CN103275278A - Synthesis method for polyester polymer polyol dispersoid - Google Patents
Synthesis method for polyester polymer polyol dispersoid Download PDFInfo
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- CN103275278A CN103275278A CN2013102408203A CN201310240820A CN103275278A CN 103275278 A CN103275278 A CN 103275278A CN 2013102408203 A CN2013102408203 A CN 2013102408203A CN 201310240820 A CN201310240820 A CN 201310240820A CN 103275278 A CN103275278 A CN 103275278A
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Abstract
The invention discloses a synthesis method for polyester polymer polyol dispersoid for improving the performance, lowering the density effect, and greatly improving the bearing and dimensional stability of a low density product. The technical scheme is that: the method is characterized by comprising the following steps: using one or various vinyl unsaturated monomers (1) in basis polyester polyol (2) to conduct radical polymerization reaction with the existing of a radical polymerization initiating agent (3); and adding a little free radical chain transfer agent (4) and two dispersing agent chemical compound (5) to obtain polyester polymer polyol dispersoid though in situ polymerization.
Description
Technical field
The present invention relates to a kind of synthetic method of polyester polymers polyol dispersions, especially a kind ofly improve performance and reduce density effect, greatly improve the synthetic method of polyester polymers polyol dispersions of load, the dimensional stability of low density goods, belong to industrial chemicals production and technical applications.
Background technology
Polymer polyatomic alcohol dispersion and be well-known in the purposes that polyurethane products are, it is to be filled in the mixture system that forms in the polyvalent alcohol with the polymkeric substance of thiazolinyl unsaturated monomer or multipolymer, be to form by the dispersion polymerization of alkenyl monomer in polyvalent alcohol, adopt vinyl monomer to connect that skill forms that the graft polymerization thing plays the dispersion agent effect and the polymer polyatomic alcohol for preparing at the ether active site as CN10677059A and CN1160061C.This polyvalent alcohol is used for flexible PU foam can provide good perforate performance, improves hardness and supporting capacity.
According to different basic polyvalent alcohols, the polymer polyatomic alcohol dispersion can be divided into polyether-type and polyester type.Polyether type polymer polyvalent alcohol preparation method is all on the books in following patent: US4172825, US4233425, US4287323, US4689354, US4745153, US4460715, US4574137, US4503207, US4554255, US4458038.Compare with the polyethers system, the polyurethane system of polyester system preparation has better mechanical property in many aspects, so polyester polymers dispersion production technology causes increasing concern.
In polyester polymers polyol dispersions synthetic because the reactive behavior of vinyl monomer and the influence that chain moves factors such as speed, cause the polymeric dispersions of body class very unstable, cause the layering of polymer polyatomic alcohol product, dispersion viscosity is excessive, granule foreign is many, easy gel during heat.In order to alleviate this problem, the method for using mostly is to add a kind of compound dispersion with unsaturated link(age) to generate stablizer in building-up process at present.It can be attached on the surface of polymer particles material grain in theory, and makes them more compatible with polyvalent alcohol external phase.
Used at least a unsaturated vinyl monomer in molecular weight is the polyester polyol of 1000～5000g/mol, to carry out polymerization among the EP0250351.Wherein maleic anhydride is attached in the polyester polyol molecular chain, in building-up process, plays the effect of stably dispersing.The dispersion agent dispersion efficiency that this method is synthesized is low, and dispersant dosage is big.Because maleic anhydride is attached to the increase of polyester chain Semi-polarity ester carbonyl group group, also produced the effect that increases viscosity, synthetic polyester polymers polyol dispersions viscosity is big.
The polyester polyol reaction of having used a kind of compound dispersing agent to contain single methanol, the polyisocyanate compound of unsaturated double-bond by lower molecular weight among the CN1995083A and not had an ethylene linkage unsaturated group forms.This method in producing specific a kind of single methanol that contains unsaturated double-bond be vinylcarbinol, vinylcarbinol is unfavorable for producing because great toxicity is arranged.
Summary of the invention
The objective of the invention is to overcome the defective of prior art, improve performance and reduce density effect, greatly improve the synthetic method of polyester polymers polyol dispersions of load, the dimensional stability of low density goods and provide a kind of.
Content of the present invention can reach by the following method: a kind of synthetic method of polyester polymers polyol dispersions, it is characterized in that comprising the following steps: the polyester polymers polyol dispersions by use one or more unsaturated vinyl monomers (1) in base polyester polyvalent alcohol (2), a kind of radical polymerization initiator (3) in the presence of carry out Raolical polymerizable, add a small amount of free radical chain transfer agent (4), and add two kinds of compound dispersing agents (5) in-situ polymerization and form.
Therein ethylene base unsaturated monomer (1) is selected from vinylbenzene, vinyl toluene, ethyl styrene, Vinyl toluene, Vinylstyrene, isopropyl benzene ethene, chloro-styrene, divinyl, isoprene, pentadiene, vinylformic acid and ester class thereof, methacrylic acid and ester class thereof, vinyl cyanide and their mixture, optimization styrene.
Base polyester polyvalent alcohol (2) is by the component preparation that does not contain olefin unit.The base polyester polyvalent alcohol is by mixture and di-carboxylic acid or their acid anhydride of dibasic alcohol or dibasic alcohol and small quantity of trihydric or have the polycondensation product of the low-molecular-weight ester of terminal hydroxy group or half ester, dibasic alcohol can be ethylene glycol, Diethylene Glycol, 1,4-butyleneglycol, 2-methyl isophthalic acid, ammediol etc., trivalent alcohol can be glycerine, trihydroxy methyl propane etc., di-carboxylic acid can be hexanodioic acid, Succinic Acid, phthalic anhydride, pentanedioic acid, nonane diacid etc., preferred hexanodioic acid.Described base polyester polyvalent alcohol (2) average hydroxy functionality is 1.9～2.2, number-average molecular weight 1000～3000g/mol, about preferred 1500g/mol, acid number is hexanodioic acid, ethylene glycol, Diethylene Glycol less than the structure below 0.8, and wherein the proportioning of ethylene glycol and Diethylene Glycol is that 1: 1 polyester polyol of quality mol ratio is as the base polyester polyvalent alcohol.
Radical polymerization initiator (3) is known radical initiator.Comprise the azo class with peroxide.For example benzoyl peroxide, acetyl peroxide, di-t-butyl peroxide, Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile) etc.Preferred Diisopropyl azodicarboxylate.
The free radical chain transfer agent (4) that is used as composition of the present invention is Virahol, iodine, butanone, n-dodecyl mercaptan, preferred n-dodecyl mercaptan.
The compound dispersing agent (5) that is used as composition of the present invention by (a) (b) two kinds of compound dispersing agents form, wherein (a) dispersion agent is a kind of macromolecular cpd that contains unsaturated double-bond, the single methanol (c) that is contained unsaturated double-bond by lower molecular weight, polyisocyanate compound (d) and base polyester polyvalent alcohol (e) reaction form, the single methanol that wherein said (c) lower molecular weight contains unsaturated double-bond is hydroxyethyl methylacrylate, Hydroxyethyl acrylate, the methacrylic hydroxypropyl acrylate, propylene ester hydroxypropyl acrylate, a kind of and several mixture of vinylcarbinol, the preferable methyl Hydroxyethyl acrylate.Described (d) polyisocyanate compound is one or more mixture such as TDI, MDI, HDI, IPDI, preferred MDI, in order to reduce (a) dispersant viscosity, can add 50%～100% the base polyester polyvalent alcohol (e) of (a) dispersion agent again, preferred 50%.Wherein said (b) compound dispersing agent is for passing through base polyester polyvalent alcohol (f) elder generation and unsaturated double-bond diprotic acid or its acid anhydrides (g) 220 ℃ of-230 ℃ of reactions, behind the reaction certain hour, generate 220 ℃ of-230 ℃ of polymerizations with dibasic alcohol (h) class of adding again, wherein (g) described unsaturated double-bond diprotic acid or its acid anhydrides are cis-butenedioic anhydride, toxilic acid, fumaric acid, preferred fumaric acid, di-alcohols is ethylene glycol, Diethylene Glycol, triethylene glycol and 1, one or more mixtures of 4-butyleneglycol, preferred Diethylene Glycol.Wherein said (5) compound dispersing agents (a) (b) proportioning are 30: 70～70: 30, preferred 50: 50.
Effect of the present invention is: dispersion agent of the present invention is the dispersion compound of two kinds of structures, polymer polyester there is good dispersion effect, resulting polyester polymer polyatomic alcohol product is shelf-stable when heating, modest viscosity, particle is few, the resulting polyester polymer polyatomic alcohol can play significant performance and the reduction density effect of improving for elastomerics fields such as soles, improves load, the dimensional stability of low density goods greatly.
The present invention is described further below in conjunction with not limiting embodiment.
Embodiment
A kind of synthetic method of polyester polymers polyol dispersions, comprise the following steps: the polyester polymers polyol dispersions by use one or more unsaturated vinyl monomers 1 in base polyester polyvalent alcohol 2, a kind of radical polymerization initiator 3 in the presence of carry out Raolical polymerizable, add a small amount of free radical chain transfer agent 4, and add two kinds of compound dispersing agent 5 in-situ polymerizations and form.
Unsaturated vinyl monomer 1 wherein is selected from vinylbenzene, vinyl toluene, ethyl styrene, Vinyl toluene, Vinylstyrene, isopropyl benzene ethene, chloro-styrene, divinyl, isoprene, pentadiene, vinylformic acid and ester class thereof, methacrylic acid and ester class thereof, vinyl cyanide and their mixture, optimization styrene.
Base polyester polyvalent alcohol 2 is by the component preparation that does not contain olefin unit.The base polyester polyvalent alcohol is by mixture and di-carboxylic acid or their acid anhydride of dibasic alcohol or dibasic alcohol and small quantity of trihydric or have the polycondensation product of the low-molecular-weight ester of terminal hydroxy group or half ester, dibasic alcohol can be ethylene glycol, Diethylene Glycol, 1,4-butyleneglycol, 2-methyl isophthalic acid, ammediol etc., trivalent alcohol can be glycerine, trihydroxy methyl propane etc., di-carboxylic acid can be hexanodioic acid, Succinic Acid, phthalic anhydride, pentanedioic acid, nonane diacid etc., preferred hexanodioic acid.(2) described base polyester polyvalent alcohol average hydroxy functionality is 1.9～2.2, number-average molecular weight 1000～3000g/mol, about preferred 1500g/mol, acid number is hexanodioic acid, ethylene glycol, Diethylene Glycol less than the structure below 0.8, and wherein the proportioning of ethylene glycol and Diethylene Glycol is that 1: 1 polyester polyol of quality mol ratio is as the base polyester polyvalent alcohol.
Radical polymerization initiator 3 is known radical initiator.Comprise the azo class with peroxide.For example benzoyl peroxide, acetyl peroxide, di-t-butyl peroxide, Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile) etc.Preferred Diisopropyl azodicarboxylate.
Free radical chain transfer agent 4 is Virahol, iodine, butanone, n-dodecyl mercaptan, preferred n-dodecyl mercaptan.
The compound dispersing agent 5 that is used as composition of the present invention by (a) (b) two kinds of compound dispersing agents form, wherein (a) dispersion agent is a kind of macromolecular cpd that contains unsaturated double-bond, the single methanol (c), polyisocyanate compound (d) and base polyester polyvalent alcohol (e) reaction that are contained unsaturated double-bond by lower molecular weight form, the single methanol that wherein said (c) lower molecular weight contains unsaturated double-bond is a kind of and several mixture of hydroxyethyl methylacrylate, Hydroxyethyl acrylate, methacrylic hydroxypropyl acrylate, propylene ester hydroxypropyl acrylate, vinylcarbinol, the preferable methyl Hydroxyethyl acrylate.Described (d) polyisocyanate compound is one or more mixture such as TDI, MDI, HDI, IPDI, preferred MDI, in order to reduce (a) dispersant viscosity, can add 50%～100% the base polyester polyvalent alcohol (e) of (a) dispersion agent again, preferred 50%.Wherein said (b) compound dispersing agent is for passing through base polyester polyvalent alcohol (f) elder generation and unsaturated double-bond diprotic acid or its acid anhydrides (g) 220 ℃ of-230 ℃ of reactions, behind the reaction certain hour, generate 220 ℃ of-230 ℃ of polymerizations with dibasic alcohol (h) class of adding again, wherein (g) described unsaturated double-bond diprotic acid or its acid anhydrides are cis-butenedioic anhydride, toxilic acid, fumaric acid, preferred fumaric acid, di-alcohols is ethylene glycol, Diethylene Glycol, triethylene glycol and 1, one or more mixtures of 4-butyleneglycol, preferred Diethylene Glycol.Wherein said (5) compound dispersing agents (a) (b) proportioning are 30: 70～70: 30, preferred 50: 50.
The method of dispersion agent compound dispersing agent of the present invention (a) preparation is as follows:
The preparation of base polyester polyvalent alcohol: hexanodioic acid 4000KG, 1784KG Diethylene Glycol and 1043KG ethylene glycol are added reactor, be evacuated to-0.098Mpa, logical nitrogen returns to normal pressure then.Heat to 140-160 ℃, held temperature 2 hours, have a large amount of water to generate therebetween.Be warmed up to 220 ℃ with 2-3 hour then, in 220-230 ℃ of adding catalyzer metatitanic acid four isopropyl ester 0.19KG, hold temperature after half an hour, slowly vacuumize and remove all the other moisture content, approximately 4-6 hour, middle acid number and the hydroxyl value of testing every half an hour.When acid number less than 0.8mgKOH/g, during hydroxyl value 75 ± 2mgKOH/g, stop to vacuumize, the cooling, the packing.
The preparation of compound dispersing agent (a):
Base polyester polyvalent alcohol and the 13.0KG hydroxyethyl methylacrylate of 300KG example 1 are added in the reactor; under nitrogen protection; add MDI60.0KG; slowly be warmed up to 80 ℃; held temperature 1 hour, vacuum outgas is 30 minutes then, adds the base polyester polyvalent alcohol 186.5KG of example 1 again; stirred the cooling packing 1 hour.
The preparation of compound dispersing agent (b):
Base polyester polyvalent alcohol and the 20KG fumaric acid of 300KG example 1 are joined in the reactor, be warmed up to 220 ℃, add catalyzer metatitanic acid four isopropyl esters that account for base polyester polyvalent alcohol total amount 50ppm, hold warm 220-230 ℃ 4～5 hours, add the 20KG glycol ether then and continued to hold temperature 2 hours, survey acid number, cooling packing after acid number drops to 1.0mgKOH/g.
The polyester polymers polyol dispersions is by using one or more unsaturated vinyl monomers (account for total number 25%) (account for total number 68.6%) in the base polyester polyvalent alcohol, in the presence of initiator (account for total number 0.3%), carry out Raolical polymerizable, add a small amount of free radical chain transfer agent (account for total number 0.1%), and add two kinds of compound dispersing agents (account for total number 6%) in-situ polymerization and form.The method of its preparation is as follows:
Compound dispersing agent (b) 9.0KG, vinylbenzene 10.0KG and Diisopropyl azodicarboxylate 0.3KG in compound dispersing agent (a) 9.0KG, the example 3 in the base polyester polyvalent alcohol of 206KG example 1, the example 2 are added reactor, be warmed up to 110 ℃, hold temperature reaction 1 hour, the reactor speed setting is 110～130rpm.Vinylbenzene 65KG, Diisopropyl azodicarboxylate 0.6KG and n-dodecyl mercaptan 0.3KG are gone into the titration still stir, at the uniform velocity drip with 0.364KG/ minute rate of titration, temperature of reaction kettle remains on 115 ± 3 ℃, after being added dropwise to complete, holds temperature 2 hours.Reduce stirring velocity to 50rpm, decompression arrive-below the 0.098Mpa, was kept 1 hour then, deviate from unreacted monomer.Cool to 80 ℃ of packings.The viscosity that records the polyester polymers polyol dispersions is 5000mPa.s (40 ℃), hydroxyl value 53.0mgKOH/g, and scraper-type grindometer test fineness is 0, placing 24 hours flowabilities at 120 ℃ of baking ovens can.
Resulting polyester polymer polyatomic alcohol dispersion of the present invention can be used separately as the polyvalent alcohol component in polyurethane sole materials, also can be used with other polyester polyol.The adding of polyester polymers polyol dispersions can be adjusted percentage of open area, raising loading strength, the polyurethane sole materials density that reduces of foam.
A component when polyester polymers polyol dispersions of the present invention is applied to polyurethane sole materials is evenly mixed by polyester polyol, polyester polymers polyol dispersions and auxiliary agent.Wherein auxiliary agent has chainextender, whipping agent, catalyzer, surfactant, color etc.; Chainextender is ethylene glycol, 1, the 4-butyleneglycol; Linking agent is for wanting trihydroxy methyl propane (TMP), glycerine or trolamine; Whipping agent is water or water and dichloro one fluoroethane (HCFC-141B); Catalyzer is 33% solution of triethylene diamine and ethylene glycol preparation; Surfactant is the DC-3043 of U.S. air company product.
Synthesizing of A component: 3 parts of 33% solution, DC-30431.2 part and a small amount of color with 2.0 parts in 40 parts of 20 parts of 80 parts of base polyester polyvalent alcohols, polyester polymers polyol dispersions, ethylene glycol, water, TMP0.8 part, triethylene diamine and the ethylene glycol of example 1 are prepared stir at 50 ℃.
Synthesizing of B component: reactor is warmed up to 50 ℃, feeds nitrogen, 51 parts of pure MDI are added reactors, again with 30 parts of polyester polyols (Mn2000), 10 parts of adding reactors of polyether glycol TED-28 (Tianjin three petroleum chemicals).Keeping temperature of reaction kettle is 70 ℃ of reactions 5 hours, cools to 50 ℃ again and adds liquefied mdi (Yantai ten thousand magnificent product MDI-100LL) 10 parts, stirred 1 hour, and discharging, nitrogen-sealed makes the B component.
Example 7: will state A, the B component mixes by a certain percentage by polyurethane foaming machine, and inject the footwear mould, the demoulding makes polyurethane product after 5 minutes, and footwear mould temperature is 55 ℃, and the material temperature of A component and B component is 42 ℃.The polyurethane product rerum natura that makes is: modification, compact density: 0.29g/cm do not appear shrinking in flat appearance
3, shore hardness: 97A.
Claims (6)
1. the synthetic method of a polyester polymers polyol dispersions, it is characterized in that comprising the following steps: the polyester polymers polyol dispersions is carried out Raolical polymerizable by using one or more unsaturated vinyl monomers (1) in base polyester polyvalent alcohol (2) and in the presence of a kind of radical polymerization initiator (3), add free radical chain transfer agent (4) simultaneously, and add two kinds of compound dispersing agents (5) in-situ polymerization and form.
2. the synthetic method of polyester polymers polyol dispersions according to claim 1, it is characterized in that: described one or more unsaturated vinyl monomers (1) are selected from vinylbenzene, vinyl toluene, ethyl styrene, Vinyl toluene, Vinylstyrene, isopropyl benzene ethene, chloro-styrene, divinyl, isoprene, pentadiene, vinylformic acid and ester class thereof, methacrylic acid and ester class thereof, vinyl cyanide and their mixture.
3. the synthetic method of polyester polymers polyol dispersions according to claim 1, it is characterized in that: described base polyester polyvalent alcohol (2) is by the component preparation that does not contain olefin unit, the base polyester polyvalent alcohol is by mixture and di-carboxylic acid or their acid anhydride of dibasic alcohol or dibasic alcohol and trivalent alcohol, or has a polycondensation product of the low-molecular-weight ester of terminal hydroxy group or half ester, dibasic alcohol can be ethylene glycol, Diethylene Glycol, 1, the 4-butyleneglycol, the 2-methyl isophthalic acid, ammediol, trivalent alcohol can be glycerine, trihydroxy methyl propane etc., di-carboxylic acid can be hexanodioic acid, Succinic Acid, phthalic anhydride, pentanedioic acid, nonane diacid, described base polyester polyvalent alcohol (2) average hydroxy functionality is 1.9～2.2, number-average molecular weight 1000～3000g/mol, preferred 1500g/mol, acid number is hexanodioic acid less than the structure below 0.8, ethylene glycol, Diethylene Glycol, wherein the proportioning of ethylene glycol and Diethylene Glycol is that 1: 1 polyester polyol of quality mol ratio is as the base polyester polyvalent alcohol.
4. the synthetic method of polyester polymers polyol dispersions according to claim 1 is characterized in that: described radical polymerization initiator (3) for the azo class with the peroxide radical polymerization initiator.
5. the synthetic method of polyester polymers polyol dispersions according to claim 1 is characterized in that: described free radical chain transfer agent (4) is Virahol, iodine, butanone, n-dodecyl mercaptan, preferred n-dodecyl mercaptan.
6. the synthetic method of polyester polymers polyol dispersions according to claim 1, it is characterized in that: described compound dispersing agent (5) is by (a), (b) two kinds of compound dispersing agents are formed, wherein (a) dispersion agent is a kind of macromolecular cpd that contains unsaturated double-bond, the single methanol (c) that is contained unsaturated double-bond by lower molecular weight, polyisocyanate compound (d) and base polyester polyvalent alcohol (e) reaction form, the single methanol that wherein said (c) lower molecular weight contains unsaturated double-bond is hydroxyethyl methylacrylate, Hydroxyethyl acrylate, the methacrylic hydroxypropyl acrylate, propylene ester hydroxypropyl acrylate, a kind of and several mixture of vinylcarbinol, the preferable methyl Hydroxyethyl acrylate; Described (d) polyisocyanate compound is one or more mixture such as TDI, MDI, HDI, IPDI, and preferred MDI in order to reduce (a) dispersion agent, can add 50%～100% the base polyester polyvalent alcohol (e) of (a) dispersion agent, preferred 50% again; Wherein said (b) compound dispersing agent is for passing through base polyester polyvalent alcohol (f) elder generation and unsaturated double-bond diprotic acid or its acid anhydrides (g) 220 ℃ of-230 ℃ of reactions, behind the reaction certain hour, generate 220 ℃ of-230 ℃ of polymerizations with dibasic alcohol (h) class of adding again, wherein (g) described unsaturated double-bond diprotic acid or its acid anhydrides are cis-butenedioic anhydride, toxilic acid, fumaric acid, preferred fumaric acid, di-alcohols is ethylene glycol, Diethylene Glycol, triethylene glycol and 1, one or more mixtures of 4-butyleneglycol, preferred Diethylene Glycol; Wherein said (5) compound dispersing agents (a) (b) proportioning are 30: 70～70: 30, preferred 50: 50.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2015058685A1 (en) * | 2013-10-21 | 2015-04-30 | 北京金汇利应用化工制品有限公司 | Aqueous acrylic acid modified saturated polyester resin |
| WO2015062960A1 (en) * | 2013-10-28 | 2015-05-07 | Basf Se | Low density polyurethane microcellular elastomer |
| CN108047435A (en) * | 2017-12-06 | 2018-05-18 | 浙江汪洋高分子材料有限公司 | A kind of preparation method of biology base synthetic elastomer |
| CN109749018A (en) * | 2018-12-19 | 2019-05-14 | 上海汇得科技股份有限公司 | A kind of grafted polyester polyalcohol and preparation method thereof |
| CN111100251A (en) * | 2018-10-25 | 2020-05-05 | 山东蓝星东大有限公司 | Synthesis process of polymer polyester polyol |
| WO2021056759A1 (en) * | 2019-09-25 | 2021-04-01 | 淮安巴德聚氨酯科技有限公司 | Dispersing agent for polymer polyol and preparation method for polymer polyol |
| CN113980219A (en) * | 2021-10-22 | 2022-01-28 | 东莞市米儿塑胶原料有限公司 | Preparation method of semitransparent antistatic TPU master batch |
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| CN1995083A (en) * | 2006-12-19 | 2007-07-11 | 中国石油化工股份有限公司 | Polyester base polymer polylol preparation method |
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| CN1683425A (en) * | 2005-02-24 | 2005-10-19 | 烟台万华聚氨酯股份有限公司 | Polymer polyester polyol, its producing process and its use |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2015058685A1 (en) * | 2013-10-21 | 2015-04-30 | 北京金汇利应用化工制品有限公司 | Aqueous acrylic acid modified saturated polyester resin |
| WO2015062960A1 (en) * | 2013-10-28 | 2015-05-07 | Basf Se | Low density polyurethane microcellular elastomer |
| CN105683236A (en) * | 2013-10-28 | 2016-06-15 | 巴斯夫欧洲公司 | Low density polyurethane microcellular elastomer |
| CN105683236B (en) * | 2013-10-28 | 2018-11-23 | 巴斯夫欧洲公司 | Low Density Polyurethane Microcellular Elastomer |
| CN108047435A (en) * | 2017-12-06 | 2018-05-18 | 浙江汪洋高分子材料有限公司 | A kind of preparation method of biology base synthetic elastomer |
| CN111100251A (en) * | 2018-10-25 | 2020-05-05 | 山东蓝星东大有限公司 | Synthesis process of polymer polyester polyol |
| CN109749018A (en) * | 2018-12-19 | 2019-05-14 | 上海汇得科技股份有限公司 | A kind of grafted polyester polyalcohol and preparation method thereof |
| WO2021056759A1 (en) * | 2019-09-25 | 2021-04-01 | 淮安巴德聚氨酯科技有限公司 | Dispersing agent for polymer polyol and preparation method for polymer polyol |
| CN113980219A (en) * | 2021-10-22 | 2022-01-28 | 东莞市米儿塑胶原料有限公司 | Preparation method of semitransparent antistatic TPU master batch |
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Application publication date: 20130904 |