basis polyether glycol is 40～60wt% in the add-on of the prescription that feeds intake.
10, polymer polyatomic alcohol used for polyurethane soft high-resilience cold molding preparation method according to claim 1, it is characterized in that: the production technique of polymer polyatomic alcohol is a continuous processing, removes finished product solid content behind the monomer greater than 44wt%.
11, polymer polyatomic alcohol used for polyurethane soft high-resilience cold molding according to claim 1, wherein polymer polyatomic alcohol is mainly used in polyurethane soft high-resilience cold molding goods.
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