CN108559033B - Preparation method of macromolecule stabilizer prepolymer - Google Patents
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Abstract
The invention relates to a preparation method of a prepolymer of a macromolecular stabilizer, which mainly solves the problems that the conversion rate of the prepolymer of the macromolecular stabilizer in the prior art is not controlled, and the prepared polymer polyol has high viscosity under the condition of certain solid content. The invention adopts a preparation method of a macromolecular stabilizer prepolymer, and the macromolecular stabilizer prepolymer is prepared by taking a macromolecular stabilizer and a vinyl monomer as raw materials and carrying out free radical copolymerization in a solvent in the presence of a free radical initiator, wherein the temperature of the free radical copolymerization is set to be 70-120 ℃, the time of the free radical copolymerization is set to be 10-45 min, and when the temperature exceeds a set temperature value, the temperature is quickly reduced, the temperature is separated from a reaction zone, so that the conversion rate of the vinyl monomer is less than or equal to 60 percent.
Description
Technical Field
The invention relates to a preparation method of a prepolymer of a macromolecular stabilizer.
Background
The polymer polyol (POP) is prepared by taking polyether polyol as a basic polyether as a continuous phase, adding a vinyl monomer and a free radical initiator, and carrying out in-situ copolymerization and graft polymerization at a certain temperature under the protection of nitrogen. The polyurethane foam prepared by the polymer polyol is characterized in that the flexible polyurethane foam has high hardness, bearing capacity and good resilience, and the foam cell structure and the physical and mechanical properties are improved.
Stability is an important characteristic of polyether polyols, and it is required that the dispersed phase must remain uniformly distributed within the base polyol phase during storage, transportation and use of the polymer polyol. Macromolecular stabilizers contain polyol-soluble groups, typically polyether segments, and can have molecular weights of thousands and more. The macromolecular stabilizer is at the other end a vinyl segment and is present at the surface of the dispersed polymer particles, where the polyol soluble groups are believed to stabilize the polymer particles by interaction of these soluble groups with the continuous phase base polyether polyol. A common macromolecular stabilizer is prepared by terminating one or more hydroxyl groups on a polyether polyol with a polymerizable unsaturated group.
Methods for stabilizing polymer particles in polymer polyols by macromolecular stabilizers are already known to the person skilled in the art. Meanwhile, a particularly advantageous method for preparing low viscosity, high solids content polymer polyols is to use a macromolecular stabilizer prepolymer, which is disclosed in patents USP5990185, USP5196476, USP7179882, USP6613827, CN103408704, but in these patents, the conversion rate of the macromolecular stabilizer prepolymer is not controlled, and a process for controlling the conversion rate of the macromolecular stabilizer prepolymer and the influence of the conversion rate of the macromolecular stabilizer prepolymer on the viscosity of the polymer polyol are not mentioned.
Disclosure of Invention
The invention aims to solve the technical problems that the conversion rate of a prepolymer of a macromolecular stabilizer in the prior art is not controlled, and the prepared polymer polyol has high viscosity under the condition of certain solid content, and provides a novel preparation method of the prepolymer of the macromolecular stabilizer.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a preparation method of a macromolecular stabilizer prepolymer is characterized in that in a reaction feeding system, a macromolecular stabilizer and a vinyl monomer are used as raw materials, and the macromolecular stabilizer and the vinyl monomer are subjected to free radical copolymerization in a solvent in the presence of a free radical initiator to obtain the macromolecular stabilizer prepolymer, wherein the temperature of the free radical copolymerization is set to be 70-120 ℃, the time of the free radical copolymerization is set to be 10-45 min, and when the temperature exceeds a set temperature value, the temperature is rapidly reduced, the temperature is separated from a reaction zone, and the conversion rate of the vinyl monomer is enabled to be less than or equal to 60%.
In the above technical solution, preferably, the macromolecular stabilizer is a copolymer of polyether polyol having a double bond at the molecular chain end and a molecular weight of not less than 12000 and a compound having a double bond or a triple bond; the vinyl monomer is at least one selected from styrene, acrylonitrile, methacrylic acid, butyl methacrylate, hydroxyethyl methacrylate and acrylic acid; the free radical initiator is at least one selected from Azobisisobutyronitrile (AIBN), dimethyl azobisisobutyrate, Benzoyl Peroxide (BPO), tert-butyl peroxy (2-ethylhexanoate) or tert-butyl peroxy diethylacetate; the solvent is at least one selected from isopropanol, tert-butanol, toluene or n-butanol.
In the above technical scheme, preferably, in the reaction feeding system, the weight percentage of the macromolecular stabilizer is 15-30%, the weight percentage of the vinyl monomer is 10-30%, the weight percentage of the free radical initiator is 0.1-0.4%, and the weight percentage of the solvent is 40-74%.
In the above technical scheme, more preferably, in the reaction feeding system, the weight percentage of the macromolecular stabilizer is 20-25%, the weight percentage of the vinyl monomer is 15-25%, the weight percentage of the free radical initiator is 0.15-0.35%, and the weight percentage of the solvent is 50-64%.
In the above technical solution, preferably, the polyether polyol in the macromolecular stabilizer is a copolymerization product of propylene oxide and ethylene oxide; the compound containing double bonds or triple bonds is a compound which can react with hydroxyl groups on polyether polyol to form a stable molecular chain.
In the above technical solution, preferably, the compound capable of reacting with hydroxyl groups on polyether polyol to form a stable molecular chain is at least one selected from a composition of polyisocyanate and hydroxyl group-containing unsaturated monomer, acrylic acid, vinyl siloxane, and unsaturated isocyanate.
In the above technical solution, preferably, the composition of the polyisocyanate and the hydroxyl group-containing unsaturated monomer is selected from at least one of hydroxyalkyl acrylate or hydroxyalkyl methacrylate.
In the technical scheme, preferably, the temperature of the free radical copolymerization is 80-110 ℃, and the time of the free radical copolymerization is 15-35 min; when the temperature is quickly reduced, the temperature reduction temperature in the reaction kettle is set to be less than or equal to 45 ℃, and the temperature reduction temperature of the external circulation heat exchanger is set to be less than or equal to 15 ℃; the conversion rate of the vinyl monomer is 20-50%.
In the technical scheme, more preferably, the temperature of the free radical copolymerization is 85-105 ℃, and the time of the free radical copolymerization is 20-35 min; when the temperature is quickly reduced, the temperature reduction temperature in the reaction kettle is set to be less than or equal to 35 ℃, and the temperature reduction temperature of the external circulation heat exchanger is set to be less than or equal to 5 ℃; the conversion rate of the vinyl monomer is 35-45%.
In the invention, the macromolecular stabilizer is subjected to free radical polymerization reaction with the vinyl monomer in the solvent in the presence of the free radical initiator, and then is rapidly cooled when the temperature exceeds a set temperature value, so that the conversion rate of the vinyl monomer is accurately controlled. The macromolecule stabilizer prepolymer obtained by the preparation method can fully play the role of the macromolecule stabilizer, and ensures the optimal dispersion stabilizing effect of the macromolecule stabilizer prepolymer in the polymer polyol, thereby ensuring that the polymer polyol prepared under the condition of certain solid content has the advantage of lower viscosity, and obtaining better technical effect.
The present invention will be further illustrated by the following examples, but is not limited to these examples.
Detailed Description
In the preparation method of the prepolymer of the macromolecular stabilizer of the invention, the polyether polyol used is described as follows:
base polyether polyol a: the polyether is prepared by taking potassium hydroxide (KOH) as a catalyst and glycerol as an initiator, and carrying out addition copolymerization on the catalyst, propylene oxide and ethylene oxide, wherein the content of the ethylene oxide is 7.5 percent (by weight), and the hydroxyl value is as follows: 56mgKOH/g, molecular weight about 3000.
Polyether polyol B: the polyether polyol is prepared by carrying out addition polymerization on an organic alkoxide catalyst and sorbitol serving as an initiator, propylene oxide and ethylene oxide, wherein the molecular weight end is capped by the ethylene oxide, the content of the ethylene oxide is 15 percent (weight), and the hydroxyl value: 24mgKOH/g, and molecular weight of about 14000.
Polyether polyol C: KOH is used as a catalyst, glycerin is used as an initiator, and the catalyst, propylene oxide and ethylene oxide are subjected to addition polymerization to prepare polyether, wherein the tail end of the molecular weight is capped by ethylene oxide, and the ethylene oxide content is as follows: 14.5% (by weight), hydroxyl value: 34mgKOH/g, molecular weight about 4800.
Preparation of macromolecular stabilizers
Macromolecular stabilizer a: the macromolecular stabilizer A is a transparent liquid with the viscosity of 1750mpa.s at 25 ℃ prepared by heating polyether polyol B and isopropenyl dimethyl benzyl isocyanate (TMI) for 3 hours at 75 ℃ under the action of stannous octoate catalyst.
Macromolecular stabilizer B: toluene Diisocyanate (TDI) is heated to 75 ℃, hydroxypropyl methacrylate is gradually and dropwise added into a reactor, after heating and curing for 2 hours, the Toluene Diisocyanate (TDI) is transferred into polyether polyol B which is heated to 80 ℃ and dehydrated, catalyst stannous octoate is added, and stirring reaction is carried out for 3 hours at 80 ℃ to prepare transparent liquid with viscosity of 2500mpa.s at 25 ℃.
Macromolecular stabilizer C: polyether polyol C and maleic anhydride react at 120 ℃ for 3 hours, then an inorganic basic catalyst is added, and ethylene oxide is added at 130 ℃ for a capping reaction for 6 hours to prepare a transparent liquid with the viscosity of 3500mpa.s at 25 ℃.
Example 1
(1) Preparing a prepolymer A1 of the macromolecular stabilizer: macromolecular stabilizer a: 250g, styrene 75g, acrylonitrile: 75g, azobisisobutyronitrile: 3g, isopropyl alcohol: 600g, the set temperature of free radical copolymerization is 95 ℃, the set time of the free radical copolymerization is 20min, the temperature of an external circulation heat exchanger is reduced to 35 ℃, an external pump is started to circulate and continuously reduce the temperature to 5 ℃, and the conversion rate of the obtained macromolecular stabilizer prepolymer A1 is 28.8%.
(2) Preparation of Polymer polyol: mixing a base polyether polyol A: 1610g, macromolecular stabilizer prepolymer A1: 500g, styrene: 900g, acrylonitrile: 500g, azobisisobutyronitrile: 12g, and after fully mixing, continuously pumping the mixture into a reaction kettle by using a dropping pump. The temperature of the reaction kettle is controlled at 130 ℃. All reactions were carried out in a nitrogen purged protected reactor. The mixed raw materials are continuously fed into the first reaction kettle for reaction, and the materials in the first reaction kettle overflow into the second reaction kettle for continuous reaction. And (3) distilling the crude product overflowing and discharged from the second reaction kettle under vacuum at the temperature of 135-145 ℃ for several hours under the mbar condition, and removing the solvent and residual monomers to obtain the needed polymer polyol. The resulting polymer polyol had a solids content of 45% by weight and a viscosity of 3569mpa.s/25 ℃. The conversion of the prepolymer to give the macromolecular stabilizer and the quality of the polymer polyol product are shown in Table 1.
Example 2
(1) Preparing a prepolymer A2 of the macromolecular stabilizer: macromolecular stabilizer a: 250g, styrene 75g, acrylonitrile: 75g, azobisisobutyronitrile: 3g, isopropyl alcohol: 600g, the set temperature of free radical copolymerization is 95 ℃, the set time of the free radical copolymerization is 25min, the temperature of an external circulation heat exchanger is reduced to 35 ℃, an external pump is started to circulate and continuously reduce the temperature to 5 ℃, and the conversion rate of the obtained macromolecular stabilizer prepolymer A2 is 41.64%.
(2) Preparation of Polymer polyol: mixing a base polyether polyol A: 1610g, macromolecular stabilizer prepolymer A2: 500g, styrene: 900g, acrylonitrile: 500g, azobisisobutyronitrile: 12g of the mixture is fully mixed and then continuously pumped into a reaction kettle by a dropping pump. The temperature of the reaction kettle is controlled at 130 ℃. All reactions were carried out in a nitrogen purged protected reactor. The mixed raw materials are continuously fed into the first reaction kettle for reaction, and the materials in the first reaction kettle overflow into the second reaction kettle for continuous reaction. And (3) distilling the crude product overflowing and discharged from the second reaction kettle under vacuum at the temperature of 135-145 ℃ for several hours under the mbar condition, and removing the solvent and residual monomers to obtain the needed polymer polyol. The resulting polymer polyol had a solids content of 45% by weight and a viscosity of 3782mpa.s/25 ℃. The conversion of the prepolymer to give the macromolecular stabilizer and the quality of the polymer polyol product are shown in Table 1.
Example 3
(1) Preparing a prepolymer A3 of the macromolecular stabilizer: macromolecular stabilizer a: 250g, styrene 75g, acrylonitrile: 75g, azobisisobutyronitrile: 3g, isopropyl alcohol: 600g, the set temperature of free radical copolymerization is 95 ℃, the set time of the free radical copolymerization is 30min, the temperature of an external circulation heat exchanger is reduced to 35 ℃, an external pump is started to circulate and continuously reduce the temperature to 5 ℃, and the conversion rate of the obtained macromolecular stabilizer prepolymer A3 is 53.98%.
(2) Preparation of Polymer polyol: mixing a base polyether polyol A: 1610g, macromolecular stabilizer prepolymer A3: 500g, styrene: 900g, acrylonitrile: 500g, azobisisobutyronitrile: 12g of the mixture is fully mixed and then continuously pumped into a reaction kettle by a dropping pump. The temperature of the reaction kettle is controlled at 130 ℃. All reactions were carried out in a nitrogen purged protected reactor. The mixed raw materials are continuously fed into the first reaction kettle for reaction, and the materials in the first reaction kettle overflow into the second reaction kettle for continuous reaction. And (3) distilling the crude product overflowing and discharged from the second reaction kettle under vacuum at the temperature of 135-145 ℃ for several hours under the mbar condition, and removing the solvent and residual monomers to obtain the needed polymer polyol. The resulting polymer polyol had a solids content of 45% by weight and a viscosity of 4059mPa.s/25 ℃. The conversion of the prepolymer to give the macromolecular stabilizer and the quality of the polymer polyol product are shown in Table 1.
Example 4
(1) Preparing a prepolymer B1 of the macromolecular stabilizer: macromolecular stabilizer B: 250g, styrene 75g, acrylonitrile: 75g, azobisisobutyronitrile: 3g, isopropyl alcohol: 600g, the set temperature of free radical copolymerization is 102 ℃, the set time of the free radical copolymerization is 30min, the temperature of an external circulation heat exchanger is reduced to 35 ℃, an external pump is started to circulate and continuously reduce the temperature to 5 ℃, and the conversion rate of the obtained macromolecule stabilizer prepolymer B1 is 65.27%.
(2) Preparation of Polymer polyol: mixing a base polyether polyol A: 1610g, macromolecular stabilizer prepolymer B1: 500g, styrene: 900g, acrylonitrile: 500g, azobisisobutyronitrile: 12g of the mixture is fully mixed and then continuously pumped into a reaction kettle by a dropping pump. The temperature of the reaction kettle is controlled at 130 ℃. All reactions were carried out in a nitrogen purged protected reactor. The mixed raw materials are continuously fed into the first reaction kettle for reaction, and the materials in the first reaction kettle overflow into the second reaction kettle for continuous reaction. And (3) distilling the crude product overflowing and discharged from the second reaction kettle under vacuum at the temperature of 135-145 ℃ for several hours under the mbar condition, and removing the solvent and residual monomers to obtain the needed polymer polyol. The resulting polymer polyol had a solids content of 45% by weight and a viscosity of 4776mPa.s/25 ℃. The conversion of the prepolymer to give the macromolecular stabilizer and the quality of the polymer polyol product are shown in Table 1.
Example 5
(1) Preparing a prepolymer B2 of the macromolecular stabilizer: macromolecular stabilizer B: 250g, styrene 75g, acrylonitrile: 75g, azobisisobutyronitrile: 3g, isopropyl alcohol: 600g, the set temperature of free radical copolymerization is 95 ℃, the set time of the free radical copolymerization is 30min, the temperature of an external circulation heat exchanger is reduced to 35 ℃, an external pump is started to circulate and continuously reduce the temperature to 5 ℃, and the conversion rate of the obtained macromolecule stabilizer prepolymer B2 is 50.80%.
(2) Preparation of Polymer polyol: mixing a base polyether polyol A: 1610g, macromolecular stabilizer prepolymer B2: 500g, styrene: 900g, acrylonitrile: 500g, azobisisobutyronitrile: 12g of the mixture is fully mixed and then continuously pumped into a reaction kettle by a dropping pump. The temperature of the reaction kettle is controlled at 130 ℃. All reactions were carried out in a nitrogen purged protected reactor. The mixed raw materials are continuously fed into the first reaction kettle for reaction, and the materials in the first reaction kettle overflow into the second reaction kettle for continuous reaction. And (3) distilling the crude product overflowing and discharged from the second reaction kettle under vacuum at the temperature of 135-145 ℃ for several hours under the mbar condition, and removing the solvent and residual monomers to obtain the needed polymer polyol. The polymer polyol obtained had a solids content of 45% by weight and a viscosity of 3986mpa.s/25 ℃. The conversion of the prepolymer to give the macromolecular stabilizer and the quality of the polymer polyol product are shown in Table 1.
Comparative example 1
(1) The macromolecule stabilizer prepolymer C is used for sampling in production, and the production formula is as follows: macromolecular stabilizer C: 250g, styrene 75g, acrylonitrile: 75g, azobisisobutyronitrile: 3g, isopropyl alcohol: 600g, the set temperature of polymerization is 95 ℃; the process comprises the following steps: the mixed material is continuously dripped into the first reaction kettle from the feeding kettle through a dripping pump, the residence time is set to be 30min, the mixed material overflows to the second reaction kettle, the second reaction kettle is cooled and put into the storage tank for standby after overflowing, and the conversion rate is 75.81%.
(2) Preparation of Polymer polyol: mixing a base polyether polyol A: 1610g, macromolecular stabilizer prepolymer C: 500g, styrene: 900g, acrylonitrile: 500g, azobisisobutyronitrile: 12g of the mixture is fully mixed and then continuously pumped into a reaction kettle by a dropping pump. The temperature of the reaction kettle is controlled at 130 ℃. All reactions were carried out in a nitrogen purged protected reactor. The mixed raw materials are continuously fed into the first reaction kettle for reaction, and the materials in the first reaction kettle overflow into the second reaction kettle for continuous reaction. And (3) distilling the crude product overflowing and discharged from the second reaction kettle under vacuum at the temperature of 135-145 ℃ for several hours under the mbar condition, and removing the solvent and residual monomers to obtain the needed polymer polyol. The resulting polymer polyol had a solids content of 45% by weight and a viscosity of 5459mPa.s/25 ℃. The conversion of the prepolymer to give the macromolecular stabilizer and the quality of the polymer polyol product are shown in Table 1.
TABLE 1
Note: in comparative example 1, the prepolymer C was taken from a sample of a continuous production apparatus, the residence time in the first reaction vessel was 30 minutes, the temperature of the reaction mixture was not lowered in time, and the reaction time was not determined.
Example 6
(1) Preparing a prepolymer A4 of the macromolecular stabilizer: macromolecular stabilizer a: 250g, styrene 100g, acrylonitrile: 100g, benzoyl peroxide: 3g, isopropyl alcohol: 550g, the temperature of free radical copolymerization is set to be 95 ℃, the time of the free radical copolymerization is set to be 25min, an external circulation heat exchanger is cooled to be 35 ℃ of the set temperature, an external pump is started to circulate and continue to be cooled to be 5 ℃ of the set temperature, and the conversion rate of the obtained macromolecular stabilizer prepolymer A4 is 42.39%.
(2) Preparation of Polymer polyol: mixing a base polyether polyol A: 1610g, macromolecular stabilizer prepolymer A4: 500g, styrene: 900g, acrylonitrile: 500g, azobisisobutyronitrile: 12g of the mixture is fully mixed and then continuously pumped into a reaction kettle by a dropping pump. The temperature of the reaction kettle is controlled at 130 ℃. All reactions were carried out in a nitrogen purged protected reactor. The mixed raw materials are continuously fed into the first reaction kettle for reaction, and the materials in the first reaction kettle overflow into the second reaction kettle for continuous reaction. And (3) distilling the crude product overflowing and discharged from the second reaction kettle under vacuum at the temperature of 135-145 ℃ for several hours under the mbar condition, and removing the solvent and residual monomers to obtain the needed polymer polyol. The resulting polymer polyol had a solids content of 45% and a viscosity of 3969mpa.s/25 ℃. The conversion of the prepolymer to give the macromolecular stabilizer and the quality of the polymer polyol product are shown in Table 2.
Example 7
(1) Preparing a prepolymer A5 of the macromolecular stabilizer: macromolecular stabilizer a: 250g, styrene 75g, acrylonitrile: 75g, azobisisobutyronitrile: 3g, tert-butanol: 600g, the set temperature of free radical copolymerization is 95 ℃, the set time of the free radical copolymerization is 25min, the temperature of an external circulation heat exchanger is reduced to 35 ℃, an external pump is started to circulate and continuously reduce the temperature to 5 ℃, and the conversion rate of the obtained macromolecular stabilizer prepolymer A5 is 36.96%.
(2) Preparation of Polymer polyol: mixing a base polyether polyol A: 1610g, macromolecular stabilizer prepolymer A5: 500g, styrene: 900g, acrylonitrile: 500g, azobisisobutyronitrile: 12g of the mixture is fully mixed and then continuously pumped into a reaction kettle by a dropping pump. The temperature of the reaction kettle is controlled at 130 ℃. All reactions were carried out in a nitrogen purged protected reactor. The mixed raw materials are continuously fed into the first reaction kettle for reaction, and the materials in the first reaction kettle overflow into the second reaction kettle for continuous reaction. And (3) distilling the crude product overflowing and discharged from the second reaction kettle under vacuum at the temperature of 135-145 ℃ for several hours under the mbar condition, and removing the solvent and residual monomers to obtain the needed polymer polyol. The resulting polymer polyol had a solids content of 45% and a viscosity of 4162mpa.s/25 ℃. The conversion of the prepolymer to give the macromolecular stabilizer and the quality of the polymer polyol product are shown in Table 2.
Example 8
(1) Preparing a prepolymer B3 of the macromolecular stabilizer: macromolecular stabilizer B: 200g, styrene 100g, acrylonitrile: 100g, benzoyl peroxide: 3g, isopropyl alcohol: 600g, setting the temperature of free radical copolymerization to 95 ℃, setting the time of the free radical copolymerization to 25min, reducing the temperature of an external circulation heat exchanger to 35 ℃, starting an external pump to circulate and continuously reducing the temperature to 5 ℃, wherein the conversion rate of the obtained macromolecular stabilizer prepolymer B3 is 45.04%.
(2) Preparation of Polymer polyol: mixing a base polyether polyol A: 1610g, macromolecular stabilizer prepolymer B3: 600g, styrene: 900g, acrylonitrile: 500g, azobisisobutyronitrile: 12g of the mixture is fully mixed and then continuously pumped into a reaction kettle by a dropping pump. The temperature of the reaction kettle is controlled at 130 ℃. All reactions were carried out in a nitrogen purged protected reactor. The mixed raw materials are continuously fed into the first reaction kettle for reaction, and the materials in the first reaction kettle overflow into the second reaction kettle for continuous reaction. And (3) distilling the crude product overflowing and discharged from the second reaction kettle under vacuum at the temperature of 135-145 ℃ for several hours under the mbar condition, and removing the solvent and residual monomers to obtain the needed polymer polyol. The polymer polyol obtained had a solids content of 45% by weight and a viscosity of 4099mpa.s/25 ℃. The conversion of the prepolymer to give the macromolecular stabilizer and the quality of the polymer polyol product are shown in Table 2.
Example 9
(1) Preparing a prepolymer B4 of the macromolecular stabilizer: macromolecular stabilizer B: 250g, styrene 75g, acrylonitrile: 75g, azobisisobutyronitrile: 4g, isopropyl alcohol: 600g, setting the temperature of free radical copolymerization to 95 ℃, setting the time of the free radical copolymerization to 25min, cooling an external circulation heat exchanger to 35 ℃, starting an external pump to circulate and continuously cool to 5 ℃, and obtaining the conversion rate of the macromolecular stabilizer prepolymer B4 of 63.65%.
(2) Preparation of Polymer polyol: mixing a base polyether polyol A: 1610g, macromolecular stabilizer prepolymer B4: 500g, styrene: 900g, acrylonitrile: 500g, azobisisobutyronitrile: 12g of the mixture is fully mixed and then continuously pumped into a reaction kettle by a dropping pump. The temperature of the reaction kettle is controlled at 130 ℃. All reactions were carried out in a nitrogen purged protected reactor. The mixed raw materials are continuously fed into the first reaction kettle for reaction, and the materials in the first reaction kettle overflow into the second reaction kettle for continuous reaction. And (3) distilling the crude product overflowing and discharged from the second reaction kettle under vacuum at the temperature of 135-145 ℃ for several hours under the mbar condition, and removing the solvent and residual monomers to obtain the needed polymer polyol. The resulting polymer polyol had a solids content of 45% by weight and a viscosity of 4675mPa.s/25 ℃. The conversion of the prepolymer to give the macromolecular stabilizer and the quality of the polymer polyol product are shown in Table 2.
TABLE 2
Claims (5)
1. A preparation method of a macromolecular stabilizer prepolymer comprises the steps of in a reaction feeding system, taking a macromolecular stabilizer and a vinyl monomer as raw materials, carrying out free radical copolymerization in a solvent in the presence of a free radical initiator to obtain the macromolecular stabilizer prepolymer, wherein the temperature of the free radical copolymerization is 85-102 ℃, the time of the free radical copolymerization is 20-35 min, and when the temperature exceeds a set temperature value, the temperature is quickly reduced to separate from the temperature of a reaction zone, so that the conversion rate of the vinyl monomer is 20-50%; the macromolecular stabilizer is a copolymer of polyether polyol with the molecular weight of not less than 12000 and a compound containing double bonds or triple bonds, which is prepared by copolymerizing sorbitol serving as an initiator with propylene oxide and ethylene oxide; wherein the compound containing a double or triple bond is selected from the group consisting of a polyisocyanate and a hydroxyalkyl acrylate or hydroxyalkyl methacrylate composition.
2. The method for preparing a prepolymer for a macromolecular stabilizer according to claim 1, wherein the prepolymer is prepared by mixing a prepolymer for a macromolecular stabilizer; the vinyl monomer is at least one selected from styrene, acrylonitrile, methacrylic acid, butyl methacrylate, hydroxyethyl methacrylate and acrylic acid; the free radical initiator is at least one selected from azobisisobutyronitrile, dimethyl azobisisobutyrate, benzoyl peroxide, tert-butyl peroxy (2-ethylhexanoate) or tert-butyl peroxy diethylacetate; the solvent is at least one selected from isopropanol, tert-butanol, toluene or n-butanol.
3. The method for preparing a prepolymer of a macromolecular stabilizer according to claim 1, wherein in the reaction feeding system, the macromolecular stabilizer is 15-30 wt%, the vinyl monomer is 10-30 wt%, the radical initiator is 0.1-0.4 wt%, and the solvent is 40-74 wt%.
4. The method for preparing a prepolymer of a macromolecular stabilizer according to claim 3, wherein in the reaction feeding system, the macromolecular stabilizer is 20-25 wt%, the vinyl monomer is 15-25 wt%, the radical initiator is 0.15-0.35 wt%, and the solvent is 50-64 wt%.
5. The method for preparing the prepolymer of the macromolecular stabilizer according to claim 1, wherein the temperature of the reaction kettle is set to be less than or equal to 35 ℃ and the temperature of the external circulation heat exchanger is set to be less than or equal to 5 ℃ during rapid cooling; the conversion rate of the vinyl monomer is 35-45%.
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| CN117430802B (en) * | 2023-12-20 | 2024-05-10 | 山东一诺威新材料有限公司 | Preparation method of polyhydroxy acrylic ester macromer, method for preparing polymer polyol by using polyhydroxy acrylic ester macromer and application of polyhydroxy acrylic ester macromer |
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| EP0510533A3 (en) * | 1991-04-22 | 1993-05-26 | The Dow Chemical Company | Process for preparing polymer polyols, and polymer polyol so made |
| US5488085A (en) * | 1994-08-18 | 1996-01-30 | Arco Chemical Technology, L.P. | Semi-batch process for producing polymer polyols |
| ES2148397T3 (en) * | 1995-10-10 | 2000-10-16 | Bayer Ag | CONTINUOUS PROCEDURE FOR THE PREPARATION OF LOW VISCOSITY POLYMERIC POLYOLES, FINALLY DIVIDED, VERY STABLE, OF SMALL AVERAGE SIZE OF PARTICLES. |
| KR100657874B1 (en) * | 2004-11-04 | 2006-12-14 | 금호석유화학 주식회사 | Distribution stabilizer for the preparation of polymer polyol |
| CN1302035C (en) * | 2005-02-24 | 2007-02-28 | 烟台万华聚氨酯股份有限公司 | Polymer polyester polyol, its producing process and its use |
| US20090018227A1 (en) * | 2005-07-07 | 2009-01-15 | Sanyo Chemical Industries, Ltd. | Fine Particle-Dispersed Polyol Composition, Method for Producing Polymer Polyol, and Method for Producing Polyurethane Resin |
| CN104045763B (en) * | 2013-03-11 | 2019-07-16 | 中国石油化工集团公司 | The method of continuous production of polymers polyalcohol performed polymer |
| CN104045791A (en) * | 2013-03-11 | 2014-09-17 | 中国石油化工集团公司 | Preparation method of polymer polyol |
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