CN100491442C - Preparing method for polymer polybasic alcohol - Google Patents
Preparing method for polymer polybasic alcohol Download PDFInfo
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- CN100491442C CN100491442C CNB031305903A CN03130590A CN100491442C CN 100491442 C CN100491442 C CN 100491442C CN B031305903 A CNB031305903 A CN B031305903A CN 03130590 A CN03130590 A CN 03130590A CN 100491442 C CN100491442 C CN 100491442C
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Abstract
A polymer polyol is prepared in a half continuous operation with a basic polyether polyol as continuous phase, in action of high molecular polymer monomers, chain transfer reagent, radical triggers, by polymerizing in situ to form stable dispersed polymer polyol, which has features as below: certain solid contained polymer polyol as substrate material, mixing raw materials, then adding continuously. The polymer polyol in this process has high solid content while low viscosity, well dispersed stability, high monomers convert rate, and is more adapted for preparing soft polyurethane foams, compared with other preparing methods.
Description
Technical field
The present invention relates to a kind of preparation method of polyether glycol, more particularly, the present invention relates to the method that one or more vinyl monomers in-situ polymerization in 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 form for the external phase in-situ polymerization with the polyether glycol.
Polymer polyatomic alcohol with commercial Practical significance is at first developed by American Paul Stamberger, and begins to have applied for multinomial patent in nineteen sixties.Occurred multiple synthetic method subsequently again, for example vinyl polymer is synthetic separately, reduces granularity again in polyvalent alcohol, 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 polyvalent alcohol continuously mutually in in-situ polymerization.In 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 lower, below 30wt%, 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 easily takes 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 among the U.S. Pat P4208314.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 P4462715, USP4390645, USP5093412, the USP4342840 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 polyol reaction system.This method synthetic polymer polyatomic alcohol solid content reaches 40wt%～43wt%, 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, continuous processing.U.S. Pat P4454255, USP5496894 disclose the method that semicontinuous and continuous processing prepares polymer polyatomic alcohol.In the half-continuous process, it is bed material that the basic polyethers of the 90wt%～10wt% of basic polyethers total amount is added in the still in advance, adds remaining polyethers and macromonomer, radical initiator, chain-transfer agent, monomeric mixed liquor then continuously.Continuous processing uses two or more reactors, adding in advance in first reactor earlier, the synthetic solid content is lower than the polymer polyatomic alcohol of target product or directly is filled to bed material with reaction mass, 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 98wt%, therefore monomer removes and to reclaim load bigger, has increased the production technique cost.
Be necessary as can be seen further to solve in the quality problems, particularly semi continuous operation of polymer polyatomic alcohol that the problem that the big transformation efficiency of product viscosity is low makes polymer polyatomic alcohol have the advantage of half-continuous process and continuous processing concurrently from prior art.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of polymer polyatomic alcohol, it is the processing method of the preparation polymer polyatomic alcohol of the good half-continuous process of a kind of synthesis of high solid content, low viscosity, high monomer transformation efficiency, filterability and dispersion stabilization.
Technical scheme of the present invention is:
A kind of preparation method of polymer polyatomic alcohol, present method adopts semi continuous operation, with a kind of basic polyether glycol is external phase, under macromonomer, chain-transfer agent, action of free radical initiator, one or more vinyl monomers of in-situ polymerization form the polymer polyatomic alcohol of stable dispersion, are bed material with the polymer polyatomic alcohol of certain solid content, raw material is mixed back continuous the adding, and wherein basic polyether glycol is the soft bubble polyether glycol of three-functionality-degree.
Bed material is a kind of and the polymer polyatomic alcohol same solid content of target product.
Bed material is selected from and enters demonomerization unit product before, or is selected from the second reactor overflow product of continuous processing.
The bed material addition is 10%～30% of a raw material total amount.
Vinyl monomer is vinylbenzene and vinyl cyanide, and the monomer usage ratio is 60:40～90:10.
Macromonomer is a kind of polyether glycol of polyfunctionality and the polyether ester that the maleic anhydride reaction forms, and addition is 2%～4% of a raw material total amount.
The consumption of chain-transfer agent is 3%～5% of a raw material total amount.
Chain-transfer agent is compound chain-transfer agent, is the mixture of Virahol and n-dodecyl mercaptan.
The usage ratio of Virahol and n-dodecyl mercaptan is 9:1～15:1 in the compound chain-transfer agent.
Radical initiator is a Diisopropyl azodicarboxylate, and consumption is 0.3%～0.5wt% of raw material total amount.
The solid content of polymer polyatomic alcohol of preparation is 45wt%～55wt%, viscosity 4000mPa.s/25 ℃～7500mPa.s/25 ℃.
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.
Bed material among the present invention is a kind of and the polymer polyatomic alcohol same solid content of target product.This bed material can be from entering demonomerization unit product before in this technology, also can be from the second reactor overflow product of continuous processing, also can adopt the final polymer polyvalent alcohol as bed material, also can adopt prior art for preparing, preferably enter in this technology before the demonomerization unit product or from the second reactor overflow product of continuous processing.The addition of bed material is the 5wt%～95wt% of raw material total amount, preferred 10wt%～30wt%.
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.
Macromonomer among the present invention is the preparation method who adopts macromonomer of the prior art.Can adopt any method of U.S. Pat P4462715, USP4390645, USP5093412, USP4342840 to be prepared.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.The macromonomer addition is the 1wt%～10wt% of raw material total amount, preferred 2wt%～4wt%.
The chain-transfer agent of selecting for use in the polyreaction can be Virahol, benzene, toluene, mercaptan, halogenated hydrocarbons or water and their mixture, the mixture of preferred Virahol and n-dodecyl mercaptan, 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, consumption is the 1wt%～10wt% of raw material total amount, preferred 3wt%～5wt%.
The radical initiator that is used for the preparation of polymer polyatomic alcohol is generally superoxide, azo-compound etc.Preferred Diisopropyl azodicarboxylate.
Each component of liftout must mix before entering reactor among the present invention, adopted static mixer or other blending means, preferentially selected the method that adopts static mixer for use.Add in advance in reactor after the bed material, to be heated to 100 ℃～110 ℃ adding reaction masses, entire reaction course is controlled at 110 ℃～120 ℃.
In the preparation of polymer polyatomic alcohol, the solids content of vinyl polymer is generally 35wt%～60wt%, preferred 40wt%～55wt%, most preferably 45wt%～55wt%.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 4000～7500mPa.s/25 ℃.
Characteristics of the present invention are: 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 45wt%～55wt% solid content, has lower viscosity, excellent dispersion stability more, monomer conversion obviously increases, technological operation in more convenient production process and the polyurethane foam preparation has improved the economy of producing, and has reduced production cost.
Specific embodiment
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: stainless steel cauldron is equipped with agitator, heating unit, refrigerating unit, temperature control unit and feeder.Make system's oxygen level be lower than 100ppm with nitrogen replacement, preferably below the 50ppm, all material oxygen levels are lower than 100ppm, preferably below the 50ppm.In reactor, add the polymer polyatomic alcohol 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 110 ℃～120 ℃.Feeding intake finishes, absorption reaction 1 hour.Vacuumize and remove volatile matter and unreacted monomer, cooling, discharging.
Method 2 (control methods): adopt the identical reactor of step 1.In reactor, add whole or most basic polyether glycol by formula calculation, chain-transfer agent, macromonomer as bed material, with residual polyether polyol, whole vinyl monomer, 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 3 (control methods): adopt the identical reactor two stills series connection of step 1, the top overflow of first reactor is as the charging of second reactor, the first reactor bed material is the polymer polyatomic alcohol that solid content is lower than the target product solid content, and general solid content is lower than 30wt%.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 takes off cooling through rotary film evaporator, discharging.
Embodiment 1
Employing method 1, bed material adds the polymer polyatomic alcohol of 120 gram 45wt% solid contents, this polymer polyatomic alcohol is without removing volatile matter and unreacted monomer, and liftout is basic polyethers 3031K348 gram, macromonomer 20.4 grams, Virahol 27.2 grams, Diisopropyl azodicarboxylate 2.8 grams, n-dodecyl mercaptan 2.8 grams, vinylbenzene 199 grams, vinyl cyanide 107 grams.Obtain polymer polyatomic alcohol A.
Embodiment 2
Employing method 2, in the reactor of 1000ml, add basic polyethers 3031K368 gram, n-dodecyl mercaptan 3.2 grams, Virahol 40 grams, macromonomer 24 grams, drop into the mixed liquor of Diisopropyl azodicarboxylate 3.6 grams, vinylbenzene 234 grams, vinyl cyanide 126 grams, basic polyethers 3031K41 gram continuously.Obtain polymer polyatomic alcohol B.
Embodiment 3
Employing method 3, the polymer polyatomic alcohol that in first reactor, adds 200 gram 30wt% solid contents, drip compound, wherein basic polyethers 3031K47.4wt%, Diisopropyl azodicarboxylate 0.4wt%, macromonomer 2.8wt%, n-dodecyl mercaptan 0.4wt%, Virahol 2.8wt%, vinylbenzene 30.0wt%, vinyl cyanide 16.2wt% continuously.Initial 1000 grams of the second reactor overflow product are collected in addition and are used, and the product of collecting is as polymer polyatomic alcohol C later on.
The quality index of polymer polyatomic alcohol A, B, C is listed in table 1.
Table 1. polymer polyatomic alcohol analytical results
| The polymer polyatomic alcohol kind | A | B | C |
| Theoretical solid content, wt% | 45 | 45 | 45 |
| Actual solid content, wt% | 44.8 | 44.8 | 44 |
| Monomer conversion, wt% | 99.6 | 99.6 | 97.8 |
| Viscosity, mPa.s/25 ℃ | 5500 | 6500 | 5300 |
| Filterability, 150 mesh filter screen percent of pass, wt% | 100 | 100 | 100 |
Embodiment 4
Employing method 1, this polymer polyatomic alcohol of polymer polyatomic alcohol that adds 120 gram 50wt% solid contents in the 1000ml reactor is without removing volatile matter and unreacted monomer, and basic polyethers 3031K315 gram, Diisopropyl azodicarboxylate 2.4 grams, n-dodecyl mercaptan 2.1 grams, Virahol 27.2 grams, macromonomer 20.4 grams, vinylbenzene 221 grams, vinyl cyanide 119 grams add feed liquid as mixing.Obtain polymer polyatomic alcohol D.
Embodiment 5
Employing method 2, in the 1000ml reactor, add basic polyethers 3031K333 gram, macromonomer 24 grams, n-dodecyl mercaptan 2.4 grams, Virahol 24 grams, basic polyethers 3031K37 gram, Diisopropyl azodicarboxylate 5 grams, vinylbenzene 260 grams, vinyl cyanide 140 grams add feed liquid as mixing.Obtain polymer polyatomic alcohol E.
Embodiment 6
Employing method 3, the polymer polyatomic alcohol that in first reactor, adds 200 gram 30wt% solid contents, drip compound, wherein basic polyethers 3031K45.0wt%, macromonomer 2.8wt%, Diisopropyl azodicarboxylate 0.4wt%, n-dodecyl mercaptan 0.3wt%, Virahol 2.9wt%, vinylbenzene 31.6wt%, vinyl cyanide 17.0wt% continuously.Initial 1000 grams of the second reactor overflow product are collected in addition and are used, and the product of collecting is as polymer polyatomic alcohol F later on.
The quality index of polymer polyatomic alcohol D, E, F is listed in table 2.
Table 2. polymer polyatomic alcohol analytical results
| The polymer polyatomic alcohol kind | D | E | F |
| Theoretical solid content, wt% | 50 | 50 | 50 |
| Actual solid content, wt% | 49.9 | 49.9 | 48.5 |
| Monomer conversion, wt% | 99.8 | 99.8 | 97 |
| Viscosity, mPa.s/25 ℃ | 7500 | 10000 | 7200 |
| Filterability, 150 mesh filter screen percent of pass, wt% | 100 | 100 | 100 |
Claims (6)
1. the preparation method of a polymer polyatomic alcohol, it is characterized in that present method is a semi continuous operation, the polymer polyatomic alcohol that with the solid content is 45wt%～55wt% is a bed material, liftout is to be external phase with a kind of basic polyether glycol, mix macromonomer, chain-transfer agent, radical initiator, one or more vinyl monomers, add in the bed material continuously, reinforced finishing, behind the absorption reaction, remove unreacted monomer, obtain the polymer polyatomic alcohol of stable dispersion, wherein basic polyether glycol is the soft bubble polyether glycol of three-functionality-degree, described bed material addition is the 10wt%～30wt% of raw material total amount, described macromonomer is that a kind of functionality is the polyether ester that 3～6 polyether glycol and maleic anhydride reaction form, addition is the 2wt%～4wt% of raw material total amount, the consumption of described chain-transfer agent is the 3wt%～5wt% of raw material total amount, described radical initiator is a Diisopropyl azodicarboxylate, consumption is the 0.3wt%～0.5wt% of raw material total amount, the solid content of polymer polyatomic alcohol of preparation is 45wt%～55wt%, viscosity 4000mPa.s/25 ℃～7500mPa.s/25 ℃.
2. according to the preparation method of the described polymer polyatomic alcohol of claim 1, it is characterized in that bed material is a kind of and the polymer polyatomic alcohol same solid content of target product.
3. according to the preparation method of the described polymer polyatomic alcohol of claim 2, it is characterized in that bed material is selected from material in the preparation process of polymer polyatomic alcohol and enters product before the demonomerization unit.
4. according to the preparation method of the described polymer polyatomic alcohol of claim 1, it is characterized in that vinyl monomer is vinylbenzene and vinyl cyanide, the monomer usage ratio is 60:40～90:10.
5. according to the preparation method of the described polymer polyatomic alcohol of claim 1, it is characterized in that chain-transfer agent is compound chain-transfer agent, is the mixture of Virahol and n-dodecyl mercaptan.
6. according to the preparation method of the described polymer polyatomic alcohol of claim 5, it is characterized in that the usage ratio of Virahol and n-dodecyl mercaptan is 9:1～15:1 in the compound chain-transfer agent.
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| CN100376616C (en) * | 2005-12-21 | 2008-03-26 | 中国科学院山西煤炭化学研究所 | Method for preparing polyester type polymer polyatomic alcohol |
| CN104045773B (en) * | 2013-03-11 | 2018-11-09 | 中国石油化工集团公司 | A kind of preparation method of polymer polyatomic alcohol |
| 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 |
| CN103342785A (en) * | 2013-07-04 | 2013-10-09 | 中国石油化工股份有限公司 | Method for preparing low-viscosity polymer polyol |
| KR102475640B1 (en) * | 2014-04-30 | 2022-12-07 | 바스프 에스이 | Stabilizer for polymer polyol production processes |
| CN103923270B (en) * | 2014-05-09 | 2016-06-01 | 河北亚东化工集团有限公司 | A kind of discontinuous method preparing low viscosity, high concrete face rock-fill dam |
| CN105585652B (en) * | 2014-10-20 | 2018-12-04 | 中国石油化工股份有限公司 | The preparation method of preformed stabilizers and the method that polymer polyatomic alcohol is prepared by it |
| CN106188425B (en) * | 2016-07-30 | 2018-06-22 | 山东隆华新材料股份有限公司 | The POP and its production method of chain-transferring agent method production need not be removed |
| 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 |
| CN108623757A (en) * | 2018-06-07 | 2018-10-09 | 山东隆华新材料股份有限公司 | The preparation method of polymer polyatomic alcohol |
| CN110387032B (en) * | 2019-07-25 | 2021-07-23 | 万华化学集团股份有限公司 | Polyether ester polyol, preparation method thereof and polyurethane elastomer prepared from polyether ester polyol |
| CN110563894A (en) * | 2019-09-18 | 2019-12-13 | 福建省天骄化学材料有限公司 | low-viscosity low-VOC high-activity polymer polyol and preparation method thereof |
| CN114479048B (en) * | 2021-12-22 | 2023-11-10 | 山东一诺威新材料有限公司 | Preparation method of polymer-based rigid foam polyether polyol |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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