CN1796427A - Method for preparing polyalcohol of polymer - Google Patents
Method for preparing polyalcohol of polymer Download PDFInfo
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- CN1796427A CN1796427A CN 200410094080 CN200410094080A CN1796427A CN 1796427 A CN1796427 A CN 1796427A CN 200410094080 CN200410094080 CN 200410094080 CN 200410094080 A CN200410094080 A CN 200410094080A CN 1796427 A CN1796427 A CN 1796427A
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Abstract
This invention publishes a preparation method for polymer polyols. This method, as a semi-continuous operation, employs a polyether polyol matrix as continuous phase, and one or several types of ethylene monomers are in situ polymerized with the aid of macromolecule monomers, chain-transfer agents and radical initiators to produce stably dispersed polymer polyols. It is characteristics that a low solid-content polymer polyol as matrix is synthesized at first and remanent raw materials are then mixed and dropped into the matrix for semi-continuous synthesis. This method has the advantages of low viscosity, high monomer conversion efficiency and good dispersion stability. Besides, the facility utility is greatly promoted and therefore it is practical for manufacturing polyurethane flexible foams.
Description
Technical field
The present invention relates to a kind of preparation method of polymer polyatomic alcohol, more particularly, the present invention relates to the method that one or more vinyl monomers in-situ polymerization in basic polyether glycol prepares polymer polyatomic alcohol.
Background technology
Polymer polyatomic alcohol is large Industrial products, can give polyurethane product good load-carrying properties, and improves the foamy perforate.It is mainly used in the production of the block soft bubble of urethane, the soft bubble of high resilience, the soft bubble of molding.Polymer polyatomic alcohol is that one or more vinyl monomers are that the external phase in-situ polymerization forms with basic polyether glycol.Polymer polyatomic alcohol with commercial Practical significance is at first developed by American PaulStamberger, and begins to have applied for multinomial patent in nineteen sixties.Occurred multiple synthetic method subsequently again, for example vinyl polymer is synthetic separately, dilutes in polyvalent alcohol again, has prepared so-called " redispersibility graft polyol " with this kind method.Yet, produce polymer polyatomic alcohol keep so far usual method be with one or more vinyl monomers the continuous foundation polyether glycol mutually in in-situ polymerization.Among the present invention, term " polymer " polyvalent alcohol " refer to the polymer polyatomic alcohol that vinyl monomer is produced by home position polymerization reaction.
Since the polymer polyatomic alcohol product came out, its production and use had run into many problems.The vinyl monomer of synthetic polymer polyatomic alcohol employing the earliest is a vinyl cyanide, the product solid content is low, below 30%, viscosity is big, surpasses 10000mPa.s/25 ℃ sometimes, is unfavorable for the technological operation in course of conveying, stop up the filter screen and the pump housing, can not satisfy the use of modernized large-scale precision equipment, color jaundice simultaneously, core is easily burnt in the foam article jaundice.This causes owing to annulation generation chromophore has taken place in single acrylonitrile monemer polymerization.
For addressing the above problem, people have carried out number of research projects, many new technologies occurred.The vinyl monomer copolymerization solves the jaundice of polymer polyatomic alcohol color and foam burns core problem, first-selected vinylbenzene and acrylonitrile monemer copolymerization with two or more are proposed in the U.S. Pat 4208314.Synthetic polymer polyatomic alcohol product was a white when styrene monomer was greater than acrylonitrile monemer in the monomer ratio, and the burning core problem of foam article is improved.The shortcoming of this kind method is the increase along with styrene content, and product viscosity increases, and transformation efficiency reduces, the dispersion stabilization variation of system.
All disclose among U.S. Pat 4462715, US5093412, the US4342840 and adopted the method for a kind of macromonomer, and used chain-transfer agent as stablizer.Macromonomer is a compound of introducing derivable carbon-carbon double bond in a kind of polyether glycol molecule in this method, can obtain by double bond containing compound such as maleic anhydride, glycidyl allyl ether, acrylic or methacrylic acid isocyano alkyl ester and polyether glycol reaction.Macromonomer is added in the reaction feed liquid when the preparation polymer polyatomic alcohol, generates a kind of stablizer of surfactant-like in synthetic reaction process, stabilization of polymer polyvalent alcohol system.This method synthetic polymer polyatomic alcohol solid content reaches 40%～50%, has reduced the viscosity of polymer polyatomic alcohol effectively, has improved the stability of product well.
The production technique of synthesis of polymer polyalcohol generally has intermittently, semicontinuous and continuous processing.U.S. Pat P4454255, USP5496894 disclose the method that semicontinuous and continuous processing prepares polymer polyatomic alcohol.In the half-continuous process, by weight percentage, be that 90%～10% of basic polyether glycol total amount is added in the reactor in advance as bed material, and then dropwise add the mixed liquor of remaining basic polyether glycol and macromonomer, radical initiator, chain-transfer agent, vinyl monomer equably, add the back and continue the reaction absorption, absorption finishes to remove unreacted monomer can obtain product.Continuous processing uses two or more reactors, adding in advance in first reactor earlier, the polymer polyatomic alcohol of the suitable solid content of synthetic is a bed material, drop into the reaction mass of preparation in proportion continuously, comprise basic polyether glycol, vinyl monomer, macromonomer, radical initiator, chain-transfer agent etc.Through first reactor overflow to the second reactor, reaction finishes to remove unreacted monomer.The polymer polyatomic alcohol monomer conversion height that half-continuous process is produced, but viscosity is bigger, and especially the prescription medium viscosity at high-phenylethylene, high solids content increases obviously, influences the transportation and the use of product.Continuous processing is fit to the production of the polymer polyatomic alcohol of extensive single variety, constant product quality, and the product viscosity that obtains than half-continuous process when identical solid content is low, but monomer conversion is low relatively, be lower than 98%, therefore monomer removes and to reclaim load bigger, has increased the production technique cost.
Be necessary further to solve the big problem of product viscosity in the quality problems, particularly semi continuous operation of polymer polyatomic alcohol from prior art as can be seen, make polyether polyol have the advantage of half-continuous process and continuous processing concurrently.
Summary of the invention
The present invention has overcome above-mentioned the deficiencies in the prior art, and a kind of preparation method of polymer polyatomic alcohol half-continuous process is provided.The purpose of this invention is to provide the preparation method of the good polymer polyatomic alcohol of a kind of synthesis of high solid content, low viscosity, high monomer transformation efficiency, filterability and dispersion stabilization, and on plant factor, also increase.
Technical scheme of the present invention is: adopt semi continuous operation, at first syntheticly a certain amount ofly be lower than the polymer polyatomic alcohol of target product solid content as bed material, to remain and drip continuously after all raw materials are mixed, be external phase with a kind of basic polyether glycol in the reaction process, under macromonomer, chain-transfer agent, action of free radical initiator, one or more vinyl monomers of in-situ polymerization, form the polymer polyatomic alcohol system of stable dispersion, by weight percentage, the solid content of the polymer polyatomic alcohol of preparation is 45%～50%.
The selection of basis polyether glycol is by the decision of the end-use of polymer polyatomic alcohol, for example polymer polyatomic alcohol is used for the production of the soft bubble of massive polyurethane, just select general flexible PU foam polyether glycol for use, be generally the polyether glycol of the three-functionality-degree of molecular weight about 3000; Be used for the production of high rebound foam, just select high rebound foam polyether glycol for use, be generally the polyether glycol of the highly active three-functionality-degree of molecular weight about 5000.The polyether glycol of the three-functionality-degree of preferred molecular weight about 3000 is as basic polyether glycol among the present invention.
Macromonomer among the present invention is the preparation method who adopts macromonomer of the prior art.Can adopt any method preparation of U.S. Pat P4462715, USP4390645, USP5093412, USP4342840.In the polyether glycol that a kind of polyfunctionality compound is an initiator, introduce derivable carbon-carbon double bond.Polyether glycol can be glycerin polyether, TriMethylolPropane(TMP) polyethers, sorbyl alcohol polyethers, castor-oil plant wet goods compound, introducing derivable carbon-carbon double bond can be by a kind of polyether ester that generates with maleic anhydride reaction, or obtains with double bond containing compounds reactions such as glycidyl allyl ether, acrylic or methacrylic acid isocyano alkyl esters.By weight percentage, the macromonomer addition is 1%～10% of a product population, preferred 2%～4%.
The chain-transfer agent of selecting for use in the polyreaction can be Virahol, benzene, toluene, mercaptan, halogenated hydrocarbons or water and their mixture, and the mixture of preferred Virahol and n-dodecyl mercaptan is as compound chain-transfer agent.The ratio of Virahol and n-dodecyl mercaptan is 6: 1～20: 1 in the compound chain-transfer agent, preferred 9: 1～15: 1 (weight ratio), by weight percentage, consumption is 1%～10% of a product population, preferred 3%～5%.
The radical initiator that is used for the preparation of polymer polyatomic alcohol is generally superoxide, azo-compound etc.Preferred Diisopropyl azodicarboxylate, by weight percentage, consumption be product population O.3%～O.5%.
Be suitable for vinyl monomer of the present invention and comprise that all generally are accepted the vinyl monomer that is suitable for preparing polymer polyatomic alcohol, comprise various acrylic compound, as vinylformic acid, methacrylic acid, methacrylic ester, methyl methacrylate etc.; Vinyl compound is as vinylchlorid and vinylidene chloride etc.; Vinyl cyanide; The mixture of vinylbenzene, brominated styrene etc. and these compounds.Optimization styrene and vinyl cyanide, monomer usage ratio are 10: 90～90: 10, preferred 60: 40～90: 10 (weight ratio).
Bed material among the present invention is a kind of polymer polyatomic alcohol lower than target product solid content.This bed material can adopt prior art for preparing, and promptly earlier with semi continuous operation synthetic polymer polyatomic alcohol that is lower than the target product solid content in reactor, it enters demonomerization unit product before as bed material.By weight percentage, the addition of bed material is 25%～50% of a product population, and filling a prescription is:
Basis polyether glycol: 60～69%
Macromonomer: 2～4%
Chain-transfer agent: 3～5%
Radical initiator: 0.3～0.5%
Vinyl monomer: 25～31%.
Among the present invention surplus stock is mixed the back as liftout, each component of liftout must mix before entering reactor, adopted static mixer or other blending means, preferentially selected the method for static mixer for use.After bed material synthesizes well in reactor, add the reaction mass that mixes, entire reaction course is controlled at 110 ℃～120 ℃.Described liftout prescription is:
Basis polyether glycol: 26～38%
Macromonomer: 2～4%
Chain-transfer agent: 3～5%
Radical initiator: 0.3～0.5%
Vinyl monomer: 58～70%.
In the preparation of polymer polyatomic alcohol, by weight percentage, the solids content of vinyl polymer is generally 35%～60%, and is preferred 40%～55%, and most preferably 45%～50%.The viscosity of product rises with the increase of solid content usually, and preferred viscosities is lower than 10000mPa.s/25 ℃, and most preferred viscosity is lower than 7500mPa.s/25 ℃.
Usually along with the increase of the solid content of polymer polyatomic alcohol, the reduction of viscosity, the stability of polymer polyatomic alcohol can descend.Have been found that synthetic polymer polyatomic alcohol product of the present invention compares with common mode synthetic polymer polyatomic alcohol product, under the situation of 45%～55% solid content, has lower viscosity, excellent dispersion stability more, monomer conversion obviously increases, and the technological operation in more convenient production process and the polyurethane foam preparation has improved the economy of producing, reduced production cost, on plant factor, also be greatly improved.
The present invention has been carried out general description, the present invention has been described in further detail below in conjunction with specific embodiment.
The general operation of preparation polymer polyatomic alcohol
Method 1 250ml four-hole bottle is equipped with agitator, heating unit, temperature control unit and feeder as reactor.At first in reactor, synthesize the polymer polyatomic alcohol lower than target product solid content, promptly in reactor, add part basis polyether glycol according to the formula calculation that is lower than the target product solid content, part chain-transfer agent and macromonomer be as bed material, with residual polyether polyol, whole vinyl monomers, remaining chain-transfer agent, radical initiator as liftout.Bed material is heated to 110 ℃ and adds liftout continuously, and temperature of reaction is controlled at 115 ℃～120 ℃.Feeding intake finishes, and adds liftout again and is the mixed solution according to the whole basic polyether glycol that is higher than target product solid content formula calculation, macromonomer, vinyl monomer, compound chain-transfer agent, radical initiator.Temperature of reaction is controlled at 115 ℃～120 ℃.Feeding intake finishes, absorption reaction 1 hour.Vacuumize and remove volatile matter and unreacted monomer, cooling, discharging.
The reactor that method 2 (control methods) employing method 1 is identical.In reactor, add the polyether polyol identical as bed material with the target product solid content, be heated to 110 ℃ and add continuously liftouts, liftout is the mixed solution by the whole basic polyether glycol of formula calculation, macromonomer, vinyl monomer, compound chain-transfer agent, radical initiator.Temperature of reaction is controlled at 115 ℃～120 ℃.Feeding intake finishes, absorption reaction 1 hour.Vacuumize and remove volatile matter and unreacted monomer, cooling, discharging.
The reactor that method 3 (control methods) employing method 1 is identical.In reactor, add part basis polyether glycol by formula calculation, part chain-transfer agent, macromonomer as bed material, with residual polyether polyol, whole vinyl monomers, remaining chain-transfer agent, radical initiator as liftout.Bed material is heated to 110 ℃ and adds liftout continuously, and temperature of reaction is controlled at 115 ℃～120 ℃.Feeding intake finishes, absorption reaction 1 hour.Vacuumize and remove volatile matter and unreacted monomer, cooling, discharging.
Method 4 (control methods) adopts two identical of 250ml four-hole bottles to connect as reactor, top overflow in first reactor is as the charging of second reactor, the first reactor bed material is that solid content is lower than the identical polymer polyatomic alcohol of target product solid content, and general solid content is lower than 30%.Liftout is the mixed solution in the basic polyether glycol of whole ratios of the calculating that feeds intake, macromonomer, vinyl monomer, compound chain-transfer agent, radical initiator.The first reactor bed material is heated to 110 ℃ and adds liftout continuously, and temperature of reaction is controlled at 115 ℃～120 ℃.The second reactor overflow product removes volatile matter and unreacted monomer through vacuumizing, cooling, discharging.
Embodiment 1 employing method 1, the polymer polyatomic alcohol of earlier synthetic 30% solid content, be that bed material adds basic polyethers 3031K 30 grams, Virahol 2 grams, macromonomer 1.5 grams, liftout is that O.18 basic polyethers 3031K3.18 gram, Diisopropyl azodicarboxylate restrain, n-dodecyl mercaptan 0.15 restrains, vinylbenzene 9.75 restrains, vinyl cyanide 5.25 grams, and 30% polymer polyatomic alcohol that obtains is as bed material.With basic polyethers 3031K 59.25 grams, Virahol 5.2 grams, macromonomer 3.9 grams, the mixing solutions of Diisopropyl azodicarboxylate 0.45 gram, n-dodecyl mercaptan 0.39 gram, vinylbenzene 42.9 grams, vinyl cyanide 23.1 grams joins in the bed material that has prepared as liftout, obtains polymer polyatomic alcohol A.
Embodiment 2 employing methods 2, bed material adds the polymer polyatomic alcohol of 50 grams, 45% solid content, this polymer polyatomic alcohol is without removing volatile matter and unreacted monomer, liftout is basic polyethers 3031K66.31 gram, macromonomer 3.9 grams, Virahol 4.2 grams, Diisopropyl azodicarboxylate 0.39 gram, n-dodecyl mercaptan 0.39 gram, vinylbenzene 38.03 grams, vinyl cyanide 20.47 grams, obtains polymer polyatomic alcohol B.
Embodiment 3 employing methods 3, in the four-hole bottle of 250ml, add basic polyethers 3031K 82.25 grams, Virahol 5.4 grams, macromonomer 5.4 grams, drop into the mixed liquor of Diisopropyl azodicarboxylate 0.63 gram, n-dodecyl mercaptan 0.72 gram, vinylbenzene 52.65 grams, vinyl cyanide 28.35 grams, basic polyethers 30.31K 10 grams continuously, obtain polymer polyatomic alcohol C.
Embodiment 4 employing methods 4, by weight percentage, the polymer polyatomic alcohol that in first reactor, adds 50 grams, 30% solid content, drip continuously compound, wherein basic polyethers 3031K 47.4%, Diisopropyl azodicarboxylate O.4%, macromonomer 2.8%, n-dodecyl mercaptan O.4%, Virahol 2.8%, vinylbenzene 30%, vinyl cyanide 16.2%.Initial 500 grams of the second reactor overflow product are collected in addition and are used, and the product of collecting is as polymer polyatomic alcohol D later on.
The quality index of polymer polyatomic alcohol A, B, C, D is listed in table 1.
Table 1, polymer polyatomic alcohol analytical results (by weight percentage)
| The polymer polyatomic alcohol kind | A | B | C | D |
| Theoretical solid content, % | 45 | 45 | 45 | 45 |
| Actual solid content, % | 44.8 | 44.6 | 44.8 | 44 |
| Monomer conversion, % | 99.6 | 99.7 | 99.6 | 97.8 |
| Viscosity, mPa.s/25 ℃ | 5500 | 5600 | 6500 | 5300 |
| Filterableness, 150 mesh filter screen percent of pass, % | 100 | 100 | 100 | 100 |
Embodiment 5 employing methods 1, the polymer polyatomic alcohol of earlier synthetic 30% solid content: bed material adds basic polyethers 3031K 30 grams, Virahol 2 grams, macromonomer 1.5 grams, liftout is that O.18 basic polyethers 3031K 3.18 grams, Diisopropyl azodicarboxylate restrain, n-dodecyl mercaptan 0.15 restrains, vinylbenzene 9.75 restrains, vinyl cyanide 5.25 grams, and 30% polymer polyatomic alcohol that obtains is as bed material.With basic polyethers 3031K 50.25 grams, Virahol 5.2 grams, macromonomer 3.9 grams, the mixing solutions of Diisopropyl azodicarboxylate 0.45 gram, n-dodecyl mercaptan 0.39 gram, vinylbenzene 48.75 grams, vinyl cyanide 26.25 grams joins in the bed material that has prepared as liftout, obtains polymer polyatomic alcohol E.
Embodiment 6 employing methods 2, bed material adds the polymer polyatomic alcohol of 50 grams, 50% solid content, this polymer polyatomic alcohol is without removing volatile matter and unreacted monomer, liftout is basic polyethers 3031K60.32 gram, macromonomer 3.9 grams, Virahol 4.2 grams, Diisopropyl azodicarboxylate 0.39 gram, n-dodecyl mercaptan 0.39 gram, vinylbenzene 42.25 grams, vinyl cyanide 22.75 grams, obtains polymer polyatomic alcohol F.
Embodiment 7 employing methods 3, in the 250ml reactor, add basic polyethers 3031K 73.43 grams, Virahol 7.2 grams, macromonomer 5.4 grams, drip the mixed liquor of Diisopropyl azodicarboxylate 0.63 gram, n-dodecyl mercaptan 0.54 gram, vinylbenzene 58.5 grams, vinyl cyanide 31.5 grams, basic polyethers 3031K 10 grams continuously, obtain polymer polyatomic alcohol G.
Embodiment 8 employing methods 4, by weight percentage, the polymer polyatomic alcohol that in first reactor, adds 50 grams, 30% solid content, drip continuously compound, wherein basic polyethers 3031K 42.35%, Diisopropyl azodicarboxylate O.35%, macromonomer 3%, n-dodecyl mercaptan 0.3%, Virahol 4%, vinylbenzene 31.5%, vinyl cyanide 18.5%.Initial 500 grams of the second reactor overflow product are collected in addition and are used, and the product of collecting is as polymer polyatomic alcohol H later on.
The quality index of polymer polyatomic alcohol D, E, F, H is listed in table 2.
Table 2, polymer polyatomic alcohol analytical results (by weight percentage)
| The polymer polyatomic alcohol kind | D | E | F | H |
| Theoretical solid content, % | 50 | 50 | 50 | 50 |
| Actual solid content, % | 49.9 | 49.8 | 49.9 | 48.5 |
| Monomer conversion, % | 99.8 | 99.7 | 99.8 | 97 |
| Viscosity, mPa.s/25 ℃ | 7600 | 7700 | 10000 | 6800 |
| Filterableness, 150 mesh filter screen percent of pass, % | 100 | 100 | 100 | 100 |
Claims (8)
1, a kind of preparation method of polymer polyatomic alcohol, present method is a semi continuous operation, with a kind of basic polyether glycol is external phase, at macromonomer, chain-transfer agent, under the action of free radical initiator, one or more vinyl monomers of in-situ polymerization, form the polymer polyatomic alcohol of stable dispersion, it is characterized in that, by above-mentioned preparation polymer polyatomic alcohol method, earlier synthetic than the low polymer polyatomic alcohol of target product solid content as bed material, by weight percentage, described bed material addition is 25～50% of a product population, and the back that again surplus stock is mixed dropwise adds in the bed material as liftout.
2, method according to claim 1, wherein said bed material for prescription is:
Basis polyether glycol: 60～69%
Macromonomer: 2～4%
Chain-transfer agent: 3～5%
Radical initiator: 0.3～0.5%
Vinyl monomer: 25～31%.
3, method according to claim 1, wherein said liftout prescription is:
Basis polyether glycol: 26～38%
Macromonomer: 2～4%
Chain-transfer agent: 3～5%
Radical initiator: 0.3～0.5%
Vinyl monomer: 58～70%.
4, according to each described method of claim 1-3, wherein basic polyether glycol is the soft bubble polyether glycol of three-functionality-degree.
5, method according to claim 4, wherein macromonomer is a kind of polyether glycol of polyfunctionality and the polyether ester that the maleic anhydride reaction forms, by weight percentage, addition is 2%～4% of a product population.
6, method according to claim 5, wherein chain-transfer agent is compound chain-transfer agent, is the mixture of Virahol and n-dodecyl mercaptan, and its weight ratio is 9: 1～15: 1, by weight percentage, the consumption of compound chain-transfer agent is 3～5% of a product population.
7, method according to claim 6, wherein radical initiator is a Diisopropyl azodicarboxylate, by weight percentage, consumption is 0.3%～0.5% of a product population.
8, method according to claim 7, therein ethylene base monomer is vinylbenzene and vinyl cyanide, monomer weight ratio is 60: 40～90: 10.
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| CN102010489A (en) * | 2010-10-22 | 2011-04-13 | 句容宁武高新技术发展有限公司 | Method for preparing polyalcohol polymer by using glyceryl polyether polyalcohol |
| CN102241799A (en) * | 2010-05-11 | 2011-11-16 | 天津大沽化工股份有限公司 | Synthesis method of polymer polyol |
| CN103242492A (en) * | 2013-04-22 | 2013-08-14 | 中国石油化工股份有限公司 | Preparation method of polymer polyhydric alcohol |
| CN106188425A (en) * | 2016-07-30 | 2016-12-07 | 山东隆华新材料股份有限公司 | Without removing POP and the production method thereof that chain-transferring agent method produces |
| CN108690172A (en) * | 2018-06-01 | 2018-10-23 | 浙江枧洋高分子科技有限公司 | A kind of acrylic polymer polyether polyol and preparation method thereof |
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| CN114085370A (en) * | 2021-12-06 | 2022-02-25 | 中国科学院长春应用化学研究所 | Poly (carbonate-ether) polyol dispersant, high-stability polymer polyol and preparation method thereof |
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| US4454255A (en) * | 1982-04-01 | 1984-06-12 | Basf Wyandotte Corporation | Process for the preparation of white graft polymer dispersions and flame-retardant polyurethane foams |
| US5496896A (en) * | 1987-03-28 | 1996-03-05 | Basf Lacke & Farben Aktiengesellschaft | Curable composition based on a Michael addition product, processes for its preparation and its use |
| US5223570A (en) * | 1990-02-07 | 1993-06-29 | Basf Corporation | Method for the preparation of graft polymer dispersions having broad particle size distribution without wildly fluctuating viscosities |
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| CN103242492A (en) * | 2013-04-22 | 2013-08-14 | 中国石油化工股份有限公司 | Preparation method of polymer polyhydric alcohol |
| CN106188425A (en) * | 2016-07-30 | 2016-12-07 | 山东隆华新材料股份有限公司 | Without removing POP and the production method thereof that chain-transferring agent method produces |
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| CN109762117A (en) * | 2017-11-09 | 2019-05-17 | 山东蓝星东大有限公司 | The synthetic method of polyether polyol |
| CN109762117B (en) * | 2017-11-09 | 2021-05-14 | 山东蓝星东大有限公司 | Method for synthesizing polymer polyether glycol |
| CN108690172A (en) * | 2018-06-01 | 2018-10-23 | 浙江枧洋高分子科技有限公司 | A kind of acrylic polymer polyether polyol and preparation method thereof |
| CN108690172B (en) * | 2018-06-01 | 2021-06-04 | 浙江枧洋高分子科技有限公司 | Acrylic resin polymer polyether polyol and preparation method thereof |
| WO2021196226A1 (en) * | 2020-04-03 | 2021-10-07 | 万华化学集团股份有限公司 | Reaction system for preparing polymer polyol and method for preparing polymer polyol |
| CN114085370A (en) * | 2021-12-06 | 2022-02-25 | 中国科学院长春应用化学研究所 | Poly (carbonate-ether) polyol dispersant, high-stability polymer polyol and preparation method thereof |
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