CN110003423B - Modified isocyanate prepolymer, polyurethane composite material, and preparation method and application thereof - Google Patents
Modified isocyanate prepolymer, polyurethane composite material, and preparation method and application thereof Download PDFInfo
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- CN110003423B CN110003423B CN201910211344.XA CN201910211344A CN110003423B CN 110003423 B CN110003423 B CN 110003423B CN 201910211344 A CN201910211344 A CN 201910211344A CN 110003423 B CN110003423 B CN 110003423B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4054—Mixtures of compounds of group C08G18/60 with other macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/60—Polyamides or polyester-amides
- C08G18/603—Polyamides
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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a modified isocyanate prepolymer, a polyurethane composite material, a preparation method and application thereof, wherein the modified isocyanate prepolymer is a reaction product of isocyanate and a polymer (A) with a reactive group to the isocyanate, and the polymer (A) with the reactive group to the isocyanate contains low molecular weight polyamide resin polyol. The polyurethane composite material comprises a polyol mixture and a modified isocyanate prepolymer; the polyurethane composite material can be used for preparing high-performance polyamide-polyurethane hybrid materials. The invention has wide addition range of filling particles, good elasticity of hybrid materials, wide adjustable range of density and hardness and wide application. The addition of the low molecular weight polyamide resin polyalcohol improves the heat resistance of the hybrid material, so that the hybrid material can be applied to high temperature environment.
Description
Technical Field
The invention relates to a low molecular weight polyamide modified isocyanate prepolymer, a polyurethane composite material, and a preparation method and application thereof.
Background
The polyurethane is a high polymer material containing a repeated structural unit of carbamate, has the advantages of high strength, wide physical property adjusting range, good process operability and the like, and is widely applied to the fields of daily life, industrial and agricultural production, medicine and the like. Other materials are filled in the polyurethane material or combined with other materials to prepare the composite material, so that the specific performance of the polyurethane can be further improved or the production cost can be reduced, and the application field of the polyurethane composite material can be enlarged. For example, ZL201210562641.7 discloses that a component A and a component B of a polyurethane stock solution are uniformly mixed with waste rubber particles to produce a polyurethane sole, and the waste rubber particles are utilized to improve the tensile strength, the wear resistance, the tear strength and the like of the sole. WO 2008/087078 discloses a hybrid material comprising a matrix consisting of polyurethane and foamed particles of thermoplastic polyurethane contained in the matrix. Isocyanate, a compound having a hydrogen atom reactive with isocyanate, a chain extender and/or a crosslinking agent, a catalyst and other additives are used to prepare an isocyanate prepolymer, and then the isocyanate prepolymer is mixed with a foamed example of thermoplastic polyurethane and the composite is cured by the action of water. WO 2014/023794 discloses a composed foam comprising a matrix composed of a polyurethane foam and foamed particles of thermoplastic polyurethane contained in the matrix, wherein the matrix and the particles are each composed of a polyol component and a polyisocyanate component, wherein at least 50% by weight of the basic structural units of the polyol component used to form the matrix and the particles are identical and at least 50% by weight of the basic structural units of the polyisocyanate component used to form the matrix and the particles are identical, wherein the matrix is completely open-celled and the foamed particles in the matrix are at least partially open-celled. Discloses a low molecular weight polyamide resin polyol, provides conditions for the combination of polyamide resin and polyurethane, and prepares the polyurethane into a rigid coating which can be applied to the fields of metal, glass, woodware and the like.
Disclosure of Invention
The invention aims to provide a modified isocyanate prepolymer, a polyurethane combined material, a preparation method and application thereof, which aim to overcome the defects in the prior art.
The modified isocyanate prepolymer is as follows: a reaction product of an isocyanate and a polymer (a) having a group reactive to isocyanate, the polymer (a) having a group reactive to isocyanate containing a low molecular weight polyamide resin polyol;
the number average molecular weight of the low molecular weight polyamide resin polyol is 700-2000, and the low molecular weight polyamide resin polyol is preferably a reaction product of dibasic acid, diamine and alcohol amine; the preparation method can be found in CN 104231260A.
Preferably, the polymer (a) having a group reactive with isocyanate further contains one or more of polyester polyol and polyether polyol;
the polymer (A) having a group reactive with isocyanate has a functionality of 2 to 3 and a number average molecular weight of 700 to 10000.
The NCO content of the modified isocyanate prepolymer is 0.1-15.0 wt%, and preferably, the NCO content of the modified isocyanate prepolymer is 0.1-10.0 wt%.
The polyester polyol is obtained by esterification reaction of organic dicarboxylic acid containing 2-14 carbon atoms and polyhydric alcohol containing 2-14 carbon atoms, the functionality is 2-3, and the number average molecular weight is 1000-6000;
the organic dicarboxylic acid is more than one of adipic acid, succinic acid, glutaric acid, suberic acid, sebacic acid, azelaic acid, phthalic acid, terephthalic acid, isophthalic acid, lauric acid, maleic acid and fumaric acid;
the polyalcohol is more than one of ethylene glycol, diethylene glycol, 1, 2-or 1, 3-propylene glycol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, glycerol and trimethylolpropane;
the polyester polyol can also be more than one of polycaprolactone polyol and polycarbonate polyol;
the polyether polyol is more than one of polypropylene oxide polyol, polyethylene oxide-propylene oxide copolymer polyol, polytetrahydrofuran diol, polytetrahydrofuran copolymer diol and polytrimethylene ether diol;
the polyether polyol has the functionality of 2-3 and the number average molecular weight of 1000-10000;
the isocyanate is more than one of toluene diisocyanate, diphenylmethane diisocyanate, carbodiimide modified diphenylmethane diisocyanate, uretonimine modified diphenylmethane diisocyanate, isophorone diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate and methylene bis (cyclohexyl diisocyanate).
The preparation method of the modified isocyanate prepolymer comprises the following steps:
reacting isocyanate and a polymer (A) with a group which is reactive to the isocyanate at 75-85 ℃ for 2.0-3.0 h to obtain the modified isocyanate prepolymer; preferably, phosphoric acid accounting for 0.002wt% -0.020 wt% of the total mass of the raw materials is added into the reaction raw materials;
the invention also relates to a polyurethane composite material, which comprises a polyol mixture and the modified isocyanate prepolymer;
the molar ratio of hydroxyl (-OH) of the polyol mixture to isocyanate (-NCO) in the modified isocyanate prepolymer is 1 (1.0-1.1);
the polyol mixture comprises a polymer (B) having isocyanate-reactive groups, a chain extender, a blowing agent, a foam stabilizer and a catalyst;
the polyol mixture comprises the following raw materials in parts by weight:
preferably, the polyol mixture further comprises an antioxidant, an antistatic agent and an anti-wear agent, wherein the antioxidant, the antistatic agent and the anti-wear agent are used in an amount of 0.01 to 3.0wt% based on the mass of the polymer (B) having the isocyanate-reactive group;
the polymer (B) having a group reactive with isocyanate is one or more of low molecular weight polyamide resin polyol, polyester polyol and polyether polyol;
the low molecular weight polyamide resin polyol is a reaction product of dibasic acid, diamine and alcohol amine, and the molecular weight is 700-2000; the preparation method is described in CN 104231260A;
the polyester polyol is prepared by esterification reaction of organic dicarboxylic acid containing 2-14 carbon atoms and polyhydric alcohol containing 2-14 carbon atoms, the functionality is 2-3, and the number average molecular weight is 1000-6000;
the organic dicarboxylic acid is more than one of adipic acid, succinic acid, glutaric acid, suberic acid, sebacic acid, azelaic acid, phthalic acid, terephthalic acid, isophthalic acid, decanedicarboxylic acid, maleic acid and fumaric acid;
the polyalcohol is more than one of ethylene glycol, diethylene glycol, 1, 2-or 1, 3-propylene glycol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, glycerol and trimethylolpropane.
The polyester polyol can also be more than one of polycaprolactone polyol and polycarbonate diol.
The polyether polyol is more than one of polypropylene oxide polyol, polyethylene oxide-propylene oxide copolymer polyol, polytetrahydrofuran diol, polytetrahydrofuran copolymer diol and polytrimethylene ether diol;
the polyether polyol has a functionality of 2-3 and a number average molecular weight of 1000-10000.
The chain extender is dihydric alcohol with the molecular weight of 62g/mol to 500 g/mol;
the foaming agent is more than one of water, cyclopentane, pentane and supercritical carbon dioxide;
the foam stabilizer is an organic silicon foam stabilizer;
the catalyst is triethylene diamine and/or stannous octoate.
The preparation method of the polyol mixture comprises the following steps:
mixing a polymer (B) with a group reactive to isocyanate, a chain extender, a foaming agent, a foam stabilizer and a catalyst at 40-45 ℃ for 2.5-3.5 h, and discharging to obtain the polyol mixture;
the polyurethane composite material can be used for preparing high-performance polyamide-polyurethane hybrid materials, and the application method comprises the following steps:
maintaining the temperature of a polyol mixture in the polyurethane composition material at 20-40 ℃, the temperature of a low molecular weight polyamide resin polyol modified isocyanate prepolymer in the polyurethane composition material at 40-70 ℃, uniformly mixing the polyol mixture, the modified isocyanate prepolymer and filling particles according to the molar ratio of-OH to-NCO of 1 (1.0-1.1), injecting into a mold at 50-80 ℃ for reaction (3-8) min for forming, demolding and curing for (45-50) h to obtain the high-performance polyamide-polyurethane hybrid material;
the filling particles are more than one of thermoplastic polyurethane foaming particles, CPU elastomer particles, rubber particles, ethylene-vinyl acetate copolymer (EVA) particles and thermoplastic polyester foaming particles;
the addition amount of the filling particles is 1wt% -90 wt% of the total mass of the hybrid material.
The diameter of the filling particles is 0.1cm to 10cm, and the filling particles are spherical or elliptical.
The filling particles are tubular particles, the length of the filling particles is 1mm to 40mm, and the diameter of the filling particles is 1mm to 40 mm.
The density of the high-performance polyamide-polyurethane hybrid material is 0.10g/cm3To 1.20g/cm3；
The high-performance polyamide-polyurethane hybrid material is used for soles, bicycle saddles, sports equipment, child playgrounds, interior and exterior decorations, automobile interiors and exteriors and sports tracks.
The invention has the beneficial effects that: the system has long initiation time, the polyurethane enhanced by the low molecular weight polyamide resin and the polyatomic alcohol has high adhesiveness with the filling particles, the addition range of the filling particles is wide, the particles with high filling amount can be effectively adhered without using an adhesive, and the prepared hybrid material has short demolding time, good elasticity, wide adjustable range of density and hardness and wide application. The addition of the low molecular weight polyamide resin polyalcohol improves the heat resistance of the hybrid material, so that the hybrid material can be applied to high temperature environment.
Detailed Description
The present invention is further illustrated by the following specific examples, but it should be understood that the specific materials, process conditions and results described in the examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and all equivalent changes and modifications made according to the spirit of the present invention should be covered by the scope of the present invention.
Preparing a modified isocyanate prepolymer:
example 1
10.0kg of MDI, 6.6kg of polyamide resin polyol (number average molecular weight: 700), 0.40kg of polyethylene glycol adipate glycol (number average molecular weight: 1000) and 0.34g of phosphoric acid were reacted at 75 ℃ for 3.0 hours to obtain a low molecular weight polyamide resin polyol modified isocyanate prepolymer 1 having an NCO content of 15.0 wt%.
Example 2
10.0kg of MDI, 5.2kg of polyamide resin polyol (number average molecular weight: 2000), 4.8kg of polyethylene glycol adipate glycol (number average molecular weight: 2000), 6.0kg of polyoxypropylene diol (number average molecular weight: 2000), and 2.6g of phosphoric acid were reacted at 80 ℃ for 2.0 hours to obtain a low molecular weight polyamide resin polyol-modified isocyanate prepolymer 2 having an NCO content of 10.3 wt%.
Example 3
10.0kg of MDI, 13.6kg of polyamide resin polyol (number average molecular weight of 1400), 9.2kg of polyethylene glycol adipate glycol (number average molecular weight of 1500), 15.6kg of polyoxypropylene diol (number average molecular weight of 1500) and 9.68g of phosphoric acid were reacted at 85 ℃ for 2.5 hours to obtain a low molecular weight polyamide resin polyol-modified isocyanate prepolymer 3 having an NCO content of 2.4 wt%.
Example 4
10.0kg of MDI, 0.83kg of carbodiimide-modified MDI, 23.9kg of polyamide resin polyol (number average molecular weight: 2000), 18.8kg of polyethylene glycol adipate glycol (number average molecular weight: 1500), 19.3kg of polyoxypropylene diol (number average molecular weight: 2000) and 9.68g of phosphoric acid were reacted at 85 ℃ for 2.5 hours to obtain a low molecular weight polyamide resin polyol-modified isocyanate prepolymer 4 having an NCO content of 1.0 wt%.
Preparing a polyurethane composite material and a hybrid material:
mixing polyamide resin polyol, polyester polyol, polyether polyol, a chain extender, a foaming agent, a foam stabilizer, a catalyst, an antioxidant and the like according to table 1, wherein in examples 5 to 7, the mixture is mixed for 3.5 hours at 40 ℃, and in examples 8 to 9, the mixture is mixed for 2.5 hours at 45 ℃, and discharging, sealing and storing are carried out to obtain the components of the polyol mixture.
The temperature of the polyol mixture in the polyurethane compositions of examples 5 to 6 was maintained at 20 ℃, the temperature of the polyol mixture in the polyurethane compositions was maintained at 40 ℃, the temperature of the polyol mixture in the polyurethane compositions of examples 7 to 9 was maintained at 40 ℃, the temperature of the polyol mixture in the polyurethane compositions was maintained at 70 ℃, the polyol mixture and the low molecular weight polyamide resin polyol modified isocyanate prepolymer in the polyurethane compositions were uniformly mixed with the filler particles according to table 1, the polyol mixture and the low molecular weight polyamide resin polyol modified isocyanate prepolymer in example 5 were injected into a mold of 50 ℃ to react for 3min for molding, the mold was removed, the curing was carried out for 46h, the polyol mixture in example 6 was injected into a mold of 60 ℃ to react for 4min for molding, the mold was removed, the curing was carried out for 45h, the polyol mixture in example 7 and the polyol modified isocyanate prepolymer in example 9 were injected into a mold of 70 ℃ to react for 6min for molding, the mold was removed, the curing was carried out for 48h, the polyol mixture in example 8 was injected into a mold of 80 ℃ to react for molding, demolding and curing for 50h to obtain the high-performance polyamide-polyurethane hybrid material.
TABLE 1
Mixing polyester polyol, polyether polyol, a chain extender, a foaming agent, a foam stabilizer, a catalyst, an antioxidant and the like according to the following table 2, wherein the polyester polyol, the polyether polyol, the chain extender, the foaming agent, the foam stabilizer, the catalyst, the antioxidant and the like are mixed in comparative examples 1-2 at 40 ℃ for 3.5h, and in examples 3-5 at 60 ℃ for 2.5h, and discharging, sealing and storing to obtain the components of the polyol mixture.
Adding isocyanate, polyester polyol, polyether polyol and phosphoric acid into a reaction kettle, reacting for 2.0-3.0 h at 75-85 ℃, mixing for 3.0h at 75 ℃ in comparative example 1 and comparative example 5, reacting for 2.0h at 80 ℃, reacting for 2.5h at 85 ℃ in comparative example 2-4, discharging, sealing and storing to obtain the isocyanate prepolymer.
The temperature of the polyol mixture in the polyurethane combined materials in comparative examples 1-3 is maintained at 20 ℃, the temperature of the prepolymer in the polyurethane combined materials is maintained at 40 ℃, the temperature of the polyol mixture in the polyurethane combined materials in comparative examples 4-5 is maintained at 40 ℃, the temperature of the isocyanate prepolymer in the polyurethane combined materials is maintained at 60 ℃, the polyol mixture, the isocyanate prepolymer and the filling particles are uniformly mixed according to the table 1, the polyol mixture, the isocyanate prepolymer and the filling particles are injected into a 50 ℃ mold for 3min for forming in comparative example 1, the mold is released and cured for 46h, the mold is injected into a 60 ℃ mold for 4min for forming in comparative example 2, the mold is released and cured for 45h, the mold is injected into a 70 ℃ mold for 6min for forming in comparative example 3 and example 5, the mold is released and cured for 48h, the mold is injected into a 80 ℃ mold for 8min for forming in comparative example 4, the mold is released and cured for 50h, and the polyurethane materials are obtained.
TABLE 2
The results of the physical property tests of the high-performance polyamide-polyurethane hybrid materials prepared in application examples 5 to 9 and the polyurethane materials prepared in comparative examples 1 to 5 are shown in table 3. Wherein: the forming density is detected by a GB/T1033.1-2008 method, the forming hardness (Shore A) is detected by a GB/T531.1-2008 method, the TGA thermal weight loss rate is detected by a thermal weight loss analyzer, the tensile strength (MPa) and the elongation (%) are detected by a GB/T528-.
TABLE 3
The TGA thermogravimetric ratio was tested using a polyurethane composition made into a foam without filled particles. Example 8 and comparative example 4 have no results of hardness tests, and are suitable for applications requiring very low hardness, since the elastomeric material is very soft. From table 3, it can be seen that the system of the present invention has a long rise time, the low molecular weight polyamide resin polyol enhanced polyurethane has high adhesion with the filler particles, the filler particles have a wide range of addition, the filler particles can be effectively adhered without using an adhesive, and the prepared hybrid material has a short demolding time, good elasticity, a wide range of adjustable density and hardness, and a wide application. The low molecular weight polyamide resin polyalcohol is added, so that the heat resistance of the hybrid material is improved, and the hybrid material can be applied to a high-temperature environment.
Although the embodiments of the present invention have been described in detail, the technical aspects of the present invention are not limited to the embodiments, and equivalent changes or modifications made to the contents of the claims of the present invention should fall within the technical scope of the present invention without departing from the spirit and the spirit of the present invention.
Claims (15)
1. The polyurethane composite material is characterized by comprising a polyol mixture and a modified isocyanate prepolymer; the molar ratio of hydroxyl (-OH) of the polyol mixture to isocyanate (-NCO) in the modified isocyanate prepolymer is 1 (1.0-1.1);
the polyol mixture comprises the following raw materials in parts by weight:
100 parts of a polymer (B) having groups reactive with isocyanates;
0.01-5.00 parts of a chain extender;
1-8 parts of a foaming agent;
0.01-5 parts of a foam stabilizer;
1-3 parts of a catalyst;
the polymer (B) with the groups reactive to isocyanate is more than one of low molecular weight polyamide resin polyol, polyester polyol and polyether polyol; the modified isocyanate prepolymer is characterized by being a reaction product of isocyanate and a polymer (A) with a group reactive to the isocyanate, wherein the polymer (A) with the group reactive to the isocyanate contains low molecular weight polyamide resin polyol;
the polymer (A) having a group reactive with isocyanate further contains one or more of polyester polyol and polyether polyol;
the low molecular weight polyamide resin polyol is a reaction product of dibasic acid, diamine and alcohol amine, and has a molecular weight of 700-2000.
2. The polyurethane composition according to claim 1, wherein the polymer (A) having an isocyanate-reactive group has a functionality of 2 to 3 and a number average molecular weight of 700 to 10000.
3. The polyurethane composite material of claim 1, wherein the NCO content of the modified isocyanate prepolymer is 0.1wt% to 15.0 wt%.
4. The polyurethane composition according to claim 1, wherein the polyester polyol in the polymer (A) having a group reactive to isocyanate is obtained by esterification of an organic dicarboxylic acid having 2 to 14 carbon atoms and a polyol having 2 to 14 carbon atoms, has a functionality of 2 to 3 and a number average molecular weight of 1000 to 6000, and the polyether polyol in the polymer (A) having a group reactive to isocyanate is at least one selected from the group consisting of a polyoxypropylene polyol, a polyoxyethylene-oxypropylene copolyol, a polytetrahydrofuran diol and a polytrimethylene ether glycol, and has a functionality of 2 to 3 and a number average molecular weight of 1000 to 10000.
5. The polyurethane composition according to claim 4, wherein the organic dicarboxylic acid is one or more of adipic acid, succinic acid, glutaric acid, suberic acid, sebacic acid, azelaic acid, phthalic acid, terephthalic acid, isophthalic acid, lauric acid, maleic acid, and fumaric acid;
the polyalcohol is more than one of ethylene glycol, diethylene glycol, 1, 2-or 1, 3-propylene glycol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, glycerol and trimethylolpropane.
6. The polyurethane composition according to claim 1, wherein the polyester polyol in the polymer (A) having a group reactive with isocyanate is a polycaprolactone polyol.
7. The polyurethane composition according to claim 1, wherein the isocyanate is at least one selected from the group consisting of toluene diisocyanate, diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, uretonimine-modified diphenylmethane diisocyanate, isophorone diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate.
8. The polyurethane composition according to claim 1, wherein the polyol mixture further comprises an antioxidant, an antistatic agent, and an anti-wear agent, and the antioxidant, the antistatic agent, and the anti-wear agent are each used in an amount of 0.01wt% to 3.0wt% based on the mass of the polymer (B) having an isocyanate-reactive group.
9. The polyurethane composition according to claim 1,
the polyester polyol in the polymer (B) with the isocyanate reactive group is subjected to esterification reaction of organic dicarboxylic acid containing 2-14 carbon atoms and polyhydric alcohol containing 2-14 carbon atoms, the functionality is 2-3, and the number average molecular weight is 1000-6000; the organic dicarboxylic acid is more than one of adipic acid, succinic acid, glutaric acid, suberic acid, sebacic acid, azelaic acid, phthalic acid, terephthalic acid, isophthalic acid, decanedicarboxylic acid, maleic acid and fumaric acid; the polyalcohol is more than one of ethylene glycol, diethylene glycol, 1, 2-or 1, 3-propylene glycol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, glycerol and trimethylolpropane;
the polyether polyol in the polymer (B) having a group reactive with isocyanate is at least one of polyoxypropylene polyol, polyoxyethylene-oxypropylene copolyol, polytetrahydrofuran diol and polytrimethylene ether glycol;
the polyether polyol in the polymer (B) with the isocyanate reactive group has the functionality of 2-3 and the number average molecular weight of 1000-10000;
the chain extender is dihydric alcohol with the molecular weight of 62 g/mol-500 g/mol;
the foaming agent is more than one of water, pentane and supercritical carbon dioxide;
the foam stabilizer is an organic silicon foam stabilizer;
the catalyst is triethylene diamine and/or stannous octoate.
10. The polyurethane composition according to claim 1, wherein the polyester polyol in the polymer (B) having an isocyanate-reactive group is a polycaprolactone polyol.
11. The preparation method of the polyurethane composition according to any one of claims 1 to 10, wherein the preparation of the modified isocyanate prepolymer comprises the following steps: and (2) reacting isocyanate with the polymer (A) with the group reactive to the isocyanate at 75-85 ℃ for 2.0-3.0 h to obtain the modified isocyanate prepolymer.
12. The method of claim 11, wherein the phosphoric acid is added to the reaction raw materials in an amount of 0.002wt% to 0.020wt% based on the total mass of the raw materials.
13. The use of the polyurethane composite of any one of claims 1 to 10 or the polyurethane composite prepared by the method of any one of claims 11 to 12 for preparing a high performance polyamide-polyurethane hybrid material.
14. The use according to claim 13, characterized in that the method of application is as follows:
maintaining the temperature of a polyol mixture in the polyurethane composite material at 20-40 ℃, the temperature of a modified isocyanate prepolymer in the polyurethane composite material at 40-70 ℃, uniformly mixing the polyol mixture, the modified isocyanate prepolymer and the filling particles according to the molar ratio of-OH to-NCO of 1: 1.0-1.1, injecting into a mold at 50-80 ℃, reacting for 3-8 min, forming, demolding, and curing for 45-50 h to obtain the high-performance polyamide-polyurethane hybrid material.
15. The use according to claim 14, wherein the filler particles are one or more of thermoplastic polyurethane foam particles, CPU elastomer particles, rubber particles, ethylene-vinyl acetate copolymer particles, thermoplastic polyester foam particles;
the addition amount of the filling particles is 1-90 wt% of the total mass of the hybrid material;
the diameter of the filling particles is 0.1cm to 10cm, and the filling particles are spherical or elliptical;
the filling particles are tubular particles, the length of the filling particles is 1mm to 40mm, and the diameter of the filling particles is 1mm to 40 mm;
the high performance polyamide-polyurethane hybrid material has a density of 0.10g/cm3 to 1.20g/cm 3.
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