High-functional composite macromolecular monomer, preparation method therefor and use thereof

Abstract

The present invention relates to the technical field of polymer polyols, and disclosed are a high-functional composite macromolecular monomer, a preparation method therefor, and a use thereof. A technical solution thereof is: S1, reacting an initiator with an epoxy compound under the action of a catalyst, to obtain a polyether polyol intermediate; S2, using the polyether polyol intermediate and a hyperbranched polyester polyol as a composite initiator, reacting with an epoxy compound under the action of a catalyst, to produce a polyether / polyester ether polyol; S3, reacting the polyether / polyester ether polyol with an unsaturated isocyanate under the action of a catalyst, to generate a high-functional composite macromolecular monomer. The present invention increases the functionality of the macromolecular monomer by means of the initiator, increases the dispersibility of the macromolecular monomer in a polymer polyol, improves the stability of styrene–acrylonitrile copolymer particles in a polymer polyol, and reduces the viscosity of a polymer polyol; introducing a polyester system into the macromolecular monomer structure increases the proportion of hydrophobic groups in polymer polyols, reducing the occurrence of hydrogel formation upon exposure to water.

Description

High-functionality complex macromonomer, preparation method and application thereof TECHNICAL FIELD

[0001] The present application relates to the technical field of polymer polyols, in particular to a high-functionality complex macromonomer, a preparation method and an application thereof. BACKGROUND

[0002] Polyurethane flexible foam is widely used in daily life such as carpets, furniture, transportation, etc. The polymer particles in the polymer polyol (POP) are filled in the polyurethane network structure, which can effectively improve the open porosity, hardness and load bearing capacity of the polyurethane flexible foam. However, with the increase of the content of the polymer particles (i.e. the increase of the solid content), the viscosity of the POP increases significantly. The solid content of the currently marketed POP product is less than 50%, and the viscosity is less than 6000 mPa·s. The macromonomer as the core part of the polymer polyol has an amphiphilic structure, which can be well miscible with the base polyether polyol on the one hand, and can improve the dispersibility of styrene-acrylonitrile copolymer in the polyether medium on the other hand. Therefore, the structure of the macromonomer significantly affects the viscosity, storage stability and water gel properties of the polymer polyol. Chinese invention patent CN111732707B discloses a macromonomer stabilizer, a preparation method and an application thereof. Nitrogen heterocycle is introduced, which effectively enhances the stability of the polymer polyol through the dispersion force interaction between the nitrogen heterocycle and the olefinic unsaturated monomer. The prepared polymer polyol has the advantages of low viscosity and uniform particle distribution.

[0003] It is generally believed that high-functionality macromonomers can have good dispersion effect in POP. It is a common method to synthesize macromonomers from high-functionality polyether polyols to reduce the viscosity of POP. For example, Chinese invention patent CN112708124A discloses a preparation method of high-functionality polyether polyol and an application thereof. Epoxy alkyl alcohol and propylene oxide are used to improve the functionality of polyether polyol. However, epoxy alkyl alcohol is toxic, which is limited in actual production. In addition, water is added as a chemical blowing agent during the polymer foaming process. The viscosity of the material will increase significantly after the addition of water. Chinese invention patent CN109796575B discloses a stabilizer, a preparation method thereof, a preparation method of polymer polyol and an application thereof. The water gel property of POP is reduced by using several urethane bonds in the stabilizer. The prepared polymer polyol still has good fluidity in the polyurethane foaming system with high moisture content (moisture content is more than 3%). Therefore, it is an urgent problem to be solved in the industry to design the structure of the macromonomer from the direction of the macromonomer, reduce the viscosity and water gel property of POP, and improve the hydrophobicity thereof. SUMMARY

[0004] The technical problem solved by the present application is to overcome the shortcomings of the prior art, provide a high-functionality composite macromonomer, a preparation method and application thereof, improve the functionality of the macromonomer through high functionality of the starter, further improve the dispersion of the macromonomer in the polymer polyol, thereby improving the stability of the styrene-acrylonitrile copolymer particles in the polymer polyol and reducing the viscosity of the polymer polyol, and increase the proportion of hydrophobic groups in the polymer polyol by introducing a polyester system into the structure of the macromonomer, thereby reducing the occurrence of water gelation.

[0005] The technical scheme of the present application is:

[0006] In a first aspect, the present application provides a preparation method of a high-functionality composite macromonomer, comprising the following steps:

[0007] S1 reacting a starter with an epoxide compound under the action of a catalyst to obtain a polyether polyol intermediate;

[0008] S2 reacting the polyether polyol intermediate obtained in step S1 with a hyperbranched polyester polyol as a composite starter with an epoxide compound under the action of a catalyst to generate a polyether / polyester ether polyol;

[0009] S3 reacting the polyether / polyester ether polyol obtained in step S2 with an unsaturated isocyanate under the action of a catalyst to generate a high-functionality composite macromonomer.

[0010] Preferably, in step S1, the starter is one or two of sucrose, solid sorbitol and liquid sorbitol; the catalyst is KOH; the number average molecular weight of the polyether polyol intermediate is 900-2000 g / mol; the mass ratio of the starter to the epoxide compound is 1:(4-8.5); and the catalyst accounts for 0.2-0.55% of the total mass of the starter, the catalyst and the epoxide compound.

[0011] Preferably, in step S2, the hyperbranched polyester polyol is Boltorn H311 with a functionality of 23; the catalyst is a DMC catalyst; the molar ratio of the polyether polyol intermediate to the hyperbranched polyester polyol is (0.6-4.5):1; the hydroxyl value of the polyether / polyester ether polyol is 28-58 mgKOH / g, and the functionality is 7-9; the mass ratio of the composite starter to the epoxide compound is 1:(3.6-7.3); and the catalyst accounts for 30-170 ppm of the total mass of the composite starter, the catalyst and the epoxide compound.

[0012] Preferably, in step S3, the unsaturated isocyanate is 3-isopropyl-dimethylbenzyl isocyanate, ethyl isocyanate of 2-methacrylate, or ethyl isocyanate acrylate; the catalyst is bismuth neodecanoate; the reaction temperature is 70-90℃; the molar ratio of polyether / polyester ether polyol to unsaturated isocyanate is (0.9-1.2):1; and the catalyst accounts for 50-100 ppm of the total mass of polyether / polyester ether polyol, unsaturated isocyanate, and catalyst.

[0013] Preferably, in step S1, the epoxy compound is propylene oxide, and the reaction temperature is 100-140℃; in step S2, the epoxy compound is propylene oxide and ethylene oxide, and the reaction temperature is 100-140℃.

[0014] Secondly, the present invention provides a high-functionality composite macromonomer, which is prepared by the above-described method for preparing a high-functionality composite macromonomer.

[0015] Thirdly, this invention provides the application of high-functionality complex macromonomers, specifically including the following steps:

[0016] (1) Under the action of chain transfer agent and initiator, the above-mentioned high-functionality complex macromolecular monomer and olefin unsaturated monomer are synthesized into a pre-reactant;

[0017] (2) Add an initiator, a basic polyether polyol and an olefinic unsaturated monomer to the pre-reactant obtained in step (1) and react to obtain a polymer polyol.

[0018] Preferably, in step (1), the chain transfer agent is isopropanol.

[0019] Preferably, in steps (1) and (2), the initiator is dimethyl azobisisobutyrate; in step (1), the olefin unsaturated monomers are styrene and acrylonitrile, with styrene accounting for 50% of the mass of the olefin unsaturated monomers; in step (2), the olefin unsaturated monomers are styrene and acrylonitrile, with styrene accounting for 80% of the mass of the olefin unsaturated monomers.

[0020] Preferably, in step (1), the chain transfer agent accounts for 60% of the total mass of the chain transfer agent, initiator, high-functionality complex macromonomer, and olefin unsaturated monomer; the initiator accounts for 0.1% of the total mass of the chain transfer agent, initiator, high-functionality complex macromonomer, and olefin unsaturated monomer; the high-functionality complex macromonomer accounts for 24% of the total mass of the chain transfer agent, initiator, high-functionality complex macromonomer, and olefin unsaturated monomer; and the olefin unsaturated monomer accounts for... 15.9% of the total mass; in step (2), the initiator accounts for 0.25% of the total mass of the pre-reactant, initiator, base polyether polyol and olefin unsaturated monomer; the pre-reactant accounts for 12.5% ​​of the total mass of the pre-reactant, initiator, base polyether polyol and olefin unsaturated monomer; the base polyether polyol accounts for 40% of the total mass of the pre-reactant, initiator, base polyether polyol and olefin unsaturated monomer; the olefin unsaturated monomer accounts for 47.25% of the total mass of the pre-reactant, initiator, base polyether polyol and olefin unsaturated monomer.

[0021] Compared with the prior art, the present invention has the following advantages:

[0022] This invention enhances the functionality of macromonomers through hyperbranched polyester polyols, forming dendritic structures within the polymer polyol. This provides a larger volume, stabilizes the polymer polyol particles, reduces their viscosity, and improves their filtration performance. Simultaneously, ester functional groups are introduced through an initiator, and urethane bonds are introduced during end-capping polymerization via unsaturated isocyanates. These two types of ester bonds enhance the hydrophobicity of the polymer polyol, reducing the impact of viscosity increase after adding water during subsequent foaming. Detailed Implementation

[0023] To enable those skilled in the art to better understand the technical solutions of this invention, the technical solutions of this invention will be clearly and completely described below in conjunction with the embodiments of this invention.

[0024] The raw materials used in the embodiments of this invention are as follows:

[0025] Basic polyether polyol: Flexible foam polyether polyol prepared by reacting glycerol with propylene oxide and ethylene oxide, F5631, Shandong Yinuowei New Material Co., Ltd.;

[0026] Liquid sorbitol, Vitamin C grade, Shandong Tianli Pharmaceutical Co., Ltd.

[0027] Solid sorbitol, Shouguang Zhongrui Biotechnology Co., Ltd.;

[0028] Sugar, COFCO Group Co., Ltd.;

[0029] Hyperbranched polyester polyol, Boltorn H311.

[0030] The method for determining the performance of polymer polyols in this invention is as follows:

[0031] Viscosity: Measured using a rotational viscometer equipped with a constant temperature bath at 25℃;

[0032] Solid content: Wash away the base polyether polyol in the polymer polyol with anhydrous ethanol, centrifuge, repeat three or more times, and weigh in a constant temperature incubator until constant weight;

[0033] Time through the sieve: Heat the polymer polyol to 100℃, add 200g of polymer polyol to a 200-mesh sieve, and record the time it takes for the polymer polyol to pass through the sieve entirely by gravity.

[0034] Example 1: Preparation of polyether polyol intermediate 1

[0035] 180g of solid sorbitol, 2g of sucrose, and 5g of KOH were added to a pressure-resistant reactor. The mixture was heated to 100℃ and dehydrated for 3 hours. 740g of propylene oxide was slowly added, and the reaction temperature was controlled at 100℃. After the addition was completed, the reactor was pressurized for 1 hour and then vacuum-dehydrated for 0.5 hours. The temperature was then lowered to 90℃, and 11.5g of phosphoric acid and 32.5g of water were added for neutralization. Then, 2g of magnesium aluminum silicate adsorbent was added, and the mixture was dehydrated and dried. The hydroxyl value of the obtained polyether polyol intermediate 1 was 374.5mgKOH / g.

[0036] Example 2 Preparation of polyether polyol intermediate 2

[0037] 91g of solid sorbitol, 130g of liquid sorbitol, and 5g of KOH were added to a pressure-resistant reactor. The mixture was heated to 100℃ and dehydrated for 6 hours. 1850g of propylene oxide was slowly added, and the reaction temperature was controlled at 120℃. After the addition was completed, the reactor was pressurized for 1 hour and vacuum-dehydrated for 0.5 hours. The temperature was then lowered to 90℃, and 22.8g of phosphoric acid and 32.5g of water were added for neutralization. Then, 2g of magnesium aluminum silicate adsorbent was added, and the mixture was dehydrated and dried. The hydroxyl value of the obtained polyether polyol intermediate 2 was 168.2mgKOH / g.

[0038] Example 3 Preparation of polyether polyol intermediate 3

[0039] 182g of solid sorbitol and 6.2g of KOH were added to a pressure-resistant reactor. The mixture was heated to 100℃ and dehydrated for 3 hours. Then, 1360g of propylene oxide was slowly added, and the reaction temperature was controlled at 140℃. After the addition was completed, the reactor was pressurized for 2 hours and then vacuum-dehydrated for 1 hour. The temperature was then lowered to 90℃, and 18.8g of phosphoric acid and 52g of water were added for neutralization. Finally, 2g of magnesium aluminum silicate adsorbent was added, and the mixture was dehydrated and dried. The hydroxyl value of the obtained polyether polyol intermediate 2 was 225.6mgKOH / g.

[0040] Example 4 Preparation of polyether / polyester ether polyol 1

[0041] 80g of polyether polyol intermediate 1 and 65g of Boltron H311 were added to a pressure-resistant reactor, heated to 100℃, and timed for 3 hours. 0.2g of DMC catalyst was added, and dehydration continued for 1 hour. 36g of propylene oxide was added dropwise to initiate the polymerization reaction. Then, a mixture of 840g of propylene oxide and 180g of ethylene oxide was added. After feeding, the reactor was pressurized for 1 hour, and monomers were removed for 0.5 hours. The product was then discharged. The hydroxyl value of the obtained polyether / polyester ether polyol 1 was 37.4mgKOH / g, the functionality was 8, and the viscosity was 3750mPa·s.

[0042] Example 5 Preparation of polyether / polyester ether polyol 2

[0043] 74g of polyether polyol intermediate 1 and 120g of Boltron H311 were added to a pressure-resistant reactor, heated to 130℃, and timed for 3 hours. 0.03g of DMC catalyst was added, and dehydration continued for 1 hour. 32g of propylene oxide was added dropwise to initiate the polymerization reaction. Then, a mixture of 540g of propylene oxide and 135g of ethylene oxide was added. After feeding, the reactor was pressurized for 1 hour, and monomers were removed for 0.5 hours. The resulting polyether / polyester ether polyol 2 had a hydroxyl value of 57.5mgKOH / g, a functionality of 9, and a viscosity of 2010mPa·s.

[0044] Example 6 Preparation of polyether / polyester ether polyol 3

[0045] 141g of polyether polyol intermediate 3 and 32.4g of Boltron H311 were added to a pressure-resistant reactor, heated to 140℃, and timed for 3 hours. 0.1g of DMC catalyst was added, and dehydration continued for 1 hour. 30g of propylene oxide was added dropwise to initiate the polymerization reaction. Then, a mixture of 990g of propylene oxide and 210g of ethylene oxide was added. After feeding, the reactor was pressurized for 1 hour, and monomers were removed for 0.5 hours. The resulting polyether / polyester ether polyol 3 had a hydroxyl value of 28mgKOH / g, a functionality of 7, and a viscosity of 2345mPa·s.

[0046] Example 7: Preparation of high-functionality composite macromonomer A

[0047] 1080g of polyether / polyester ether polyol 1 and 20.1g of 3-isopropyl-dimethylbenzyl isocyanate were added to a pressure-resistant reactor, followed by 0.056g of bismuth neodecanoate. The mixture was heated to 80℃, and the infrared spectrum was recorded at 2261cm. -1 When the peak disappears, the reaction ends, and a high-functionality complex macromolecular monomer A is obtained.

[0048] Example 8: Preparation of high-functionality composite macromonomer B

[0049] 1320g of polyether / polyester ether polyol 1 and 20.1g of 3-isopropyl-dimethylbenzyl isocyanate were added to a pressure-resistant reactor, followed by 0.13g of bismuth neodecanoate. The mixture was heated to 70℃, and the infrared spectrum was recorded at 2261cm. -1 When the peak disappears, it marks the end of the reaction, and the high-functionality complex macromolecular monomer B is obtained.

[0050] Example 9: Preparation of high-functionality composite macromonomer C

[0051] 900g of polyether / polyester ether polyol 2 and 15.5g of ethyl isocyanate 2-methacrylate were added to a pressure-resistant reactor, followed by the addition of 0.09g of bismuth neodecanoate. The mixture was heated to 80℃, and the infrared spectrum was recorded at 2261cm. -1 When the peak disappears, it marks the end of the reaction, and the high-functionality complex macromolecular monomer C is obtained.

[0052] Example 10: Preparation of high-functionality composite macromonomer D

[0053] 1400g of polyether / polyester ether polyol 3 and 14.1g of ethyl isocyanate acrylate were added to a pressure-resistant reactor, followed by 0.11g of bismuth neodecanoate. The mixture was heated to 90℃, and the infrared spectrum was recorded at 2261cm. -1 When the peak disappears, it marks the end of the reaction, and the highly functional composite macromolecular monomer D is obtained.

[0054] Comparative Example 1: Preparation of macromonomer E

[0055] 1080g of polyether polyol intermediate 1 was added to a pressure-resistant reactor, along with 0.04g of DMC catalyst. Dehydration was continued for 1 hour, and 37g of propylene oxide was added dropwise to initiate the polymerization reaction. Then, a mixture of 910g of propylene oxide and 183g of ethylene oxide was added. After feeding, the reactor was pressurized for 1 hour and the monomer was removed for 0.5 hours before being discharged. The hydroxyl value of the obtained polyether polyol was 28.3mgKOH / g, and the viscosity was 3853mPa·s.

[0056] 1074 g of the above-mentioned polyether polyol and 20.1 g of 3-isopropyl-dimethylbenzyl isocyanate were added to a pressure-resistant reactor, along with 0.06 g of bismuth neodecanoate. The mixture was heated to 80 °C, and the infrared spectrum was recorded at 2261 cm⁻¹. -1 When the peak disappears, the reaction ends, and the macromolecular monomer E is obtained.

[0057] Comparative Example 2: Preparation of macromonomer F

[0058] 200g of polyether polyol intermediate 2 was added to a pressure-resistant reactor, along with 0.04g of DMC catalyst. Dehydration was continued for 1 hour, and 32g of propylene oxide was added dropwise to initiate the polymerization reaction. Then, a mixture of 1150g of propylene oxide and 180g of ethylene oxide was added. After feeding, the reactor was pressurized for 1 hour and the monomer was removed for 0.5 hours before being discharged. The hydroxyl value of the obtained polyether polyol was 28.6mgKOH / g, and the viscosity was 2903mPa·s.

[0059] 1180g of the above-mentioned polyether polyol and 15.5g of ethyl isocyanate 2-methacrylate were added to a pressure-resistant reactor, along with 0.05g of zinc neodecanoate. The mixture was heated to 80℃, and the infrared spectrum was recorded at 2261cm. -1 When the peak disappears, the reaction ends, and the macromolecular monomer F is obtained.

[0060] Comparative Example 3: Preparation of Macromonomer G

[0061] 2000g of the polyether polyol from Comparative Example 2 and 16.5g of maleic anhydride were added to a reactor, heated to 150℃ for esterification reaction, and timed for 3 hours. Then, 3g of KOH was added and the reaction continued for another 3 hours. Finally, 30g of ethylene oxide was added for further reaction. The acid value was tested to be <0.5mgKOH / g. The mixture was then discharged to obtain the macromonomer G.

[0062] Preparation of polymer polyols:

[0063] (1) Preparation of prereactants

[0064] The prepared macromonomers A, B, C, D, E, F, and G were respectively added to a mixing tank along with a mixture of isopropanol, styrene (SM), and acrylonitrile (AN) and the initiator dimethyl azobisisobutyrate. The materials in the mixing tank were then pumped from the mixing tank to a static mixer using a horizontal flow pump, and subsequently fed into two pressure-resistant reactors connected in series for polymerization. The reaction temperature of both reactors was set at 110°C, and the residence time of the materials in each reactor was 60 min. Pre-reactants PA, PB, PC, PD, PE, PF, and PG were obtained. After cooling the pre-reactants PA, PB, PC, PD, PE, PF, and PG using a cooler, they were collected for later use. The mass percentages of the macromonomers, isopropanol, styrene, acrylonitrile mixture, and initiator are shown in Table 1.

[0065] Table 1. Mass percentage of the mixture of macromonomers, isopropanol, styrene, and acrylonitrile, and the initiator.

[0066] (2) Preparation of polymer polyols

[0067] Pre-reactants PA, PB, PC, PD, PE, PF, PG, a mixture of base polyether polyol, styrene and acrylonitrile, and initiator dimethyl azobisisobutyrate were added to a mixing tank. The materials in the mixing tank were then pumped from the mixing tank to a static mixer via a horizontal flow pump. From there, the materials were sequentially fed into a first and a second pressure-resistant reactor via feed pipes for reaction. The reaction temperature in both reactors was set at 125°C, and the residence time of the materials in each reactor was 60 min. The crude product from the second pressure-resistant reactor was fed into a desaturation reactor, where a vacuum was applied to remove unreacted volatiles, ultimately yielding polymer polyols 1-7. The mass percentages of the pre-reactants, base polyether polyol, styrene and acrylonitrile mixture, and initiator are shown in Table 2.

[0068] Table 2. Mass percentages of pre-reactants, base polyether polyols, mixtures of styrene and acrylonitrile, and initiators.

[0069] The performance of polymer polyols 1-7 was tested, and the test results are shown in Table 3:

[0070] Table 3 Performance test results of polymer polyols 1-7

[0071] As can be seen from Table 3, compared with the polymer polyols 5-7 prepared from the macromonomer EG in Comparative Examples 1-3, the polymer polyols 1-4 prepared from the macromonomer AD in Examples 7-10 showed a significant decrease in viscosity, a significant reduction in filtration time, and a decrease in viscosity increase after adding water. This is attributed to the fact that the high-functionality composite macromonomer prepared in Examples 7-10 can have a large dispersion volume in the polymer polyol, thereby improving the stability of the polymer polyol.

Claims

1. A process for the preparation of a high-functionality complex macromonomer, characterized in that, The method comprises the following steps: S1: reacting a starter with an epoxide compound under the action of a catalyst to obtain a polyether polyol intermediate; S2: reacting the polyether polyol intermediate obtained in step S1 with a hyperbranched polyester polyol as a composite starter, and reacting with an epoxide compound under the action of a catalyst to obtain a polyether / polyester ether polyol; S3: reacting the polyether / polyester ether polyol obtained in step S2 with an unsaturated isocyanate under the action of a catalyst to obtain a high-functionality composite macromonomer.

2. The method for preparing a high-functionality complex macromonomer according to claim 1, wherein In step S1, the starter is one or two of sucrose, solid sorbitol and liquid sorbitol; the catalyst is KOH; the number average molecular weight of the polyether polyol intermediate is 900-2000 g / mol; the mass ratio of the starter to the epoxide compound is 1:(4-8.5); and the catalyst accounts for 0.2-0.55% of the total mass of the starter, the catalyst and the epoxide compound.

3. The method of claim 1, wherein the high-functionality complex macromonomer is prepared by the reaction of a polyfunctional compound with a macromonomer having a functional group. In step S2, the hyperbranched polyester polyol is Boltorn H311 with a functionality of 23; the catalyst is DMC catalyst; the molar ratio of the polyether polyol intermediate to the hyperbranched polyester polyol is (0.6-4.5):1; the hydroxyl value of the polyether / polyester ether polyol is 28-58 mgKOH / g, and the functionality is 7-9; the mass ratio of the composite starter to the epoxide compound is 1:(3.6-7.3); and the catalyst accounts for 30-170 ppm of the total mass of the composite starter, the catalyst and the epoxide compound.

4. The method of claim 1, wherein the high-functionality complex macromonomer is prepared by the reaction of a polyfunctional compound with a macromonomer having a functional group. In step S3, the unsaturated isocyanate is 3-isopropyl-dimethylbenzyl isocyanate, isocyanate ethyl methacrylate or isocyanate ethyl acrylate; the catalyst is bismuth neodecanoate; the reaction temperature is 70-90℃; the molar ratio of the polyether / polyester ether polyol to the unsaturated isocyanate is (0.9-1.2):1; and the catalyst accounts for 50-100 ppm of the total mass of the polyether / polyester ether polyol, the unsaturated isocyanate and the catalyst.

5. The method of claim 1, wherein the high-functionality complex macromonomer is prepared by the reaction of a polyfunctional monomer with a macromonomer having a functional group. In step S1, the epoxide compound is propylene oxide, and the reaction temperature is 100-140℃; and in step S2, the epoxide compound is propylene oxide and ethylene oxide, and the reaction temperature is 100-140℃.

6. A high-functionality complex macromonomer characterized in that, The high-functionality composite macromonomer is prepared by the method as claimed in any one of claims 1-5.

7. Use of a high-functionality complex macromonomer, characterized in that The high-functionality composite macromonomer is used to prepare a polymer polyol, specifically comprising the following steps: (1) synthesizing a pre-reaction product by reacting the high-functionality composite macromonomer as claimed in claim 6 and an olefinically unsaturated monomer under the action of a chain transfer agent and an initiator; (2) adding an initiator, a base polyether polyol and an olefinically unsaturated monomer to the pre-reaction product obtained in step (1) to obtain a polymer polyol by reaction.

8. Use of a high-functionality complex macromonomer according to claim 7, wherein In step (1), the chain transfer agent is isopropyl alcohol.

9. The use of a high-functionality complex macromonomer according to claim 7, wherein In steps (1) and (2), the initiator is dimethyl azobis isobutyrate; in step (1), the olefinically unsaturated monomer is styrene and acrylonitrile, and the mass fraction of styrene in the olefinically unsaturated monomer is 50%; and in step (2), the olefinically unsaturated monomer is styrene and acrylonitrile, and the mass fraction of styrene in the olefinically unsaturated monomer is 80%.

10. The use of the high-functionality complex macromonomer according to claim 7, wherein In step (1), the chain transfer agent is 60% of the total mass of the chain transfer agent, initiator, high-functionality complex macromonomer, and olefinically unsaturated monomer; the initiator is 0.1% of the total mass of the chain transfer agent, initiator, high-functionality complex macromonomer, and olefinically unsaturated monomer; the high-functionality complex macromonomer is 24% of the total mass of the chain transfer agent, initiator, high-functionality complex macromonomer, and olefinically unsaturated monomer; and the olefinically unsaturated monomer is 15.9% of the total mass of the chain transfer agent, initiator, high-functionality complex macromonomer, and olefinically unsaturated monomer; in step (2), the initiator is 0.25% of the total mass of the pre-reactant, initiator, base polyether polyol, and olefinically unsaturated monomer; the pre-reactant is 12.5% of the total mass of the pre-reactant, initiator, base polyether polyol, and olefinically unsaturated monomer; the base polyether polyol is 40% of the total mass of the pre-reactant, initiator, base polyether polyol, and olefinically unsaturated monomer; and the olefinically unsaturated monomer is 47.25% of the total mass of the pre-reactant, initiator, base polyether polyol, and olefinically unsaturated monomer.

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