CN109294215B - Polyurethane resin composite material, application thereof and high-strength high-modulus polyurethane material - Google Patents
Polyurethane resin composite material, application thereof and high-strength high-modulus polyurethane material Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
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- C08G18/6677—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
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- C08G18/6688—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
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Abstract
The invention discloses a polyurethane resin composite material, application and a polyurethane material. The high-strength high-modulus polyurethane resin composite material comprises: the component A comprises oligomer polyol, a small molecular chain extender and a compatilizer; the component B comprises one or more of polymethylene polyphenyl isocyanate, diisocyanate and diisocyanate derivatives; and the component C is epoxy functionalized polyphenyl ether microsphere particles. A, B and the component C are stirred and mixed and then are subjected to heat curing to obtain the high-strength high-modulus polyurethane material, wherein the tensile strength can reach 62-82MPa, the bending strength can reach 110-135MPa, and the bending modulus can reach 2.8-3.0 GPa.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a high-strength high-modulus polyurethane resin composite material, application thereof and a high-strength high-modulus polyurethane material.
Background
The polyurethane as a polymer material can be used for preparing products with different performance requirements, and has excellent toughness, impact resistance, wear resistance and tear resistance. The polyurethane processing and forming process is simple, can adopt one-time injection molding and one-time casting molding, and can realize different curing processes and performances through formula design. However, polyurethane generally has only low rigidity, and with further expansion of the application field of polyurethane, users also put new requirements on polyurethane materials in the practical application process, and hope that polyurethane has high modulus and use strength. With the rapid development of the composite material industry, polyurethane plays an increasingly important role, and high use strength and modulus are urgently needed. Therefore, the development of high modulus polyurethane materials which not only have high strength, but also maintain the original toughness of polyurethane, so that the application of the high modulus polyurethane materials in wider fields is a development direction of future polyurethane materials.
Chinese patent CN 201110330929 discloses a preparation method of rigid polyurethane. The material is prepared by a prepolymer method, polymer polyol with 3 functionality is introduced, and certain carbamate chemical crosslinking is generated among rigid polyurethane molecules, so that the influence of intermolecular hydrogen bond breakage and intermolecular force weakening at high temperature is compensated, and the heat resistance of a rigid polyurethane product is improved. The main characteristic of the material of the invention is that polymer polyol with high functionality is used to make the material form a certain degree of chemical crosslinking, and the main purpose is to improve the heat resistance of the material, and no specific requirements are made on the properties of the material, such as strength, modulus and the like.
European patent WO2009/062985 discloses aromatic aldimines based on solids at room temperature which can be used as blocked amines in curable compositions, in particular in one-and two-component compositions having isocyanate groups. These compositions have a relatively long open time, cure rapidly, and the process is free of strong odor and bubble formation. After curing, they have good mechanical properties, in particular high strength and ductility, and good stability against heat and moisture. The patent realizes the high strength of the material by forming a urea structure through amine curing, and simultaneously needs to seal the amine before use, thus easily bringing about the problems of high processing cost and high system viscosity.
Chinese patent CN201210566238.1 discloses a high-strength high-toughness polyurethane material and a preparation method thereof, wherein polymethylene polyphenyl isocyanate and diisocyanate derivatives react with polyol to prepare a component A polyurethane prepolymer, and then the component A polyurethane prepolymer is mixed with a component B including a micromolecular chain extender and a component C auxiliary agent, the bending strength of the polyurethane material prepared by heating and curing can reach 95MPa to the maximum, and the bending modulus can reach 2950MPa to the maximum. The method needs to prepare the polyurethane prepolymer, has high energy consumption and cost, large viscosity of raw materials, inconvenient use and limited improvement effect.
Chinese patent CN 105384891a discloses a carbon fiber polyurethane composite material. The adhesive comprises 36-42 parts of polytetrahydrofuran ether glycol, 24-31 parts of diphenylmethane diisocyanate, 25-27 parts of butanediol, 10-14 parts of non-adhesive carbon fiber, 5-11 parts of a coupling agent and 2-5 parts of an antioxidant. The material improves the rigidity and stability of polyurethane, but concentrated nitric acid is used in the process, so that the material is high in danger and high in carbon fiber cost.
Chinese patent CN201210440051.7 discloses a continuous glass fiber reinforced thermoplastic polyurethane composite material and a preparation method thereof. The composite material is prepared from the following components in parts by weight: 50-70% of glass fiber cloth and 30-50% of thermoplastic polyurethane. The glass fiber cloth reinforced thermoplastic polyurethane composite material prepared in the invention has higher strength and modulus, but the method needs to add a large amount of inorganic fibers, has the problem of poor wettability of the two, and has complex preparation process.
In order to solve the defects of complex operation and limited performance improvement in the prior art, a new high-strength high-modulus polyurethane resin composite needs to be developed.
Disclosure of Invention
The invention aims to solve the problems of the existing polyurethane material and provide a polyurethane composite material, and the polyurethane material prepared from the composite material has high strength and high modulus, and is simple to operate and low in cost.
The invention also provides a high-strength high-modulus polyurethane material, which has the tensile strength of 62-82MPa, the bending strength of 110-135MPa and the bending modulus of 2.8-3.0 GPa.
The invention also aims to expand the application field of the polyurethane material, and the prepared polyurethane material has high flexural modulus and strength in use and can be applied to the field of composite materials.
In order to achieve the above objects and achieve the above technical effects, the technical solution of the present invention is as follows:
a high-strength high-modulus polyurethane composite material comprises A, B and C:
the component A comprises oligomer polyol, a small molecular chain extender and a compatilizer, and accounts for 39-59 wt% of the total composition, preferably 43-54 wt%;
the B component comprises one or more of polymethylene polyphenyl isocyanate, diisocyanate and diisocyanate derivatives, and accounts for 39-59 wt% of the total composition, preferably 43-54 wt%;
the component C comprises epoxy functionalized polyphenyl ether microsphere particles, and accounts for 2-12 wt% of the total composition, preferably 3-7 wt%.
The polyphenyl ether (PPE) is a thermoplastic engineering plastic with excellent performance, has good creep resistance, low molding shrinkage and excellent heat resistance, and maintains higher toughness while having higher modulus. The glass transition temperature of the PPE is highest in thermoplastic plastics, the creep resistance at high temperature is excellent in thermoplastic engineering plastics, and the high creep resistance is the most outstanding characteristic, so that the PPE is particularly suitable for manufacturing industrial structural parts bearing long-term loads. The invention designs a polyphenyl ether microsphere particle with epoxy functionalized surface, and designs a polyurethane elastomer composition formula containing the particle, epoxy groups enriched on the surface of the particle can improve the compatibility of the particle with a polyurethane raw material, the particle is easy to disperse in a system, and the particle is embedded in a curing network through a chemical bond with stronger action, so that the polyurethane has higher modulus while keeping the original toughness, and other properties of the polyurethane are improved.
In the present invention, the molar ratio of free isocyanate groups in component B to active hydrogen in component A is from 1.0 to 1.2: 1, preferably from 1.05 to 1.15: 1.
In the invention, the oligomer polyol content in the component A is 84-94 wt%, preferably 87-92 wt%, the small molecular chain extender content is 4-12 wt%, preferably 6-10 wt%, and the compatilizer content is 1-4 wt%, preferably 1.5-3 wt%, based on the total mass of the component A.
In the invention, the oligomer polyol in the component A is polyoxypropylene polyol and/or polyoxypropylene-ethylene polyol, preferably has a functionality of 2-6, more preferably 2-3, and preferably has a hydroxyl value of 56-430 mgKOH/g, more preferably 110-340 mgKOH/g; the small-molecule chain extender in the component A is small-molecule polyalcohol and/or alcohol amine, preferably one or more of glycerol, trimethylolpropane, 1,2, 6-hexanetriol, triisopropanolamine and diethanolisopropanolamine; the compatilizer in the component A is one or more of zinc stearate, zinc laurate and zinc acetylacetonate. The compatilizer improves the compatibility of isocyanate and polyphenyl ether by forming a coordinate bond with the isocyanate and the polyphenyl ether, and facilitates the dispersion of polyphenyl ether particles.
In the invention, the diisocyanate in the component B comprises one or more of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, naphthalene diisocyanate, cyclohexane dimethylene diisocyanate, p-phenylene diisocyanate and phenylene dimethylene diisocyanate, and diphenylmethane diisocyanate and/or cyclohexane dimethylene diisocyanate are preferred.
In the invention, the polymethylene polyphenyl isocyanate in the component B is one or more of PM-100, PM-200, PM-300, PM-400, PM2010 and PM6302, and PM200 is preferred.
In the present invention, the diisocyanate derivative in the B component includes one or more of liquefied diphenylmethane diisocyanate, tolylene diisocyanate dimer, isophorone trimer, tolylene diisocyanate trimer, hexamethylene diisocyanate biuret, tolylene diisocyanate-trimethylolpropane adduct and hexamethylene diisocyanate-trimethylolpropane adduct, and preferably tolylene diisocyanate-trimethylolpropane adduct and/or tolylene diisocyanate trimer.
In the invention, the preparation of epoxy functionalized polyphenyl ether microsphere particles in the component C comprises the following steps:
(1) dissolving hydroxyl-terminated polyphenyl ether in toluene at 60-70 ℃, adding isothermal 30 wt% sodium hydroxide solution, stirring at high speed, wherein the volume ratio of the sodium hydroxide solution to the toluene is 1.5-2: 1, adding ethanol with the same volume as the toluene after 50-70min, stirring for 40-50min, cooling, filtering, and washing with water to obtain polyphenyl ether microsphere powder with the surface enriched with sodium phenolate;
(2) adding the polyphenyl ether microspheres into epoxy chloropropane at the temperature of 50-60 ℃, wherein the mass ratio of the epoxy propane to the polyphenyl ether is 4-5: 1, adding a catalyst, stirring at a high speed for 50-60min to enable the epoxy chloropropane to react with functional groups on the surfaces of the polyphenyl ether microspheres, filtering, and washing to obtain the polyphenyl ether microsphere particles with epoxy functionalized surfaces.
According to the invention, the high-strength high-modulus polyurethane material is prepared from the combined material by a casting molding process: a, B and C components are stirred and mixed at a high speed, the mixture is cured for 1.5 to 2 hours at the temperature of 100 ℃ to 150 ℃, then the demolding is carried out, and the mixture is cured for 7 to 10 hours at normal temperature to prepare the high-strength and high-modulus polyurethane material, wherein the preferable polyurethane material has the tensile strength of 62 to 82MPa, the bending strength of 110 ℃ and 135MPa and the bending modulus of 2.8 to 3.0 GPa.
In the present invention, the polyurethane composition is applied to injection molding, injection compression molding, flow molding, Reaction Injection Molding (RIM), RTM (resin transfer molding), VARTM (vacuum assisted RTM), tape product lamination, coil coating, filament winding, hand lamination, pultrusion, thermal reactive bonding, and high temperature hardening coating.
Various additives such as a light stabilizer, an antioxidant, an oil-soluble dye, a filler, and a flame retardant may be added to the composition of the present invention depending on the purpose of use.
The mechanism of the high-strength and high-modulus material prepared by the polyurethane composition is as follows: when the material deforms, the polyphenyl ether microsphere particles become stress concentration points of a system and are linked with the curing network through chemical bonds, so that plastic deformation and yield of the polyurethane matrix are initiated. When the damage exceeds a certain bearing capacity of the material, the particles can induce the system to generate a large number of silver lines and generate shear yield, the stress concentration at the tip of the crack continuously induces more silver lines, on one hand, the silver lines disperse the stress, the damage strength is weakened, and on the other hand, a large amount of energy is consumed for the propagation of the silver lines in the system. Thus, the presence of a large amount of silver streaks and shear bands absorbs a large amount of the destructive energy of the system. Meanwhile, the polyphenyl ether is used as a strong and tough material, has high toughness and modulus, and thus the mechanical property of the polyurethane material is enhanced.
The invention has the positive effects that:
(1) the material processed by the composite material has high strength and modulus, and simultaneously has high creep resistance and heat resistance, wherein the tensile strength can reach 62-82MPa, the bending strength can reach 110-135MPa, and the bending modulus can reach 2.8-3.0 GPa.
(2) The use method of the composite material provided by the invention is that the oligomer polyol, the micromolecule chain extender, the isocyanate resin and the epoxy functionalized polyphenyl ether microsphere particles are directly mixed and react, and the operation process is simple.
(3) The high-strength high-modulus polyurethane material provided by the invention has wide application, can be used for composite material products needing high strength and high modulus, and can also be used for workpieces needing high creep resistance, adhesives and the like.
Detailed Description
The technical scheme of the invention is further explained by combining the embodiment.
And (3) tensile test: GB/T2567-2008, Zwick Z005 testing machine, the test temperature is 25 +/-2 ℃, and the test speed is 10 mm/min.
Bending test: GB/T2567-2008, Zwick Z005 testing machine, the test temperature is 25 +/-2 ℃, and the test speed is 10 mm/min.
Preparing surface epoxidized polyphenyl ether microsphere particles:
preparing surface epoxidized polyphenyl ether microsphere particles:
(1) taking 200ml of toluene (analytically pure, West Longsu science) and 180g of hydroxyl-terminated polyphenyl ether (Asahi Kasei) to a 1000ml four-neck flask, stirring and heating at 70 ℃, adding 300ml of NaOH (analytically pure, Aladdin) solution with the mass fraction of 30% at 70 ℃ after the polyphenyl ether is completely dissolved, stirring at 6000r/min at a high speed, reacting for 50min, then adding 200ml of ethanol (analytically pure, West Longsu science), stopping heating, and continuing stirring for 50 min. Filtering, and washing with water for 3 times to obtain polyphenylene oxide microsphere particles.
(2) 50g of the polyphenylene oxide microsphere particles are put into a 500ml four-neck flask, 250g of epichlorohydrin (analytically pure, West Long science) and 0.5g of tetramethylammonium bromide (analytically pure, Bailingwei) are added, and the mixture is heated to 60 ℃ and stirred at 6000r/min for reaction for 60 min. Filtering, washing with ethanol for 3 times to obtain the surface epoxidized polyphenyl ether microsphere particles.
Preparing surface epoxidation polyphenyl ether microsphere particles (II):
(1) 200ml of toluene (analytically pure, science of West Longsu) and 180g of hydroxyl-terminated polyphenylene ether (industrial grade, Asahi chemical) are taken and stirred and heated in a 1000ml four-neck flask at 60 ℃, 400ml of NaOH (analytically pure, Aradin) solution with the mass fraction of 30% at 60 ℃ is added after the polyphenylene ether is completely dissolved, 6000r/min is stirred at a high speed for reaction for 70min, then 200ml of ethanol (analytically pure, science of West Longsu) is added, the heating is stopped, and the stirring is continued for 40 min. Filtering, and washing with water for 3 times to obtain polyphenylene oxide microsphere particles.
(2) 50g of the polyphenylene oxide (industrial grade, Asahi Kasei) microsphere particles are put into a 500ml four-neck flask, 200g of epichlorohydrin (analytically pure, West Longjing) is added, 0.5g of tetramethylammonium bromide (analytically pure, Bailingwei) is added, the mixture is heated to 50 ℃, and stirred and reacted at 6000r/min for 50 min. Filtering, washing with ethanol (analytically pure, science of west longu) for 3 times to obtain the surface epoxidized polyphenylene oxide microsphere particles (c).
Example 1
The component A is prepared by mixing 45g of polyoxypropylene polyol TMN400 (Tianjin petrochemical, hydroxyl value of 410 and functionality of 3), 49g of TMN500 (Tianjin petrochemical, hydroxyl value of 330 and functionality of 3), 5g of triisopropanolamine (Michael) and 1g of zinc stearate (Furunda chemical).
The B component consisted of 25g of PM200 (Tantawawa, NCO amount 31.2 wt%, based on PM200 weight), 26.7g of p-phenylene diisocyanate (PPDI, DuPont, NCO amount 52.5 wt%, based on PPDI weight) mixed with 30g of diphenylmethane diisocyanate (MDI-50, Tantawa, NCO amount 33.5 wt%, based on MDI-50 weight).
The component C is 14g of epoxy functionalized polyphenylene ether microsphere particles (i).
Mixing the component A, the component B and the component C, stirring for 3 minutes at 1000r/min, defoaming in vacuum, pouring into a mold, carrying out thermocuring for 2 hours at 120 ℃, and carrying out curing for 10 hours at normal temperature to obtain a polyurethane resin cured product, wherein the mechanical properties are shown in Table 1.
Example 2
The A component consisted of 21g of polyoxypropylene polyol TDiol2000 (Tianjin petrochemical, hydroxyl number 56, functionality of 2), 67g of sucrose-initiated polyoxypropylene polyol 8336 (Tantawa, hydroxyl number 410, functionality of 6), 10g of trimethylolpropane (Customo) and 2g of zinc acetylacetonate (Aike reagent) mixed.
The B component consisted of 58g of toluene diisocyanate trimer (TDI trimer, Triwell Japan, NCO amount 7.5 wt%, based on the weight of TDI trimer) mixed with 86g of dicyclohexylmethane diisocyanate (HMDI, Tantawawa, NCO amount 32 wt%, based on the weight of HMDI).
The component C is 5.5g of epoxy functionalized polyphenyl ether microsphere particles.
Mixing the component A, the component B and the component C, stirring for 3 minutes at 1000r/min, defoaming in vacuum, pouring into a mold, thermally curing at 150 ℃ for 1.5 hours, and curing at normal temperature for 7 hours to obtain a polyurethane resin cured product, wherein the mechanical properties are shown in Table 1.
Example 3
The component A is prepared by mixing 60g of polyoxypropylene polyol TMN400 (Tianjin petrochemical, hydroxyl value of 410 and functionality of 3), 26g of TMN700 (Tianjin petrochemical, hydroxyl value of 240 and functionality of 3), 12g of triethanolamine (Basofu) and 2g of zinc stearate (Furunda chemical).
The B component consisted of 37g of PM100 (Tantawawa, NCO amount 31.2% by weight, based on PM100 weight), 34g of hexamethylene diisocyanate trimer (HDI trimer, Bayer, NCO amount 22% by weight) mixed with 52g of naphthalene diisocyanate (NDI, Bayer, NCO amount 40% by weight, based on NDI weight).
The component C is 26g of epoxy functionalized polyphenyl ether microsphere particles.
Mixing the component A, the component B and the component C, stirring for 3 minutes at 1000r/min, defoaming in vacuum, pouring into a mold, carrying out thermocuring for 2 hours at 130 ℃, and carrying out curing for 10 hours at normal temperature to obtain a polyurethane resin cured product, wherein the mechanical properties are shown in Table 1.
Example 4
The component A is prepared by mixing 54g of polyoxypropylene polyol TMN500 (Tianjin petrochemical, hydroxyl value of 330 and functionality of 3), 32g of 560S (Shanghai Gaoqiao petrochemical, hydroxyl value of 56 and functionality of 3), 10g of trimethylolpropane (Bestton) and 4g of zinc laurate (alatin).
The B component consists of 42g of liquefied MDI (Tahitawa MDI100LL, NCO content 29% by weight, based on the weight of the liquefied MDI), 12.4g of dimethylene diisocyanate (HXDI, Tahitawa, NCO content 43% by weight, based on the total HXDI) and 28g of MDI-50 (Tahitawa, NCO content 33.5% by weight, based on the weight of MDI-50).
And the component C comprises 23g of epoxy functionalized polyphenyl ether microsphere particles.
Mixing the component A, the component B and the component C, stirring for 3 minutes at 1000r/min, defoaming in vacuum, pouring into a mold, carrying out thermocuring for 2 hours at 110 ℃, and carrying out curing for 8 hours at normal temperature to obtain a polyurethane resin cured product, wherein the mechanical properties are shown in Table 1.
Example 5
The component A is prepared by mixing 62g of polyoxypropylene polyol TMN500 (Tianjin petrochemical, hydroxyl value of 330 and functionality of 3), 30g of TMN700 (Tianjin petrochemical, hydroxyl value of 240 and functionality of 3), 5g of glycerol (West Longsco) and 3g of zinc acetylacetonate (Aike reagent).
The B component consisted of 20g of hexamethylene diisocyanate-trimethylolpropane adduct (Bayer, NCO amount 23.5% by weight, based on the weight of hexamethylene diisocyanate-trimethylolpropane adduct), 35g of liquefied MDI (Nicotiana Wawawa MDI100LL, NCO amount 29% by weight, based on the weight of liquefied MDI) and 45g of MDI-50 (Nicotiana Wawa, NCO amount 33.5% by weight, based on the weight of MDI-50).
The component C is 11g of epoxy functionalized polyphenyl ether microsphere particles.
Mixing the component A, the component B and the component C, stirring for 3 minutes at 1000r/min, defoaming in vacuum, pouring into a mold, carrying out thermocuring for 2 hours at 120 ℃, and carrying out curing for 9 hours at normal temperature to obtain a polyurethane resin cured product, wherein the mechanical properties are shown in Table 1.
Comparative example 1
The component A is prepared by mixing 50g of TMN500 (Tianjin petrochemical, hydroxyl value of 330 and functionality of 3) and 50g of TMN400 (Tianjin petrochemical, hydroxyl value of 410 and functionality of 3).
The B component consisted of 30g of PM200 (Tanbaiwa, NCO amount 31.2 wt%, based on PM200 weight) mixed with 70g of MDI-50 (Tanbaiwa, NCO amount 33.5 wt%, based on MDI-50 weight).
Mixing the component A and the component B, stirring for 3 minutes at 1000r/min, defoaming in vacuum, pouring into a preheated mold at 120 ℃, curing for 2 hours, and curing at normal temperature for 10 hours to obtain a polyurethane resin cured product, wherein the mechanical properties are shown in Table 1.
TABLE 1 physical Properties of polyurethane materials prepared in examples and comparative examples
As can be seen from the data in Table 1, the mechanical properties of the high-strength and high-modulus polyurethane resin prepared in the example are significantly better than those of the comparative example in terms of strength and modulus.
The above description is only a specific embodiment of the present invention, and the present invention is not limited to the description of the embodiment. Any conceivable variations or modifications within the spirit of the present invention by those skilled in the art are intended to be included within the scope of the present invention.
Claims (20)
1. A polyurethane composite material, which comprises A, B and C three components:
the component A comprises oligomer polyol, a small molecular chain extender and a compatilizer, and accounts for 39-59 wt% of the total amount of the composition;
the component B comprises one or more of polymethylene polyphenyl isocyanate, diisocyanate and diisocyanate derivatives, and accounts for 39-59 wt% of the total composition;
the component C comprises epoxy functionalized polyphenyl ether microsphere particles, and accounts for 2-12 wt% of the total amount of the composition.
2. The polyurethane composition according to claim 1, wherein:
the component A accounts for 43 to 54 weight percent of the total amount of the combined material;
the component B accounts for 43 to 54 weight percent of the total amount of the composition;
the component C accounts for 3-7 wt% of the total amount of the composition.
3. The polyurethane composition according to claim 1 or 2, wherein the molar ratio of free isocyanate groups in component B to active hydrogen in component a is 1.0-1.2: 1.
4. The polyurethane composition according to claim 3, wherein the molar ratio of free isocyanate groups in component B to active hydrogen groups in component A is 1.05-1.15: 1.
5. The polyurethane composition according to claim 1 or 2, wherein the oligomer polyol content in the A component is 84-94 wt%, the small molecule chain extender content is 4-12 wt%, and the compatibilizer content is 1-4 wt%, based on the total mass of the A component.
6. The polyurethane composition according to claim 5, wherein the oligomer polyol content in the component A is 87-92 wt%, the small molecule chain extender content is 6-10 wt%, and the compatibilizer content is 1.5-3 wt%, based on the total mass of the component A.
7. The polyurethane composition according to claim 1 or 2, wherein the oligomer polyol in the a component is a polyoxypropylene polyol and/or a polyoxypropylene-ethylene polyol; the micromolecule chain extender in the component A is micromolecule polyalcohol and/or alcohol amine; the compatilizer in the component A is one or more of zinc stearate, zinc laurate and zinc acetylacetonate.
8. The polyurethane composition according to claim 7, wherein the A component has a functionality of 2 to 6 and a hydroxyl value of 56 to 430 mgKOH/g; the small molecular chain extender in the component A is one or more of glycerol, trimethylolpropane, 1,2, 6-hexanetriol, triisopropanolamine and diethanolisopropanolamine.
9. The polyurethane composition according to claim 8, wherein the A component has a functionality of 2 to 3 and a hydroxyl value of 110 to 340 mgKOH/g.
10. The polyurethane composition according to claim 1 or 2, wherein the diisocyanate in the B component comprises one or more of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, naphthalene diisocyanate, cyclohexane dimethylene diisocyanate, p-phenylene diisocyanate and xylylene diisocyanate.
11. The polyurethane composition according to claim 10, wherein the diisocyanate in the component B comprises diphenylmethane diisocyanate and/or cyclohexanedimethylene diisocyanate.
12. The polyurethane composition according to claim 1 or 2, wherein the polymethylene polyphenyl isocyanate in the component B is one or more of PM-100, PM-200, PM-300, PM-400, PM2010 and PM 6302.
13. The polyurethane composition according to claim 12, wherein the polymethylene polyphenyl isocyanate in the B component is PM 200.
14. The polyurethane composition according to claim 1 or 2, wherein the diisocyanate derivative in the B component comprises one or more of liquefied diphenylmethane diisocyanate, tolylene diisocyanate dimer, isophorone diisocyanate trimer, tolylene diisocyanate trimer, hexamethylene diisocyanate biuret, tolylene diisocyanate-trimethylolpropane adduct and hexamethylene diisocyanate-trimethylolpropane adduct.
15. The polyurethane composition according to claim 14, wherein the diisocyanate derivative of the component B comprises a tolylene diisocyanate-trimethylolpropane adduct and/or a tolylene diisocyanate trimer.
16. The polyurethane composition according to claim 1 or 2, wherein the preparation of the epoxy-functionalized polyphenylene ether microsphere particles in the C component comprises the following steps:
(1) dissolving hydroxyl-terminated polyphenyl ether in toluene at 60-70 ℃, adding isothermal 30 wt% sodium hydroxide solution, stirring at high speed, wherein the volume ratio of the sodium hydroxide solution to the toluene is 1.5-2: 1, adding ethanol with the same volume as the toluene after 50-70min, stirring for 40-50min, cooling, filtering, and washing with water to obtain polyphenyl ether microsphere powder;
(2) adding the polyphenyl ether microspheres into epoxy chloropropane at the temperature of 50-60 ℃, wherein the mass ratio of the epoxy chloropropane to the polyphenyl ether is 4-5: 1, adding a catalyst, stirring at a high speed for 50-60min, filtering, and washing to obtain the polyphenyl ether microsphere particles with the epoxy functionalized surfaces.
17. A high strength and high modulus polyurethane material, wherein the polyurethane composition of any one of claims 1 to 16 is prepared by a casting process: a, B and the component C are stirred and mixed at a high speed, the mixture is cured for 1.5 to 2 hours at the temperature of 100 ℃ and 150 ℃, then the demolding is carried out, and the mixture is cured for 7 to 10 hours at normal temperature, thus obtaining the high-strength and high-modulus polyurethane material.
18. The high strength and high modulus polyurethane material as claimed in claim 17, wherein said polyurethane material has a tensile strength of 62-82MPa, a bending strength of 110-135MPa and a bending modulus of 2.8-3.0 GPa.
19. The polyurethane composition of any one of claims 1-16 for use in injection molding, flow molding, resin transfer molding, tape lamination, coil coating, filament winding, hand lamination, pultrusion, heat reactive bonding, and high temperature cure coating processes.
20. Use of the polyurethane composition according to claim 19, wherein the polyurethane composition is used in injection compression molding or reaction injection molding.
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| CN111040114B (en) * | 2019-12-27 | 2021-02-12 | 鸿羽腾风材料科技有限公司 | Polyurethane composition for carbon fiber RTM (resin transfer molding) process |
| CN113583566A (en) * | 2021-08-26 | 2021-11-02 | 青岛费米新材料科技有限公司 | High-modulus rapid repairing and reinforcing material for cave depot |
| CN114605810A (en) * | 2022-03-22 | 2022-06-10 | 中国船舶重工集团公司第七一三研究所 | Marine high-molecular polymer filling material and preparation method thereof |
| CN116080211B (en) * | 2022-10-14 | 2023-12-29 | 江苏耀鸿电子有限公司 | Low-dielectric-loss PPO resin-based copper-clad plate and preparation method thereof |
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| US5069818A (en) * | 1985-09-26 | 1991-12-03 | General Electric Company | Functionalized polyphenylene ethers and blends with polyamides |
| US4994525A (en) * | 1986-05-27 | 1991-02-19 | General Electric Company | Functionalized polyphenylene ethers, method of preparation, and polyphenylene ether-polyamide compositions prepared therefrom |
| US5015698A (en) * | 1986-05-27 | 1991-05-14 | General Electric Company | Polyphenylene ether-polyester copolymers, precursors therefor, compositions containing said copolymers, and methods for their preparation |
| BR8707316A (en) * | 1986-05-27 | 1988-09-13 | Gen Electric | POLYPHENYLENE-POLYESTER ETER COPOLYMER, PRECURSORS FOR THE SAME, COMPOSITIONS CONTAINING THE REFERRED COPOLYMERS AND PROCESSES FOR THEIR PREPARATION |
| DE69123799T2 (en) * | 1990-08-14 | 1997-05-15 | Mitsubishi Chem Corp | Thermoplastic resin composition |
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| US5214099A (en) * | 1992-02-25 | 1993-05-25 | General Electric Company | Epoxy-functionalized polyphenylene ethers of low gel content, method for their preparation, and copolymer-containing compositions prepared therefrom |
| JPH10110020A (en) * | 1996-08-13 | 1998-04-28 | Du Pont Mitsui Polychem Co Ltd | Crosslinkable composition and its use |
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