CN103408704A - Continuous method for preparing high-stability polymer polyols - Google Patents
Continuous method for preparing high-stability polymer polyols Download PDFInfo
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Abstract
The invention relates to a continuous method for preparing high-stability polymer polyols, which mainly solves the problem that in the process that polymer polyols prepared in the prior art are used for preparing foamed plastics, the elongation at break, tensile strength and bearing property of products can not be simultaneously kept in a good level. According to the invention, by using a technical scheme that a method for preparing high-performance polymer polyols are prepared in a reactor at a reaction temperature of at least 85 DEG C in the presence of a radical initiator by using a mixture of styrene, acrylonitrile, polyoxyalkylene polyether polyols and macromonomer prepolymers, wherein the weight percentage of the macromonomer prepolymers in a product is 8-25%, and the content of solids in the polymer polyol is 20-50%, the problem is solved better, so that the continuous method can be applied to the industrial production of polymer polyols.
Description
Technical field
The present invention relates to a kind of continuation method for preparing the high stability polymer polyatomic alcohol.
Background technology
Polymer polyatomic alcohol (POP); to take general polyether glycol to be basic polyether (generally with general soft bubble polyethers, high activity polyether); add vinyl monomer and radical initiator, under certain temperature and nitrogen protection, carry out in-situ copolymerization and graft polymerization forms.The characteristics of the polyurethane foam prepared by this polymer polyatomic alcohol are that flexible urethane foam has higher hardness, supporting capacity and good rebound performance, and the foam structure of foam, physical and mechanical properties are improved.At present, POP is widely used in preparation high-mechanic or the soft and semi-hard polyurethane foam plastic goods of high-modulus, is molding, the block soft and semi-hard polyurethane foam plastic important kind of a class with polyvalent alcohol.
At present, the basic polyether for preparing polymer polyatomic alcohol is generally soft bubble polyethers and the high activity polyether prepared by interrupter method polyethers production technique; In the interrupter method polyether glycol is produced, usually adopt alkali (KOH) for the olefin oxide ring-opening polymerization, to prepare polyether glycol for catalyzer, but isomerization easily occurs propylene oxide under the KOH effect generates allyl alcohol, vinyl carbinol carries out epoxide ring-opening polymerization as initiator and obtains the monohydroxy unsaturated polyether, the functionality of polyether glycol is diminished, molecular weight distribution broadens, unstable product quality.This monohydroxy unsaturated polyether causes crosslinked too early when the preparation polyurethane foam, the use properties of polyether glycol can be affected, thereby performance and the quality that is prepared the POP product by it can be affected, and then the performance of the polyurethane foam product of impact preparation.In order to reduce the content of the monohydroxy unsaturated polyether in polyether glycol, many patent reports were once arranged (as US5010187, US5114619, US4282387) adopt the oxyhydroxide of rubidium, caesium, the oxyhydroxide of barium, lithium and oxide compound, the carboxylate salt equipotential catalyzer of alkaline-earth metal, but all have DeGrain, the catalyzer costliness, all many-sided problems such as toxic.
And have now a new technology to adopt bimetallic cyaniding complex (DMC) to be catalyzer, such catalyzer is a kind of effective catalyst of standby polyether glycol, has high reactivity, consumption is the ppm level, polymerization rate is very fast, and do not need follow-up in and refining step, can directly obtain the product polyethers, but the polyreaction serialization; Simultaneously, such catalyzer can not make propylene oxide generation isomerization generate vinyl carbinol, thereby avoided because take the production of the monohydroxy unsaturated polyether that vinyl carbinol obtains as the initiator polymerization, the polyether glycol that it prepares, the characteristics such as its molecular weight is high, narrow molecular weight distribution, steady quality.Our company adopts DMC continuous processing polyethers production technique to prepare POP basic polyether (soft bubble polyethers and high activity polyether), and the degree of unsaturation of basic polyether product is low, and quality is good, the characteristics such as narrow molecular weight distribution.
People have used Semi-batch Process and two kinds of methods of continuous processing to produce polymer polyatomic alcohol, distinguish by their size-grade distribution by product prepared by these two kinds of methods.In the technique of the polymer polyatomic alcohol prepared with Semi-batch Process, most of particle is to produce in the early stage of reaction, the further growth that the polymerization in later stage has just produced particle, the narrow diameter distribution of the polymer polyatomic alcohol therefore prepared, viscosity is high under certain solid content; And in the technique of the polymer polyatomic alcohol prepared by continuous processing, the material that is mixed is continuous discharge after continuously feeding, spill-over, the continuous formation in reaction process of the particle of polymer polyatomic alcohol, continuous growth of the particle formed, therefore in reactor, continuous overturning or the discharging of particle in the competitiveness growth that has generated particle and the generation of new particle and reactor, the size distribution that has caused it to prepare polymer polyatomic alcohol is wide, under certain solid content, the viscosity of the polymer polyatomic alcohol prepared than Semi-batch Process is low.
Patent US5364906 discloses a kind of continuous processing of producing the improved low viscosity polymer polyols of dispersion stability.The method is used two step continuous processings, wherein the first reaction product by make to be less than 50% total monomer mixture mainly contain large monomer and polymer controls agent be greater than 50% total polyvalent alcohol in the reaction generation.In the second reactor, remaining starting material are added in the first reaction product.
A kind of little mean particle size, high stability, continuation method in small, broken bits, low viscosity polymer polyols of preparing disclosed patent ZL96112759.7(CN1069654C).In the document, adopting ethylbenzene or propyl carbinol is solvent, the enol ether of take is reaction control agent, the intermediate solid content made is 15～30%(weight), the consumption of large monomer is at least 12%(weight), intermediate is as seed, by the technology that vinylbenzene and vinyl cyanide minute multistep add, obtain that mean particle size is little, high stability, in small, broken bits, low viscous polymer polyatomic alcohol.In the document, do not relate to the polymer color problem.When simultaneously the polymer polyatomic alcohol that makes of the document was for the preparation of porous plastics, in the porous plastics performance made, elongation at break was lower, is generally less than 126%, and tensile strength is also general.
Patent ZL01107850.2(CN1312302A) disclose a kind of preparation method of continuous processing polymer polyatomic alcohol, dispersion agent is activated in activating still and overflow is pipetted into the seeding polymerization still continuously; Vinylbenzene, vinyl cyanide and the dispersion agent that is activated under AIBN causes in polyether glycol, solvent copolyreaction form the seed polymer polyether glycol, overflow moves liquid continuously to polymeric kettle; In 1～2 polymeric kettle of mutually connecting, seed polymer is grown up by vinylbenzene, vinyl cyanide, solvent institute's swelling polymerization, forms the crude polymer polyether glycol; Through flash drum, steam tower and the falling-film evaporator drying obtains solid content 42%, viscosity >=4500mpas(25 ℃) polyether polyol.
In above-mentioned publication, all introduce separately the preparation method that semi-continuous process or continuous processing prepare polymer polyatomic alcohol, but all do not relate in the continuous production processes that basic polyether prepared by the DMC continuous processing is applied to polymer polyatomic alcohol, its basic polyether is generally single interrupter method and prepares polyether glycol, with its prepare that the load of urethane foam is poor, elongation at break and tensile strength can not keep level preferably.
Summary of the invention
Technical problem to be solved by this invention is the polymer polyatomic alcohol that makes in conventional art as in preparing the porous plastics process, the elongation at break of product, tensile strength and load can not keep the problem of better level simultaneously, and a kind of continuation method of new preparation high stability polymer polyatomic alcohol is provided.With the polymer polyatomic alcohol that the method makes, be used as and prepare in the porous plastics process, have advantages of that elongation at break, tensile strength and the load-carrying properties of product can keep better level simultaneously.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of continuation method for preparing the high stability polymer polyatomic alcohol, at first make monomer styrene, the monomer vinyl cyanide, the mixture of polyoxyalkylene polyether glycol and large monomer performed polymer is under the existence of radical initiator, under the temperature of reaction of at least 85 ℃, reaction prepares polymer polyatomic alcohol in the stirred-tank reactor of or at least two series connection, in polymer polyatomic alcohol, the weight content of large monomer performed polymer is 8～25%, the solid weight content of polymer polyatomic alcohol is 20～50%, wherein large monomer performed polymer be by large monomer in the solvent with moderate chain transfer activity, under the initiation of radical initiator, under at least 85 ℃, carry out copolymerization or grafting pre-polymerization and obtain with vinyl monomer, the polyoxyalkylene polyether glycol, in parts by weight, comprises 30～70 parts of polyoxyalkylene polyether glycol A and 70～30 parts of polyoxyalkylene polyether glycol B, the molecular weight of polyoxyalkylene polyether glycol A is 500～12000, and hydroxy functionality is 2～6, and the weight content of oxyethane is 2～12%, and by interrupter method, adopting alkali KOH is that catalyzer prepares the olefin oxide ring-opening polymerization, the molecular weight of polyoxyalkylene polyether glycol B is 500～12000, and hydroxy functionality is 2～6, and the weight content of oxyethane is 2～12%, and by continuous processing, adopting bimetallic cyaniding complex DMC is that catalyzer prepares the olefin oxide ring-opening polymerization.
In technique scheme, preferably, the part by weight of monomer styrene and monomer vinyl cyanide is
The molecular weight of polyoxyalkylene polyether glycol A is 1500～8000, and hydroxy functionality is 3～5, and the weight content of oxyethane is 5～9%, and molecular weight distributing index is 1.15～1.5, and degree of unsaturation is 0.01～0.03mol/kg; The molecular weight of polyoxyalkylene polyether glycol B is 1500～8000, and hydroxy functionality is 3～5, and the weight content of oxyethane is 5～9%, and molecular weight distributing index is 1.0～1.15, degree of unsaturation≤0.01mol/kg; The solvent for preparing large monomer performed polymer is selected from least a in benzene, toluene, ethylbenzene, dimethylbenzene, hexane, Virahol, propyl carbinol, 2-butanols, ethyl acetate, butylacetate, mercaptan or dimethyl formamide, and its consumption is 35%～60% of large monomer performed polymer weight; Radical initiator is selected from least a in Diisopropyl azodicarboxylate, azo-bis-iso-dimethyl, benzoyl peroxide, peroxidation (2 ethyl hexanoic acid) tert-butyl ester, and its consumption accounts for 0.5%～5% of vinyl monomer gross weight.More preferably, the solvent of the large monomer performed polymer of preparation is selected from least a in toluene, Virahol or mercaptan; The part by weight of monomer styrene and monomer vinyl cyanide is: 60/40～80/20.
In technique scheme, preferably, in polymer polyatomic alcohol, the weight content of large monomer performed polymer is 10～20%, and the solid weight content of polymer polyatomic alcohol is 35～50%, and viscosity is at≤4500mpas(25 ℃).
In technique scheme, large monomer is the polyether graft copolymers that contains unsaturated double-bond, and the molecular weight of large monomer is 3000～12000.More preferably, the molecular weight of large monomer is 5000～8000.
In technique scheme, preferably, the vinyl monomer for preparing large monomer performed polymer is at least a in the unsaturated carboxylic monomer of vinylbenzene, vinyl cyanide, methacrylonitrile, alpha-methyl styrene, butylstyrene, unsaturated monocarboxylic acid and replacement.More preferably, vinyl monomer is vinylbenzene, vinyl cyanide, and the weight of vinyl monomer is 7%～20% of large monomer performed polymer weight.
In technique scheme, preferably, in the preparation of high-performance polymer polyvalent alcohol, also comprise at least a monomer be selected from methacrylic acid, alpha-methyl styrene, vinylformic acid, methacrylonitrile, methyl acrylate, methyl methacrylate, HEMA.
In technique scheme, preferably, temperature of reaction is 100～135 ℃.
The preparation of large monomer is directly or indirectly by making molecular weight be at least 2500, hydroxy functionality is at least 3 polyether glycol and with reactive unsaturated compound, reacts preparation, the amount of reactive unsaturated compound used is 0.3～1.5 mole of every mole of polyvalent alcohol in the preparation of large monomer, and the molecular weight of the large monomer made is 3000～12000.
In the present invention polymer polyatomic alcohol be make vinylbenzene and vinyl cyanide mixture under the existence of composite polyethers, large monomer performed polymer and radical initiator, reaction generates.Polymerization process is first material fully to be mixed; mixture is under temperature of reaction; be continuously fed in the conversion unit of rare gas element (as nitrogen, argon gas etc.) displacement protection; reach certain residence time; the spill-over discharging is in flash vaporization kettle; method by conventional vacuum distilling by the volatile-type composition particularly solvent and residual monomer deviate from, both the polymer polyatomic alcohol product.
Polymer polyatomic alcohol prepared by the present invention is suitable for soft and semi-hard polyurethane foam plastic, is known for the preparation of the method for urethane foam; The method make polyisocyanates and polymer polyatomic alcohol, optional can with isocyanate reaction, contain active hydrogen atom, other compound in 40～12000 scopes of molecular weight (oxy-compound is preferably produced polyester that urethane foam is commonly used or polyethers etc.), under the existence of catalyzer, whipping agent and other known additives, react and make.Polymer polyatomic alcohol is for soft molding and piece material and semi-hard polyurethane foam plastic, can give hardness and the heavy burden ability of improvement, also for example beam drilling performance and the anti-shrinkability of flex foam produce favorable influence to this material to other performance of porous plastics.
Adopt method of the present invention, employing comprises that polyether glycol B prepared by polyether glycol A prepared by interrupter method and bimetallic cyaniding complex (DMC) catalysis, continuous processing is basic polyether, adopt the continuation method of stirring tank series connection, the stabilization of the performed polymer by the macromole stablizer, prepare polymer polyatomic alcohol, this polymer polyatomic alcohol is used in urethane foam, the porous plastics of preparation has simultaneously that elongation at break is high, tensile strength and the high characteristics of load, has obtained technique effect preferably.
The invention will be further elaborated below by embodiment, but be not limited only to the present embodiment.
Embodiment
[embodiment 1-3]
Definition:
Polyether glycol A: be that catalyzer makes glycerine react the polyethers of preparation with the mixture interrupter method of propylene oxide and oxyethane by adopting KOH, wherein the content of oxyethane is 7.5%(weight), mainly contain secondary hydroxy group, contain a small amount of primary hydroxyl group, hydroxyl value is: 56mgKOH/g, molecular weight are 3000, and molecular weight distributing index is 1.15～1.5, hydroxy functionality is 3.0, and degree of unsaturation is 0.022mol/kg.
Polyether glycol B: prepare polyethers by DMC catalysis continuous processing, take the mixture of low-molecular-weight polyether glycol (functionality is 3.0) and propylene oxide and oxyethane, under the catalysis of bimetallic cyaniding complex DMC, the continuously feeding reaction, spill-over discharging reaction makes, the content of its oxyethane is 7.56%(weight), hydroxyl value is 56mgKOH/g, and molecular weight is 3000, and molecular weight distributing index is between 1.0～1.15, hydroxy functionality is 3.0, and degree of unsaturation is 0.0086mol/kg.
Polyether glycol C: be 3.0 glycerine and propylene oxide and oxyethane rhythmic reaction by making hydroxy functionality, polyethers prepared by the propylene oxide end capping, wherein the content of oxyethane is 5.5%(weight), molecule chain end is secondary hydroxyl, hydroxyl value is: 56mgKOH/g, molecular weight distributing index is between 1.15～1.5, and degree of unsaturation is 0.020mol/kg.
Radical initiator: Diisopropyl azodicarboxylate (AIBN), outsourcing.
Large monomer performed polymer CS-B: the polyether graft copolymers that is contained unsaturated double-bond by large monomer CS-A(, molecular weight is 5000～8000), the mixture of solvent (Virahol), vinyl monomer (vinylbenzene, vinyl cyanide weight ratio are 1: 1), radical initiator (AIBN), in the reactor of two-stage series connection, by constantly being fed to reactor, under 95 ℃, with vinyl monomer, carry out copolymerization or grafting pre-polymerization, spill-over discharging cooling down and obtaining.
TDI: tolylene diisocyanate, outsourcing.
The preparation of polymer polyatomic alcohol:
The polymer polyatomic alcohol of continuous production embodiment in the two-stage series connection stirred-tank reactor.After composite basic polyether, CS-B, vinylbenzene, vinyl cyanide and radical initiator are fully mixed, be driven into continuously in reactor with dripping pump, temperature of reaction kettle is controlled at 125 ℃.In the reactor of respond all under the nitrogen replacement protection, carry out.Composite polyethers weight content is 40～50%, and the part by weight of vinylbenzene and vinyl cyanide is 2: 3, and the vinyl monomer weight content is 35～45%, and the radical initiator consumption accounts for 1% of vinyl monomer gross weight, and the weight content of large monomer performed polymer is 15%.Mixing raw material is continuously fed into the first reaction kettle for reaction, and the first reactor material spill-over continues reaction in the second reactor.And, can also use similarly other reactor where necessary, product distribution is in each reactor.Last reactor of tandem reactor is used as post-reactor, in this reactor, add again initiator and solvent, to increase the conversion of monomer to polymkeric substance, the thick product of reactor spill-over discharging is being less than 1 millibar and 125 ℃ of lower vacuum distilling a few hours, after deviating from solvent and residual monomer, both obtained required polymer polyatomic alcohol, then, by the production of polymer polyatomic alcohol for urethane foam.
The preparation of urethane foam:
Table 1 has been listed the formula of typical free-rise urethane foam.With the polymer polyatomic alcohol of determining in embodiment 1～3, comparative example 1～4, prepare the free-rise porous plastics.
Table 1: free-rise foam recipe
| Composition | Parts by weight |
| Polymer polyatomic alcohol | 90 |
| Polyether glycol C | 10 |
| Water | 4.6 |
| Silicone oil stablizer (L-580), outsourcing, US Air gasification work company | 1.2 |
| Amines catalyst 1(A-33), outsourcing, US Air gasification work company | 0.15 |
| Tin class catalyzer 2(T-9), outsourcing, US Air gasification work company | 0.125 |
| TDI | 60 |
By all the components (except polyisocyanates) being dropped into to container violent the mixing, under agitation add again polyisocyanates and subsequently mixture poured in open mold, allow urethane foam rise and send out and at room temperature solidify, make the free-rise urethane foam.
Analysis and determination:
Transformation efficiency: monomer is calculated from distillate to the transformation efficiency of polymkeric substance.
Viscosity: the viscosity of polymer polyatomic alcohol adopts the rotary viscosity design determining that temperature bath is housed, and measures 25 ℃ of temperature.
Solid content: solvent washes away basic polyether, centrifugation, and more than triplicate, thermostat container is weighed into constant weight.
Density: the density of porous plastics is according to the determination of experimental method of GBT6343-95.
Indentation force deflection: the hardness of porous plastics is according to the determination of experimental method of GBT10807-89.
Elongation: the elongation at break of porous plastics is according to the determination of experimental method of GBT6344-2008.
Tensile strength: the tensile strength of porous plastics is according to the determination of experimental method of GBT6344-2008.
Rebound resilience: the tensile strength of porous plastics is according to the determination of experimental method of GBT6670-1997.
Subordinate embodiment 1～3 and comparative example are listed in table 2, in comparative example, choose the better POP product in market as a comparison.
Table 2
[embodiment 4]
According to the described method of embodiment 1 and step, in polyether glycol A, the content of oxyethane is 2%(weight), molecular weight is 6000, and molecular weight distributing index is 1.05, and hydroxy functionality is 2.6, and degree of unsaturation is 0.012mol/kg; In polyether glycol B, the content of oxyethane is 7.5%(weight), molecular weight is 3000, and molecular weight distributing index is 1.15, and hydroxy functionality is 3, and degree of unsaturation is 0.01mol/kg.Temperature of reaction kettle is controlled at 110 ℃.The part by weight of vinylbenzene and vinyl cyanide is 4: 1, the vinyl monomer weight content is 38%, radical initiator is azo-bis-iso-dimethyl, the radical initiator consumption accounts for 2% of vinyl monomer gross weight, and the solvent of preparation CS-B is toluene, and the weight percentage of solvent is 35%, preparation CS-B medium vinyl monomer is vinylbenzene and methacrylonitrile, the weight ratio of vinylbenzene and methacrylonitrile is 1: 1, and its weight content is 20% of CS-B weight, and the weight content of CS-B is 25%.By the production of the polymer polyatomic alcohol of preparation for urethane foam.Analysis indexes and porous plastics performance are as shown in table 3.
Table 3
[embodiment 5]
According to the described method of embodiment 1 and step, in polyether glycol A, the content of oxyethane is 8%(weight), molecular weight is 1500, and molecular weight distributing index is 1.35, and hydroxy functionality is 4, and degree of unsaturation is 0.03mol/kg; In polyether glycol B, the content of oxyethane is 7.56%(weight), molecular weight is 3000, and molecular weight distributing index is 1.08, and hydroxy functionality is 3, and degree of unsaturation is 0.005mol/kg.Temperature of reaction kettle is controlled at 120 ℃.The part by weight of vinylbenzene and vinyl cyanide is 3: 2, the vinyl monomer weight content is 45%, radical initiator is azo-bis-iso-dimethyl, the radical initiator consumption accounts for 2% of vinyl monomer gross weight, and the solvent of preparation CS-B is toluene, and the weight percentage of solvent is 35%, preparation CS-B medium vinyl monomer is vinylbenzene and methacrylonitrile, the weight ratio of vinylbenzene and methacrylonitrile is 1: 1, and its weight content is 20% of CS-B weight, and the weight content of CS-B is 25%.By the production of the polymer polyatomic alcohol of preparation for urethane foam.Analysis indexes and porous plastics performance are as shown in table 4.
Table 4
[embodiment 6]
According to the described method of embodiment 1 and step, in polyether glycol A, the content of oxyethane is 8%(weight), molecular weight is 3000, and molecular weight distributing index is 1.3, and hydroxy functionality is 3, and degree of unsaturation is 0.023mol/kg; In polyether glycol B, the content of oxyethane is 12%(weight), molecular weight is 4800, and molecular weight distributing index is 1.28, and hydroxy functionality is 3, and degree of unsaturation is 0.026mol/kg.Temperature of reaction kettle is controlled at 135 ℃.The part by weight of vinylbenzene and vinyl cyanide is 2: 1, radical initiator is peroxidation (2 ethyl hexanoic acid) tert-butyl ester, the radical initiator consumption accounts for 3% of vinyl monomer gross weight, the solvent of preparation CS-B is toluene and mercaptan, the weight ratio of toluene and mercaptan is 1: 1, the weight percentage of solvent is 40%, vinyl monomer is vinyl cyanide and alpha-methyl styrene, the weight ratio of vinyl cyanide and alpha-methyl styrene is 1.2: 1, and the weight of vinyl monomer is 14% of large monomer performed polymer weight.By the production of the polymer polyatomic alcohol of preparation for urethane foam.Analysis indexes and porous plastics performance are as shown in table 5.Table 5
Claims (9)
1. continuation method for preparing the high stability polymer polyatomic alcohol, at first make the mixture of monomer styrene, monomer vinyl cyanide, polyoxyalkylene polyether glycol and large monomer performed polymer under the existence of radical initiator, under the temperature of reaction of at least 85 ℃, reaction prepares polymer polyatomic alcohol in the stirred-tank reactor of or at least two series connection, in polymer polyatomic alcohol, the weight content of large monomer performed polymer is 8～25%, and the solid weight content of polymer polyatomic alcohol is 20～50%; Wherein large monomer performed polymer be by large monomer in the solvent with moderate chain transfer activity, under the initiation of radical initiator, under at least 85 ℃, carry out copolymerization or grafting pre-polymerization and obtain with vinyl monomer; The polyoxyalkylene polyether glycol, in parts by weight, comprises 30～70 parts of polyoxyalkylene polyether glycol A and 70～30 parts of polyoxyalkylene polyether glycol B; The molecular weight of polyoxyalkylene polyether glycol A is 500～12000, and hydroxy functionality is 2～6, and the weight content of oxyethane is 2～12%, and by interrupter method, adopting alkali KOH is that catalyzer prepares the olefin oxide ring-opening polymerization; The molecular weight of polyoxyalkylene polyether glycol B is 500～12000, and hydroxy functionality is 2～6, and the weight content of oxyethane is 2～12%, and by continuous processing, adopting bimetallic cyaniding complex DMC is that catalyzer prepares the olefin oxide ring-opening polymerization.
2. prepare according to claim 1 the continuation method of high stability polymer polyatomic alcohol, it is characterized in that the part by weight of monomer styrene and monomer vinyl cyanide is
The molecular weight of polyoxyalkylene polyether glycol A is 1500～8000, and hydroxy functionality is 3～5, and the weight content of oxyethane is 5～9%, and molecular weight distributing index is 1.15～1.5, and degree of unsaturation is 0.01～0.03mol/kg; The molecular weight of polyoxyalkylene polyether glycol B is 1500～8000, and hydroxy functionality is 3～5, and the weight content of oxyethane is 5～9%, and molecular weight distributing index is 1.0～1.15, degree of unsaturation≤0.01mol/kg; The solvent for preparing large monomer performed polymer is selected from least a in benzene, toluene, ethylbenzene, dimethylbenzene, hexane, Virahol, propyl carbinol, 2-butanols, ethyl acetate, butylacetate, mercaptan or dimethyl formamide, and its consumption is 35%～60% of large monomer performed polymer weight; Radical initiator is selected from least a in Diisopropyl azodicarboxylate, azo-bis-iso-dimethyl, benzoyl peroxide, peroxidation (2 ethyl hexanoic acid) tert-butyl ester, and its consumption accounts for 0.5%～5% of vinyl monomer gross weight.
3. prepare according to claim 2 the continuation method of high stability polymer polyatomic alcohol, the solvent that it is characterized in that preparing large monomer performed polymer is selected from least a in toluene, Virahol or mercaptan; The part by weight of monomer styrene and monomer vinyl cyanide is: 60/40～80/20.
4. prepare according to claim 1 the continuation method of high stability polymer polyatomic alcohol, it is characterized in that in polymer polyatomic alcohol, the weight content of large monomer performed polymer is 10～20%, and the solid weight content of polymer polyatomic alcohol is 35～50%, and viscosity is at≤4500mpas(25 ℃).
5. prepare according to claim 1 the continuation method of high stability polymer polyatomic alcohol, it is characterized in that described large monomer is the polyether graft copolymers that contains unsaturated double-bond, the molecular weight of large monomer is 3000～12000.
6. prepare according to claim 1 the continuation method of high stability polymer polyatomic alcohol, the vinyl monomer that it is characterized in that preparing large monomer performed polymer is to be selected from least a in the unsaturated carboxylic monomer of vinylbenzene, vinyl cyanide, methacrylonitrile, alpha-methyl styrene, butylstyrene, unsaturated monocarboxylic acid and replacement; In the preparation of high-performance polymer polyvalent alcohol, also comprise at least a monomer be selected from methacrylic acid, alpha-methyl styrene, vinylformic acid, methacrylonitrile, methyl acrylate, methyl methacrylate, HEMA.
7. prepare according to claim 6 in the continuation method of high stability polymer polyatomic alcohol, the vinyl monomer for preparing large monomer performed polymer is vinylbenzene, vinyl cyanide, and the weight of vinyl monomer is 7%～20% of large monomer performed polymer weight.
8. prepare according to claim 1 the continuation method of high stability polymer polyatomic alcohol, it is characterized in that temperature of reaction is 100～135 ℃.
9. prepare according to claim 5 the continuation method of high stability polymer polyatomic alcohol, the molecular weight that it is characterized in that described large monomer is 5000～8000.
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| CN106589251B (en) * | 2015-10-20 | 2019-04-12 | 中国石油化工集团公司 | A method of continuously preparing polymer polyatomic alcohol |
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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 |
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| CN108570130A (en) * | 2018-04-10 | 2018-09-25 | 长华化学科技股份有限公司 | The preparation method of high-performance polymer polyalcohol |
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| CN111253531B (en) * | 2020-04-24 | 2022-10-11 | 辽宁方大工程设计有限公司 | Process for preparing polymer polyols |
| CN114656602A (en) * | 2022-02-16 | 2022-06-24 | 万华化学集团股份有限公司 | Prepolymer for polymer polyol and preparation method thereof |
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