CN111748073A - Method for preparing polyurethane pultrusion composite material - Google Patents
Method for preparing polyurethane pultrusion composite material Download PDFInfo
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- CN111748073A CN111748073A CN201910235171.5A CN201910235171A CN111748073A CN 111748073 A CN111748073 A CN 111748073A CN 201910235171 A CN201910235171 A CN 201910235171A CN 111748073 A CN111748073 A CN 111748073A
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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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/40—Shaping or impregnating by compression not applied
- B29C70/50—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC]
- B29C70/52—Pultrusion, i.e. forming and compressing by continuously pulling through a die
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/40—Shaping or impregnating by compression not applied
- B29C70/50—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC]
- B29C70/52—Pultrusion, i.e. forming and compressing by continuously pulling through a die
- B29C70/525—Component parts, details or accessories; Auxiliary operations
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/40—Shaping or impregnating by compression not applied
- B29C70/50—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC]
- B29C70/52—Pultrusion, i.e. forming and compressing by continuously pulling through a die
- B29C70/525—Component parts, details or accessories; Auxiliary operations
- B29C70/528—Heating or cooling
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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
- C08G18/30—Low-molecular-weight compounds
- C08G18/36—Hydroxylated esters of higher fatty acids
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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
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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
- C08G18/44—Polycarbonates
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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
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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
- C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
Abstract
The invention relates to a method for preparing a polyurethane pultrusion composite material by using a polyurethane pultrusion process, the polyurethane pultrusion composite material prepared by the method and application thereof. The method for preparing the polyurethane pultrusion composite material uses the short die, improves the production efficiency and saves the cost.
Description
Technical Field
The invention belongs to the field of a polyurethane pultrusion process. In particular, the present invention relates to a method for preparing a polyurethane pultruded composite using a polyurethane pultrusion process, the polyurethane pultruded composite prepared by the method, and uses thereof.
Background
The pultrusion composite material has the characteristics of high fiber content, uniform quality and the like, and is deeply concerned by the industry. The pultrusion process is simple and efficient, can realize continuous production, and is widely adopted. The general specific operation mode of the pultrusion process is as follows: continuously leading the fiber yarn or the fiber fabric out of a creel, carrying out resin infiltration through an open impregnation tank or a closed impregnation box, putting the fiber after resin infiltration into a mold with a certain cross section shape for heating and curing, continuously pulling out the mold by a traction device, and finally cutting the fiber yarn or the fiber fabric into required length on line, thereby preparing the corresponding composite material.
The existing pultrusion process usually uses a longer curing die, typically 90-100cm or even longer. Longer dies mean heavier, especially for larger articles, the dies are too bulky, which can result in long time spent in production preparation such as die maintenance, threading and heating; meanwhile, the mold is long and heavy, so that the energy consumption is high during heating, and the energy conservation, emission reduction and environmental protection are not facilitated.
CN101341018B discloses a system (100) for manufacturing a pultruded component (50) comprising an impregnation die (150) for wetting a fiber yarn (110) with a polymer resin precursor (141). The impregnation die (150) includes a first chamber (154) that coats the outer surface of the yarn (110) and a second chamber (156) that coats the fibers within the yarn (110). The cross-sectional area of the second chamber (156) decreases between the second chamber (156) inlet and the second chamber (156) outlet. The system (100) also includes a means (151) for separating the yarn (110) prior to entering the first chamber (154) to enable the polymer resin precursor (141) to flow around the outer surface of the yarn (110).
CN106626445A discloses a polyurethane pultrusion integral injection mold and a method of use thereof. The die comprises a die main body, wherein the die main body comprises a lower die and an upper die; the left end of the die main body is fixed with an electric heating plate, the top surface of the die main body is provided with a feeding port, and the right end of the die main body is fixed with a backing plate, a supporting bar, a right end feeding supporting plate and a middle supporting plate. After the mold is erected, the two electric heating sheets start to heat, felt is input to the middle supporting plate through the inner-layer felt feeding holes, glass fiber yarns are led into the middle supporting plate through the glass fiber yarn inlet holes, then the outer-layer felt is led into the middle supporting plate through the outer-layer felt feeding holes in the periphery of the glass fiber yarn inlet holes, in the advancing process, the polyurethane matrix starts to be injected into the injection port, in order to avoid the polyurethane matrix from being heated and solidified, the temperature reduction area is specially arranged on the left side of the injection port, and after the resin matrix, the felt and the glass fiber bundles are fully combined, the temperature is increased and solidified at the left end of the mold main body.
CN101312999B discloses a resin precursor composition for the preparation of composite parts, said composition comprising an isocyanate component comprising a material selected from the group consisting of diphenylmethane diisocyanate, polymeric isomers of diphenylmethane diisocyanate, and mixtures thereof. The resin precursor composition also includes at least one polyether polyol having a functionality of 3 in an amount such that the ratio of the isocyanate component to the at least one polyether polyol is from about 80% to 115% of stoichiometric. The resin precursor composition also includes a mold release material and a filler.
Despite the above disclosures, there is still a need for improved processes and molds to improve production efficiency and meet the requirements of energy saving, emission reduction and environmental friendliness.
Disclosure of Invention
In one aspect of the present invention, a method for preparing a polyurethane pultrusion composite material by using a polyurethane pultrusion process is provided, which comprises the following steps:
impregnating a fibrous reinforcement with a polyurethane composition comprising:
component A comprising one or more organic polyisocyanates;
component B, comprising:
b1) one or more organic polyols in an amount of 21-60 wt.%, preferably 21-40 wt.%, based on the total weight of the polyurethane composition in 100 wt.%;
b2) one or more compounds having the structure of formula (I),
wherein R1 is selected from hydrogen, methyl or ethyl; r2 is selected from alkylene having 2 to 6 carbon atoms, 2-bis (4-phenylene) -propane, 1, 4-bis (methylene) benzene, 1, 3-bis (methylene) benzene, 1, 2-bis (methylene) benzene; n is an integer selected from 1 to 6; and
component C, a free radical initiator;
and (2) drawing the soaked fiber reinforced material through a mold with the length of 21-55cm, preferably 25-55cm, more preferably 30-50 cm, and the temperature controlled at 110-230 ℃, preferably 150-220 ℃, at the speed of 0.2-2m/min, preferably 0.4-1.5m/min, and curing and molding to prepare the polyurethane pultrusion composite material.
Preferably, wherein the polyurethane resin is prepared by a reaction condition under which a radical polymerization reaction and an addition polymerization reaction of an isocyanate group and a hydroxyl group are simultaneously present in the polyurethane composition.
Preferably, said b1) is selected from organic polyols, wherein said organic polyols are selected from polyols having a functionality of from 1.7 to 6, preferably from 1.9 to 4.5, and a hydroxyl value of 150-.
Preferably, the b2) component is selected from: hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, or combinations thereof. Preferably, the content of b2) is 4.6 to 33 wt.%, based on the total weight of the polyurethane composition, in 100 wt.%.
Preferably, the fiber reinforcement is selected from glass fibers, carbon fibers, polyester fibers, natural fibers, aramid fibers, nylon fibers, basalt fibers, boron fibers, silicon carbide fibers, asbestos fibers, whiskers, hard particles, metal fibers, or combinations thereof.
Preferably, the free radical initiator used in the present invention may be added to either the polyol component or the isocyanate component or separately to both of the foregoing components. Examples of the radical initiator include, but are not limited to, peroxides, persulfides, peroxycarbonates, peroxyboric acids, azo compounds, or other suitable radical initiators that can initiate curing of a double bond-containing compound, and include t-butyl peroxyisopropylcarbonate, t-butyl peroxy-3, 5, 5-trimethylhexanoate, methyl ethyl ketone peroxide, cumene hydroperoxide.
Preferably, the curing time of the polyurethane composition at 150-220 ℃ is 10-120 seconds, preferably 15-90 seconds.
Preferably, the polyurethane composition has a gel time of 15 to 90 minutes, preferably 20 to 60 minutes, at room temperature.
Preferably, the infiltration is performed in an infiltration device, and the infiltration device comprises an impregnation box and an open impregnation tank.
Preferably, the glue injection pressure in the glue injection box is 0.1-15 bar, preferably 0.1-10 bar.
It is well known to those skilled in the art that the length of the die of the polyurethane composition (not containing the b2 component and the free radical initiator component of the present invention) typically used in the pultrusion process in the prior art is typically 90-100 cm. The inventive mold can be shortened by 45% to 76.7%, preferably 45% to 72.2%, more preferably 50% to 66.7% (calculated on the basis of the longest/shortest mold in the aforementioned prior art) compared to the use of molds commonly used in the prior art.
Through repeated experiments, the method for preparing the polyurethane pultrusion composite material by the polyurethane pultrusion process shortens the length of a die, improves the production efficiency of the pultrusion process, saves raw materials and prepares the polyurethane pultrusion composite material with satisfactory quality.
In another aspect of the invention, a polyurethane pultruded composite is produced by the method of producing a polyurethane composite by a polyurethane pultrusion process. The polyurethane pultrusion composite material is prepared by reacting a polyurethane composition comprising the following components:
component A comprising one or more polyisocyanates;
component B, comprising:
b1) one or more polyols in an amount of 21 to 60 wt.%, preferably 21 to 40 wt.%, based on the total weight of the polyurethane composition in 100 wt.%;
b2) one or more compounds having the structure of formula (I)
Wherein R1 is selected from hydrogen, methyl or ethyl; r2 is selected from alkylene having 2 to 6 carbon atoms, 2-bis (4-phenylene) -propane, 1, 4-bis (methylene) benzene, 1, 3-bis (methylene) benzene, 1, 2-bis (methylene) benzene; n is an integer selected from 1 to 6; and
and component C, including a free radical initiator.
Preferably, wherein the polyurethane resin is prepared by a reaction condition under which a radical polymerization reaction and an addition polymerization reaction of an isocyanate group and a hydroxyl group are simultaneously present in the polyurethane composition.
Preferably, said b1) is selected from organic polyols, wherein said organic polyols are selected from polyols having a functionality of from 1.7 to 6, preferably from 1.9 to 4.5, and a hydroxyl value of 150-.
Preferably, the content of b2) is 4.6 to 33 wt.%, based on the total weight of the polyurethane composition, in 100 wt.%.
Preferably, the curing time of the polyurethane composition at 150-220 ℃ is 10-120 seconds, preferably 15-90 seconds.
Optionally, the polyurethane composition has a gel time at room temperature of 15 to 90 minutes, preferably 20 to 60 minutes.
In yet another aspect of the present invention, a polyurethane product is provided, including a polyurethane pultruded composite made according to the method of the present invention for making a polyurethane composite using a polyurethane pultrusion process.
Preferably, the polyurethane product of the present invention can be selected from cable bridges, door and window curtain wall frames, ladder frames, tent poles or pipes, antiglare panels, floors, sucker rods, utility poles and crossarms, guardrails, grilles, architectural profiles, container profiles and sheets, bicycle frames, fishing rods, cable cores, insulator mandrels, radomes, single or sandwich continuous sheets or fan blade caps.
The method for preparing the polyurethane composite material by the polyurethane pultrusion process adopts the polyurethane composition, skillfully designs the mould matched with the polyurethane composition, and uses a proper method, thereby improving the production efficiency of the polyurethane pultrusion composite material and saving the cost. Shorter moulds mean lighter, especially for larger articles, the reduction in weight of the moulds results in considerable time savings in production preparation such as maintenance of the moulds, threading and heating; meanwhile, the mold is short and light, so that the energy consumption is low during heating, and the energy conservation, emission reduction and environmental protection are facilitated. In addition, the mold is short, so that the manufacturing and maintenance cost of the mold can be greatly saved, and the raw material loss of the polyurethane composite material can be reduced.
In addition, the polyurethane composition has longer gel time, and can realize better polyurethane pultrusion. The polyurethane composite material has excellent physical properties and high glass fiber content.
In addition, the polyurethane composition has shorter curing time and longer gel time, can be better and more flexibly (for example, can be soaked and molded for a longer time) and is suitable for preparing a polyurethane pultrusion composite material, in particular a large polyurethane pultrusion composite material. In particular, the fibrous reinforcement material can be wetted and shaped for a longer period of time at normal temperatures, for example before entering the mould, and can be cured more quickly at high temperatures, for example after entering the mould.
Detailed Description
The following describes specific embodiments for carrying out the present invention.
According to a first aspect of the present invention there is provided a method of preparing a polyurethane pultruded composite using a polyurethane pultrusion process, comprising the steps of:
impregnating a fibrous reinforcement with a polyurethane composition comprising:
component A comprising one or more organic polyisocyanates;
component B, comprising:
b1) one or more organic polyols in an amount of 21-60 wt.%, preferably 21-40 wt.%, based on the total weight of the polyurethane composition in 100 wt.%;
b2) one or more compounds having the structure of formula (I)
Wherein R1 is selected from hydrogen, methyl or ethyl; r2 is selected from alkylene having 2 to 6 carbon atoms, 2-bis (4-phenylene) -propane, 1, 4-bis (methylene) benzene, 1, 3-bis (methylene) benzene, 1, 2-bis (methylene) benzene; n is an integer selected from 1 to 6; and
component C, a free radical initiator;
and (2) drawing the soaked fiber reinforced material through a mold with the length of 21-55cm, preferably 25-55cm, more preferably 30-50 cm, and the temperature controlled at 110-230 ℃, preferably 150-220 ℃, at the speed of 0.2-2m/min, preferably 0.4-1.5m/min, and curing and molding to prepare the polyurethane pultrusion composite material.
Preferably, wherein the polyurethane resin is prepared by a reaction condition under which a radical polymerization reaction and an addition polymerization reaction of an isocyanate group and a hydroxyl group are simultaneously present in the polyurethane composition.
Preferably, said b1) is selected from organic polyols, wherein said organic polyols are selected from polyols having a functionality of from 1.7 to 6, preferably from 1.9 to 4.5, and a hydroxyl value of 150-.
Preferably, the content of b2) is 4.6 to 33 wt.%, based on the total weight of the polyurethane composition, in 100 wt.%.
Optionally, the reinforcing material is selected from a fibrous reinforcing material, carbon nanotubes, hard particles or a combination thereof, more preferably from a fibrous reinforcing material. The reinforcing material is present in an amount of 60 to 90 wt.%, preferably 75 to 85 wt.%, based on the total weight of the polyurethane composite in 100 wt.%.
When used in the present invention, the fibrous reinforcement is not required in shape and size, and may be, for example, continuous fibers, a web formed by bonding, or a fabric.
In some embodiments of the invention, the fibrous reinforcement material is selected from: glass fibers, carbon fibers, polyester fibers, natural fibers, aramid fibers, nylon fibers, basalt fibers, boron fibers, silicon carbide fibers, asbestos fibers, whiskers, metal fibers, or combinations thereof.
Optionally, the organic polyisocyanate may be any aliphatic, cycloaliphatic or aromatic isocyanate known for use in the preparation of polyurethanes. Examples include, but are not limited to: toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polyphenylmethane polyisocyanate (pMDI), 1, 5-naphthalene diisocyanate (ndi), Hexamethylene Diisocyanate (HDI), methylcyclohexyl diisocyanate (TDI), 4' -dicyclohexylmethane diisocyanate, isophorone diisocyanate (IPDI), p-phenylene diisocyanate (PPDI), p-phenylene diisocyanate (XDI), tetramethyldimethylene diisocyanate (TMXDI), and polymers thereof or combinations thereof. The isocyanates which can be used according to the invention preferably have a functionality of from 2.0 to 3.5, particularly preferably from 2.1 to 2.9. The isocyanate viscosity is preferably from 5 to 700 mPas, particularly preferably from 10 to 300 mPas, determined at 25 ℃ in accordance with DIN 53019-1-3.
When used in the present invention, the organic polyisocyanate includes an isocyanate dimer, trimer, tetramer, pentamer or a combination thereof.
In a preferred embodiment of the present invention, the isocyanate component a is selected from the group consisting of diphenylmethane diisocyanate (MDI), polyphenylmethane polyisocyanate (pMDI), and polymers, prepolymers or combinations thereof.
Blocked isocyanates may also be used as isocyanate component a, which may be prepared by reacting an excess of an organic polyisocyanate or mixtures thereof with a polyol compound. These compounds and their preparation are well known to those of ordinary skill in the art.
The polyurethane composition of the present invention comprises one or more organic polyols b 1). The organic polyol is present in an amount of 21 to 60 wt.%, based on the total weight of the polyurethane composition in 100 wt.%. The organic polyol may be an organic polyol commonly used in the art for making polyurethanes, including but not limited to: polyether polyols, polyether carbonate polyols, polyester polyols, polycarbonate diols, polymer polyols, vegetable oil based polyols, or combinations thereof.
The polyether polyols may be prepared by known processes, for example by reacting an olefin oxide with an initiator in the presence of a catalyst. The catalyst is preferably, but not limited to, alkali hydroxide, alkali alkoxide, antimony pentachloride, boron fluoride etherate, or a mixture thereof. The alkylene oxide is preferably, but not limited to, tetrahydrofuran, ethylene oxide, propylene oxide, 1, 2-butylene oxide, 2, 3-butylene oxide, styrene oxide, or a mixture thereof, and ethylene oxide and/or propylene oxide is particularly preferred. The initiator is preferably, but not limited to, a polyol, preferably, but not limited to, water, ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, diethylene glycol, trimethylolpropane, glycerol, bisphenol a, bisphenol S, or mixtures thereof, or a polyamine, preferably, but not limited to, ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, diethylenetriamine, tolylenediamine, or mixtures thereof.
The polyether carbonate polyols, which can be prepared by addition of carbon dioxide and alkylene oxides onto starters containing active hydrogen using double metal cyanide catalysts, can also be used in the present invention.
The polyester polyol is prepared by reacting dicarboxylic acid or dicarboxylic anhydride with polyhydric alcohol. The dicarboxylic acid is preferably, but not limited to, an aliphatic carboxylic acid having 2 to 12 carbon atoms, and the aliphatic carboxylic acid having 2 to 12 carbon atoms is preferably, but not limited to, succinic acid, malonic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecane carboxylic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, or a mixture thereof. The dicarboxylic acid anhydride is preferably, but not limited to, phthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride, or a mixture thereof. The polyhydric alcohol reacted with the dicarboxylic acid or dicarboxylic acid anhydride is preferably, but not limited to, ethylene glycol, diethylene glycol, 1, 2-propanediol, 1, 3-propanediol, dipropylene glycol, 1, 3-methylpropanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, neopentyl glycol, 1, 10-decanediol, glycerol, trimethylolpropane, or a mixture thereof. The polyester polyol also comprises polyester polyol prepared from lactone. The polyester polyol prepared from lactone, preferably but not limited to, -caprolactone. Preferably, the polyester polyol has a molecular weight of 200-3000 and a functionality of 2-6, preferably 2-5, more preferably 2-4.
The polycarbonate diol can be prepared by reacting dihydric alcohol with dialkyl carbonate or diaryl carbonate or phosgene. The diol is preferably, but not limited to, 1, 2-propanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, diethylene glycol, trioxymethylene glycol, or a mixture thereof. The dialkyl carbonate or diaryl carbonate is preferably, but not limited to, diphenyl carbonate.
The polymer polyol may be a polymer modified polyether polyol, preferably a graft polyether polyol, polyether polyol dispersion. The graft polyether polyol, preferably based on styrene and/or acrylonitrile; the styrene and/or acrylonitrile can be prepared by in-situ polymerization of styrene, acrylonitrile and a mixture of styrene and acrylonitrile; in the mixture of styrene and acrylonitrile, the ratio of styrene to acrylonitrile is 90: 10 to 10: 90, preferably 70: 30 to 30: 70. The polymer polyol can also be bio-based polyol such as castor oil, wood tar and the like. The polymer polyether polyol dispersion comprises a disperse phase, for example, a free-radical filler, a polyurea, a polyhydrazide, a polyurethane containing tertiary amino groups in bonded form and/or melamine. The amount of the dispersed phase is 1 to 50 wt.%, preferably 1 to 45 wt.%, based on 100 wt.% of the weight of the polymeric polyether polyol. Preferably the polymer polyether polyol has a polymer solids content of from 20% to 45% and a hydroxyl number of from 20 to 50mg KOH/g, based on 100% weight of the polymer polyether.
When used in the present invention, the vegetable oil-based polyol includes vegetable oil, vegetable oil polyol or a modified product thereof. Vegetable oils are compounds prepared from unsaturated fatty acids and glycerol or oils extracted from fruits, seeds, germs of plants, preferably but not limited to peanut oil, soybean oil, linseed oil, castor oil, rapeseed oil, palm oil. The vegetable oil polyol is a polyol initiated by one or more vegetable oils. Synthetic vegetable oil polyol starters include, but are not limited to, soybean oil, palm oil, peanut oil, canola oil, and castor oil. The vegetable oil polyol starter may be used to introduce hydroxyl groups by cleavage, oxidation, or transesterification, and the corresponding vegetable oil polyol may be prepared by processes well known to those skilled in the art for preparing organic polyols.
Methods for measuring hydroxyl number are well known to the person skilled in the art, for example in Houben Weyl, Methoden der Organischen Chemie, vol.XIV/2Makromolekulare Stoffe, p.17, Georg Thieme Verlag; stuttgart 1963. The entire contents of this document are incorporated herein by reference.
When used in the present invention, unless otherwise indicated, the functionality, hydroxyl number of the organic polyol all refer to the average functionality and average hydroxyl number.
Optionally, the polyurethane composition of the invention also comprises one or more compounds b2 having the structure of formula (I)
Wherein R is1Selected from hydrogen, methyl or ethyl; r2Selected from alkylene groups having 2 to 6 carbon atoms; n is an integer selected from 1 to 6.
In a preferred embodiment of the invention, R2Selected from ethylene, propylene, butylene, pentylene, 1-methylThe radicals 1, 2-ethylene, 2-methyl-1, 2-ethylene, 1-ethyl-1, 2-ethylene, 2-ethyl-1, 2-ethylene, 1-methyl-1, 3-propylene, 2-methyl-1, 3-propylene, 3-methyl-1, 3-propylene, 1-ethyl-1, 3-propylene, 2-ethyl-1, 3-propylene, 3-ethyl-1, 3-propylene, 1-methyl-1, 4-butylene, 2-methyl-1, 4-butylene, 3-methyl-1, 4-butylene and 4-methyl-1, 4-butylene, 2, 2-bis (4-phenylene) -propane, 1, 4-dimethylene-benzene, 1, 3-dimethylene-benzene, 1, 2-dimethylene-benzene.
Preferably, said b1) is selected from organic polyols, wherein said organic polyols are selected from polyols having a functionality of from 1.7 to 6, preferably from 1.9 to 4.5, and a hydroxyl value of 150-.
In a preferred embodiment of the invention, said b2) component is selected from: hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, or combinations thereof.
The compounds of formula (I) can be prepared by methods customary in the art, for example by (meth) acrylic anhydride or (meth) acrylic acid, (meth) acryloyl halide compounds with HO- (R)2O)n-H is prepared by esterification reactions, the preparation process being well known to the person skilled in the art, for example as described in handbook of polyurethane raw materials and auxiliaries (bang of liu yi jun, published 4/1/2005) third chapter, and chapter ii of polyurethane elastomers (bang of liu yi jun, published 8/2012), the entire contents of which are incorporated herein by reference.
The polyurethane composition of the present invention further comprises a C radical reaction initiator. The free radical initiator used in the present invention may be added to either the polyol component or the isocyanate component or both components. Such initiators include, but are not limited to, peroxides, persulfides, peroxycarbonates, peroxyboric acids, azo compounds, or other suitable free radical initiators that can initiate curing of double bond containing compounds, examples of which include t-butyl peroxyisopropylcarbonate, t-butyl peroxy-3, 5, 5-trimethylhexanoate, methyl ethyl ketone peroxide, cumene hydroperoxide. Preferably, the free radical reaction initiator of the present invention is present in an amount of 0.1 to 8 wt.%, based on 100 wt.% of the total weight of the polyurethane composition of the present invention. In addition, an accelerator, such as a cobalt compound or an amine compound, may be present.
Optionally, the polyurethane composition may further comprise a catalyst for catalyzing the reaction of isocyanate groups (NCO) with hydroxyl groups (OH). Suitable catalysts for the polyurethane reaction are preferably, but not limited to, amine catalysts, organometallic catalysts, or mixtures thereof. The amine catalyst is preferably, but not limited to, triethylamine, tributylamine, triethylenediamine, N-ethylmorpholine, N, N, N ', N' -tetramethyl-ethylenediamine, pentamethyldiethylenetriamine, N, N-methylaniline, N, N-dimethylaniline, or a mixture thereof. The organometallic catalyst is preferably, but not limited to, organotin compounds, such as: tin (II) acetate, tin (II) octoate, tin ethylhexanoate, tin laurate, dibutyltin oxide, dibutyltin dichloride, dibutyltin diacetate, dibutyltin maleate, dioctyltin diacetate, or mixtures thereof. Preferably, the catalyst is used in an amount of 0.001 to 10 wt.%, based on 100 wt.% of the total weight of the polyurethane composition of the present invention.
In the addition polymerization reaction of isocyanate groups and hydroxyl groups in the embodiment of the present invention, the isocyanate groups may be contained in the isocyanate groups in the organic polyisocyanate (component a), may also be contained in the reaction intermediate product of the organic polyisocyanate (component a) and the organic polyol (b1) component) or b2) component, and the hydroxyl groups may be contained in the reaction intermediate product of the organic polyol (b1) component) or b2) component, or may be contained in the reaction intermediate product of the organic polyisocyanate (component a) and the organic polyol (b1) component) or b2) component.
In the embodiment of the present invention, the radical polymerization is an addition polymerization of the olefinic bond, wherein the olefinic bond may be the olefinic bond contained in the b2) component or the olefinic bond contained in the intermediate product of the reaction of the b2) component with the organic polyisocyanate.
In the present example, the polyurethane addition polymerization (i.e., the addition polymerization of isocyanate groups and hydroxyl groups) was carried out simultaneously with the radical polymerization. As known to those skilled in the art, suitable reaction conditions can be selected so that the polyurethane addition polymerization reaction and the free radical polymerization reaction are carried out in sequence, but the polyurethane matrix prepared in the way is different from the polyurethane resin matrix prepared by simultaneously carrying out the polyurethane addition polymerization reaction and the free radical polymerization reaction, so that the mechanical properties and the manufacturability of the prepared polyurethane composite material are different.
Optionally, the polyurethane composition described above may also contain adjuvants or additives, including but not limited to: fillers, internal mold release agents, flame retardants, smoke suppressants, dyes, pigments, antistatic agents, antioxidants, UV stabilizers, diluents, defoamers, coupling agents, surface wetting agents, leveling agents, water scavengers, catalysts, molecular sieves, thixotropic agents, plasticizers, blowing agents, foam stabilizers, foam homogenizers, free radical reaction inhibitors or combinations thereof, which components may optionally be comprised in the isocyanate component a) and/or the polyurethane composition B) of the invention. These components can also be stored separately as component D) and, when used for the preparation of polyurethane composites, are mixed with the isocyanate component A) and/or the polyurethane composition B) according to the invention before the preparation.
In some embodiments of the invention, the filler is selected from: aluminum hydroxide, bentonite, fly ash, wollastonite, perlite powder, cenosphere, calcium carbonate, talcum powder, mica powder, porcelain clay, fumed silica, expandable microspheres, diatomite, volcanic ash, barium sulfate, calcium sulfate, glass microspheres, stone powder, wood powder, sawdust, bamboo powder, bamboo sawdust, rice grains, straw scraps, sorghum straw scraps, graphite powder, metal powder, thermosetting composite material recycled powder, plastic particles or powder or a combination thereof. Wherein the glass microspheres can be solid or hollow.
The internal mold release agent which can be used in the present invention includes any conventional mold release agent used for producing polyurethane, and examples thereof include long-chain carboxylic acids, particularly fatty acids such as stearic acid, amines of long-chain carboxylic acids such as stearamide, fatty acid esters, metal salts of long-chain carboxylic acids such as zinc stearate, or polysiloxanes.
Examples of flame retardants that can be used in the present invention include triaryl phosphate, trialkyl phosphate, triaryl or trialkyl phosphate with halogen, melamine resins, halogenated paraffins, red phosphorus, or combinations thereof.
Other adjuvants useful in the present invention include water scavengers such as molecular sieves; defoamers, such as polydimethylsiloxane; coupling agents, such as monoepoxyethane or organic amine functional trialkoxysilane or combinations thereof. Coupling agents are particularly preferred for improving the adhesion of the resin matrix to the fibrous reinforcement. Finely particulate fillers, such as clays and fumed silicas, are commonly used as thixotropic agents.
The radical reaction inhibitor which can be used in the present invention includes polymerization inhibitors and retarders, etc., such as some phenols, quinone compounds or hindered amine compounds, examples of which include methylhydroquinone, p-methoxyphenol, benzoquinone, polymethine piperidine derivatives, low valent copper ions, etc.
Preferably, the polyurethane composition of the present invention has a curing time of 10 to 120 seconds, preferably 15 to 90 seconds, at 150 to 220 ℃.
Preferably, the polyurethane compositions of the present invention have a gel time of 15 to 90 minutes, preferably 20 to 60 minutes, at room temperature. Generally, the term "gel time" refers to the time until the reaction system A-and B-components begin to mix until the viscosity reaches a certain value (e.g., about 10000 mPa.s). The gel time mentioned in the examples of the present invention is a time measured by using a gel tester.
Preferably, the impregnation according to the invention is carried out in an impregnation apparatus comprising a gumming box and an open gumming bath.
Preferably, the glue injection pressure in the glue injection box is 0.1-15 bar, preferably 0.1-10 bar.
As previously mentioned, the length of the mold of the polyurethane composition (without the b2 component and the radical initiator component of the present invention) commonly used in the prior art pultrusion process is typically 90-100Cm, and the mold of the present invention can be shortened by 45% -76.7%, preferably 45% -72.2%, more preferably 50% -66.7% (calculated on the basis of the aforementioned longest/shortest mold of the prior art) compared to the mold commonly used in the prior art.
Through repeated experiments, the method for preparing the polyurethane pultrusion composite material by the polyurethane pultrusion process shortens the length of a die, improves the production efficiency of the pultrusion process, saves raw materials and prepares the polyurethane pultrusion composite material with satisfactory quality.
In addition, the polyurethane composition has shorter curing time and longer gel time, can be better and more flexibly (for example, can be soaked and molded for a longer time) and is suitable for preparing a polyurethane pultrusion composite material, in particular a large polyurethane pultrusion composite material. In particular, the fibrous reinforcement material can be wetted and shaped for a longer period of time at normal temperatures, for example before entering the mould, and can be cured more quickly at high temperatures, for example after entering the mould.
According to another aspect of the invention, a polyurethane pultruded composite is provided that is produced by a method of producing a polyurethane composite by a polyurethane pultrusion process. The polyurethane pultrusion composite material is prepared by reacting a polyurethane composition comprising the following components:
component A comprising one or more polyisocyanates;
component B, comprising:
b1) one or more polyols in an amount of 21 to 60 wt.%, preferably 21 to 40 wt.%, based on the total weight of the polyurethane composition in 100 wt.%;
b2) one or more compounds having the structure of formula (I)
Wherein R1 is selected from hydrogen, methyl or ethyl; r2 is selected from alkylene having 2 to 6 carbon atoms, 2-bis (4-phenylene) -propane, 1, 4-bis (methylene) benzene, 1, 3-bis (methylene) benzene, 1, 2-bis (methylene) benzene; n is an integer selected from 1 to 6; and
component C, a radical initiator.
Preferably, wherein the polyurethane resin is prepared by a reaction condition under which a radical polymerization reaction and an addition polymerization reaction of an isocyanate group and a hydroxyl group are simultaneously present in the polyurethane composition.
Preferably, said b1) is selected from organic polyols, wherein said organic polyols are selected from polyols having a functionality of from 1.7 to 6, preferably from 1.9 to 4.5, and a hydroxyl value of 150-.
Preferably, the content of b2) is 4.6 to 33 wt.%, based on the total weight of the polyurethane composition, in 100 wt.%.
Preferably, the curing time of the polyurethane composition at 150-220 ℃ is 10-120 seconds, preferably 15-90 seconds.
Optionally, the polyurethane composition has a gel time at room temperature of 15 to 90 minutes, preferably 20 to 60 minutes.
In yet another aspect of the invention, a polyurethane product is provided. The polyurethane product comprises the polyurethane pultrusion composite material prepared by the method for preparing the polyurethane composite material by the polyurethane pultrusion process.
Preferably, the polyurethane product of the present invention can be selected from cable bridges, door and window curtain wall frames, ladder frames, tent poles or pipes, antiglare panels, floors, sucker rods, utility poles and crossarms, guardrails, grilles, architectural profiles, container profiles and sheets, bicycle frames, fishing rods, cable cores, insulator mandrels, radomes, single or sandwich continuous sheets or fan blade caps.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In the event that a definition of a term in this specification conflicts with a meaning commonly understood by those skilled in the art to which the invention pertains, the definition set forth herein shall govern.
The present invention is illustrated by the following examples, but it should be understood that the scope of the present invention is not limited to these examples.
Drawings
The invention is illustrated below with reference to the accompanying drawings:
FIG. 1 illustrates a die and a process flow shown in a method of preparing a polyurethane pultruded composite according to an embodiment of the present invention, wherein: 1 and 2 represent fibers; 3 a yarn guide device; 4 denotes an infiltration apparatus; 5 denotes a mold; 6 represents a profile; 7 denotes a traction device; and 8 and 9 denote heating means.
Examples
The performance parameter test in the examples of the present application shows:
functionality, means according to the industry formula: a functionality of hydroxyl value (Mw/56100); wherein the molecular weight is determined by GPC high performance liquid chromatography;
isocyanate index, which means a value calculated by the following formula:
the NCO content, which is the NCO group content in the system, was determined by GB/T12009.4-2016.
Pultrusion rate/degree, i.e. the speed at which the migrating fibrous reinforcement passes through the die, is the length of pultruded fibrous reinforcement passing through the die per minute, i.e. the length of the product produced per minute; the specific test method comprises the following steps: the length of the pultruded fibre reinforcement material measured using a speed sensor or stopwatch plus a ruler divided by the time used is the length of passage through the die per unit time, i.e. the rate/degree of pultrusion.
The curing time refers to the time from the beginning of mixing of the A component and the B component of the reaction system to curing.
The gel time is a time until the reaction system A-and B-components begin to be mixed until the viscosity reaches a certain value (for example, about 10000mPa. s). The gel time of the present invention is measured using a gel tester. The specific test method comprises the steps of uniformly mixing the component A and the component B, placing the mixture in a gel tester, and recording the time from pressing a start button to stopping the gel tester as the gel time.
Raw material sources and descriptions
TABLE 1 raw materials List
Example 1:
as shown in figure 1, 240 bundles of glass fibers are led out from a creel, enter a glue injection box and a mould (the length of the mould is 40cm) through a preformed plate in sequence, and are pulled forwards through a pulling device to be fully straightened. The heating device of the mold is started, and the mold temperature is controlled from the inlet to the outlet in sequence as follows: 120 ℃/220 ℃. After the temperature stabilized, the glue injector was started and component a (Desmodur 0223) and component B (100 parts by weight of Baydur18 BD207 and 3 parts by weight of Baydur18BD101) were mixed in the weight ratio 92: 100, continuously pumping to a static mixing head of the glue injection box, filling the glue injection box after the static mixing head is mixed, fully soaking the glass fiber, and controlling the glue injection pressure in the glue injection box to be 0.1-15 bar. The glass fiber soaked by the glue injection box is continuously pulled through the die by a traction device at the speed of 0.4m/min to obtain the polyurethane pultrusion composite material. When the polyurethane pultrusion composite material is knocked by metal 1m after the material is taken out of the mold, the sound is crisp, and the curing is good.
The polyurethane composition of example 1 had a cure time of about 40 seconds; the gel time was 40 minutes.
Comparative example 1:
as shown in figure 1, 240 bundles of glass fiber yarns are led out from a creel, sequentially pass through a preforming plate and enter a glue injection box, and after a mould (the length of the mould is 40cm), the glass fiber yarns are pulled forwards by a traction device to be completely straightened. The heating device of the mold is started, and the mold temperature is controlled from the inlet to the outlet in sequence as follows: 120C/190C, starting the glue injection machine after the temperature is stable, and enabling the glue injection machine to mix the component A (Desmodur 1511L) and the component B (100 parts of Baydur18BD 001: 5 parts of Baydur18BD101) according to the weight ratio of 114: 100, continuously pumping to a static mixing head, mixing by the mixing head, filling the glue injection box to ensure that the fiber yarns are fully soaked, and controlling the glue injection pressure in the glue injection box to be 0.1-15 bar. The fiber yarns soaked in the glue injection box are continuously pulled through the die by a traction device at the speed of 0.4m/min, and when the section bar is knocked by metal at the position 1m after the section bar is taken out of the die, the sound is dull, and the curing is poor.
The polyurethane composition of comparative example 1 had a cure time of about 70 seconds; the gel time was about 23 minutes.
From the experimental results of example 1 above and comparative example 1, it can be seen that the method of the present invention for preparing a polyurethane pultruded composite using a suitable mold and a corresponding polyurethane composition enables the preparation of a well-cured polyurethane pultruded composite. The short die is used, so that the production efficiency is improved, the cost and the energy consumption are saved, and the method is more environment-friendly. The same mold, pultruded using a polyurethane composition of the prior art that does not contain b2) component, does not result in a well cured pultruded composite. In addition, the polyurethane composition of the invention has shorter curing time and longer gel time, can be better and more flexibly (for example, can be soaked and molded for a longer time) and is suitable for the preparation of polyurethane composite materials, in particular large polyurethane composite materials.
Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.
Claims (15)
1. A method for preparing a polyurethane pultrusion composite material by using a polyurethane pultrusion process comprises the following steps:
impregnating a fibrous reinforcement with a polyurethane composition comprising:
component A comprising one or more organic polyisocyanates;
component B, comprising:
b1) one or more organic polyols in an amount of 21-60 wt.%, preferably 21-40 wt.%, based on the total weight of the polyurethane composition in 100 wt.%;
b2) one or more compounds having the structure of formula (I)
Wherein R1 is selected from hydrogen, methyl or ethyl; r2 is selected from alkylene having 2 to 6 carbon atoms, 2-bis (4-phenylene) -propane, 1, 4-bis (methylene) benzene, 1, 3-bis (methylene) benzene, 1, 2-bis (methylene) benzene; n is an integer selected from 1 to 6; and
component C, a free radical initiator;
and (2) drawing the soaked fiber reinforced material through a mold with the length of 21-55cm, preferably 25-55cm, more preferably 30-50 cm, and the temperature controlled at 110-230 ℃, preferably 150-220 ℃, at the speed of 0.2-2m/min, preferably 0.4-1.5m/min, and curing and molding to prepare the polyurethane pultrusion composite material.
2. The method as set forth in claim 1, wherein said b2) component is selected from the group consisting of: hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, or combinations thereof.
3. The process as claimed in claim 1 or 2, wherein b2) is present in an amount of from 4.6 to 33% by weight, based on 100% by weight of the total weight of the polyurethane composition.
4. The method of claim 1 or 2, wherein the fibrous reinforcement is selected from glass fibers, carbon fibers, polyester fibers, natural fibers, aramid fibers, nylon fibers, basalt fibers, boron fibers, silicon carbide fibers, asbestos fibers, whiskers, hard particles, metal fibers, or combinations thereof.
5. The process according to claim 1 or 2, characterized in that the polyurethane composition has a curing time of 10 to 120 seconds, preferably 15 to 90 seconds, at 150 to 220 ℃.
6. The process according to claim 1 or 2, characterized in that the polyurethane composition has a gel time of 15 to 90 minutes, preferably 20 to 60 minutes, at room temperature.
7. The method according to claim 1 or 2, wherein the impregnation is carried out in an impregnation device comprising a cartridge and an open dip tank.
8. The method according to claim 6, wherein the injection pressure in the injection box is 0.1 to 15bar, preferably 0.1 to 10 bar.
9. A pultruded polyurethane composite produced by the method of producing a polyurethane composite according to any of claims 1 to 8 using a pultrusion process for polyurethane.
10. The pultruded polyurethane composite according to claim 9, wherein said pultruded polyurethane composite is produced by reacting a polyurethane composition comprising:
component A comprising one or more polyisocyanates;
component B, comprising:
b1) one or more polyols in an amount of 21 to 60 wt.%, preferably 21 to 40 wt.%, based on the total weight of the polyurethane composition in 100 wt.%;
b2) one or more compounds having the structure of formula (I)
Wherein R1 is selected from hydrogen, methyl or ethyl; r2 is selected from alkylene having 2 to 6 carbon atoms, 2-bis (4-phenylene) -propane, 1, 4-bis (methylene) benzene, 1, 3-bis (methylene) benzene, 1, 2-bis (methylene) benzene; n is an integer selected from 1 to 6; and
and component C, including a free radical initiator.
11. The process as claimed in claim 9 or 10, wherein b2) is present in an amount of from 4.6 to 33% by weight, based on 100% by weight of the total weight of the polyurethane composition.
12. The pultruded composite polyurethane material according to claim 9 or 10, wherein the curing time of the polyurethane composition at 150 to 220 ℃ is 10 to 120 seconds, preferably 20 to 90 seconds.
13. The pultruded composite polyurethane material according to claim 9 or 10, wherein the gel time of the polyurethane composition at room temperature is 15-90 minutes, preferably 20-60 minutes.
14. A polyurethane product comprising the pultruded polyurethane composite of any of claims 1 to 8 produced by the process of producing a polyurethane composite by the pultrusion of polyurethane.
15. The polyurethane product of claim 14, selected from the group consisting of: cable trays, door and window curtain wall frames, ladder frames, tent poles or tubes, antiglare shields, flooring, sucker rods, utility poles and crossarms, guard rails, grilles, architectural profiles, container profiles and panels, bicycle racks, fishing poles, cable cores, insulator mandrels, antenna covers, single or sandwich continuous panels, or fan blade caps.
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| CN201910235171.5A CN111748073A (en) | 2019-03-26 | 2019-03-26 | Method for preparing polyurethane pultrusion composite material |
| US17/439,878 US20220184901A1 (en) | 2019-03-26 | 2020-03-20 | Method for preparing a pultruded polyurethane composite |
| PCT/EP2020/057752 WO2020193396A1 (en) | 2019-03-26 | 2020-03-20 | Method for preparing a pultruded polyurethane composite |
| EP20711207.9A EP3947508A1 (en) | 2019-03-26 | 2020-03-20 | Method for preparing a pultruded polyurethane composite |
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