CN115232256A - Preparation method of high-resilience polymer polyol, polymer polyol obtained by preparation method and application of polymer polyol - Google Patents
Preparation method of high-resilience polymer polyol, polymer polyol obtained by preparation method and application of polymer polyol Download PDFInfo
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- CN115232256A CN115232256A CN202110434006.XA CN202110434006A CN115232256A CN 115232256 A CN115232256 A CN 115232256A CN 202110434006 A CN202110434006 A CN 202110434006A CN 115232256 A CN115232256 A CN 115232256A
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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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
- C08G18/632—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers onto polyethers
Abstract
The invention discloses a preparation method of high-resilience polymer polyol, the obtained polymer polyol and application thereof, wherein the preparation method comprises the following steps: carrying out reaction on raw materials including basic polyether polyol, a stabilizer precursor, an unsaturated monomer, an initiator and a chain transfer agent to obtain the high-resilience polymer polyol; wherein the base polyether polyol is selected from the group consisting of a combination of a glyceryl polyether polyol and a sorbitol-based polyether polyol. The polyurethane foam prepared by the polymer polyol has the characteristics of high indentation ratio, high resilience, low permanent deformation and the like.
Description
Technical Field
The invention belongs to the field of preparation of polymer polyols, and particularly relates to a preparation method of a high-resilience polymer polyol, the obtained polymer polyol and application.
Background
Polymer polyols are obtained by grafting vinyl monomers onto a base polyether polyol by free radical in situ polymerization. Polymer polyols are mainly used for the production of flexible polyurethane foams. Polyurethane flexible foam materials made from polymer polyols are largely classified into slabstock flexible foams and molded foams. Polyurethane slabstock foams are used in carpets, furniture and bedding. Polyurethane molded foams are used primarily in the automotive and aircraft industries. Polyurethanes prepared using polymer polyols can improve the properties of flexible polyurethane foams, particularly hardness and load-bearing capacity.
CN110577636A discloses a dispersant for polymer polyol and a preparation method of polymer polyol, wherein polymer polyol is prepared at a temperature of 100-130 ℃ by base polyol, unsaturated vinyl monomers styrene and acrylonitrile, polymerization initiator, dispersant and optional chain transfer agent; the base polyether is polyether polyol with functionality of 3-8, and is block polymerized with propylene oxide and ethylene oxide, and has ethylene oxide content of 0-50% and molecular weight of 5000-20000. The invention can obtain stable, colorless and transparent dispersant, and the polymer polyol prepared by the dispersant has relatively low viscosity, fine particles, high whiteness and good water solubility, but does not relate to the requirements of high resilience and low permanent deformation.
CN103601860A discloses a polymer polyol for slow rebound polyurethane foam, which is synthesized by adopting slow rebound basic polyether, self-made efficient dispersant, novel initiator dimethyl azodiisobutyrate, basic polyether and vinyl monomer in the presence of a continuous operation process, wherein the solid content of the slow rebound polymer polyol is 10-40%, the viscosity is 400-3000mPa.s/25 ℃, the particle size is moderate and stable: the polymer polyol provided by the invention is used for preparing the slow-rebound polyurethane foam, so that the operation is simple, the foam hardness is obviously improved, and the mechanical property of the slow-rebound foam can be obviously improved.
The CN111471142A patent discloses a modified polymer polyol, which uses a polyol synthesized by using a small molecular polyol with a functionality of 4-8 as an initiator as a base polyether and then used for preparing the polymer polyol to improve the odor and the hardness of the polymer polyol, but the used catalyst dimethylamine or potassium hydroxide obtains a base polyether polyol with higher unsaturation, which improves the compression hardness to a certain extent, but does not improve the aspects of high resilience and low permanent deformation.
The CN103601860A patent discloses a polymer polyol for the preparation of slow resilience polyurethane foams, but does not meet the requirements of high resilience and low permanent set.
Disclosure of Invention
In order to solve the problem that polyurethane foam in the prior art cannot meet the requirements of high resilience, high sag ratio and low permanent deformation, the invention provides a preparation method of high-resilience polymer polyol, the obtained polymer polyol and application thereof, wherein the high-resilience, high sag ratio and low permanent deformation requirements can be met when the obtained polymer polyol is applied to polyurethane foam by introducing combined polyether polyol with high activity, low unsaturation degree and different functionality degrees as basic polyether and preparing a stabilizer precursor by adopting polyether polyol with low unsaturation degree and high functionality degrees.
One of the objects of the present invention is to provide a method for preparing a high resilience polymer polyol, comprising: carrying out reaction on raw materials including basic polyether polyol, a stabilizer precursor, an unsaturated monomer, an initiator and a chain transfer agent to obtain the high-resilience polymer polyol; wherein the base polyether polyol is selected from a combination of at least two of a glyceryl polyether polyol, a sorbitol-based polyether polyol, and a pentaerythritol-based polyether polyol.
Preferably, the base polyether polyol is selected from the group consisting of a combination of at least one of a sorbitol-based polyether polyol and a pentaerythritol-based polyether polyol and a glyceryl polyether polyol. More preferably, a combination of sorbitol-based polyether polyol and glyceryl polyether polyol.
In a preferred embodiment, the glyceryl polyether polyol, sorbitol-based polyether polyol or pentaerythritol-based polyether polyol is obtained by: respectively taking glycerol, sorbitol and pentaerythritol as initiators, adding an epoxy compound in the presence of a catalyst I to react, and then optionally capping with ethylene oxide to respectively obtain the glyceryl polyether polyol, the sorbitol polyether polyol or the pentaerythritol polyether polyol.
That is, the glyceryl polyether polyol is obtained by taking glycerol as an initiator, adding an epoxy compound in the presence of a catalyst I to react, and then optionally blocking with ethylene oxide; the sorbitol-based polyether polyol is obtained as follows: taking sorbitol as an initiator, adding an epoxy compound in the presence of a catalyst I to react, and then optionally blocking with ethylene oxide to obtain the sorbitol-based polyether polyol; the pentaerythritol-based polyether polyol is obtained as follows: pentaerythritol is taken as an initiator, an epoxy compound is added in the presence of a catalyst I for reaction, and then ethylene oxide is optionally adopted for end capping to obtain the pentaerythritol-based polyether polyol. Wherein, the preparation of the glyceryl polyether polyol, the sorbitol-based polyether polyol or the pentaerythritol-based polyether polyol is carried out by adopting the temperature and the pressure disclosed in the prior art.
In a further preferred embodiment, the catalyst I is selected from at least one of phosphazene catalysts, alkali metal catalysts and bi/multimetallic catalysts.
Wherein the phosphazene catalyst, the alkali metal catalyst and the bi/multi-metal catalyst are disclosed in the prior art.
In a still further preferred embodiment, the epoxy compound is selected from ethylene oxide and/or propylene oxide.
In a preferred embodiment, the glyceryl polyether polyol has an unsaturation of less than 0.04mol/kg, a primary hydroxyl content of greater than 70%, and a molecular weight of 3000 to 8000.
In a further preferred embodiment, the glyceryl polyether polyol has an unsaturation of less than 0.04mol/kg, a primary hydroxyl group content of greater than 75%, and a molecular weight of 4500 to 8000.
In a preferred embodiment, the sorbitol-based polyether polyols have a degree of unsaturation of less than 0.04mol/kg, a primary hydroxyl content of greater than 70%, and a molecular weight of 4000 to 14000, each independently.
In a further preferred embodiment, the sorbitol-based polyether polyol has an unsaturation of less than 0.04mol/kg, a primary hydroxyl group content of greater than 75%, and a molecular weight of 4500-12000.
In a preferred embodiment, the pentaerythritol-based polyether polyol has an unsaturation of less than 0.04mol/kg, a primary hydroxyl content of greater than 70%, and a molecular weight of 4000 to 12000.
In a preferred embodiment, the base polyether polyol is selected from the group consisting of sorbitol-based polyether polyols and pentaerythritol-based polyether polyols in combination with a glyceryl polyether polyol.
In a further preferred embodiment, the weight ratio of at least one of the sorbitol-based polyether polyol and the pentaerythritol-based polyether polyol to the glyceryl polyether polyol is 1 (0.5 to 5), preferably 1 (1 to 3).
Among them, sorbitol polyol and/or pentaerythritol have high functionality, and thus can increase product hardness when producing a product, but the rebound resilience is affected by the amount of sorbitol polyol and/or pentaerythritol used, and thus, it is necessary to control the amount within the above range.
In a preferred embodiment, the stabilizer precursor is obtained by: the stabilizer precursor is obtained by reacting raw materials including polyether polyol, polyisocyanate, isocyanate containing unsaturated reaction bonds and a catalyst II.
In a further preferred embodiment, the viscosity of the stabiliser precursor is from 1500 to 8000 mPas, preferably from 2000 to 6000 mPas/25 ℃, more preferably from 2000 to 5000 mPas/25 ℃.
In a preferred embodiment, the polyether polyol is a copolymer of propylene oxide and ethylene oxide (preferably a propylene oxide-ethylene oxide block copolymer) containing from 2 to 8 (preferably from 3 to 8, more preferably from 3 to 6) hydroxyl groups at the end.
In a further preferred embodiment, the polyether polyol has a molecular weight of 900 to 12000, preferably 9000 to 12000.
In a still further preferred embodiment, the polyether polyol has an ethylene oxide unit content of 5 to 20% by weight, preferably 8 to 16% by weight.
Specifically, the polyether polyol is obtained as follows: taking polyhydric alcohol as an initiator, and adding propylene oxide and ethylene oxide in the presence of a catalyst I (preferably sequentially) to react to obtain the catalyst I, wherein the polyhydric alcohol is selected from at least one of ethylene glycol, propylene glycol, glycerol, trimethylolpropane, pentaerythritol, sorbitol and sucrose, and is preferably sorbitol; and/or the catalyst I is selected from at least one of a phosphazene catalyst, an alkali metal catalyst and a bi/multi-metal catalyst.
Wherein, the polyether polyol is prepared by adopting the temperature and the pressure disclosed in the prior art.
In a preferred embodiment, the isocyanate containing unsaturated reactive bond is at least one selected from 3-isopropyl-dimethylbenzyl isocyanate and ethyl isocyanate methacrylate.
In a preferred embodiment, the polyisocyanate is selected from compounds containing at least two isocyanate groups, such as diisocyanates.
In a further preferred embodiment, the polyisocyanate is selected from at least one of isophorone diisocyanate, 4 '-dicyclohexylmethane diisocyanate, 1, 4-cyclohexane diisocyanate, norbornane diisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, and 4,4' -diphenylmethane diisocyanate.
In a preferred embodiment, the catalyst II is selected from at least one of tin-based catalysts, amine-based catalysts and other metal catalysts, preferably from tin-based catalysts.
In a further preferred embodiment, the catalyst II is selected from at least one of dibutyl tin dilaurate, stannous octoate, tetrabutyl titanate, triethylenediamine.
In a preferred embodiment, the isocyanate is used in an amount of 0.05 to 5 parts by weight, the unsaturated reaction bond-containing isocyanate is used in an amount of 0.05 to 5 parts by weight, and the catalyst II is used in an amount of 10 to 1000ppm by weight, based on 100 parts by weight of the polyether polyol.
In a further preferred embodiment, the isocyanate is used in an amount of 0.2 to 2 parts by weight, the unsaturated reaction bond-containing isocyanate is used in an amount of 0.2 to 2 parts by weight, and the catalyst II is used in an amount of 50 to 500ppm by weight, based on 100 parts by weight of the polyether polyol.
For example, the isocyanate may be used in an amount of 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.2, 1.5, 1.8, or 2 parts by weight based on 100 parts by weight of the polyether polyol; the isocyanate containing unsaturated reaction bonds is used in an amount of 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.2, 1.5, 1.8 or 2 parts by weight; the amounts of catalyst II used are 50, 60, 70, 80, 90, 100, 120, 150, 200, 300, 400, 500ppm by weight.
In a preferred embodiment, the unsaturated monomer is selected from at least one of butadiene, isoprene, alpha-methylstyrene, (tert-butyl) styrene, chlorostyrene, cyanostyrene, bromostyrene, styrene, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, N-dimethylacrylamide, N- (dimethylaminomethyl) acrylamide, vinyl ethers, vinyl ketones, vinylidene halides.
In a further preferred embodiment, the unsaturated monomer is selected from acrylonitrile and styrene, wherein the mass ratio of acrylonitrile to styrene is 1 (0.5-3), preferably 1 (1.5-2.5).
In a preferred embodiment, the chain transfer agent is selected from at least one of methanol, ethanol, butanol, isopropanol, and mercaptans.
In a preferred embodiment, the initiator is selected from at least one of alkyl hydroperoxides, aryl hydroperoxides, persulfates, perborates, percarbonates and azo compounds.
In a further preferred embodiment, the initiator is selected from at least one of hydrogen peroxide, di (t-butyl) peroxide, t-butylperoxy diethyl acetate, t-butyl peroctoate, t-butyl peroxy isobutyrate, t-butyl peroxide, t-butyl peroxy pivalate, t-amyl peroxy pivalate, t-butyl peroxy-2-ethyl hexanoate, lauroyl peroxide, cumene hydroperoxide, azobisisobutyronitrile and dimethyl azobisisobutyrate.
In a preferred embodiment, the method of making the polymer polyol comprises the steps of:
step 1, pre-reacting the stabilizer precursor with the unsaturated monomer in the presence of the initiator and the chain transfer agent to obtain a pre-reactant (PFS);
and 2, in the presence of the initiator, reacting the pre-reactant obtained in the step 1 with the base polyether polyol and the unsaturated monomer to obtain the polymer polyol.
In a preferred embodiment, in step 1, the amount of the initiator is 0.01 to 1%, the amount of the chain transfer agent is 20 to 80%, the amount of the stabilizer precursor is 10 to 50%, and the amount of the unsaturated monomer is 5 to 30%, based on 100% by weight of the total reaction raw materials in step 1.
In a further preferred embodiment, in step 1, the amount of the initiator is 0.05 to 0.5%, the amount of the chain transfer agent is 50 to 70%, the amount of the stabilizer precursor is 15 to 30%, and the amount of the unsaturated monomer is 10 to 20%, based on 100% by weight of the total reaction raw materials.
For example, in step 1, the initiator is used in an amount of 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, 0.1%, 0.12%, 0.15%, 0.18%, 0.2%, 0.3%, 0.4%, or 0.5%, the chain transfer agent is used in an amount of 50%, 55%, 60%, 65%, or 70%, the stabilizer precursor is used in an amount of 15%, 20%, 25%, or 30%, and the unsaturated monomer is used in an amount of 10%, 12%, 15%, 18%, or 20%, based on 100% by weight of the total reaction raw materials.
In a preferred embodiment, in step 2, the amount of the initiator is 0.05 to 2%, the amount of the pre-reactant is 1 to 20%, the amount of the base polyether polyol is 20 to 80%, and the amount of the unsaturated monomer is 20 to 70%, based on 100% by weight of the total weight of the reaction raw materials in step 2.
In a further preferred embodiment, in step 2, the amount of the initiator is 0.1 to 1%, the amount of the pre-reactant is 5 to 15%, the amount of the base polyether polyol is 30 to 60%, and the amount of the unsaturated monomer is 30 to 60%, based on 100% by weight of the total weight of the reaction raw materials in step 2.
For example, in step 2, the initiator is used in an amount of 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, or 1%, based on 100% by weight of the total reaction raw materials in step 2; the pre-reactant is present in an amount of 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14% or 15%, the base polyether polyol is present in an amount of 30%, 35%, 40%, 45%, 50%, 55% or 60%, and the unsaturated monomer is present in an amount of 30%, 35%, 40%, 45%, 50%, 55% or 60%.
In a preferred embodiment, in step 1, the pre-reaction is carried out at 80 to 150 ℃, preferably at 100 to 140 ℃.
In a preferred embodiment, in step 2, the reaction is carried out at 80 to 140 ℃, preferably at 100 to 130 ℃.
The second object of the present invention is to provide a polymer polyol obtained by the production method described in the first object of the present invention.
Wherein the polymer polyol has a solids content of 40% or more and a viscosity of less than 8000 cps at 25 ℃.
It is a further object of the present invention to provide the use of the polymer polyols obtained by the process according to one of the objects of the present invention in polyurethane foams.
The polyurethane foam synthesized by the polymer polyol has the characteristics of high resilience, high sinking ratio, low permanent deformation and the like.
The endpoints of the ranges and any values disclosed in the present application are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For numerical ranges, each range between its endpoints and individual point values, and each individual point value can be combined with each other to give one or more new numerical ranges, and such numerical ranges should be construed as specifically disclosed herein. In the following, various technical solutions can in principle be combined with each other to obtain new technical solutions, which should also be regarded as specifically disclosed herein.
Compared with the prior art, the invention has the following beneficial effects: the polyurethane foam synthesized by the polymer polyol has the characteristics of high resilience, high sinking ratio, low permanent deformation and the like.
Detailed Description
While the present invention will be described in conjunction with specific embodiments thereof, it is to be understood that the following embodiments are presented by way of illustration only and not by way of limitation, and that numerous insubstantial modifications and adaptations of the invention may be made by those skilled in the art in light of the teachings herein.
It is to be further understood that the various features described in the following detailed description may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention can be made, as long as the idea of the present invention is not violated, and the technical solution formed thereby is part of the original disclosure of the present specification, and also falls into the protection scope of the present invention.
The MMC catalyst adopted in CN100430136C, example 2; phosphazene catalyst, laboratory synthesis used example 3 in CN 111087599A.
[ example 1] preparation of a glyceryl polyether polyol A1
Adding 32g of glycerol and 1.8g of phosphazene catalyst into a 2L closed reaction kettle, replacing air in the kettle with nitrogen, heating to 110 ℃, adding 1760g of propylene oxide, controlling the reaction pressure to be less than 0.4MPa, reacting at 110 ℃, keeping the internal pressure for 2 hours after the reaction is finished, continuously adding 268g of ethylene oxide after the internal pressure is finished, controlling the reaction pressure to be less than 0.4MPa, reacting at 110 ℃, keeping the internal pressure for 2 hours after the reaction is finished, transferring into a refining kettle, dehydrating, and filtering to obtain the glyceryl polyether polyol A1.
The glyceryl polyether polyol A1 has an unsaturation degree of 0.015mol/kg, a primary hydroxyl group content of 76% and a molecular weight of 5450.
[ example 2 ] preparation of a glyceryl polyether polyol A2
Adding 25g of glycerol and 1.8g of phosphazene catalyst into A2-liter closed reaction kettle, replacing air in the kettle with nitrogen, heating to 110 ℃, adding 1760g of propylene oxide, controlling the reaction pressure to be less than 0.4MPa, reacting at 110 ℃, keeping the internal pressure for 2 hours after the reaction is finished, continuously adding 268g of ethylene oxide after the internal pressure is finished, controlling the reaction pressure to be less than 0.4MPa, reacting at 110 ℃, keeping the internal pressure for 2 hours after the reaction is finished, transferring into a refining kettle, dehydrating, and filtering to obtain the glyceryl polyether polyol A2.
The glyceryl polyether polyol A2 had an unsaturation degree of 0.017mol/kg, a primary hydroxyl group content of 75% and a molecular weight of 6900.
[ example 3 ] preparation of sorbitol-based polyether polyol B1
Adding 7g of sorbitol and 1.8g of phosphazene catalyst into a 2-liter closed reaction kettle, replacing air in the kettle with nitrogen, heating to 110 ℃, adding 1521g of propylene oxide, controlling the reaction pressure to be less than 0.4MPa, reacting at 110 ℃, keeping the internal pressure for 2 hours after the reaction is finished, continuing adding 270g of ethylene oxide after the internal pressure is finished, controlling the reaction pressure to be less than 0.4MPa, reacting at 110 ℃, keeping the internal pressure for 2 hours after the reaction is finished, transferring into a refining kettle, dehydrating, and filtering to obtain the sorbitol-based polyether polyol B1.
The unsaturation degree of the sorbitol-based polyether polyol B1 is 0.013mol/kg, the primary hydroxyl group content is 76 percent, and the molecular weight is 12000.
[ example 4 ] preparation of sorbitol-based polyether polyol B2
Adding 16g of sorbitol and 1.8g of phosphazene catalyst into a 2L closed reaction kettle, replacing air in the kettle with nitrogen, heating to 110 ℃, adding 1521g of propylene oxide, controlling the reaction pressure to be less than 0.4MPa, reacting at 110 ℃, keeping the internal pressure for 2 hours after the reaction is finished, continuously adding 270g of ethylene oxide after the internal pressure is finished, controlling the reaction pressure to be less than 0.4MPa, reacting at 110 ℃, moving into a refining kettle after the internal pressure is finished for 2 hours, dehydrating, and filtering to obtain the sorbitol-based polyether polyol B2.
The unsaturation degree of the sorbitol-based polyether polyol B2 is 0.019mol/kg, the primary hydroxyl group content is 81 percent, and the molecular weight is 8700.
[ example 5 ] preparation of pentaerythritol-based polyether polyol C1
Adding 9g of pentaerythritol and 1.8g of phosphazene catalyst into a 2L closed reaction kettle, replacing air in the kettle with nitrogen, heating to 110 ℃, adding 1519g of propylene oxide, controlling the reaction pressure to be less than 0.4MPa, reacting at 110 ℃, keeping the internal pressure for 2 hours after the reaction is finished, continuously adding 270g of ethylene oxide after the internal pressure is finished, controlling the reaction pressure to be less than 0.4MPa, reacting at 110 ℃, keeping the internal pressure for 2 hours after the reaction is finished, transferring into a refining kettle, dehydrating, and filtering to obtain the pentaerythritol-based polyether polyol C1.
The unsaturation degree of the pentaerythritol-based polyether polyol C1 is 0.016mol/kg, the primary hydroxyl content is 82 percent, and the molecular weight is 7800.
[ COMPARATIVE EXAMPLE 1] preparation of sorbitol-based polyether polyol B3
Adding 7g of sorbitol and 1.8g of potassium hydroxide catalyst into a 2L closed reaction kettle, replacing air in the kettle with nitrogen, heating to 110 ℃, adding 1521g of propylene oxide, controlling the reaction pressure to be less than 0.4MPa, reacting at 110 ℃, keeping the internal pressure for 2 hours after the reaction is finished, continuously adding 270g of ethylene oxide after the internal pressure is finished, controlling the reaction pressure to be less than 0.4MPa, reacting at 110 ℃, moving into a refining kettle to dehydrate after the internal pressure is finished for 2 hours, and filtering to obtain the sorbitol-based polyether polyol B1.
The unsaturation degree of the sorbitol-based polyether polyol B1 is 0.043mol/kg, the primary hydroxyl group content is 75 percent, and the molecular weight is 12000.
Comparative example 2 preparation of (Glycerol-sorbitol) polyether polyol AB
Adding 20g of glycerol, 2.5g of sorbitol and 1.8g of phosphazene catalyst into a 2L closed reaction kettle, replacing air in the kettle with nitrogen, heating to 110 ℃, adding 1673g of propylene oxide, controlling the reaction pressure to be less than 0.4MPa, reacting at 110 ℃, keeping the internal pressure for 2 hours after the reaction is finished, continuously adding 268g of ethylene oxide after the internal pressure is finished, controlling the reaction pressure to be less than 0.4MPa, reacting at 110 ℃, keeping the internal pressure for 2 hours after the reaction is finished, transferring into a refining kettle, dehydrating and filtering to obtain the glycerol-sorbitol-based polyether polyol AB.
[ example 6 ] preparation of stabilizer precursor D1
Adding 7g of sorbitol and 1.8g of phosphazene catalyst into a 2L closed reaction kettle, replacing air in the kettle with nitrogen, heating to 110 ℃, adding 1521g of propylene oxide, controlling the reaction pressure to be less than 0.4MPa, reacting at 110 ℃, keeping the internal pressure for 2 hours after the reaction is finished, continuously adding 288g of ethylene oxide after the internal pressure is finished, controlling the reaction pressure to be less than 0.4MPa, reacting at 110 ℃, keeping the internal pressure for 2 hours after the reaction is finished, transferring into a refining kettle, dehydrating, and filtering to obtain polyether polyol.
The stabilizer precursor D1 was obtained by heating polyether polyol (100 parts), 3-isopropyl-dimethylbenzyl isocyanate TMI (0.5 part), diphenylmethane diisocyanate MDI (0.5 part), and 100ppm stannous octoate catalyst at 80 ℃ for 2 hours.
[ examples 7 to 13 ] and comparative examples 3 to 7 ] preparation of Polymer polyol
(1) Preparation of the pre-reactant PFS:
the preparation of the pre-reactants was carried out using a two-stage reaction system comprising a continuous stirred tank reactor (first reactor) equipped with an impeller and a plug flow reactor (second reactor).
The stabilizer precursor prepared in example 5, isopropanol, a mixture of Styrene (SM) and Acrylonitrile (AN) [ SM/AN (mol) = 2. The pre-reactant PFS from the second reactor is then passed through a cooler into a collection vessel to obtain the pre-reactant PFS.
Wherein the weight percentages of stabilizer precursor, isopropanol, a mixture of Styrene (SM) and Acrylonitrile (AN), and initiator are listed in Table 1.
Table 1:
| kind of raw material | The weight content of the PFS1 product |
| Isopropanol (I-propanol) | 60 |
| Stabiliser precursors D1 | 24 |
| SM+AN | 15.9 |
| Initiator | 0.1 |
(2) Preparation of Polymer polyol:
the preparation of polymer polyol was carried out using a two-stage reaction system comprising a continuous stirred tank reactor (first reactor) equipped with an impeller and a plug flow reactor (second reactor).
Adding a pre-reactant PFS, a base polyether polyol, a mixture of Styrene (SM) and Acrylonitrile (AN) and AN initiator AIBN azobisisobutyronitrile into a feed tank, continuously pumping the mixture from the feed tank through a series of static mixers, then sequentially entering a first reactor (a continuous stirred tank reactor) and a second reactor (a plug flow reactor) which are connected in series through feed pipes to fully mix and react the components, wherein the mixing reaction temperature of the two reactors is 115 +/-1 ℃, the residence time of the two reactors in the reactors is 60 minutes, and passing a product polymer polyol from the second reactor through a cooler to a collection container. The crude product was vacuum stripped to remove volatiles. The total weight% of polymer in the product was calculated by the monomer concentration measured in the virgin polymer polyol.
Wherein the percentages of the pre-reactants, the base polyether polyol, the mixture of Styrene (SM) and Acrylonitrile (AN), and the initiator are listed in table 2.
[ Experimental example ] preparation of polyurethane foam
Weighing a certain amount of auxiliary agents such as polyether polyol, polymer polyol, a catalyst, a foaming agent, a cross-linking agent and the like according to a formula shown in Table 3, uniformly stirring the auxiliary agents serving as a component A, and controlling the temperature of the component A to be 20-25 ℃; in another container, a certain amount of isocyanate is weighed according to the formula to be used as a component B, and the temperature is controlled to be 20-25 ℃. The component B is quickly poured into a container of the component A, the mixture is stirred at a high speed for 4 to 7 seconds, the mixture is poured into a mold with the size of 380mm multiplied by 100mm and a certain temperature, after curing for a certain time, the sample is quickly demoulded, after curing for 72 hours at room temperature, the test of the physical properties is carried out, and the results are shown in Table 4.
Table 3:
the foam performance test method is carried out by adopting the national standard GB/T10802-2006 Universal Soft polyether polyurethane foam plastics and the cited test standard thereof.
Table 4:
the invention has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to limit the invention. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the embodiments and implementations of the invention without departing from the spirit and scope of the invention, and are within the scope of the invention. The scope of the invention is defined by the appended claims.
Claims (14)
1. A method of making a high resilience polymer polyol, comprising: carrying out reaction on raw materials including basic polyether polyol, a stabilizer precursor, an unsaturated monomer, an initiator and a chain transfer agent to obtain the high-resilience polymer polyol; wherein the base polyether polyol is selected from a combination of at least two of a glyceryl polyether polyol, a sorbitol-based polyether polyol, and a pentaerythritol-based polyether polyol.
2. The method according to claim 1, wherein the glyceryl polyether polyol, sorbitol-based polyether polyol or pentaerythritol-based polyether polyol is obtained by: respectively taking glycerol, sorbitol or pentaerythritol as an initiator, adding an epoxy compound in the presence of a catalyst I to react, and then optionally capping with ethylene oxide to respectively obtain the glyceryl polyether polyol, the sorbitol polyether polyol or the pentaerythritol polyether polyol.
3. The method according to claim 1,
the unsaturation degree of the glyceryl polyether polyol is less than 0.04mol/kg, the primary hydroxyl content is more than 70 percent, and the molecular weight is 3000-8000; and/or the presence of a gas in the gas,
the unsaturation degree of the sorbitol-based polyether polyol is less than 0.04mol/kg, the primary hydroxyl content is more than 70 percent, and the molecular weight is 4000-14000; and/or the presence of a gas in the gas,
the unsaturation degree of the pentaerythritol-based polyether polyol is less than 0.04mol/kg, the primary hydroxyl content is more than 70 percent, and the molecular weight is 4000-12000.
4. The production method according to claim 1, characterized in that the base polyether polyol is a combination of at least one member selected from the group consisting of sorbitol-based polyether polyol and pentaerythritol-based polyether polyol, and glycerin-based polyether polyol; preferably, the weight ratio of at least one of the sorbitol-based polyether polyol and the pentaerythritol-based polyether polyol to the glyceryl polyether polyol is 1 (0.5-5), preferably 1 (1-3).
5. The method of claim 1, wherein the stabilizer precursor is obtained by: the stabilizer precursor is obtained by reacting raw materials including polyether polyol, polyisocyanate, isocyanate containing unsaturated reaction bonds and a catalyst II.
6. The method according to claim 5,
the polyether polyol is a copolymer of propylene oxide and ethylene oxide, and the tail end of the polyether polyol contains 2-8 hydroxyl groups; and/or the presence of a gas in the gas,
the molecular weight of the polyether polyol is 900-12000; and/or the presence of a gas in the atmosphere,
the weight content of the ethylene oxide unit in the polyether polyol is 5-20%.
7. The production method according to claim 5,
the polyisocyanate is selected from compounds containing at least two isocyanate groups, preferably at least one selected from isophorone diisocyanate, 4 '-dicyclohexylmethane diisocyanate, 1, 4-cyclohexane diisocyanate, norbornane diisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate and 4,4' -diphenylmethane diisocyanate; and/or the presence of a gas in the atmosphere,
the catalyst II is at least one selected from tin catalysts, amine catalysts and other metal catalysts, preferably at least one selected from dibutyl tin dilaurate, stannous octoate, tetrabutyl titanate and triethylene diamine; and/or the presence of a gas in the gas,
the isocyanate containing unsaturated reaction bonds is at least one of 3-isopropyl-dimethylbenzyl isocyanate and ethyl isocyanate methacrylate.
8. The process according to claim 5, wherein the isocyanate is used in an amount of 0.05 to 5 parts by weight, the isocyanate having an unsaturated reactive bond is used in an amount of 0.05 to 5 parts by weight, and the catalyst II is used in an amount of 10 to 1000ppm by weight, based on 100 parts by weight of the polyether polyol.
9. The method according to claim 1,
the unsaturated monomer is selected from at least one of butadiene, isoprene, alpha-methyl styrene, (tert-butyl) styrene, chlorostyrene, cyanostyrene, bromostyrene, styrene, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, N-dimethylacrylamide, N- (dimethylaminomethyl) acrylamide, vinyl ether, vinyl ketone and vinylidene halide; and/or the presence of a gas in the gas,
the chain transfer agent is selected from at least one of methanol, ethanol, butanol, isopropanol and mercaptan; and/or the presence of a gas in the atmosphere,
the initiator is selected from at least one of alkyl hydroperoxide, aryl hydroperoxide, persulfate, perborate, percarbonate, and azo compounds.
10. The method according to any one of claims 1 to 9, wherein the method for producing the polymer polyol comprises the steps of:
step 1, carrying out pre-reaction on the stabilizer precursor and the unsaturated monomer in the presence of the initiator and the chain transfer agent to obtain a pre-reactant;
and 2, in the presence of the initiator, reacting the pre-reactant obtained in the step 1 with the base polyether polyol and the unsaturated monomer to obtain the polymer polyol.
11. The production method according to claim 10,
in the step 1, based on 100 percent of the total weight of the raw materials for reaction in the step 1, the dosage of the initiator is 0.01 to 1 percent, the dosage of the chain transfer agent is 20 to 80 percent, the dosage of the stabilizer precursor is 10 to 50 percent, and the dosage of the unsaturated monomer is 5 to 30 percent; and/or the presence of a gas in the gas,
in the step 2, based on 100 percent of the total weight of the raw materials in the step 2, the amount of the initiator is 0.05 to 2 percent, the amount of the pre-reactant is 1 to 20 percent, the amount of the base polyether polyol is 20 to 80 percent, and the amount of the unsaturated monomer is 20 to 70 percent.
12. The method of claim 10,
in step 1, the pre-reaction is carried out at 80-150 ℃, preferably at 100-140 ℃; and/or the presence of a gas in the gas,
in step 2, the reaction is carried out at 80 to 140 ℃, preferably at 100 to 130 ℃.
13. A polymer polyol obtained by the production process according to any one of claims 1 to 12.
14. Use of a polymer polyol obtained by the process according to any one of claims 1 to 12 in polyurethane foams.
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