Polymer polyol as well as preparation method and application thereof

Abstract

The invention provides polymer polyol as well as a preparation method and application thereof, the polymer polyol is prepared from the following raw materials in percentage by mass: 0.1%-1% of an initiator, 18%-60% of styrene and acrylonitrile, 3%-12% of a dispersing agent, 5%-12% of a chain transfer agent and 30%-70% of polyol, and the polyol comprises the following components in percentage by mass: 15%-70% of modified polyol and 30%-85% of polyether polyol. A polyurethane product prepared from the polymer polyol product disclosed by the invention has relatively good tear strength and tensile strength.

Description

Technical Field

[0001] The invention belongs to the technical field of petrochemical industry, and specifically relates to a polymer polyol and a preparation method and application thereof. Background Art

[0002] Polymer polyol (POP) is prepared by in-situ polymerization of one or more ethylenically unsaturated monomers in polyether polyol in the presence of a free radical polymerization initiator. It is a mixture of polyether polyol, grafted polyether polyol, self-polymer or copolymer of ethylenically unsaturated monomers, etc. Polymer polyol is widely used in the preparation of high-resilience, high-load polyurethane soft, semi-rigid foam plastics and elastomers. Due to the effect of polymer particles in polymer polyol, the performance of polyurethane foam can be improved, especially the hardness and load bearing capacity. However, due to the presence of polymer particles, the original foam pore wall is destroyed, so that the tear and tensile strength of polyurethane foam are affected.

[0003] In order to solve the above problems, people have conducted a lot of research work. CN109762117 relates to a method for synthesizing polymer polyether polyols. The method is prepared by a two-step method. First, a polymer polyether polyol prepolymer is prepared, wherein the polymer polyether polyol prepolymer is composed of a top material and a bottom material, and the mass ratio of the top material to the bottom material is 2:1-6:1; second, a polymer polyether polyol is synthesized, wherein the polymer polyether polyol is composed of a top material and a bottom material, and the mass ratio of the top material to the bottom material is 2:1-6:1. The polymer polyether polyol residue mass content prepared by this method is less than 0.008‰, and the viscosity is 4000-5000mPa.s. When it is used for high-resilience sponge, the elongation at break of the product is greater than that of similar products, but the depression hardness is lower.

[0004] CN110437398 relates to a method for preparing polymer polyether polyol by continuous dispersion polymerization process, which adopts a copolymer of poly(meth)acrylic acid polyether ester containing dithiocarboxylate groups as a stabilizer, and continuously injects a monomer liquid prepared by vinyl monomer and polyether polyol; and an initiator liquid prepared by polyether polyol and initiator (the stabilizer is configured in the monomer liquid and / or the initiator liquid) into a stirred reactor with a set reaction temperature in proportion, and maintains a certain residence time; the outflowing reaction liquid enters a maturation reactor, and continuously injects an initiator solution, and maintains a certain residence time; the reaction liquid is removed from the vacuum reactor to remove residual monomers, and the product POP is obtained. The POP product prepared by this method has the characteristics of high solid content and low viscosity, and the polymerization process and the product POP have good stability and reproducibility; but it has no obvious enhancement effect on the compression limit hardness, tear strength and tensile strength of the polyurethane product.

[0005] The polymer polyol product obtained by the invention has a polyurethane elastomer product prepared with the polymer polyol product, which has not only good resilience and hardness, but also high tear strength and tensile strength. Summary of the invention

[0006] In order to solve the above problems in the prior art, the present invention provides a polymer polyol and a preparation method and application thereof.

[0007] In the first aspect, the present invention provides a polymer polyol, wherein the raw materials for its preparation include, by weight percentage of the total raw materials: 0.1%-1% of initiator, 18%-60% of the total weight of styrene and acrylonitrile, 3%-12% of dispersant, 5%-12% of chain transfer agent, and 30%-70% of polyol;

[0008] The polyol comprises 15%-70% of modified polyol and 30%-85% of polyether polyol in terms of the total weight percentage of the polyol components.

[0009] As a specific embodiment of the present invention, the initiator is an azo free radical initiator, and the azo free radical initiator includes azobisisobutyronitrile.

[0010] As a specific embodiment of the present invention, the dispersant is a polyether ester formed by the reaction of a multifunctional polyether polyol and maleic anhydride. The dispersant technology is relatively mature, and this expression can limit the type of dispersant, which is a common expression in the industry.

[0011] As a specific embodiment of the present invention, the chain transfer agent is dodecyl mercaptan or isopropanol.

[0012] As a specific embodiment of the present invention, the modified polyol is formed by polymerizing a first diol with furandicarboxylic acid and propylene oxide; wherein the first diol is selected from at least one of ethylene glycol, diethylene glycol, propylene glycol and dipropylene glycol; preferably, the polymerization method comprises the following steps:

[0013] S1: first polymerizing furandicarboxylic acid and a first diol to obtain a first polymer product;

[0014] S2: vacuum dehydrating the first polymer product obtained in step S1;

[0015] S3: adding the first diol and propylene oxide to the first polymer product obtained by vacuum dehydration in step S2 to continue the polymerization reaction to obtain a modified polyol.

[0016] More preferably, in step S1, the amount of the first diol added is 15-35% of the total mass of the input product; the molar ratio of furandicarboxylic acid to the first diol is 1:(2-2.5), the polymerization temperature is 210-250° C., and the polymerization time is 3-5 h;

[0017] The first polymer product obtained in step S2 is dehydrated to an acid value of <1 mgKOH / g;

[0018] In the step S3, the amount of the first diol added is 1.5-3%, the amount of propylene oxide added is 42-68%, the polymerization temperature is 100-150° C., and the polymerization time is 3-5 hours.

[0019] Specifically, the preparation method of modified polyols is as follows:

[0020] S1: using a small molecule diol as an initiator, adding a diol of 15-35% of the total mass of the product, adding furandicarboxylic acid, the molar ratio of furandicarboxylic acid to diol is 1:(2-2.5), and polymerizing at 210-250° C. for 3-5 hours to obtain a first polymerization product;

[0021] S2: vacuum dehydrating the first polymer product obtained in step S1 to an acid value of <1 mgKOH / g,

[0022] S3: Adding 1.5-3% of the total mass of the diol and 45-55% of propylene oxide to the first polymer product obtained by vacuum dehydration in step S2, and polymerizing at 100-150° C. for 3-5 hours to obtain a modified polyol.

[0023] As a specific embodiment of the present invention, the polyether polyol includes a second diol and an epoxy compound polymerized; the mass ratio of the second diol to the epoxy compound is (1-8): (42-49); the second diol is selected from at least one of ethylene glycol, propylene glycol, and polytetrahydrofuran diol; the alkoxylating agent includes propylene oxide, ethylene oxide, cyclohexene oxide, and butylene oxide; preferably, the amount of propylene oxide in the epoxy compound is 40-80% of the total amount of the epoxy compound; the amount of ethylene oxide is 1-15% of the total amount of the epoxy compound; the amount of cyclohexene oxide is 1-20% of the total amount of the epoxy compound; the amount of butylene oxide is 1-30% of the total amount of the epoxy compound; the mass of the bimetallic catalyst accounts for 20-150ppm of the total amount of the feed. Specifically, different epoxy compound ratios result in different structures of the obtained polyether products, thereby affecting the application performance of the polyether products. The ratio of epoxy compounds is one of the main innovations of the present invention.

[0024] Specifically, the preparation method of polyether polyol is as follows:

[0025] Using diol as initiator, at 0-0.4MPa pressure and 100-150°C, it is polymerized step by step with one or more of propylene oxide, ethylene oxide, cyclohexene oxide and butylene oxide to obtain polyether polyol; wherein the mass of diol accounts for 2-16% of the total feed amount, and the mass of epoxy compound accounts for 84-98% of the total feed amount.

[0026] The mass of the double metal cyanide catalyst accounts for 20-150ppm of the total feed amount.

[0027] Specifically, the bimetallic catalyst is a DMC catalyst.

[0028] The above raw materials in the present invention can be prepared in-house or commercially available, and the present invention is not particularly limited thereto.

[0029] In a second aspect, the present invention provides a method for preparing the polymer polyol described in the first aspect, comprising: uniformly mixing an initiator, styrene, acrylonitrile, a dispersant, a chain transfer agent, and a polyol, and polymerizing them using a continuous polymerization process; wherein the polyol comprises a polyether polyol and a modified polyol.

[0030] As a specific embodiment of the present invention, based on the total mass percentage of raw materials, the initiator is 0.1%-1%, the total mass percentage of styrene and acrylonitrile is 18%-60%, the dispersant is 3%-12%, the chain transfer agent is 5%-12%, and the polyol is 30-70%.

[0031] The polyol comprises 15%-70% of modified polyol and 30%-85% of polyether polyol in terms of the total weight percentage of the polyol components.

[0032] As a specific embodiment of the present invention, the polymerization reaction conditions include: reaction temperature of 100-130° C., reaction pressure of 0-0.4 MPa, and reaction residence time of 1.5-3 hours.

[0033] In a third aspect, the present invention provides the use of the polymer polyol described in the first aspect or the polymer polyol prepared by the preparation method described in the second aspect in the field of polyurethane foam.

[0034] In a fourth aspect, the present invention provides a polymer polyol prepared by the polymer polyol described in the first aspect or the preparation method described in the second aspect, having a tear strength of 140-152 kN / m and a tensile strength of 35-40 MPa.

[0035] Compared with the prior art, the present invention has the following beneficial effects:

[0036] 1. The present invention introduces furandicarboxylate structure and cyclohexene oxide and butylene oxide polyether structure into the polymer polyol structure, breaking the crystallinity of the molecular chain, so that the products prepared with the same as raw materials have better rigidity.

[0037] 2. The polymer polyol product obtained by the present invention has high tear strength and tensile strength for the polyurethane elastomer product prepared therefrom. The tensile strength can be increased by 15-25%, and the tear strength can be increased by 12-17%.

[0038] 3. The polymer product obtained by the present invention has excellent application performance. Under the premise of ensuring the application requirements of polyurethane products, the product density can be reduced and the amount of raw materials can be saved. DETAILED DESCRIPTION

[0039] The present invention will be further described below in conjunction with specific embodiments, but they do not constitute any limitation to the present invention.

[0040] The reactor used in Examples 1-5 of the present invention is a 2L stainless steel pressure-resistant reactor.

[0041] The bimetallic catalyst is a Huaian Bader bimetallic cyanide complex catalyst.

[0042] Example 1

[0043] The preparation method of the modified polyol in this embodiment has a total product mass of 1000g, and the specific details are as follows:

[0044] 150g of ethylene glycol and 187.2g of furandicarboxylic acid were added to the reactor, the reaction pressure was 0.3MPa, the polymerization reaction was carried out at 220°C for 3h, and then vacuum dehydration was carried out until the acid value was <1mgKOH / g; then 30g of ethylene glycol and 0.1g of bimetallic catalyst were added, and 680g of propylene oxide were added step by step, the reaction pressure was 0.4MPa, and the polymerization reaction was carried out at 130°C for 5h. Modified polyol product A was obtained.

[0045] Among them, based on the total mass percentage of raw materials, the amount of ethylene glycol input is 15%, the molar ratio of furandicarboxylic acid to ethylene glycol is 1:2, the amount of ethylene glycol input in the back stage is 3%, the bimetallic catalyst is 100 ppm, and the propylene oxide is 68%.

[0046] Example 2

[0047] The preparation method of the modified polyol in this embodiment has a total product mass of 1000g, and the specific details are as follows:

[0048] 350g of propylene glycol and 287g of furandicarboxylic acid were added to the reactor, the reaction pressure was 0.2MPa, the polymerization reaction was carried out at 210°C for 5h, and then vacuum dehydration was carried out until the acid value was <1mgKOH / g; then 15g of propylene glycol and 0.05g of bimetallic catalyst were added, and 420g of propylene oxide were added step by step, the reaction pressure was 0.1MPa, and the polymerization reaction was carried out at 100°C for 4h. Modified polyol product B was obtained.

[0049] Among them, based on the total mass percentage of raw materials, the input amount of propylene glycol is 35%, the molar ratio of furandicarboxylic acid to propylene glycol is 1:2.5, the input amount of propylene glycol in the back stage is 1.5%, the bimetallic catalyst is 50ppm, and the propylene oxide is 42%.

[0050] Example 3

[0051] The preparation method of the modified polyol in this embodiment has a total product mass of 1000g, and the specific details are as follows:

[0052] 250g of diethylene glycol and 167g of furandicarboxylic acid were added to the reactor, the reaction pressure was 0.1MPa, the polymerization reaction was carried out at 230°C for 4h, and then vacuum dehydration was carried out until the acid value was <1mgKOH / g; then 25g of diethylene glycol and 0.03g of bimetallic catalyst were added, and 596g of propylene oxide were added step by step, the reaction pressure was 0.2MPa, and the polymerization reaction was carried out at 150°C for 3h. Modified polyol product C was obtained.

[0053] Among them, based on the total mass percentage of raw materials, the amount of diethylene glycol input is 25%, the molar ratio of furandicarboxylic acid to diol is 1:2.2, the amount of diethylene glycol input in the back stage is 2.5%, the bimetallic catalyst is 30ppm, and the propylene oxide is 59.6%.

[0054] Example 4

[0055] The preparation method of the modified polyol in this embodiment has a total product mass of 1000g, and the specific details are as follows:

[0056] 300g of dipropylene glycol and 145g of furandicarboxylic acid were added to the reactor, the reaction pressure was 0.25MPa, the polymerization reaction was carried out at 250°C for 4.5h, and then vacuum dehydration was carried out until the acid value was <1mgKOH / g; then 30g of ethylene glycol and 0.01g of bimetallic catalyst were added, and 558g of propylene oxide were added step by step, the reaction pressure was 0.3MPa, and the polymerization reaction was carried out at 120°C for 5h. Modified polyol product D was obtained.

[0057] Among them, based on the total mass percentage of raw materials, the input amount of dipropylene glycol is 30%, the molar ratio of furandicarboxylic acid to diol is 1:2.4, the input amount of dipropylene glycol in the back stage is 3%, the bimetallic catalyst is 10ppm, and the propylene oxide is 55.8%.

[0058] Example 5

[0059] The preparation method of the modified polyol in this embodiment has a total product mass of 1000g, and the specific details are as follows:

[0060] 200g propylene glycol and 178g furandicarboxylic acid were added to the reactor, the reaction pressure was 0.15MPa, the polymerization reaction was carried out at 240°C for 3.5h, and then vacuum dehydration was carried out until the acid value was <1mgKOH / g; then 18g propylene glycol and 0.08g bimetallic catalyst were added, and 643g propylene oxide was added stepwise, the reaction pressure was 0.2MPa, and the polymerization reaction was carried out at 110°C for 4h. Modified polyol product E was obtained.

[0061] Among them, based on the total mass percentage of raw materials, the input amount of propylene glycol is 20%, the molar ratio of furandicarboxylic acid to diol is 1:2.3, the input amount of propylene glycol in the back stage is 2%, the bimetallic catalyst is 80ppm, and the propylene oxide is 64.3%.

[0062] The reactor used in Examples 6-9 of the present invention is a 3L stainless steel pressure-resistant reactor.

[0063] The bimetallic catalyst is a Huaian Bader bimetallic cyanide complex catalyst.

[0064] Example 6

[0065] The preparation method of polyether polyol in this embodiment has a total product mass of 2000g, and the specific details are as follows:

[0066] 40 g of ethylene glycol and 0.3 g of a bimetallic catalyst were put into a reactor, and reacted step by step with 1960 g of an epoxy compound at a pressure of 0.4 MPa and 150° C., including 1568 g of propylene oxide, 196 g of ethylene oxide, 19.6 g of cyclohexane oxide and 176.4 g of butylene oxide, to finally obtain polyether polyol a.

[0067] Among them, based on the total mass percentage of raw materials, the mass of diols accounts for 2% and the mass of epoxy compounds accounts for 98%. Among the epoxy compounds, the amount of propylene oxide is 80% of the total amount of epoxy compounds; the amount of ethylene oxide is 10% of the total amount of epoxy compounds; the amount of cyclohexene oxide is 1% of the total amount of epoxy compounds; the amount of butylene oxide is 9% of the total amount of epoxy compounds; the mass of the bimetallic catalyst accounts for 150ppm of the total amount of feed.

[0068] Example 7

[0069] The preparation method of polyether polyol in this embodiment has a total product mass of 2000g, and the specific details are as follows:

[0070] 320 g of propylene glycol and 0.04 g of a bimetallic catalyst were put into a reactor, and reacted step by step with 1680 g of an epoxy compound at a pressure of 0.2 MPa and 130° C., including 1629.6 g of propylene oxide, 16.8 g of ethylene oxide, 16.8 g of cyclohexane oxide and 16.8 g of butylene oxide, to finally obtain polyether polyol b.

[0071] Among them, calculated as a percentage of the total mass of raw materials, the mass of diols accounts for 16% of the total feed amount, the epoxy compounds account for 84% of the total feed amount, the feed amount of propylene oxide in the epoxy compounds is 97% of the total feed amount of epoxy compounds; the feed amount of ethylene oxide is 1% of the total feed amount of epoxy compounds; the feed amount of cyclohexene oxide is 1% of the total feed amount of epoxy compounds; the feed amount of butylene oxide is 1% of the total feed amount of epoxy compounds; the mass of the bimetallic catalyst accounts for 20ppm of the total feed amount.

[0072] Example 8

[0073] The preparation method of polyether polyol in this embodiment has a total product mass of 2000g, and the specific details are as follows:

[0074] 200 g of polytetrahydrofuran diol and 0.2 g of a bimetallic catalyst were added into a reactor, and reacted step by step with 1800 g of an epoxy compound, including 720 g of propylene oxide, 270 g of ethylene oxide, 360 g of cyclohexane oxide and 450 g of butylene oxide, at a pressure of 0.3 MPa and at 120° C., to finally obtain polyether polyol c.

[0075] Among them, calculated as a percentage of the total mass of raw materials, the mass of diols accounts for 10% of the total feed amount, the epoxy compound accounts for 90% of the total feed amount, the feed amount of propylene oxide in the epoxy compound is 40% of the total feed amount of the epoxy compound; the feed amount of ethylene oxide is 15% of the total feed amount of the epoxy compound; the feed amount of cyclohexene oxide is 20% of the total feed amount of the epoxy compound; the feed amount of butylene oxide is 25% of the total feed amount of the epoxy compound; the mass of the bimetallic catalyst accounts for 100ppm of the total feed amount.

[0076] Example 9

[0077] The preparation method of polyether polyol in this embodiment has a total product mass of 2000g, and the specific details are as follows:

[0078] 100 g of propylene glycol and 0.1 g of a bimetallic catalyst were added into a reactor, and reacted step by step with 1900 g of an epoxy compound, including 950 g of propylene oxide, 95 g of ethylene oxide, 285 g of cyclohexane oxide and 570 g of butylene oxide, at a pressure of 0.1 MPa and at 100° C., to finally obtain polyether polyol d.

[0079] Among them, calculated as a percentage of the total mass of raw materials, the mass of diols accounts for 5% of the total feed amount, the epoxy compounds account for 95% of the total feed amount, the feed amount of propylene oxide in the epoxy compounds is 50% of the total feed amount of the epoxy compounds; the feed amount of ethylene oxide is 5% of the total feed amount of the epoxy compounds; the feed amount of cyclohexene oxide is 15% of the total feed amount of the epoxy compounds; the feed amount of butylene oxide is 30% of the total feed amount of the epoxy compounds; the mass of the bimetallic catalyst accounts for 50ppm of the total feed amount.

[0080] The reactor used in Examples 10-14 of the present invention is a 2L two-kettle continuous polymer polyether polyol reactor.

[0081] The dispersant is a self-made maleic anhydride type polyether ester dispersant.

[0082] The initiator, styrene, acrylonitrile, dispersant, chain transfer agent and polyol are mixed evenly, and the reaction temperature is 100-130°C and the reaction pressure is 0-0.4MPa, and the reaction residence time is maintained for 2-3 hours.

[0083] Example 10

[0084] The preparation method of the polymer polyol in this embodiment has a total product mass of 1000g, and the specific details are as follows:

[0085] The polymer polyether polyol was synthesized by a two-pot continuous synthesis process: 1 g of azobisisobutyronitrile and 300 g of styrene and acrylonitrile, including 180 g of styrene, 120 g of acrylonitrile, 30 g of dispersant, 50 g of chain transfer agent isopropanol, 469 g of modified polyol A and 201 g of polyether polyol a in the polyol. The initiator, styrene, acrylonitrile, dispersant, chain transfer agent and polyol were evenly mixed. The reaction temperature was 100°C and the reaction pressure was 0.4 MPa. The reaction residence time was maintained for 3 hours to obtain polymer polyol 1.

[0086] Among them, calculated by the total mass percentage of raw materials, azobisisobutyronitrile is 0.1%, the total amount of styrene and acrylonitrile is 30%, the mass ratio of styrene to acrylonitrile is 60:40, the dispersant is 3%, the chain transfer agent is 5%, and the polyol is 67%; the polyol contains 70% of modified polyol A and 30% of polyether polyol a.

[0087] Embodiment 11

[0088] The preparation method of the polymer polyol in this embodiment has a total product mass of 1000g, and the specific details are as follows:

[0089] The polymer polyether polyol was synthesized by a two-pot continuous synthesis process: 10 g of azobisisobutyronitrile, 600 g of styrene and acrylonitrile in total: 390 g of styrene, 210 g of acrylonitrile, 100 g of dispersant, 120 g of chain transfer agent isopropanol, 45 g of modified polyol B and 255 g of polyether polyol b in the polyol. The initiator, styrene, acrylonitrile, dispersant, chain transfer agent and polyol were evenly mixed. The reaction temperature was 130°C and the reaction pressure was 0.3 MPa. The reaction residence time was maintained for 2 hours to obtain polymer polyol 2.

[0090] Among them, calculated by the total mass percentage of raw materials, azobisisobutyronitrile is 1%, the total amount of styrene and acrylonitrile is 60%, the mass ratio of styrene to acrylonitrile is 65:35, the dispersant is 10%, the chain transfer agent is 12%, and the polyol is 30%; the polyol contains 15% of modified polyol B and 85% of polyether polyol b.

[0091] Example 12

[0092] The preparation method of the polymer polyol in this embodiment has a total product mass of 1000g, and the specific details are as follows:

[0093] The polymer polyether polyol is synthesized by a two-pot continuous synthesis process: 5 g of azobisisobutyronitrile and 450 g of the total amount of styrene and acrylonitrile: 225 g of styrene, 225 g of acrylonitrile, 80 g of dispersant, 80 g of chain transfer agent isopropanol, 235 g of modified polyol C and 235 g of polyether polyol C in the polyol. The initiator, styrene, acrylonitrile, dispersant, chain transfer agent and polyol are mixed evenly. The reaction temperature is 120°C and the reaction pressure is 0.2 MPa. The reaction residence time is maintained for 2.5 hours to obtain polymer polyol 3.

[0094] Among them, calculated by the total mass percentage of raw materials, azobisisobutyronitrile is 0.5%, the total amount of styrene and acrylonitrile is 45%, the mass ratio of styrene to acrylonitrile is 50:50, the dispersant is 8%, the chain transfer agent is 8%, and the polyol is 47%; the polyol contains 50% of modified polyol C and 50% of polyether polyol C.

[0095] Embodiment 13

[0096] The preparation method of the polymer polyol in this embodiment has a total product mass of 1000g, and the specific details are as follows:

[0097] The polymer polyether polyol was synthesized by a two-pot continuous synthesis process: 3 g of azobisisobutyronitrile and 500 g of styrene and acrylonitrile in total: 350 g of styrene, 150 g of acrylonitrile, 100 g of dispersant, 100 g of chain transfer agent isopropanol, 160 g of modified polyol D and 340 g of polyether polyol d in the polyol. The initiator, styrene, acrylonitrile, dispersant, chain transfer agent and polyol were mixed evenly. The reaction temperature was 110°C and the reaction pressure was 0.1 MPa. The reaction residence time was maintained for 1.5 hours to obtain polymer polyol 4.

[0098] Among them, calculated by the total mass percentage of raw materials, azobisisobutyronitrile is 0.3%, the total amount of styrene and acrylonitrile is 50%, the mass ratio of styrene to acrylonitrile is 70:30, the dispersant is 10%, the chain transfer agent is 10%, and the polyol is 40%; the polyol contains 40% of modified polyol D and 60% of polyether polyol d.

[0099] Embodiment 14

[0100] The preparation method of the polymer polyol in this embodiment has a total product mass of 1000g, and the specific details are as follows:

[0101] The polymer polyether polyol was synthesized by a two-pot continuous synthesis process: 3 g of azobisisobutyronitrile and 180 g of styrene and acrylonitrile, including 72 g of styrene and 108 g of acrylonitrile, 120 g of dispersant, 100 g of chain transfer agent isopropanol, 455 g of modified polyol D and 245 g of polyether polyol d in the polyol. The initiator, styrene, acrylonitrile, dispersant, chain transfer agent and polyol were evenly mixed. The reaction temperature was 115°C and the reaction pressure was 0 MPa. The reaction residence time was maintained for 2.8 hours to obtain polymer polyol 5.

[0102] Among them, calculated by the total mass percentage of raw materials, azobisisobutyronitrile is 0.3%, the total amount of styrene and acrylonitrile is 18%, the mass ratio of styrene to acrylonitrile is 40:60, the dispersant is 12%, the chain transfer agent is 10%, and the polyol is 70%; the polyol contains 65% of modified polyol D and 35% of polyether polyol e.

[0103] The reactor used in the comparative example is a 2L two-pot continuous polymer polyether polyol reactor.

[0104] The dispersant is a self-made maleic anhydride type polyether ester dispersant.

[0105] The polyol is TDB-2000, a pure propylene oxide polyether polyol product produced by the polyether department of Tianjin Petrochemical.

[0106] Comparative Example

[0107] The polymer polyether polyol was synthesized by a two-pot continuous synthesis process, with 5g of azobisisobutyronitrile, 450g of styrene and acrylonitrile in total: 225g of styrene, 225g of acrylonitrile, 80g of dispersant, 80g of chain transfer agent isopropanol, and 470g of polyol. The initiator, styrene, acrylonitrile, dispersant, chain transfer agent, and polyol were mixed evenly, and the reaction residence time was maintained at a reaction temperature of 120°C and a reaction pressure of 0.2MPa for 2.5 hours to obtain a comparative polymer polyol product 6.

[0108] Among them, calculated by total mass percentage of raw materials, azobisisobutyronitrile is 0.5%, the total amount of styrene and acrylonitrile is 45%, the mass ratio of styrene to acrylonitrile is 50:50, the dispersant is 8%, the chain transfer agent is 8%, and the polyol is 47%.

[0109] The properties of the polyurethane products produced from the polymer polyols obtained in Examples 10-14 of the present invention are shown in Table 1, and the properties of the polyurethane products produced from the polymer polyol comparative products obtained in the comparative examples are shown in Table 1.

[0110] Table 1 Polyurethane product performance analysis results

[0111]

[0112] It can be seen from Table 1 that the polyurethane elastomer product prepared from the polymer polyol product of the present invention has good tear strength and tensile strength.

[0113] In summary, the present invention introduces furandicarboxylate structure and epoxycyclohexane, butylene oxide polyether structure into the polymer polyol structure, breaks the crystallinity of the molecular chain, and makes the products prepared with the polymer polyol product as raw material have better rigidity. The polymer polyol product obtained by the present invention has higher tear strength and tensile strength, and the tensile strength can be increased by 15-25%, and the tear strength can be increased by 12-17%. The polymer product obtained by the present invention has excellent application performance. Under the premise of ensuring the application requirements of polyurethane products, the product density can be reduced and the amount of raw materials can be saved.

[0114] Any numerical value mentioned in the present invention, if there is only an interval of two units between any minimum value and any maximum value, includes all values ​​from the minimum value to the maximum value each time increasing by one unit. For example, if the amount of a component, or the value of a process variable such as temperature, pressure, time, etc. is declared to be 50-90, in this specification it means that 51-89, 52-88... and 69-71 and 70-71 are specifically listed. For non-integer values, 0.1, 0.01, 0.001 or 0.0001 can be appropriately considered as a unit. These are just some specially specified examples. In this application, in a similar manner, all possible combinations of numerical values ​​between the listed minimum and maximum values ​​are considered to have been disclosed.

[0115] It should be noted that the embodiments described above are only used to explain the present invention and do not constitute any limitation to the present invention. The present invention has been described with reference to typical embodiments, but it should be understood that the words used therein are descriptive and explanatory words, rather than restrictive words. The present invention may be modified as specified within the scope of the claims of the present invention, and the present invention may be revised without departing from the scope and spirit of the present invention. Although the present invention described therein relates to specific methods, materials and embodiments, it does not mean that the present invention is limited to the specific examples disclosed therein, on the contrary, the present invention can be extended to all other methods and applications with the same functions.

Claims

1. A polymer polyol, characterized in that The raw materials for preparation include, by percentage of the total mass of raw materials: 0.1%-1% of initiator, 18%-60% of the total mass of styrene and acrylonitrile, 3%-12% of dispersant, 5%-12% of chain transfer agent, and 30%-70% of polyol; The polyol comprises 15%-70% of modified polyol and 30%-85% of polyether polyol in terms of the total weight percentage of the polyol components.

2. The polymer polyol according to claim 1, characterized in that The initiator is an azo free radical initiator, and the azo free radical initiator includes azobisisobutyronitrile.

3. The polymer polyol according to claim 1 or 2, characterized in that The dispersant is a polyether ester formed by the reaction of multifunctional polyether polyol and maleic anhydride.

4. The polymer polyol according to any one of claims 1 to 3, characterized in that The chain transfer agent is dodecyl mercaptan or isopropanol.

5. The polymer polyol according to any one of claims 1 to 4, characterized in that The modified polyol is formed by polymerizing the first diol with furandicarboxylic acid and propylene oxide; Preferably, the first diol is selected from at least one of ethylene glycol, diethylene glycol, propylene glycol and dipropylene glycol; Preferably, the polymerization method comprises the following steps: S1: first polymerizing furandicarboxylic acid and a first diol to obtain a first polymer product; S2: vacuum dehydrating the first polymer product obtained in step S1; S3: adding the first diol and propylene oxide to the first polymer product obtained by vacuum dehydration in step S2 to continue polymerization reaction to obtain a modified polyol; More preferably, in step S1, the amount of the first diol added is 15-35% of the total mass of the input product; the molar ratio of furandicarboxylic acid to the first diol is 1:(2-2.5), the polymerization temperature is 210-250° C., and the polymerization time is 3-5 h; The first polymer product obtained in step S2 is dehydrated to an acid value of <1 mgKOH / g; In the step S3, the amount of the first diol added is 1.5-3%, the amount of propylene oxide added is 42-68%, the polymerization temperature is 100-150° C., and the polymerization time is 3-5 hours.

6. The polymer polyol according to any one of claims 1 to 5, characterized in that The polyether polyol comprises a polymerization product of a second diol and an epoxy compound; the mass ratio of the second diol to the epoxy compound is (1-8): (42-49); Preferably, the second diol is selected from at least one of ethylene glycol, propylene glycol and polytetramethylene glycol; The epoxy compound includes propylene oxide, ethylene oxide, cyclohexyl oxide and butylene oxide; preferably, the amount of propylene oxide in the epoxy compound is 40-80% of the total amount of the epoxy compound; The amount of ethylene oxide is 1-15% of the total amount of epoxy compounds; the amount of cyclohexene oxide is 1-20% of the total amount of epoxy compounds; The amount of butylene oxide is 1-30% of the total amount of epoxy compounds; The polymerization reaction is carried out under the action of a bimetallic catalyst, and the mass of the bimetallic catalyst accounts for 20-150 ppm of the total feed amount.

7. A method for preparing a polymer polyol according to any one of claims 1 to 6, characterized in that: The preparation method comprises: adopting a continuous polymerization process to polymerize raw materials including an initiator, styrene, acrylonitrile, a dispersant, a chain transfer agent and a polyol; wherein the polyol comprises a polyether polyol and a modified polyol.

8. The preparation method according to claim 7, characterized in that: Based on the total mass percentage of the raw materials, the initiator is 0.1%-1%, the total mass percentage of styrene and acrylonitrile is 18%-60%, the dispersant is 3%-12%, the chain transfer agent is 5%-12%, and the polyol is 30-70%. The polyol comprises 15%-70% of modified polyol and 30%-85% of polyether polyol in terms of the total weight percentage of the polyol components.

9. Use of the polymer polyol according to any one of claims 1 to 6 or the polymer polyol prepared by the preparation method according to claim 7 or 8 in the field of polyurethane foam.

10. A polyurethane product prepared from the polymer polyol according to any one of claims 1 to 6 or the polymer polyol prepared by the preparation method according to claim 7 or 8, having a tear strength of 140-152 kN / m and a tensile strength of 35-40 MPa.

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