CN112194763A - Formula and preparation method of polymer polyol - Google Patents

Formula and preparation method of polymer polyol Download PDF

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Publication number
CN112194763A
CN112194763A CN202011078218.0A CN202011078218A CN112194763A CN 112194763 A CN112194763 A CN 112194763A CN 202011078218 A CN202011078218 A CN 202011078218A CN 112194763 A CN112194763 A CN 112194763A
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polyol
parts
polymer polyol
prepared
unsaturated
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CN112194763B (en
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陈登龙
吕志仁
吴丹丹
陈明鹏
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Quangang Petrochemical Research Institute of Fujian Normal University
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Quangang Petrochemical Research Institute of Fujian Normal University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/062—Polyethers

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Graft Or Block Polymers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention relates to the field of polymer polyol, and discloses a formula of polymer polyol, which is prepared from 45-55 parts of unsaturated polyol prepolymer, 37-49 parts of vinyl monomer, 2-8 parts of dispersant, 0.2-0.6 part of initiator and 5-10 parts of chain transfer agent; the unsaturated polyol prepolymer is obtained by carrying out ester exchange reaction on polyether polyol and 2- (hydroxymethyl) methyl acrylate, and the weight part ratio of the polyether polyol to the 2- (hydroxymethyl) methyl acrylate is 100: 1-500: 1. The polymer polyol prepared according to the formula can effectively improve the solid content of the prepared polymer polyol on the premise that the viscosity of the prepared polymer polyol is not greatly increased.

Description

Formula and preparation method of polymer polyol
Technical Field
The invention relates to the technical field of polymer polyol, in particular to a formula of polymer polyol and a preparation method thereof.
Background
The polymer polyol (POP) is a polyol containing organic fillers, can replace inorganic fillers, not only enables polyurethane foam to have higher bearing capacity and good resilience, but also enables the cell structure and the physical and mechanical properties of the foam to be improved.
Polymer polyols (POPs) are mixtures of grafted polyether polyols, and autopolymers or copolymers of ethylenically unsaturated monomers containing solid particles, which are prepared by in situ polymerization of ethylenically unsaturated monomers with polyether polyols in the presence of an initiator.
In general, the viscosity of a polymer polyol system increases as its solids content increases. With the increasing demand of people on product quality, the demand of preparing stable polymer polyol with high solid content is also increasing, but the preparation and application of the polymer polyol are limited by the increased system viscosity. Therefore, the improvement of the existing production technology can effectively improve the solid content of the polymer polyol on the premise of not greatly increasing the viscosity of the polymer polyol, and the technical problem to be solved urgently in the industry is solved.
Disclosure of Invention
The invention aims to provide a formula of polymer polyol, and the polymer polyol prepared according to the formula can ensure that the solid content of the prepared polymer polyol is higher on the premise of keeping the viscosity of the polymer polyol not to be greatly increased.
The above object of the present invention is achieved by the following technical solutions: the formula of the polymer polyol is prepared from the following components in parts by weight: 45-55 parts of unsaturated polyol prepolymer, 37-49 parts of vinyl monomer, 2-8 parts of dispersant, 0.2-0.6 part of initiator and 5-10 parts of chain transfer agent; the unsaturated polyol prepolymer is obtained by carrying out ester exchange reaction on polyether polyol and 2- (hydroxymethyl) methyl acrylate, and the weight part ratio of the polyether polyol to the 2- (hydroxymethyl) methyl acrylate is 100: 1-500: 1.
By adopting the technical scheme, ester exchange reaction is firstly carried out on excessive polyether polyol and 2- (hydroxymethyl) methyl acrylate, so that a part of polyether polyol obtains unsaturated double bonds, and the unsaturated double bonds can be polymerized with vinyl monomers in further reaction to increase dispersed phase components and reduce continuous phases, thereby increasing the solid content of the finally prepared polymer polyol; moreover, due to the similar compatibility principle, the dispersed phase polymerized with the unsaturated polyol is easier to disperse in the polyether continuous phase, so that the prepared polymer polyol is more stable; finally, the method effectively increases the hydroxyl content in the dispersed phase, and can be used as a component to participate in the reaction during the later polyurethane foaming reaction, so that the strength of the prepared product is enhanced. Research shows that the viscosity of the prepared polymer polyol is not greatly increased by the scheme after the weight part ratio of the polyether polyol to the methyl 2- (hydroxymethyl) acrylate is limited to 100: 1-500: 1.
Further, 47 parts of unsaturated polyol prepolymer, 43 parts of vinyl monomer, 3 parts of dispersant, 0.5 part of initiator and 6.5 parts of chain transfer agent.
By adopting the technical scheme, when the ratio of the components is limited to the mass fraction, the bulk property of the prepared polymer polyol is better.
Further, the vinyl monomer is a mixture of styrene, acrylonitrile and hydroxyethyl acrylate.
By adopting the technical scheme, compared with the polymer polyol prepared by adopting single acrylonitrile as a vinyl monomer, the viscosity of the prepared polymer polyol is lower, and the performance is excellent.
Further, the weight ratio of the styrene to the acrylonitrile is 60: 40-75: 25, and the amount of the hydroxyethyl methacrylate accounts for 3-5% of the total amount of the vinyl monomers.
By adopting the technical scheme, the weight ratio of the styrene to the acrylonitrile is limited to 60: 40-75: 25, the solid content of the prepared polymer polyol is high, the prepared polymer polyol is white, in addition, when the hydroxyethyl methacrylate, the styrene and the acrylonitrile are used as vinyl monomers to participate in the reaction, the hydroxyethyl methacrylate has hydroxyl, so that the dispersed phase and the continuous phase of the polymer polyol have better compatibility.
Further, the initiator is azobisisobutyronitrile.
By adopting the technical scheme, when the polyatomic alcohol is polymerized during preparation, the initiation efficiency is high, and the initiation efficiency for styrene and acrylonitrile is respectively 80% and 100%.
Further, the chain transfer agent is one or more of aliphatic mercaptan or isopropanol.
By adopting the technical scheme, the chain transfer agent enables a high-molecular active chain to generate chain transfer during the formation of a polymer polyol dispersion system, so as to generate a new active center.
The invention also aims to provide a preparation method of the polymer polyol, which has the characteristics of simple process and convenient operation, and the polymer polyol prepared by the method has high solid content and good stability.
The above object of the present invention is achieved by the following technical solutions: a method of preparing a polymer polyol, comprising the steps of:
s1, uniformly mixing polyether polyol and 2- (hydroxymethyl) methyl acrylate at the temperature of 80-140 ℃, and dehydrating under reduced pressure for 2-8 hours to obtain an unsaturated polyol prepolymer;
s2, cooling the prepared unsaturated polyol prepolymer to room temperature, adding a vinyl monomer, a dispersant, an initiator and a chain transfer agent into the unsaturated polyol prepolymer, and uniformly mixing to obtain a reaction solution;
s3, continuously injecting the reaction liquid into a reaction kettle, reacting at the temperature of 115-125 ℃ and under the pressure of 0.3-0.5 MPa, and controlling the material residence time to be 2 hours to prepare polymer polyol containing other impurities;
s4, treating the prepared polymer polyol containing other impurities by a short-range rectification process, controlling the demonomerization temperature to be 120-150 ℃, controlling the demonomerization pressure to be-0.08-0.1 MPa, controlling the vacuum demonomerization time to be 3-5 hours, removing small molecular substances, and finally preparing the polymer polyol containing no other impurities.
In conclusion, the invention has the following beneficial effects:
1. carrying out ester exchange reaction on polyether polyol and 2- (hydroxymethyl) methyl acrylate to obtain an unsaturated polyol prepolymer, and then reacting the obtained unsaturated polyol prepolymer with a vinyl monomer, a dispersing agent, an initiator and a chain transfer agent to obtain polymer polyol which has higher solid content compared with the polymer polyol prepared by the existing method;
2. due to the similar compatibility principle, the vinyl disperse phase polymerized with the unsaturated polyol is easier to disperse in the polyether continuous phase, so that the prepared polymer polyol is more stable;
3. after the weight part ratio of the polyether polyol to the 2- (hydroxymethyl) methyl acrylate is limited to 100: 1-500: 1, the polyether polyol and the 2- (hydroxymethyl) methyl acrylate are firstly prepared into an unsaturated polyol prepolymer, and then the unsaturated polyol prepolymer is reacted with other substances to prepare the polymer polyol, so that the viscosity of the prepared polymer polyol is not greatly increased.
Detailed Description
The present invention will be described in further detail with reference to examples.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
BDF-4: one type of polymer polyol dispersant is an unsaturated macromolecule, and is available from Huaian Bade polyurethane science and technology Limited under the name BDF-4.
Solid content of POP: determined according to the method of 5.7 in GB/T31062-.
Viscosity: viscosity measured according to the method of GB/T12008.7-2010 at 25 ℃.
The first embodiment is as follows: a formula of polymer polyol is provided, wherein an unsaturated polyol prepolymer is prepared by the transesterification of polyether polyol and 2- (hydroxymethyl) methyl acrylate, the weight part ratio of the polyether polyol to the 2- (hydroxymethyl) methyl acrylate is 100:1)45kg, vinyl monomers (styrene 4.07kg, acrylonitrile 2.72kg and hydroxyethyl acrylate 0.21kg)7kg, a dispersing agent (BDF-4)2kg, an initiator (azobisisobutyronitrile) 0.2kg and a chain transfer agent (aliphatic mercaptan) 5 kg.
Example two: a formula of polymer polyol is provided, wherein 47kg of unsaturated polyol prepolymer (prepared by the transesterification of polyether polyol and hydroxyethyl methacrylate, the weight part ratio of the polyether polyol to the hydroxyethyl methacrylate is 300:1), 43kg of vinyl monomer (styrene 28.90g, acrylonitrile 12.38g and hydroxyethyl acrylate 1.72g), 3kg of dispersing agent (BDF-4), 0.5kg of initiator (azobisisobutyronitrile) and 6.5kg of chain transfer agent (isopropanol).
Example three: a formula of polymer polyol is provided, wherein an unsaturated polyol prepolymer is prepared by freely polymerizing polyether polyol and hydroxyethyl methacrylate, the weight ratio of the polyether polyol to the hydroxyethyl methacrylate is 500:1)55kg, vinyl monomers (styrene 34.91kg, acrylonitrile 11.64kg and hydroxyethyl acrylate 2.45kg)49kg, a dispersing agent (BDF-4)8kg, an initiator (azobisisobutyronitrile) 0.6kg and a chain transfer agent (isopropanol 6kg and aliphatic mercaptan 4kg)10 kg.
According to the proportions shown in the first to third embodiments:
s1, uniformly mixing polyether polyol and hydroxyethyl methacrylate at the temperature of 80-140 ℃, and dehydrating under reduced pressure for 2-8 hours to obtain an unsaturated polyol prepolymer;
s2, cooling the prepared unsaturated polyol prepolymer to room temperature, adding a vinyl monomer, a dispersant, an initiator and a chain transfer agent into the unsaturated polyol prepolymer, and uniformly mixing to obtain a reaction solution;
s3, continuously injecting the reaction liquid into a reaction kettle, reacting at the temperature of 115-125 ℃ and under the pressure of 0.3-0.5 MPa, and controlling the material residence time to be 2 hours to prepare polymer polyol containing other impurities;
s4, treating the prepared polymer polyol containing other impurities by a short-range rectification process, controlling the demonomerization temperature to be 120-150 ℃, controlling the demonomerization pressure to be-0.08-0.1 MPa, controlling the vacuum demonomerization time to be 3-5 hours, removing small molecular substances, and finally preparing the polymer polyol containing no other impurities.
The polymer polyols obtained in the above examples were subjected to performance tests, and the specific test results are shown in table 1.
Table 1 results of performance testing of each example.
Test items Example one Example two EXAMPLE III
POP solid content/% 45.9 50.1 47.5
viscosity/mPa · s/25 DEG C 5650 5950 5500
As can be seen from the data in Table 1, the polymer polyols obtained in the above examples are not very high in viscosity and have a high solids content.
Comparative example:
comparative example one: a polymer polyol formulation which differs from the first embodiment in that: replacing the unsaturated polyol prepolymer with polyether polyol, and taking 45kg of the polyether polyol.
Comparative example two: a polymer polyol formulation which differs from example two in that: the unsaturated polyol prepolymer was replaced with polyether polyol, and 47kg of this polyether polyol was taken.
Comparative example three: a polymer polyol formulation which differs from example three in that: the unsaturated polyol prepolymer was replaced with polyether polyol, and 55kg of this polyether polyol was taken.
The polymer polyols prepared according to the above respective proportions were subjected to performance tests, and specific test results are shown in table 2.
Table 2 results of performance test of polymer polyols prepared in comparative examples one to three.
Test items Comparative example 1 Comparative example No. two Comparative example No. three
POP solid content/% 40.2 43 41.6
viscosity/mPa · s/25 DEG C 5100 5500 5150
The POP solid contents of the first test item, the second test item and the third test item are respectively 40.2%, 43% and 41.6%, while the POP solid contents of the first test item, the second test item and the third test item are respectively 45.9%, 50.1% and 47.5%, the POP solid contents of the first test item, the second test item and the third test item are compared with the first test item, the POP solid contents of the second test item, the third test item and the third test item are compared with the second test item, the POP solid contents of the third test item and the third test item are compared with the third test item, and the POP solid contents of the polymer polyol prepared by preparing the unsaturated polyol prepolymer and then reacting the prepared unsaturated polyol prepolymer with other components are found to be remarkably improved compared with the POP solid contents of the polymer polyol prepared by.
Test items the viscosities of comparative example one, comparative example two, and comparative example three were: 5100mPa · s, 5500mPa · s, 5150mPa · s, and 5650mPa · s, 5950mPa · s, 5500mPa · s for the first, second, and third examples, respectively, comparing the first comparative example with the first example, comparing the second comparative example with the second example, and comparing the third comparative example with the third example, it was found that the viscosity of a polymer polyol obtained by preparing an unsaturated polyol prepolymer first and then reacting the obtained unsaturated polyol prepolymer with other components did not greatly increase the viscosity with respect to the viscosity of a polymer polyol obtained by directly reacting a conventional polyether polyol with other components, and a new problem was caused.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (7)

1. The formula of the polymer polyol is characterized by being prepared from the following components in parts by weight: 45-55 parts of unsaturated polyol prepolymer, 37-49 parts of vinyl monomer, 2-8 parts of dispersant, 0.2-0.6 part of initiator and 5-10 parts of chain transfer agent; the unsaturated polyol prepolymer is obtained by carrying out ester exchange reaction on polyether polyol and 2- (hydroxymethyl) methyl acrylate, and the weight part ratio of the polyether polyol to the 2- (hydroxymethyl) methyl acrylate is 100: 1-500: 1.
2. The formulation of claim 1, wherein the unsaturated polyol prepolymer is 47 parts, the vinyl monomer is 43 parts, the dispersant is 3 parts, the initiator is 0.5 part, and the chain transfer agent is 6.5 parts.
3. The polymer polyol formulation of claim 1, wherein said vinyl monomer is a mixture of styrene, acrylonitrile, and hydroxyethyl acrylate.
4. The formulation of claim 3, wherein the weight ratio of styrene to acrylonitrile is 60:40 to 75:25, and the amount of hydroxyethyl methacrylate is 3 to 5% of the total amount of vinyl monomers.
5. The formulation of claim 1, wherein said initiator is azobisisobutyronitrile.
6. The formulation of claim 1, wherein the chain transfer agent is one or more of an aliphatic thiol or isopropanol.
7. A process for preparing a polymer polyol according to any of claims 1 to 6, comprising the steps of:
s1, uniformly mixing polyether polyol and 2- (hydroxymethyl) methyl acrylate at the temperature of 80-140 ℃, and dehydrating under reduced pressure for 2-8 hours to obtain an unsaturated polyol prepolymer;
s2, cooling the prepared unsaturated polyol prepolymer to room temperature, adding a vinyl monomer, a dispersant, an initiator and a chain transfer agent into the unsaturated polyol prepolymer, and uniformly mixing to obtain a reaction solution;
s3, continuously injecting the reaction liquid into a reaction kettle, reacting at the temperature of 115-125 ℃ and under the pressure of 0.3-0.5 MPa, and controlling the material residence time to be 2 hours to prepare polymer polyol containing other impurities;
s4, treating the prepared polymer polyol containing other impurities by a short-range rectification process, controlling the demonomerization temperature to be 120-150 ℃, controlling the demonomerization pressure to be-0.08-0.1 MPa, controlling the vacuum demonomerization time to be 3-5 hours, removing small molecular substances, and finally preparing the polymer polyol containing no other impurities.
CN202011078218.0A 2020-10-10 2020-10-10 Polymer polyol and preparation method thereof Active CN112194763B (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01221403A (en) * 1988-02-26 1989-09-04 Sanyo Chem Ind Ltd Manufacture of polymeric polyol and polyurethane foam
US5225481A (en) * 1988-07-29 1993-07-06 Arco Chemical Technology, L.P. Polyol polyacrylate dispersants
CN104487469A (en) * 2012-04-18 2015-04-01 拜尔材料科学有限公司 Preformed stabilizers useful for the production of polymer polyols and polymer polyols produced therefrom
CN106866893A (en) * 2017-03-06 2017-06-20 索进（厦门）化工技术有限公司 A kind of preparation method for preparing the low VOC polymer polyatomic alcohols of high solids content

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01221403A (en) * 1988-02-26 1989-09-04 Sanyo Chem Ind Ltd Manufacture of polymeric polyol and polyurethane foam
US5225481A (en) * 1988-07-29 1993-07-06 Arco Chemical Technology, L.P. Polyol polyacrylate dispersants
CN104487469A (en) * 2012-04-18 2015-04-01 拜尔材料科学有限公司 Preformed stabilizers useful for the production of polymer polyols and polymer polyols produced therefrom
CN106866893A (en) * 2017-03-06 2017-06-20 索进（厦门）化工技术有限公司 A kind of preparation method for preparing the low VOC polymer polyatomic alcohols of high solids content

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