Polyurethane resin for pultruded composites and use thereof

Abstract

The application discloses a polyurethane resin for pultrusion composite materials and application thereof, which is composed of A material and B material according to a mass ratio of 100:(110-140), the A material is a hydroxyl compound component, which is made of raw materials including the following mass fractions: polyhydric alcohol 80-95%, antioxidant 0.001-0.02%, light stabilizer 0.3-1.0%, defoaming agent 0.05-0.2%, catalyst 0.1-0.6%, release agent 1-3%, flame retardant 1-10%, 2,3-dimethyl-2,3-diphenylbutane 0.5-3%, silane coupling agent 0.1-0.6%; the B material is polymeric MDI. The polyurethane resin keeps the easy-release property of PPG, and the glass transition temperature of the polyurethane resin is improved, so that the temperature resistance of the pultrusion composite photovoltaic frame is improved, and the pultrusion composite material is not prone to deformation in a high-temperature environment.

Description

Technical Field

[0001] This invention belongs to the field of polyurethane resin technology, specifically relating to a polyurethane resin for pultruded composite materials and its applications. Background Technology

[0002] Photovoltaic modules are the supporting framework structure in solar cell modules, and they are placed in outdoor environments where they are exposed to wind and rain. Therefore, a photovoltaic module with high strength, good temperature and weather resistance, strong UV resistance, and good corrosion resistance is needed to extend its service life.

[0003] Most solar photovoltaic (PV) module frames are made of aluminum alloy, a material widely used due to its light weight, high strength and durability, and corrosion resistance. However, a high voltage can form between the circuitry of the PV module and the grounded metal frame. After a period of outdoor operation, the PV module's output power decreases, leading to reduced power generation efficiency and overall power plant efficiency. This further contributes to the continuous degradation of the PV module's performance, a phenomenon known as the PID effect. Once the PID effect occurs, it significantly impacts the operation and return on investment of the power plant.

[0004] Polyurethane pultrusion composites are a relatively new process developed in recent years. They are formed by mixing and curing polyols with highly reactive isocyanates. The components have low viscosity and good wetting properties, allowing for the molding of complex frame shapes and designs. For example, patent document CN116284653A discloses a pultruded polyurethane-epoxy copolymer resin composite material for photovoltaic modules, comprising components A, B, and C. Component A contains the following raw materials: 20-65% epoxy resin, 30-78% polyol, and 2-12% plasticizer; component B contains the following raw materials: 5-25% reaction accelerator, 40-85% silane coupling agent, 5-30% water absorbent, and 2-15% light stabilizer; component C contains the following raw materials: 30-75% isocyanate and 25-70% acid anhydride curing agent; the ratio of components A, B, and C is 1:0.02-0.2:0.5-2. However, the formulation in this document is relatively complex and costly.

[0005] Patent document CN105358598A discloses a fiber-reinforced polyurethane composite material for pultrusion molding, comprising: a) a polyisocyanate component containing at least one polyisocyanate, and b) an isocyanate reactive component containing at least one cashew oil-based polyether polyol, wherein the cashew oil-based polyol is present in an amount of 20% to 30% by weight, based on the total weight of the isocyanate reactive component, and wherein the cashew oil-based polyol has a hydroxyl value of 175 to 550 and a functionality of 2 to 5. However, the raw materials in this document are quite special and expensive, making large-scale production unsuitable.

[0006] Patent document CN114716644A discloses a rapid-release two-component pultruded polyurethane. The white component includes MN400, MN500, PPG series polyether polyols, glycerol, 1,4-butanediol, defoamer, antioxidant, and organometallic catalyst; the black component includes PM200 and MDI50. Because PPG series polyethers themselves have excellent lubrication and release properties, only a small amount of internal release agent is needed for good demolding of the sheets, reducing raw material costs. At the same pultrusion speed, the overall tensile force required by the machine is reduced, which helps extend the machine's service life. However, this document does not consider the photothermal degradation and deformation problems of polyurethane under strong light.

[0007] Patent document CN116041645A discloses a pultruded two-component polyurethane resin containing an internal release agent. The internal release agent is a diol with long carbon chains on the side groups, formulated from a polyfunctional alcohol, a long-chain carboxylic acid, and a first catalyst. The pultruded resin includes: a small molecule polyol, a polyether polyol, a polyester polyol, an internal release agent, a second catalyst, and an antioxidant. The use of a diol with long carbon chains on the side groups reacting with isocyanate as an internal release agent greatly improves the separation characteristics of the composite material from the inner surface of the mold. The other end of the long carbon chain is fixed to the polymer network by chemical bonds.

[0008] Since most photovoltaic products are used in the high-temperature desert regions of Northwest China, where there are large temperature differences between day and night, and daytime temperatures can even exceed 80°C under prolonged exposure to the sun in summer, the polyurethane resin used in the pultrusion process described in the aforementioned literature has a TG point of 100°C or even lower, affecting the temperature resistance of the products. When used in photovoltaic frames, the heat resistance is still insufficient, and the photovoltaic frames are prone to deformation under high summer temperatures and sunlight. This can lead to a decrease in the power generation performance of photovoltaic modules, and even microcracks in the photovoltaic cells, resulting in a significant reduction in the power generation efficiency of photovoltaic modules and potential safety hazards. Summary of the Invention

[0009] The purpose of this invention is to provide a polyurethane resin for pultruded composite materials, its preparation method, and its application, to solve the problems of insufficient heat resistance in existing polyurethane technologies. The solvent-free polyurethane resin of this invention can give pultruded composite materials with excellent heat resistance and good resistance to deformation at high temperatures when processing glass fiber (carbon fiber or basalt fiber) reinforced pultruded composite materials.

[0010] To achieve the above objectives, the technical solution of the present invention is as follows:

[0011] The present invention discloses a polyurethane resin for pultruded composite materials, comprising component A and component B in a mass ratio of 100:(110-140), characterized in that component A is a hydroxyl compound component, made from raw materials comprising the following mass fractions: 80%-95% polyol, 0.001%-0.02% antioxidant, 0.3%-1.0% light stabilizer, 0.05%-0.2% defoamer, 0.1%-0.6% catalyst, 1%-3% mold release agent, 1%-10% flame retardant, 0.5%-3% 2,3-dimethyl-2,3-diphenylbutane (Lycor), and 0.1%-0.6% silane coupling agent;

[0012] Material B is polymeric MDI, such as Huntsman's 5005.

[0013] The polyol is a mixture of 3%–20% polyester diol (PE) and 97%–80% polypropylene oxide ether polyol (PPG) by mass fraction; the polypropylene oxide ether polyol uses p-phenylenediamine as an initiator, has a functionality of 2–3, and a number-average molecular weight of 300–1000, with 400–600 being optimal; if the mass fraction of the polypropylene oxide ether polyol is less than 80%, the hydrolysis resistance of the resulting pultruded composite polyurethane resin will not meet the application requirements. The polyester polyol is formed by high-temperature dehydration condensation of a diacid and a small-molecule diaol, with a functionality of 2-3 and a number-average molecular weight of 300-1000, preferably 400-600. The diacid is a mixture of terephthalic acid and / or isophthalic acid with 1,6-adipic acid and / or 1,4-succinic acid. The small-molecule polyol is at least one selected from 1,6-hexanediol, 1,4-butanediol, ethylene glycol, neopentyl glycol, 1,3-propanediol, glycerol, and pentaerythritol.

[0014] Variations in the types of polyether polyol initiators result in different functionalities, chemical structures, and functions. Compared to other PPG initiators, this invention uses p-phenylenediamine as an initiator, which introduces a benzene ring structure into the polyoxypropylene ether polyol, improving the tensile strength of the polyurethane resin products used in pultrusion composites and giving the resulting polyurethane materials better heat resistance and dimensional stability. However, under the intense sunlight of hot desert areas, the benzene ring is prone to ring-opening degradation, leading to a decrease in the mechanical properties of the polyurethane resin. This invention adds a small amount of methylbenzene; when exposed to intense sunlight, methylbenzene can form carbon free radicals under ultraviolet light, which then undergo graft polymerization with the degraded benzene ring, preventing and reducing further degradation of the benzene ring, thereby mitigating the decay of mechanical properties and extending product life.

[0015] Preferably, the antioxidant is 2,6-di-tert-butyl-4-methylphenol (BHT).

[0016] Preferably, the light stabilizer is one or more of triazine UV absorbers, hindered amine light stabilizers, hindered phenolic light stabilizers, and phosphites, such as SARASTAB 3164 triazine UV absorber and SARASTABB8501 composite light stabilizer.

[0017] Preferably, the defoamer is an organosilicon defoamer.

[0018] Preferably, the catalyst is a tertiary amine polyurethane catalyst, and more preferably one or more of triethylenediamine, bis-(3-dimethylpropylamino)amine, tri-(dimethylpropylamino)amine, N-N-dimethylbenzylamine, and composite tertiary amine liquid catalysts, such as those from Evonik. SA8 delayed-sensor composite tertiary amine liquid catalyst.

[0019] Preferably, the release agent is at least one of polyethylene micropowder and / or EVA micropowder with a melting point of 60–150°C, such as Honeywell's ACumisist A-12 polyethylene micropowder and Lotte's VS430 EVA micropowder. During pultrusion, this high-melting-point, low-surface-energy powder release agent melts upon heating and precipitates from the resin system onto the inner surface of the mold, acting as a lubricant to aid demolding and pultrusion. After the profile is pultruded and cooled, the micropowder recrystallizes, thus preventing migration to the surface and not affecting paint film adhesion. In contrast, conventional liquid release agents continuously migrate to the surface, severely reducing their surface energy, affecting paint film adhesion, and even causing peeling. However, the amount of this release agent added cannot be too much, otherwise it will lead to a decrease in mechanical properties.

[0020] Preferably, the flame retardant is at least one of triethyl phosphate (TEP), tri(2-chloropropyl) phosphate (TCPP), triphenyl phosphate (TPP), resorcinol bis(diphenyl phosphate) (RDP), and bisphenol A bis(diphenyl phosphate) (BDP). The amount of flame retardant added is mainly adjusted according to the requirements of the flame retardant grade. Too much flame retardant will also lead to a decrease in the physical properties of the product and fail to meet the usage requirements.

[0021] Preferably, the silane coupling agent is an amino-containing silane coupling agent, such as at least one of 3-aminopropyltriethoxysilane (KH-550), 3-aminopropyltrimethoxysilane (KH-540), 3-aminopropylmethyldiethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldiethoxysilane, and N-(2-aminoethyl)-3-aminopropylmethyldiethoxysilane, and more preferably KH-550.

[0022] The polyurethane resin for pultruded composite materials described in this invention is mainly used to prepare pultruded composite materials, such as pultruded composite materials prepared by pultrusion bonding with glass fiber, which are used to produce frames or brackets for photovoltaic modules. It can also be used to prepare other similar products, such as frames or brackets for home sunrooms. A specific usage method can be illustrated as follows: Material A and Material B are respectively loaded into a polyurethane-specific injection equipment, the dispensing ratio, dispensing temperature, and pultrusion speed are set, and the resin is bonded with glass fiber through pultrusion to obtain the pultruded composite material.

[0023] Compared with the prior art, the present invention has the following beneficial effects:

[0024] This invention uses p-phenylenediamine as an initiator, PPG, and a polyester polyol containing a benzene ring structure, with the PPG content being ≥80%. This not only maintains the easy demolding properties of PPG, but also, because the benzene ring is a rigid structure, it can promote the formation of more crystals with the benzene ring structure in the isocyanate, thereby increasing the glass transition temperature of the polyurethane resin. This significantly improves the rigidity and temperature resistance of the polyurethane resin, thereby enhancing the temperature resistance of the pultruded composite photovoltaic frame and making the pultruded composite less prone to deformation when used in high-temperature environments. Detailed Implementation

[0025] The present invention will be further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. After reading the contents of this invention, those skilled in the art can make various alterations or modifications to the invention, and these equivalent forms also fall within the scope defined by the claims of this application.

[0026] The raw materials used in the examples are all commercially available products, including:

[0027] Polypropylene oxide ether polyols (PPG) initiated with toluene diamine: Ningbo Guodu TD-405

[0028] Polypropylene oxide ether polyol (PPG) with bisphenol A as the initiator: Ningbo Guodu BP11S;

[0029] Polypropylene oxide ether polyol (PPG) with pentaerythritol as the initiator: Ningbo Guodu G304F;

[0030] Polyester polyol PBTA500, Asahikawa Chemical, uses butanediol, terephthalic acid and adipic acid as raw materials, with a molar ratio of terephthalic acid and adipic acid of 50 / 50 and a molecular weight of 500.

[0031] PBIA500, a polyester polyol, is produced by Asahikawa Chemical. Its raw materials are butanediol, isophthalic acid, and adipic acid, with a molar ratio of isophthalic acid to adipic acid of 50 / 50 and a molecular weight of 500.

[0032] Polymer MDI: Huntsman's 5005.

[0033] Example 1

[0034] In a reactor equipped with a stirring device and a nitrogen protection device, PPG TD-405 (initiated with toluene diamine) and polyester polyol PBTA500 (the sum of the two accounts for 90% of the total mass of raw materials) with a mass ratio of 80:20, 45 ppm of antioxidant BHT, 0.3% of light stabilizer SAREX 3164 and 0.4% of light stabilizer SAREX B8501, 2.7% of release agent polyethylene micro powder ACumistA-12, 4.6% of flame retardant triethyl phosphate, 1.5% of methyl methacrylate, 0.2% of silane coupling agent KH550, 0.1% of defoamer and 0.2% of catalyst SA-8 were added. After stirring evenly at a reaction temperature of 45-50℃, the mixture was discharged and packaged, and designated as material A1.

[0035] A1 material and polymeric MDI were separately loaded into a polyurethane-specific injection molding machine. The mass ratio of the extruded material was set to 100:130, the material temperature was set to 30℃, the first-stage mold temperature was set to 165℃, the second-stage mold temperature was set to 185℃, the pultrusion speed was set to 800mm / min, and the mass ratio of glass fiber to polyurethane resin was 80:20. The pultruded composite produced in this way was named pultruded composite S1.

[0036] Comparative Example 1: PPG TD-405, with toluene diamine as the initiator, was replaced with PPGBP11S, with bisphenol A as the initiator; all other aspects remained the same as in Example 1. The pultruded composite produced in this way was named Pultruded Composite D1.

[0037] Comparative Example 2: PPG TD-405, with toluene diamine as the initiator, was replaced with PPG G304F, with pentaerythritol as the initiator; all other aspects remained the same as in Example 1. The pultruded composite produced in this way was named Pultruded Composite D2.

[0038] Comparative Example 3: The polyester polyol PBTA500 was replaced with polyester polyol PBA500 (polybutylene adipate diol with a molecular weight of 500), and the rest was the same as in Example 1. The pultruded composite produced in this way was named pultruded composite D3.

[0039] Comparative Example 4: The amount of release agent ACumistor A-12 added was increased to 3.5% (PPG TD-405 was added 0.8% less), and the rest was the same as in Example 1. The pultruded composite produced in this way was named pultruded composite D4.

[0040] Comparative Example 5: The mold release agent ACumistor A-12 was replaced with the liquid mold release agent INT-1968RAC manufactured by AXEL Corporation, USA; otherwise, it was the same as in Example 1. The pultruded composite produced in this way was named Pultruded Composite D5.

[0041] Comparative Example 6: No addition of tannin (total amount of PPG TD-405 and PBTA500 increased by 1.5%), otherwise the same as in Example 1. The pultruded composite produced in this way was named Pultruded Composite D6.

[0042] Example 2

[0043] In a reactor equipped with a stirring device and a nitrogen protection device, PPG TD-405 (initiated with toluene diamine) and polyester polyol PBTA500 (the sum of the two accounts for 90% of the total mass of raw materials) with a mass ratio of 90:10, 45 ppm of antioxidant BHT, 0.3% of light stabilizer SAREX 3164 and 0.4% of light stabilizer SAREX B8501, 2.7% of release agent EVA micro powder VS430, 4.6% of flame retardant triethyl phosphate, 1.5% of methyl methacrylate, 0.2% of silane coupling agent KH550, 0.1% of defoamer and 0.2% of catalyst SA-8 were added. After stirring evenly at a reaction temperature of 45-50℃, the mixture was discharged and packaged, and designated as material A2.

[0044] A2 material and polymeric MDI were separately loaded into a polyurethane-specific injection molding machine. The mass ratio of the extruded material was set to 100:130, the material temperature was set to 30℃, the first-stage mold temperature was set to 165℃, the second-stage mold temperature was set to 185℃, the pultrusion speed was set to 800mm / min, and the mass ratio of glass fiber to polyurethane resin was 80:20. The pultruded composite produced in this way was named pultruded composite S2.

[0045] Example 3

[0046] In a reactor equipped with a stirring device and a nitrogen protection device, PPG TD-405 (initiated with toluene diamine) and polyester polyol PBIA500 (the sum of the two accounts for 90% of the total mass of raw materials) with a mass ratio of 80:20, 50 ppm of antioxidant BHT, 0.3% of light stabilizer SAREX 3164 and 0.4% of light stabilizer SAREX B8501, 2.7% of release agent polyethylene micro powder ACumistA-12, 4.6% of flame retardant triethyl phosphate, 1.5% of methyl methacrylate, 0.2% of silane coupling agent KH550, 0.1% of defoamer and 0.2% of catalyst SA-8 were added. After stirring evenly at a reaction temperature of 45-50℃, the mixture was discharged and packaged, and designated as material A3.

[0047] A3 material and polymeric MDI were separately loaded into a polyurethane-specific injection molding machine. The mass ratio of the extruded material was set to 100:130, the material temperature was set to 30℃, the first-stage mold temperature was set to 165℃, the second-stage mold temperature was set to 185℃, the pultrusion speed was set to 800mm / min, and the mass ratio of glass fiber to polyurethane resin was 80:20. The pultruded composite produced in this way was named pultruded composite S3.

[0048] Example 4

[0049] In a reactor equipped with a stirring device and a nitrogen protection device, PPG TD-405 (initiated with toluene diamine) and polyester polyol PBIA500 (the sum of the two accounts for 90% of the total mass of raw materials) with a mass ratio of 85:15, 50 ppm of antioxidant BHT, 0.3% of light stabilizer SAREX 3164 and 0.4% of light stabilizer SAREX B8501, 2.7% of release agent EVA micro powder VS430, 4.6% of flame retardant triethyl phosphate, 1.5% of methyl methacrylate, 0.2% of silane coupling agent KH550, 0.1% of defoamer and 0.2% of catalyst SA-8 were added. After stirring evenly at a reaction temperature of 45-50℃, the mixture was discharged and packaged, and designated as material A4.

[0050] A4 material and polymeric MDI were separately loaded into a polyurethane-specific injection molding machine. The mass ratio of the extruded material was set to 100:130, the material temperature was set to 30℃, the first-stage mold temperature was set to 165℃, the second-stage mold temperature was set to 185℃, the pultrusion speed was set to 800mm / min, and the mass ratio of glass fiber to polyurethane resin was 80:20. The pultruded composite produced in this way was named pultruded composite S4.

[0051] Example 5

[0052] In a reactor equipped with a stirring device and a nitrogen protection device, PPG TD-405 (initiated with toluene diamine) and polyester polyol PBIA500 (the sum of the two accounts for 90% of the total mass of raw materials) with a mass ratio of 80:20, 50 ppm of antioxidant BHT, 0.3% of light stabilizer SAREX 3164 and 0.4% of light stabilizer SAREX B8501, 2.5% of release agent polyethylene micro powder ACumistA-12, 5.3% of flame retardant TCPP, 1.0% of methyl methacrylate, 0.2% of silane coupling agent KH550, 0.1% of defoamer and 0.2% of catalyst SA-8 were added. After stirring evenly at a reaction temperature of 45-50℃, the mixture was discharged and packaged, and designated as material A5.

[0053] A5 material and polymeric MDI were separately loaded into a polyurethane-specific injection molding machine. The mass ratio of the extruded material was set to 100:120, the material temperature was set to 30℃, the first-stage mold temperature was set to 165℃, the second-stage mold temperature was set to 185℃, the pultrusion speed was set to 800mm / min, and the mass ratio of glass fiber to polyurethane resin was 80:20. The pultruded composite produced in this way was named pultruded composite S5.

[0054] Test Experiment Example

[0055] The pultruded composites of Examples 1-5 and Comparative Examples 1-6 were tested with polyurethane resin. The TG value of the polyurethane resin was determined according to GB / T40396-2021; the longitudinal tensile strength of the pultruded composites was determined according to ISO 527-5; the coating adhesion of the pultruded composites was determined according to GB / T 9286-1998; and the composites were aged under high-powered ultraviolet light for 4 months according to IEC 62215-2, with a total irradiation of 1500 kWh / m². 2 Then, the longitudinal tensile strength of the pultruded composite after aging was determined according to the provisions of ISO 527-5; the results are listed in Table 1.

[0056] Table 1 Performance test results of Examples 1-5 and Comparative Examples 1-6

[0057]

[0058] As can be seen from Table 1, PPG TD-405 in Examples 1-5, which uses toluene diamine as an initiator, combined with polyester polyols containing benzene rings synthesized with terephthalic acid or isophthalic acid, has the effect of improving the tensile strength and temperature resistance of polyurethane resins for pultruded composites.

[0059] When Comparative Example 1 uses PPG BP11S with bisphenol A as the initiator or Comparative Example 2 uses PPG G304F with pentaerythritol as the initiator, the tensile strength and temperature resistance of the pultruded composite material decrease.

[0060] In Comparative Example 3, replacing the polyester polyol PBTA with the benzene ring-containing polyol PBA resulted in a decrease in the tensile strength and temperature resistance of the pultruded composite.

[0061] When the amount of release agent added in Comparative Example 4 exceeds 3.0%, it will lead to a decrease in the tensile strength of the pultruded composite.

[0062] When a liquid release agent is used in Comparative Example 5, the coating adhesion of the pultruded composite material decreases.

[0063] When no tannin is added in Comparative Example 6, the aging resistance of the pultruded composite material decreases.

Claims

1. A polyurethane resin for pultruded composite materials, comprising component A and component B in a mass ratio of 100:(110-140), characterized in that, Material A is a hydroxyl compound component, made from the following raw materials in the indicated mass fractions: 80%–95% polyol, 0.001%–0.02% antioxidant, 0.3%–1.0% light stabilizer, 0.05%–0.2% defoamer, 0.1%–0.6% catalyst, 1%–3% mold release agent, 1%–10% flame retardant, 0.5%–3% 2,3-dimethyl-2,3-diphenylbutane, and 0.1%–0.6% silane coupling agent; Material B is polymeric MDI. The polyol is a mixture of 3%–20% by mass of polyester diol and 97%–80% by mass of polyoxypropylene ether polyol; the polyoxypropylene ether polyol uses p-phenylenediamine as an initiator, has a functionality of 2–3, and a number-average molecular weight of 300–1000; the polyester diol is formed by high-temperature dehydration condensation of a diacid and a small-molecule diol, has a functionality of 2–3, and a number-average molecular weight of 300–1000; the diacid is a mixture of terephthalic acid and / or isophthalic acid with 1,6-adipic acid and / or 1,4-succinic acid; the small-molecule diol is at least one of 1,6-hexanediol, 1,4-butanediol, ethylene glycol, neopentyl glycol, and 1,3-propanediol; the release agent is at least one of polyethylene micropowder and / or EVA micropowder with a melting point of 60–150°C.

2. The polyurethane resin for pultruded composite materials according to claim 1, characterized in that, The antioxidant is 2,6-di-tert-butyl-4-methylphenol; the defoamer is an organosilicon defoamer.

3. The polyurethane resin for pultruded composite materials according to claim 1, characterized in that, The light stabilizer is one or more of triazine UV absorbers, hindered amine light stabilizers, hindered phenolic light stabilizers, and phosphites; the catalyst is a tertiary amine polyurethane catalyst.

4. The polyurethane resin for pultruded composite materials according to claim 1, characterized in that, The flame retardant is at least one of triethyl phosphate, tri(2-chloropropyl) phosphate, triphenyl phosphate, resorcinol bis(diphenyl phosphate), and bisphenol A bis(diphenyl phosphate); the silane coupling agent is an amino-containing silane coupling agent.

5. The polyurethane resin for pultruded composite materials according to claim 4, characterized in that, The silane coupling agent is at least one of 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldiethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldiethoxysilane, and N-(2-aminoethyl)-3-aminopropylmethyldiethoxysilane.

6. The application of the polyurethane resin for pultruded composite materials according to any one of claims 1 to 5, characterized in that, Pultruded composite materials were prepared by combining glass fiber with glass fiber through pultrusion.

7. The application of the polyurethane resin for pultruded composite materials according to claim 6, characterized in that, The method of use is as follows: Material A and Material B are respectively loaded into a polyurethane-specific injection equipment, the dispensing ratio, dispensing temperature and pultrusion speed are set, and the materials are compounded with glass fiber through pultrusion to obtain a pultruded composite material.

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