Macromonomers, methods for making the same, polymer polyols made using the same, and methods for making the same

Abstract

The application belongs to the technical field of polymer polyols, and particularly relates to a macromonomer and a preparation method thereof, a polymer polyol prepared by using the macromonomer and a preparation method thereof. The macromonomer is a macromonomer with a structure of TMI-terminated polytetrahydrofuran modified polyether polyol. The application synthesizes a high-branched macromonomer base polyether polyol A by using sucrose / sorbitol as a starting agent, and then introduces a polytetrahydrofuran flexible segment to form a macromonomer base polyether polyol B with high functionality and good compatibility. The polytetrahydrofuran segment is a key component of the macromonomer base polyether, and the flexible segment formed by four continuous methylene groups in the main chain effectively improves the compatibility with the polyol and reduces phase separation, thereby giving the foam a more uniform and fine cell structure, and realizing the improvement of the tensile and tear resistance of the polymer polyol foaming sponge.

Description

Technical Field

[0001] This invention belongs to the field of polymer polyol technology, specifically relating to macromolecular monomers and their preparation methods, polymer polyols prepared using them, and their preparation methods. Background Technology

[0002] Polymer polyols (POPs) are bulk organic raw materials that use basic polyether polyols as solvents. Through special modified polyether polyols (macromonomers), polymer particles containing unsaturated double bonds, such as styrene and acrylonitrile, are uniformly dispersed within the basic polyether phase. They are primarily used to improve the support and breathability of polyurethane foam. In recent years, with economic and social development, end-users have placed higher demands on the physical properties of polyurethane foam, such as tensile strength and tear strength.

[0003] To improve the tensile strength and tear strength of polyurethane foam, polyurethane foam manufacturers often use a composite method of polyester polyol, polyether polyol and polymer polyol for foaming. However, due to the poor compatibility between polyester polyol and polyether polyol and the high viscosity of polyester polyol, problems such as coarse foam cells and uneven density are caused.

[0004] In recent years, many industry practitioners have attempted to improve the aforementioned problems by adjusting the microstructure of polymer polyols. Patent CN116396443A discloses a method for synthesizing polytetrahydrofuran ether diol-modified polymer polyols. This invention introduces polytetrahydrofuran ether diol segments to composite-modify the base polyether of the polymer polyol, giving the polymer polyol foam products higher tensile strength and tear resistance. However, this method significantly increases the production cost of the polymer polyol due to the high amount of polytetrahydrofuran ether diol added. Patent CN111154095A discloses a method for preparing and applying silicon-modified macromonomers. Although this scheme can improve the performance of sponges, it is not fully demonstrated in the patent. Patent CN109796580A discloses a macromonomer with a tetrahydropyran structure, its preparation method, and a method for preparing polymer polyols using it. While the technical route disclosed in this patent can improve the mechanical properties of polyurethane sponges, the process is relatively complex and can easily affect the product stability of the polymer polyol. Summary of the Invention

[0005] To address the shortcomings of existing technologies, the purpose of this invention is to provide a macromolecular monomer with high activity and good dispersibility.

[0006] This invention also provides a simple and easy method for its preparation.

[0007] The present invention also provides polymer polyols prepared therefrom, which can significantly improve the physical properties of polymer polyol foamed sponges, such as support, tensile strength and elongation at break.

[0008] The present invention also provides a preparation method that is easy to operate, simple to produce, and suitable for large-scale production.

[0009] The macromonomer described in this invention is a polytetrahydrofuran-modified polyether polyol macromonomer with a 3-isopropenyl-α,α-dimethylbenzyl isocyanate (TMI) end-capped structure.

[0010] The method for preparing the macromonomer of the present invention includes the following steps:

[0011] a. Synthesis of macromonomer-based polyether polyol A:

[0012] Using sucrose and sorbitol as initiators, macromolecular monomer-based polyether polyol A was prepared by reacting it with propylene oxide under the catalysis of a catalyst.

[0013] Specifically, sucrose, sorbitol, and KOH solid are added to a reaction vessel. The reaction vessel is fully purged with high-purity nitrogen at room temperature to ensure that the oxygen content does not exceed 200 ppm. Then, the temperature is raised to 110-130℃, and the reaction vessel is stirred and dehydrated for 3 hours under an absolute pressure of 0.05 kPa. Then, propylene oxide is added to carry out the polymerization reaction. After the addition is completed, the reaction is carried out under internal pressure for 1 hour. Then, 85 wt.% phosphoric acid, deionized water, and adsorbent are added for post-treatment to remove potassium ions, thus obtaining the macromolecular monomer basic polyether polyol A.

[0014] b. Synthesis of macromonomer-based polyether polyol B:

[0015] Using macromonomer-based polyether polyol A and polytetrahydrofuran ether diol as initiators, macromonomer-based polyether polyol B was prepared by reacting it with an epoxy compound under the catalysis of a catalyst.

[0016] Specifically, the macromonomer base polyether polyol A and polytetrahydrofuran ether diol are mixed and added to a reaction vessel, along with 80 ppm of bimetallic catalyst. After complete replacement with nitrogen, the temperature is raised to 130-160℃. Then, the epoxy compound is added to the reaction vessel at a mass flow rate of 16-35 g / min. After the epoxy compound is added, the reaction is carried out under internal pressure for 1 hour to obtain macromonomer base polyether polyol B.

[0017] c. Synthesis of macromonomers:

[0018] The macromonomer was prepared by reacting the basic polyether polyol B with 3-isopropenyl-α,α-dimethylbenzyl isocyanate under the catalysis of a catalyst.

[0019] Specifically, 100 parts by mass of the macromonomer base polyether polyol B are added to the reactor, heated to 85°C, and then 3-isopropenyl-α,α-dimethylbenzyl isocyanate is added. After reacting for 2 hours, 200 ppm of T-12 is added, and after further reaction for 2 hours, the macromonomer is obtained.

[0020] The mass ratio of sucrose to sorbitol in step a is 0.5-10:1, preferably 1:1-6:1, the amount of solid KOH catalyst added is 1% of the mass of the two initiators, and the hydroxyl value of the macromolecular monomer base polyether polyol A is 190-200 mg KOH / g.

[0021] The number-average molecular weight of the polytetrahydrofuran ether diol mentioned in step b is 650-2000 g / mol, and the mass ratio of polytetrahydrofuran ether diol to the macromonomer base polyether polyol A is 0.05-1.0:1. Considering the influence of the degree of branching of the macromonomer base polyether, the preferred mass ratio is 0.1-0.6:1, and the more preferred ratio is 0.2-0.5:1.

[0022] The epoxy compound in step b is a mixture of propylene oxide and ethylene oxide, wherein ethylene oxide accounts for 0%-35% of the total mass of propylene oxide, ethylene oxide, and the initiator in step b, preferably 5%-30%, and more preferably 8%-20%; the hydroxyl value of the macromonomer base polyether polyol B is 21.00-30.00 mg KOH / g, preferably 23.00-29.00 mg KOH / g, and more preferably 26.00-28.00 mg KOH / g.

[0023] In step c, the mass ratio of the macromolecular monomer base polyether polyol B to the added 3-isopropenyl-α,α-dimethylbenzyl isocyanate is 100:0.5-3.0, preferably 100:1.0-2.5, and more preferably 100:1.6-2.4.

[0024] The polymer polyol prepared from the macromonomer of the present invention is obtained from the following raw materials in parts by mass:

[0025] Basic polyether polyol X: 30-150 parts;

[0026] Pre-made stabilizer: 3-15 parts;

[0027] Mixed ingredients: 120-180 parts;

[0028] The mixture is a mixture of base polyether polyol X, pre-made stabilizer, chain transfer agent, initiator, styrene and acrylonitrile monomers;

[0029] The pre-made stabilizer is a copolymer of macromolecular monomers, styrene, and acrylonitrile.

[0030] The base polyether polyol X is a flexible foam polyether polyol with 3 functions and a number average molecular weight of 3000 g / mol.

[0031] The method for preparing the polymer polyol of the present invention comprises the following steps:

[0032] (1) Preparation of pre-made stabilizers:

[0033] A pre-prepared stabilizer is prepared by reacting macromolecular monomers, styrene, acrylonitrile, chain transfer agents, and initiators.

[0034] Specifically, 24.0 wt.% of macromonomer, 7.95 wt.% of styrene, 7.95 wt.% of acrylonitrile, 60.0 wt.% of chain transfer agent (isopropanol), and 0.1 wt.% of initiator are added to a reactor and mixed evenly. The mixture is heated to 120±1℃ and reacted for 2 hours. Then the mixture is cooled and discharged to obtain the pre-prepared stabilizer.

[0035] (2) Preparation of the mixture:

[0036] The base polyether polyol X, pre-made stabilizer, chain transfer agent, initiator, styrene and acrylonitrile monomers are mixed evenly to obtain a mixture.

[0037] (3) Synthesis of polymer polyols:

[0038] The base polyether polyol X and the pre-made stabilizer are added to the reaction vessel, the temperature is raised and maintained, and then the mixture is continuously introduced to carry out the polymerization reaction. After the addition is completed, the temperature is maintained to remove the chain transfer agent, and the polymer polyol is obtained.

[0039] The continuous feeding of the mixture in step (3) is to feed the mixture at a flow rate of 16-54 g / min.

[0040] The heating in step (3) is to raise the temperature to 110-150℃.

[0041] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0042] 1) This invention uses sucrose / sorbitol as an initiator to synthesize a highly branched macromonomer-based polyether polyol A, and then introduces a flexible polytetrahydrofuran segment to form a macromonomer-based polyether polyol B with both high functionality and good compatibility. This structure acts as a pre-prepared stabilizer anchoring group, significantly enhancing the dispersion stability of polymer particles in the continuous phase.

[0043] 2) In this invention, the styrene-acrylonitrile copolymer backbone is grafted with polytetrahydrofuran-modified macromonomer segments via TMI. This structure acts as a pre-stabilizing anchoring group, significantly enhancing the dispersion stability of polymer particles in the continuous phase. The polytetrahydrofuran segments, as key components of the macromonomer-based polyether, form relatively long "flexible segments" with four consecutive methylene (-CH2-) groups in the backbone, effectively improving compatibility with polyols and reducing phase separation. This results in a more uniform and fine pore structure in the foam, improving the tensile and tear resistance of the polymer polyol foam.

[0044] 3) When the polymer polyol described in this invention is used for foaming, it can simultaneously improve the tensile strength, tear strength and elongation at break of the foam. This is because the polytetrahydrofuran segments enhance the interfacial forces and act as flexible spacers to alleviate stress concentration.

[0045] 4) The process described in this invention is simple and cost-controllable: by optimizing the amount of polytetrahydrofuran introduced and the grafting method, the performance is significantly improved while avoiding a significant increase in cost. The synthesis route has mild conditions, good reproducibility, and good industrialization potential. Detailed Implementation

[0046] The present invention will be further described below with reference to the embodiments.

[0047] Unless otherwise specified, all raw materials used in the examples were commercially available.

[0048] Basic polyether polyol X: DEP-5631D produced by Sinochem Dongda (Zibo) Co., Ltd., with 3 functionalities and a number-average molecular weight of 3000 g / mol;

[0049] Polytetrahydrofuran ether diol: PTMEG 650, with a number average molecular weight of 650 g / mol; PTMEG 1000, with a number average molecular weight of 1000 g / mol; PTMEG 2000, with a number average molecular weight of 2000 g / mol, produced by Hyosung Chemical (Jiaxing) Co., Ltd.

[0050] T-12 / T-9: Guangdong Yourun Chemical Co., Ltd.;

[0051] tert-amyl peroxy-2-ethylhexanoate: Peroxide initiator, Nourion Chemicals Ltd.

[0052] Example 1

[0053] The preparation method of the polymer polyol comprises the following steps:

[0054] (1) Preparation of pre-made stabilizers:

[0055] a. Synthesis of macromonomer-based polyether polyol A:

[0056] 400g of a mixture of sucrose and sorbitol in a mass ratio of 0.5:1 and 4g of KOH solid were added to a reactor. The reactor was fully purged with high-purity nitrogen at room temperature to ensure that the oxygen content did not exceed 200ppm. The temperature was then raised to 110℃ and the reactor was stirred and dehydrated for 3 hours under an absolute pressure of 0.05kPa. Then, 3200g of propylene oxide was added to carry out the polymerization reaction. After the addition was completed, the reactor was subjected to internal pressure reaction for 1 hour. Then, 8.2g of 85wt.% phosphoric acid, 180g of deionized water and 3.6g of magnesium aluminum silicate adsorbent were added for post-treatment to remove potassium ions, thus obtaining the macromolecular monomer basic polyether polyol A with a hydroxyl value of 190mgKOH / g.

[0057] b. Synthesis of macromonomer-based polyether polyol B:

[0058] 400g of a mixture of macromonomer basic polyether polyol A and PTMEG650 with a mass ratio of 0.05:1 was added to a reactor, along with 80ppm of a bimetallic catalyst. After complete purging with nitrogen, the temperature was raised to 130℃, and then the system was evacuated to -98kPa. 3200g of propylene oxide was then added to the reactor at a mass flow rate of 25g / min. After the addition of the epoxy compound was completed, the reactor was subjected to internal pressure reaction for 1 hour to obtain macromonomer basic polyether polyol B with a hydroxyl value of 21.00 mg KOH / g.

[0059] c. Synthesis of macromonomers:

[0060] 600g of the macromonomer basic polyether polyol B was added to the reactor and heated to 85℃. Then, 3g of 3-isopropenyl-α,α-dimethylbenzyl isocyanate was added. After reacting for 2 hours, 200ppm of T-12 was added. After reacting for another 2 hours, the macromonomer was obtained.

[0061] d. Preparation of pre-made stabilizers:

[0062] 24.0 wt.% macromonomer, 7.95 wt.% styrene, 7.95 wt.% acrylonitrile, 60.0 wt.% isopropanol, and 0.1 wt.% tert-amyl peroxy-2-ethylhexanoate were added to a reactor and mixed evenly. The mixture was heated to 120±1℃ and reacted for 2 hours. The mixture was then cooled and discharged to obtain the pre-prepared stabilizer.

[0063] (2) Preparation of the mixture:

[0064] At room temperature, the base polyether polyol X, pre-prepared stabilizer, isopropanol, tert-amyl peroxy-2-ethylhexanoate, styrene and acrylonitrile monomer mixture were poured into a three-necked flask at a mass ratio of 100:10:3:0.6:190 (styrene and acrylonitrile in a mass ratio of 1:1) and stirred at 60 r / min for 30 min to obtain a homogeneous mixture.

[0065] (3) Synthesis of polymer polyols:

[0066] Add 300g of basic polyether polyol X and 30g of pre-made stabilizer to the reaction vessel. Purge with nitrogen five times at room temperature, raise the temperature to 110℃ and maintain it. Then, feed 1200g of the mixture at a mass flow rate of 20g / min to carry out the polymerization reaction. After the feeding is completed, continue to maintain the temperature and react for 1 hour. Then, turn on the vacuum pump and remove the chain transfer agent under a pressure of -0.1MPa to obtain the polymer polyol.

[0067] Example 2

[0068] The preparation method of the polymer polyol comprises the following steps:

[0069] (1) Preparation of pre-made stabilizers:

[0070] a. Synthesis of macromonomer-based polyether polyol A:

[0071] 220g of a mixture of sucrose and sorbitol in a mass ratio of 10:1 and 2.2g of KOH solid were added to a reactor. The reactor was fully purged with high-purity nitrogen at room temperature to ensure that the oxygen content did not exceed 200ppm. The temperature was then raised to 130℃ and the reactor was stirred and dehydrated for 3 hours under an absolute pressure of 0.05kPa. Then 2322g of propylene oxide was added to carry out the polymerization reaction. After the addition was completed, the reaction was carried out under internal pressure for 1 hour. Then 5.5g of 85wt.% phosphoric acid, 100g of deionized water and 3g of magnesium aluminum silicate adsorbent were added for post-treatment to remove potassium ions, thus obtaining the macromolecular monomer basic polyether polyol A with a hydroxyl value of 200mgKOH / g.

[0072] b. Synthesis of macromonomer-based polyether polyol B:

[0073] 400g of a mixture of macromonomer basic polyether polyol A and PTMEG2000 in a mass ratio of 1:1 was added to a reactor, along with 80ppm of a bimetallic catalyst. After complete purging with nitrogen, the temperature was raised to 130℃, and then evacuated to -98kPa. 1007g of propylene oxide and 298.6g of ethylene oxide were then added to the reactor at a mass flow rate of 18g / min. After the addition of the epoxy compounds was completed, the reactor was subjected to internal pressure reaction for 1 hour to obtain macromonomer basic polyether polyol B with a hydroxyl value of 30.00 mg KOH / g.

[0074] c. Synthesis of macromonomers:

[0075] 600g of the macromonomer base polyether polyol B was added to the reactor and heated to 85℃. Then 18g of 3-isopropenyl-α,α-dimethylbenzyl isocyanate was added. After reacting for 2 hours, 200ppm of T-12 was added. After reacting for another 2 hours, the macromonomer was obtained.

[0076] d. Preparation of pre-made stabilizers:

[0077] 24.0 wt.% macromonomer, 7.95 wt.% styrene, 7.95 wt.% acrylonitrile, 60.0 wt.% isopropanol, and 0.1 wt.% tert-amyl peroxy-2-ethylhexanoate were added to a reactor and mixed evenly. The mixture was heated to 120±1℃ and reacted for 2 hours. Then the mixture was cooled and discharged to obtain the pre-prepared stabilizer.

[0078] (2) Preparation of the mixture:

[0079] At room temperature, the base polyether polyol X, pre-prepared stabilizer, isopropanol, tert-amyl peroxy-2-ethylhexanoate, styrene and acrylonitrile monomer mixture were poured into a three-necked flask at a mass ratio of 100:10:3:0.6:190 (styrene and acrylonitrile mass ratio 1:1), and stirred at 60 r / min for 30 min to mix evenly to obtain the mixture.

[0080] (3) Synthesis of polymer polyols:

[0081] Take 900g of basic polyether polyol X and 90g of pre-made stabilizer and add them to the reaction vessel. Purge with nitrogen five times at room temperature, raise the temperature to 110℃ and maintain it, then introduce 1500g of the mixture at a flow rate of 27g / min to carry out the polymerization reaction. After the addition is completed, continue to maintain the temperature and react for 1 hour. Turn on the vacuum pump and remove the chain transfer agent under a pressure of -0.1MPa to obtain the polymer polyol.

[0082] Example 3

[0083] The preparation method of the polymer polyol comprises the following steps:

[0084] (1) Preparation of pre-made stabilizers:

[0085] a. Synthesis of macromonomer-based polyether polyol A:

[0086] 400g of a mixture of sucrose and sorbitol in a mass ratio of 5.25:1 and 4g of KOH solid were added to a reactor. The reactor was fully purged with high-purity nitrogen at room temperature to ensure that the oxygen content did not exceed 200ppm. The temperature was then raised to 130℃ and the reactor was stirred and dehydrated for 3 hours under an absolute pressure of 0.05kPa. Then, 2322g of propylene oxide was added to carry out the polymerization reaction. After the addition was completed, the reaction was carried out under internal pressure for 1 hour. Then, 11g of 85wt.% phosphoric acid, 90g of deionized water and 11g of magnesium aluminum silicate adsorbent were added for post-treatment to remove potassium ions, thus obtaining the macromolecular monomer basic polyether polyol A with a hydroxyl value of 195mgKOH / g.

[0087] b. Synthesis of macromonomer-based polyether polyol B:

[0088] 300g of a mixture of macromonomer-based polyether polyol A and PTMEG1000 (mass ratio 0.495:1) was added to a reactor along with 80ppm of a bimetallic catalyst. After complete purging with nitrogen, the mixture was heated to 140℃ and then evacuated to -98kPa. 786.2g of propylene oxide and 584.8g of ethylene oxide were then added to the reactor at a mass flow rate of 19g / min. After the addition of the epoxy compounds was completed, the mixture was subjected to internal pressure reaction for 1 hour to obtain macromonomer-based polyether polyol B with a hydroxyl value of 25.5 mg KOH / g.

[0089] c. Synthesis of macromonomers:

[0090] 400g of the macromonomer base polyether polyol B was added to the reactor and heated to 85℃. Then 7g of 3-isopropenyl-α,α-dimethylbenzyl isocyanate was added. After reacting for 2 hours, 200ppm of T-12 was added. After reacting for another 2 hours, the macromonomer was obtained.

[0091] d. Preparation of pre-made stabilizers:

[0092] 24.0 wt.% macromonomer, 7.95 wt.% styrene, 7.95 wt.% acrylonitrile, 60.0 wt.% isopropanol, and 0.1 wt.% tert-amyl peroxy-2-ethylhexanoate were added to a reactor and mixed evenly. The mixture was heated to 120±1℃ and reacted for 2 hours. Then the mixture was cooled and discharged to obtain the pre-prepared stabilizer.

[0093] (2) Preparation of the mixture:

[0094] At room temperature, the basic polyether polyol X, pre-prepared stabilizer, isopropanol, tert-amyl peroxy-2-ethylhexanoate, styrene and acrylonitrile monomer mixture were poured into a three-necked flask at a mass ratio of 100:10:3:0.6:190 (styrene:acrylonitrile mass ratio of 1:1) and stirred at 60 r / min for 30 min to obtain a homogeneous mixture.

[0095] (3) Synthesis of polymer polyols:

[0096] Take 1500g of basic polyether polyol X and 150g of pre-made stabilizer and add them to the reaction vessel. Purge with nitrogen 5 times at room temperature, raise the temperature to 110℃ and maintain it, and then introduce 1800g of the mixture at a mass flow rate of 54g / min to carry out the polymerization reaction. After the addition is completed, continue to maintain the temperature and react for 1 hour. Turn on the vacuum pump and remove the chain transfer agent under a pressure of -0.1MPa to obtain the polymer polyol.

[0097] Comparative Example 1

[0098] The preparation method of the polymer polyol comprises the following steps:

[0099] (1) Preparation of pre-made stabilizers:

[0100] a. Synthesis of macromonomer-based polyether polyol A:

[0101] 400g of a mixture of sucrose and sorbitol in a mass ratio of 0.5:1 and 4g of KOH solid were added to a reactor. The reactor was fully purged with high-purity nitrogen at room temperature to ensure that the oxygen content did not exceed 200ppm. The temperature was then raised to 110℃ and the reactor was stirred and dehydrated for 3 hours under an absolute pressure of 0.05kPa. Then, 3200g of propylene oxide was added to carry out the polymerization reaction. After the addition was completed, the reactor was subjected to internal pressure reaction for 1 hour. Then, 8.2g of 85wt.% phosphoric acid, 180g of deionized water and 3.6g of magnesium aluminum silicate adsorbent were added for post-treatment to remove potassium ions, thus obtaining the macromolecular monomer basic polyether polyol A with a hydroxyl value of 190mgKOH / g.

[0102] b. Synthesis of macromonomer-based polyether polyol B:

[0103] 400g of macromonomer basic polyether polyol A was added to a reactor along with 80ppm of bimetallic catalyst. After complete replacement with nitrogen, the temperature was raised to 130℃ and then evacuated to -98kPa. 3219g of propylene oxide was then added to the reactor at a mass flow rate of 30g / min. After the addition of the epoxy compound was completed, the reactor was subjected to internal pressure reaction for 1 hour to obtain macromonomer basic polyether polyol B with a hydroxyl value of 21.00 mg KOH / g.

[0104] c. Synthesis of macromonomers:

[0105] 600g of the macromonomer base polyether polyol B was added to the reactor and heated to 85℃. Then, 3g of 3-isopropenyl-α,α-dimethylbenzyl isocyanate was added. After reacting for 2 hours, 200ppm of T-12 was added. After reacting for another 2 hours, the macromonomer was obtained.

[0106] d. Preparation of pre-made stabilizers:

[0107] 24.0 wt.% macromonomer, 7.95 wt.% styrene, 7.95 wt.% acrylonitrile, 60.0 wt.% isopropanol, and 0.1 wt.% tert-amyl peroxy-2-ethylhexanoate were added to a reactor and mixed evenly. The mixture was heated to 120±1℃ and reacted for 2 hours. Then the mixture was cooled and discharged to obtain the pre-prepared stabilizer.

[0108] (2) Preparation of the mixture:

[0109] At room temperature, the base polyether polyol X, pre-prepared stabilizer, isopropanol, tert-amyl peroxy-2-ethylhexanoate, styrene and acrylonitrile monomer mixture were poured into a three-necked flask at a mass ratio of 100:10:3:0.6:190 (styrene and acrylonitrile in a mass ratio of 1:1) and stirred at 60 r / min for 30 min to obtain a homogeneous mixture.

[0110] (3) Synthesis of polymer polyols:

[0111] Take 300g of basic polyether polyol X and 30g of pre-made stabilizer and add them to the reaction vessel. Purge with nitrogen 5 times at room temperature, raise the temperature to 110℃ and maintain it, and then introduce 1200g of the mixture at a flow rate of 20g / min to carry out the polymerization reaction. After the addition is completed, continue to maintain the temperature and react for 1 hour. Turn on the vacuum pump and remove the chain transfer agent under a pressure of -0.1MPa to obtain the polymer polyol.

[0112] Comparative Example 2

[0113] The preparation method of the polymer polyol comprises the following steps:

[0114] (1) Preparation of pre-made stabilizers:

[0115] a. Synthesis of macromonomer-based polyether polyol A:

[0116] 220g of a mixture of sucrose and sorbitol in a mass ratio of 10:1 and 2.2g of KOH solid were added to a reactor. The reactor was fully purged with high-purity nitrogen at room temperature to ensure that the oxygen content did not exceed 200ppm. The temperature was then raised to 130℃ and the reactor was stirred and dehydrated for 3 hours under an absolute pressure of 0.05kPa. Then 2322g of propylene oxide was added to carry out the polymerization reaction. After the addition was completed, the reaction was carried out under internal pressure for 1 hour. Then 5.5g of 85wt.% phosphoric acid, 100g of deionized water and 3g of magnesium aluminum silicate adsorbent were added for post-treatment to remove potassium ions, thus obtaining the macromolecular monomer basic polyether polyol A with a hydroxyl value of 200mgKOH / g.

[0117] b. Synthesis of macromonomer-based polyether polyol B:

[0118] 400g of macromonomer basic polyether polyol A was added to a reactor along with 80ppm of bimetallic catalyst. After complete nitrogen purging, the temperature was raised to 130℃ and then evacuated to -98kPa. 1333g of propylene oxide and 933g of ethylene oxide were then added to the reactor at a mass flow rate of 25g / min. After the addition of the epoxy compounds was completed, the reactor was subjected to internal pressure reaction for 1 hour to obtain macromonomer basic polyether polyol B with a hydroxyl value of 30.00 mg KOH / g.

[0119] c. Synthesis of macromonomers:

[0120] 600g of the macromonomer base polyether polyol B was added to the reactor and heated to 85℃. Then 18g of 3-isopropenyl-α,α-dimethylbenzyl isocyanate was added. After reacting for 2 hours, 200ppm of T-12 was added. After reacting for another 2 hours, the macromonomer was obtained.

[0121] d. Preparation of pre-made stabilizers:

[0122] 24.0 wt.% macromonomer, 7.95 wt.% styrene, 7.95 wt.% acrylonitrile, 60.0 wt.% isopropanol, and 0.1 wt.% tert-amyl peroxy-2-ethylhexanoate were added to a reactor and mixed evenly. The mixture was heated to 120±1℃ and reacted for 2 hours. Then the mixture was cooled and discharged to obtain the pre-prepared stabilizer.

[0123] (2) Preparation of the mixture:

[0124] At room temperature, the base polyether polyol X, pre-prepared stabilizer, isopropanol, tert-amyl peroxy-2-ethylhexanoate, styrene and acrylonitrile monomer mixture were poured into a three-necked flask at a mass ratio of 100:10:3:0.6:190 (styrene and acrylonitrile mass ratio 1:1), and stirred at 60 r / min for 30 min to mix evenly to obtain the mixture.

[0125] (3) Synthesis of polymer polyols:

[0126] Add 900g of basic polyether polyol X and 90g of pre-made stabilizer to the reaction vessel. Purge with nitrogen five times at room temperature, raise the temperature to 110℃ and maintain it, then feed 1500g of the mixture at a mass flow rate of 27g / min to carry out the polymerization reaction. After the feeding is completed, continue to maintain the temperature and react for 1 hour. Turn on the vacuum pump and remove the chain transfer agent under a pressure of -0.1MPa to obtain the polymer polyol.

[0127] Comparative Example 3

[0128] Example 2 from patent CN 116396443 A is selected as comparative example 3 of this patent.

[0129] The polymer polyols obtained in the examples and comparative examples were used to prepare high-strength foams, and the foam composition formulations are shown in Table 1 below:

[0130] Table 1. Polymer Polyol Foam Composition Formulation

[0131]

[0132] The foaming silicone oil and organic amine catalyst in Table 1 were purchased from Evonik Specialty Chemicals Ltd. During foaming, the polymer polyol, foaming silicone oil, organic amine catalyst, and water were first stirred at 800 rpm for 5 minutes, and then the temperature of the materials was controlled to 25°C. After temperature control, T-9 metal catalyst was added, followed by TDI, and then stirring was stopped at 800 rpm for 5 seconds. After foaming, the foamed silicone was placed in an oven at a constant temperature of 40°C for 48 hours before being taken out to analyze its physical properties.

[0133] The surface hardness test data of different polymer polyols in the examples and comparative examples are shown in Table 2 below, and the tensile strength test results (GB / T 528-2009) are shown in Table 3 below.

[0134] Table 2. Surface hardness data of different polymer polyols for nylon (unit: A)

[0135]

[0136] Table 3 Tensile strength of different polymer polyols for high-strength cotton (unit: kN)

[0137]

[0138] The tear strength (GB / T 529-2008) test results of different polymer polyols in the examples and comparative examples are shown in Table 4 below:

[0139] Table 4. Tear strength of different polymer polyols in nylon (unit: MPa)

[0140]

[0141] As shown in Tables 2, 3, and 4, modifying the polymer polyol macromonomer base polyether with polytetrahydrofuran ether diol can significantly improve the tear resistance and tensile properties of polymer polyol foam within a certain range, while the hardness of the foam does not change significantly. Furthermore, comparing the examples in Tables 3 and 4 with Comparative Example 3, it can be seen that modifying the macromonomer polyether with a small amount of PTMEG results in a similar improvement in the tensile and tear resistance of the polyurethane foam, but the amount used can be significantly reduced.

Claims

1. A polymeric polyol, characterized in that, It is prepared from the following parts by weight of raw materials: Basic polyether polyol X: 30-150 parts; Pre-made stabilizer: 3-15 parts; Mixed ingredients: 120-180 parts; The mixture is a mixture of base polyether polyol X, pre-made stabilizer, chain transfer agent, initiator, styrene and acrylonitrile monomers; The pre-made stabilizer is a copolymer of macromolecular monomers, styrene, and acrylonitrile; The basic polyether polyol X is a flexible foam polyether polyol with 3 functions and a number average molecular weight of 3000 g / mol; The macromonomer is a 3-isopropenyl-α,α-dimethylbenzyl isocyanate-terminated polytetrahydrofuran-modified polyether polyol macromonomer, which is prepared by the following steps: a. Synthesis of macromonomer-based polyether polyol A: Using sucrose and sorbitol as initiators, macromolecular monomer-based polyether polyol A was prepared by reacting it with propylene oxide under the catalysis of a catalyst. b. Synthesis of macromonomer-based polyether polyol B: Using macromonomer-based polyether polyol A and polytetrahydrofuran ether diol as initiators, macromonomer-based polyether polyol B was prepared by reacting it with an epoxy compound under the catalysis of a catalyst. c. Synthesis of macromonomers: The macromonomer was prepared by reacting the basic polyether polyol B with 3-isopropenyl-α,α-dimethylbenzyl isocyanate under the catalysis of a catalyst.

2. The polymer polyol according to claim 1, characterized in that, The mass ratio of sucrose to sorbitol in step a is 0.5-10:1, and the hydroxyl value of the macromonomer base polyether polyol A in step a is 190-200 mg KOH / g.

3. The polymer polyol according to claim 1, characterized in that, The number-average molecular weight of the polytetrahydrofuran ether diol mentioned in step b is 650-2000 g / mol, and the mass ratio of the polytetrahydrofuran ether diol to the macromonomer basic polyether polyol A in step b is 0.05-1.0:

1.

4. The polymer polyol according to claim 1, characterized in that, The epoxy compound in step b is a mixture of propylene oxide and ethylene oxide, wherein ethylene oxide accounts for 0%-35% of the total mass of propylene oxide, ethylene oxide and the initiator in step b.

5. The polymer polyol according to claim 1, characterized in that, The hydroxyl value of the macromonomer base polyether polyol B described in step b is 21.00-30.00 mg KOH / g.

6. The polymer polyol according to claim 1, characterized in that, The mass ratio of the macromonomer base polyether polyol B in step c to the added 3-isopropenyl-α,α-dimethylbenzyl isocyanate is 100:0.5-3.

0.

7. A method for preparing the polymer polyol according to any one of claims 1-6, characterized in that, It is prepared by the following steps: (1) Preparation of pre-made stabilizers: A pre-prepared stabilizer is prepared by reacting macromolecular monomers, styrene, acrylonitrile, chain transfer agents, and initiators. (2) Preparation of the mixture: The base polyether polyol X, pre-made stabilizer, chain transfer agent, initiator, styrene and acrylonitrile monomers are mixed evenly to obtain a mixture. (3) Synthesis of polymer polyols: Add the base polyether polyol X and the pre-made stabilizer into the reaction vessel, raise the temperature and maintain it, then continuously pass the mixture through to carry out the polymerization reaction. After the addition is completed, continue to maintain the temperature to remove the chain transfer agent, and the polymer polyol is obtained.

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