WO2023284618A1 - Resin composition, polyurethane material, polyurethane composite material, and preparation methods - Google Patents

Abstract

The present invention provides a resin composition comprising an isocyanate component, a reactive component, and a free radical initiator. In the reactive component, the sum of the average number of acrylate double bonds and active hydrogen contained in each molecule is not less than 2.1. The acrylate double bonds are double bonds on acrylic acid groups or on methacrylic acid groups, and can help improve product performance, and effectively reduce the water sensitivity of the resin composition, thereby avoiding, to the greatest extent, a foaming problem in the subsequent production, preparation, and processing process of the composite material. The present invention further provides a polyurethane material, which is prepared from the resin composition, a polyurethane composite material comprising the polyurethane material, and preparation methods for the resin composition, the polyurethane material, and the polyurethane composite material.

Description

Resin composition, polyurethane material, polyurethane composite material and preparation method

cross reference

This application claims the priority of a Chinese patent application with an application date of July 15, 2021, an application number of 2021108009470, and an invention title of "resin composition, polyurethane material, polyurethane composite material and preparation method". The entire content of the Chinese patent application with the application number 2021108009470 and the invention title "resin composition, polyurethane material and polyurethane composite material and preparation method" is incorporated into this application by reference.

technical field

The invention relates to the technical field of polyurethane materials, in particular to a resin composition, a polyurethane material, a polyurethane composite material and a preparation method.

technical background

Traditional polyurethane resins are based on the addition polymerization reaction of isocyanate groups and hydroxyl groups, and cross-linking and curing occur; however, due to the fast reactivity of this type of resin, the operation time is relatively short, and its water sensitivity is relatively high, so it needs to be very strict during use. Humidity control, so it is not suitable for all kinds of composite materials to prepare products. In the preparation process of the new polyurethane composite material, the addition polymerization reaction of isocyanate group and hydroxyl group and free radical polymerization reaction exist at the same time. When the resin composition is in a liquid state, it is used to wet the reinforcing material, such as glass fiber cloth, and the simultaneous addition polymerization reaction and free radical polymerization reaction gradually generate a solid polyurethane matrix, which is fused with the wetted reinforcing material. Integrate to form a polyurethane composite material.

The water sensitivity of the resin composition is critical to the resulting polyurethane composite properties. If the water sensitivity is too high, it is easy to produce foaming reaction with water vapor. During the curing process of the resin, these newly generated air bubbles will remain in the interface between the resin and the composite material. After curing, the final composite product will contain many holes and cause product defects, which will significantly reduce the mechanical properties of the material and deteriorate the product quality. It is difficult to effectively control, which increases the risk of product quality accidents, and will also lead to a decrease in the yield of composite products.

The viscosity of the resin composition is critical to the properties of the resulting polyurethane composite. If the viscosity is too low and easy to flow, the resin composition cannot be effectively absorbed by the glass fiber cloth, and the resin composition will be lost and the glass fiber cloth will lack glue. This phenomenon will leave a lot of pores in the glass fiber cloth, and will The final composite product contains a lot of holes and produces product defects, which is not suitable for hand lay-up, winding and other processes.

Therefore, it is necessary to develop novel resin compositions to solve the above-mentioned problems existing in the prior art.

Summary of the invention

The object of the present invention is to provide a resin composition, a polyurethane material prepared from the resin composition, a polyurethane composite material comprising the polyurethane material, and the resin composition, the polyurethane material and the polyurethane The preparation method of the composite material is to effectively reduce the water sensitivity of the resin composition, further improve product performance, and avoid foaming problems in the subsequent production, preparation and processing of the composite material to the greatest extent.

To achieve the above object, the resin composition of the present invention comprises an isocyanate component, a reactive component and a free radical initiator; the isocyanate component comprises at least one organic isocyanate; in the reactive component: an average of each The molecule contains at least one acrylate double bond, either a double bond on an acrylic group or a methacrylic group, for free radical polymerization under the action of said free radical initiator double bond; each molecule contains at least one active hydrogen to react with the at least one organic isocyanate addition polymerization; the average number of acrylate double bonds and active hydrogen contained in each molecule is not less in 2.1.

The beneficial effect of the resin composition of the present invention is that: in the reactive components, the sum of the number of acrylate double bonds and active hydrogen contained in each molecule on average is not less than 2.1, and the acrylate The double bond is the double bond on the acrylic group or the double bond on the methacrylic group, which not only helps to improve product performance, but also can effectively reduce the water sensitivity of the resin composition, and avoid subsequent composite material production to the greatest extent. Foaming problems occurred during preparation and processing.

Preferably, each molecule of the reactive component contains 1-4 acrylate groups on average, and each of the acrylate groups contains the acrylate double bond. The beneficial effect is that: the addition of the at least one active hydrogen helps to improve product performance, and can effectively reduce the water sensitivity of the resin composition.

Preferably, the reactive component contains 1.1-4.9 hydroxyl groups on average per molecule, and each of the hydroxyl groups contains the active hydrogen. The beneficial effect is that: the combination of the at least one acrylate double bond helps to improve product performance, and can effectively reduce the water sensitivity of the resin composition.

Preferably, the reactive component comprises an ester product obtained by esterification reaction of at least one organic polyol with an acrylic substance, and the at least one organic polyol has an average of at least 2.1 active components per molecule. hydrogen. The beneficial effect is that it helps to improve product performance and can effectively reduce the water sensitivity of the resin composition.

Further preferably, the at least one organic polyol comprises at least one polyether polyol comprising the active hydrogens.

Further preferably, the average functionality of the at least one polyether polyol is 2.1-6, and the hydroxyl value is 25-1100 mg potassium hydroxide/g.

Preferably, based on the mass percentage of the reactive components, the content of the free radical initiator is 0.01%-7%. The beneficial effect is that it helps to improve product performance and can effectively reduce the water sensitivity of the resin composition.

Preferably, a catalyst is also included to accelerate the cross-linking reaction of the carbamate group, and the content of the catalyst is greater than 0 and less than or equal to 5% based on the mass percentage of the reactive component, and the carbamic acid The ester group is obtained by the addition polymerization reaction between the active hydrogen and the at least one organic isocyanate. The beneficial effect is that it helps to improve product performance and can effectively reduce the water sensitivity of the resin composition.

Preferably, several auxiliary agents are also included to facilitate regulation and control of the physical and chemical properties of the polyurethane material prepared by the resin composition.

The polyurethane material of the present invention comprises a polyurethane matrix, and the polyurethane matrix is prepared from the resin composition. Due to the reactive components of the resin composition, the average number of acrylate double bonds contained in each molecule The sum of the number of active hydrogen and the number of active hydrogen is not less than 2.1, and the double bond of the acrylate type is a double bond on the acrylic acid group or a double bond on the methacrylic acid group, which can help improve product performance and effectively reduce the The water sensitivity of the above-mentioned resin composition can be avoided to the greatest extent to avoid foaming problems in the subsequent production, preparation and processing of composite materials.

The preparation method of the polyurethane material of the present invention includes: providing the resin composition, the resin composition includes a reactive component, a free radical initiator and at least one organic isocyanate, and the average amount of the reactive component is Each molecule contains at least one acrylate double bond and at least one active hydrogen; the free radical polymerization reaction of the at least one acrylate double bond is initiated by the free radical initiator, and the at least one active hydrogen is combined with the at least one active hydrogen An organic isocyanate undergoes addition polymerization.

The preparation method of the polyurethane material uses the resin composition as a raw material, because in the reactive components of the resin composition, the average number of acrylate double bonds and active hydrogen contained in each molecule is quite a lot In 2.1, the acrylate double bond is a double bond on an acrylic acid group or a double bond on a methacrylic group, which can help improve product performance and effectively reduce the water sensitivity of the resin composition, Minimize the lack of glue in the subsequent preparation and processing of composite materials, making the finished product prone to foaming problems.

Preferably, the resin composition further includes a catalyst, and the mass percentage of the catalyst in the reactive component is controlled to be greater than 0 and less than or equal to 5%, so as to accelerate the reaction between the active hydrogen and the at least one organic isocyanate. The cross-linking reaction of the carbamate group obtained by the addition polymerization reaction. The beneficial effect is that it can help improve product performance and effectively reduce the water sensitivity of the resin composition.

Preferably, the resin composition further includes additives to regulate the physical and chemical properties of the polyurethane material.

Preferably, the average functionality of the at least one organic isocyanate is 2.0-3.6. The beneficial effect is that it can help improve product performance and effectively reduce the water sensitivity of the resin composition. Preferably, said at least one organic isocyanate has a viscosity measured according to DIN 53019-1-3 at 25° C. of 4-2500 mPa.s. The beneficial effect is that it can help improve product performance and effectively reduce the water sensitivity of the resin composition.

The polyurethane composite material of the present invention comprises a reinforcing material and the polyurethane material. Since the polyurethane material is prepared from the resin composition, in the reactive components of the resin composition, the average number of acrylate double bonds and active hydrogen contained in each molecule is not less than 2.1 , the acrylate double bond is a double bond on an acrylic acid group or a double bond on a methacrylic acid group, which can help improve product performance and effectively reduce the water sensitivity of the resin composition to the greatest extent Avoid foaming problems in the subsequent preparation and processing of composite materials.

Preferably, the reinforcing material accounts for 1-91% by mass of the polyurethane composite material. The beneficial effect is that the mechanical strength can be flexibly adjusted according to the use requirements.

The preparation method of the polyurethane composite material of the present invention uses reinforcing materials and the polyurethane material as raw materials, through vacuum introduction process, pultrusion forming process, winding forming process, resin transfer process, hand lay-up forming process, compression molding process and spray forming Prepared by at least one of the techniques. Since the preparation method of the polyurethane composite material uses the polyurethane material as one of the raw materials, in the reactive components of the resin composition, the sum of the number of acrylate double bonds and active hydrogen contained in each molecule on average is not equal to Less than 2.1, the acrylate double bond is a double bond on the acrylic acid group or a double bond on the methacrylic group, which can help improve product performance and effectively reduce the water sensitivity of the resin composition , to avoid foaming problems in the subsequent production, preparation and processing of composite materials to the greatest extent.

Contents of the invention

In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are part of the embodiments of the present invention, not all of them. the embodiment. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without creative efforts fall within the protection scope of the present invention. Unless otherwise defined, the technical terms or scientific terms used herein shall have the usual meanings understood by those skilled in the art to which the present invention belongs. As used herein, "comprising" and similar words mean that the elements or items appearing before the word include the elements or items listed after the word and their equivalents, without excluding other elements or items.

An embodiment of the present invention provides a resin composition, which includes an isocyanate component, a reactive component and a free radical initiator.

In the embodiment of the present invention, for the specific description of organic polyisocyanates, polyether polyols, polyester polyols, other polyols and active hydrogen-containing oligomers, reference can be made to the second part of "Handbook of Polyurethane Raw Materials and Auxiliaries" Edition, edited by Liu Yijun, 2013, Chapters 1, 2, 3, and 4 of "Chemical Industry Press", the entire content of the above disclosure is incorporated herein by reference.

In an embodiment of the present invention, the isocyanate component includes at least one organic isocyanate.

In some embodiments, the at least one organic isocyanate is at least one of any chain aliphatic isocyanate, alicyclic isocyanate and aromatic isocyanate known to be used in the preparation of polyurethane.

In some specific embodiments, the at least one organic isocyanate is 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate , a mixture of monomeric diphenylmethane diisocyanate and higher homologues of diphenylmethane diisocyanate (abbreviated as polymeric MDI), isophorone diisocyanate (IPDI) or its oligomers, 2,4-toluene Diisocyanate or 2,6-toluene diisocyanate (TDI) or mixtures thereof; tetramethylene diisocyanate or its oligomers; pentamethylene diisocyanate or its oligomers; hexamethylene diisocyanate (HDI) or its oligomers; 4,4'-dicyclohexylmethane diisocyanate (HMDI), methylcyclohexyl diisocyanate (HTDI), 1,5-naphthyl diisocyanate (NDI) or mixtures thereof, p-phenylene diisocyanate (PPDI), p-xylylene diisocyanate (XDI), tetramethyl dimethylene diisocyanate (TMXDI) and their multimers or combinations thereof.

In some embodiments, at least one of the at least one organic isocyanate exists in the form of a polyisocyanate prepolymer, and the polyisocyanate prepolymer is an isocyanate dimer, trimer, tetramer, and pentamer any kind of body.

In some specific embodiments, the NCO weight percentage of the polyisocyanate prepolymer is 10-48%. In other specific embodiments, the NCO weight percentage of the polyisocyanate prepolymer is any one of 16-38% and 19-33%.

In some specific embodiments, the at least one organic isocyanate is diphenylmethane diisocyanate (MDI), polyphenylmethane polyisocyanate (PMDI), and their multimers, prepolymers or combinations thereof.

In some embodiments, the at least one organic isocyanate has an average functionality of 2.0-3.6. In some other embodiments, the average functionality of the at least one organic isocyanate is 2.1-2.8.

In some embodiments, the viscosity of the at least one organic isocyanate measured according to DIN53019-1-3 at 25° C. is 4-2500 mPa.s.

In some embodiments, the at least one organic isocyanate has a viscosity measured according to DIN53019-1-3 at 25° C. in any one of 5-800 mPa.s and 10-300 mPa.s.

In an embodiment of the present invention, each molecule of the reactive component contains at least one acrylate double bond and at least one active hydrogen, and the average number of acrylate double bonds and active hydrogen contained in each molecule is the sum of Not less than 2.1.

Specifically, the at least one acrylate double bond undergoes a radical polymerization reaction under the action of the radical initiator, and the at least one active hydrogen undergoes an addition polymerization reaction with the at least one organic isocyanate.

In some embodiments, the acrylate double bond is a double bond on an acrylic group or a double bond on a methacrylic group.

In some embodiments, the reactive component comprises 1-4 acrylate groups per molecule on average, each of the acrylate groups comprising the acrylate double bond.

In some embodiments, the number of acrylate groups contained in each molecule of the reactive component is any one of 1.05-3, 1.1-2.5, 1.15-2.4 and 1.2-2.3.

In some embodiments, the reactive component comprises, on average, 1.1-4.9 hydroxyl groups per molecule, each of the hydroxyl groups comprising the active hydrogen.

In some embodiments, the number of hydroxyl groups contained in each molecule of the reactive component is any one of 1.2-4, 1.25-3.5, 1.3-3, 1.35-2.6, 1.4-2.5 and 1.5-2.4 kind.

In some embodiments, the reactive component is an ester product obtained through an esterification reaction of at least one organic polyol and an acrylic substance, and the at least one organic polyol has an average of at least 2.1 the active hydrogen.

In some embodiments, the acrylic substance is acrylic anhydride, methacrylic anhydride, acryloyl chloride, methacryloyl chloride, acryloyl bromide, methacryloyl bromide, acrylic acid, methacrylic acid, methyl acrylate, methacrylic acid Methyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, butyl acrylate, butyl methacrylate, tert-butyl acrylate and At least one kind of tert-butyl methacrylate.

In some embodiments, said at least one organic polyol comprises at least one polyether polyol comprising said active hydrogen.

In some embodiments, the at least one organic polyol is at least one of polyether polyol, polyether carbonate polyol, polyester polyol, polycarbonate diol, polymer polyol, and vegetable oil-based polyol .

In some embodiments, the at least one organic polyol is polyoxypropylene diol, polyether triol, polyether tetraol, polyether pentaol, polyurea polyol, polytetrahydrofuran diol, adipate polyester At least one of diol, aromatic polyester polyol, polycaprolactone polyol, polycarbonate diol, polyacrylate polyol, and polyolefin polyol.

In some embodiments, the average functionality of the at least one polyether polyol is 2.1-6, and the hydroxyl value is 25-1100 mg potassium hydroxide/g.

In some embodiments, the average functionality of the at least one polyether polyol is 2.5-5, and the hydroxyl value is 35-800 mg potassium hydroxide/g.

In some embodiments, the average functionality of the at least one polyether polyol is 2.7-4.6, and the hydroxyl value is 50-660 mg potassium hydroxide/g.

In some embodiments, the average functionality of the at least one polyether polyol is 2.8-4.4, and the hydroxyl number is 80-630 mg potassium hydroxide/g.

In some embodiments, the average functionality of the at least one polyether polyol is 3.0-4.3, and the hydroxyl value is 100-600 mg potassium hydroxide/g.

In some embodiments, the average functionality of the at least one polyether polyol is 3.1-4.2, and the hydroxyl number is 110-570 mg potassium hydroxide/g.

In some embodiments, the reactive component is obtained by esterifying at least one organic polyol with at least one acrylic or methacrylic group.

In some embodiments, the reactive component is obtained by esterifying at least one organic polyol with at least one acrylic anhydride or methacrylic anhydride.

In some embodiments, the reactive component is obtained by esterifying at least one organic polyol with at least one acryloyl halide or methacryloyl halide.

Specifically, the acryloyl halide is any one of acryloyl chloride and acryloyl bromide.

Specifically, the methacryloyl halide is any one of methacryloyl chloride and methacryloyl bromide.

In some embodiments, the reactive component is obtained by esterifying at least one organic polyol with at least one acrylic acid or methacrylic acid under catalyst conditions.

In some embodiments, the reactive component is obtained by transesterifying at least one organic polyol with at least one methacrylate or acrylate under catalyst conditions.

Specifically, the acrylate is any one of methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate and tert-butyl acrylate.

Specifically, the methacrylate is any one of methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate and tert-butyl methacrylate.

The esterification reaction of at least one organic polyhydric alcohol with acrylic anhydride or methacrylic anhydride, the esterification reaction with acryloyl halide or methacryloyl halide, the esterification reaction with acrylic acid or methacrylic acid, and the For the transesterification reaction of acrylate or methacrylate, those skilled in the art are familiar with the specific operation methods of these reactions. Some esterification methods can refer to the records in CN101983959B or CN101475502B.

In some embodiments, based on the mass percentage of the reactive component, the content of the free radical initiator is 0.01%-7%.

In some embodiments, the free radical initiator is a free radical initiator capable of initiating curing of the double bond-containing compound.

In some embodiments, the free radical initiator is added to at least one of the at least one organic isocyanate and the reactive component.

In some embodiments, the free radical initiator is any one of peroxide, persulfide, peroxycarbonate, peroxyboric acid and azo compound.

In some specific embodiments, the free radical initiator is tert-butyl isopropyl carbonate, tert-butyl peroxy-3,5,5-trimethylhexanoate, methyl ethyl ketone peroxide, cumene peroxide Hydrogen peroxide, persulfate, azobisisobutyronitrile, azobisisoheptanonitrile, dimethyl azobisisobutyrate, benzoyl peroxide, benzoyl tert-butyl peroxide and hydrogen peroxide at least one of .

In some embodiments, the resin composition further includes a catalyst to accelerate the crosslinking reaction of the carbamate group, and the content of the catalyst is greater than 0 and less than or equal to 5%, the urethane group is obtained by the addition polymerization of the active hydrogen and the at least one organic isocyanate.

In some embodiments, the mass percentage of the catalyst in the reactive component is 0.001-2%.

In some specific embodiments, the catalyst is 2,3-dimethyl-3,4,5,6-tetrahydropyrimidine, triethylamine, tributylamine, triethylenediamine, dimethylbenzylamine, N-methylmorpholine, N-ethylmorpholine, N-cyclohexylmorpholine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethyl butyldiamine, N,N,N',N'-tetramethylhexamethylenediamine, pentamethyldiethylenetriamine, tetramethyldiaminoethylether, bis(dimethylaminopropyl)urea, Any of dimethylpiperazine, 1,2-dimethylimidazole, and 1-azabicyclo(3,3,0)octane.

In some embodiments, the catalyst is 1,4-diazabicyclo(2,2,2)octane, triethanolamine, triisopropanolamine, N-methyldiethanolamine, N-ethyldiethanolamine and Any one of dimethylethanolamine.

In some embodiments, the catalyst is an organometallic compound. In some other embodiments, the catalyst consists of the organometallic compound and a strongly basic amine.

In some specific embodiments, the organometallic compound is tin(II) acetate, tin(II) octoate, tin(II) ethylhexanoate, tin(II) laurate, dibutyltin diacetate, dilaurate dilaurate Any of butyltin, dibutyltin maleate, and dioctyltin diacetate.

In some specific embodiments, the organometallic compound is bismuth (III) neodecanoate, bismuth 2-ethylhexanoate, bismuth octoate or mixtures thereof.

In some embodiments, the resin composition also includes several additives to facilitate regulation and control of the physical and chemical properties of the polyurethane material prepared by the resin composition, the physical and chemical properties include viscosity, degree of crosslinking, waterproof performance, flame retardant At least one of performance, anti-smoke performance, anti-staining performance, antistatic performance, anti-oxidation performance, ultraviolet stability performance, leveling performance and adsorption performance.

In some specific embodiments, the several auxiliary agents are fillers, internal release agents, flame retardants, smoke suppressants, dyes, pigments, antistatic agents, antioxidants, UV stabilizers, diluents, defoamers , coupling agent, surface wetting agent, leveling agent, water remover, catalyst, molecular sieve, thixotropic agent, plasticizer and free radical reaction inhibitor.

In some specific embodiments, the filler is aluminum hydroxide, bentonite, fly ash, wollastonite, perlite powder, floating beads, calcium carbonate, talcum powder, mica powder, china clay, fumed silica, expandable Microspheres, diatomaceous earth, volcanic ash, barium sulfate, calcium sulfate, solid and/or hollow glass microspheres, stone powder, wood flour, wood chips, bamboo powder, bamboo chips, rice grains, straw chips, coffee grounds, sorghum stalks At least one of scrap, graphite powder, metal powder, recycled thermosetting composite powder, plastic granules or powder.

For specific descriptions of catalysts, flame retardants, mold release agents, anti-aging additives and stabilizers, coupling agents, fillers, and reinforcing materials in the embodiments of the present invention, you can also refer to the "Handbook of Polyurethane Raw Materials and Auxiliaries" The second edition, edited by Liu Yijun, 2013, Chapters 6, 7, 8, 9, 11, and 12 of "Chemical Industry Press", the entire content of the above disclosure is incorporated into this article by reference.

The embodiment of the present invention also provides a polyurethane material, the polyurethane material includes a polyurethane matrix, the polyurethane matrix is prepared from the resin composition, because in the reactive components of the resin composition, the average The sum of the number of acrylate double bonds and active hydrogen contained is not less than 2.1, and the acrylate double bonds are double bonds on acrylic acid groups or double bonds on methacrylic acid groups, which can help to improve The product performance is improved, and the water sensitivity of the resin composition is effectively reduced, so as to avoid foaming problems in the production, preparation and processing of subsequent composite materials to the greatest extent.

The embodiment of the present invention also provides that the preparation method of the polyurethane material includes: providing the resin composition, the resin composition includes a reactive component, a free radical initiator and at least one organic isocyanate, and the reactive component On average, each molecule of the fraction contains at least one acrylate double bond and at least one active hydrogen; the free radical polymerization reaction of the at least one acrylate double bond is initiated by the free radical initiator, and the at least one active hydrogen Addition polymerization takes place with the at least one organic isocyanate.

The preparation method of the polyurethane material uses the resin composition as a raw material, because in the reactive components of the resin composition, the average number of acrylate double bonds and active hydrogen contained in each molecule is quite a lot In 2.1, the acrylate double bond is a double bond on an acrylic acid group or a double bond on a methacrylic group, which can help improve product performance and effectively reduce the water sensitivity of the resin composition, To avoid foaming problems in the subsequent production, preparation and processing of composite materials to the greatest extent.

In some embodiments, the mass percentage of the catalyst in the reactive component is controlled to be greater than 0 and less than or equal to 5%, so as to accelerate the addition polymerization reaction of the active hydrogen and the at least one organic isocyanate to obtain The crosslinking reaction of the carbamate group.

In some embodiments, the additive regulates the physical and chemical properties of the polyurethane material, and the physical and chemical properties include viscosity, degree of crosslinking, waterproof performance, flame retardant performance, smoke-proof performance, anti-dyeing performance, antistatic performance, oxidation resistance At least one of performance, UV stability performance, leveling performance and adsorption performance.

The embodiment of the invention also provides the polyurethane composite material and its preparation method.

The polyurethane composite material of the embodiment of the present invention includes a reinforcing material and the polyurethane material. Since the polyurethane material is prepared from the resin composition, in the reactive components of the resin composition, the average number of acrylate double bonds and active hydrogen contained in each molecule is not less than 2.1 , the acrylate double bond is a double bond on an acrylic acid group or a double bond on a methacrylic acid group, which can help improve product performance and effectively reduce the water sensitivity of the resin composition to the greatest extent Avoid foaming problems in the subsequent preparation and processing of composite materials.

In some embodiments, the mass percentage of the reinforcing material in the polyurethane composite material is any one of 1-91%, 15-90%, 35-85%, 45-83% and 50-81%.

In some embodiments, the reinforcing material includes glass fiber, carbon fiber, carbon nanotube, polyester fiber, aramid fiber, nylon fiber, natural fiber, basalt fiber, silicon carbide fiber, boron fiber, asbestos fiber, whisker , at least one of hard particles and metal fibers.

In some embodiments, polyurethane addition polymerization, that is, addition polymerization of isocyanate groups and hydroxyl groups, and free radical polymerization occur simultaneously. When the resin composition is in a liquid state, it is used to wet the reinforcing material, and the simultaneous addition polymerization reaction and free radical polymerization reaction gradually generate the solid polyurethane matrix, and the wetted reinforcing material integrated to form the polyurethane composite.

The preparation method of the polyurethane composite material in the embodiment of the present invention uses the reinforcing material and the polyurethane material as raw materials, through vacuum introduction process, pultrusion forming process, winding forming process, resin transfer process, hand lay-up forming process, compression molding process and Prepared by at least one of the injection molding processes. Since the preparation method of the polyurethane composite material uses the polyurethane material as one of the raw materials, in the reactive components of the resin composition, the sum of the number of acrylate double bonds and active hydrogen contained in each molecule on average is not equal to Less than 2.1, the acrylate double bond is a double bond on the acrylic acid group or a double bond on the methacrylic group, which can help improve product performance and effectively reduce the water sensitivity of the resin composition , to avoid foaming problems in the subsequent production, preparation and processing of composite materials to the greatest extent.

The above-mentioned vacuum introduction process, pultrusion forming process, winding forming process, resin transfer process, hand lay-up process, compression molding process and spray forming process are all conventional technical means for those skilled in the art.

The technical solutions of the embodiments of the present invention will be described in detail below through specific examples.

Resin tensile properties of specific examples were determined according to ISO 527-2.

The tensile properties of the polyurethane composites of the specific examples were determined according to ISO 527-5.

The raw materials used in specific embodiments are as follows:

Isocyanate components: isocyanate PM200 and isocyanate WANNATE MDI-50;

The raw materials for preparing the reactive components are polyether polyol P1, polyether polyol P2, polyether polyol P3 and polyether polyol P4. in:

Polyether polyol P1 is a trifunctional polyol prepared with glycerin as the initiator and propylene oxide as the main body of the polymerization reaction, with a hydroxyl value of 235 mg KOH/g;

Polyether polyol P2 is a trifunctional polyol prepared with glycerin as the initiator and propylene oxide as the main body of the polymerization reaction, with a hydroxyl value of 330 mgKOH/g;

Polyether polyol P3 is a tetrafunctional polyol prepared by using pentaerythritol as the initiator and propylene oxide as the main body of the polymerization reaction, with a hydroxyl value of 450mgKOH/g;

Polyether polyol P4 is a six-functional polyol prepared with sorbitol as the initiator and propylene oxide as the main body of the polymerization reaction, with a hydroxyl value of 430 mgKOH/g;

Free radical initiators: benzoyl peroxide (PERKADOX CH-50L) and methyl ethyl ketone peroxide (Butanox M-50), purchased from Nouryon.

The additives are 5A molecular sieve activated powder and defoamer BYKA560. The 5A molecular sieve activated powder is purchased from Xintao Technology, and the defoamer is purchased from BYK Chemicals.

In some embodiments, at least one organic polyol and the acrylic substance are subjected to an esterification reaction in an organic solvent under the action of a catalyst until no more water is produced in the esterification reaction. The temperature of the esterification reaction is 60-140 degrees Celsius.

Specifically, in parts by mass, the at least one organic polyol is 30-100 parts, the acrylic substance is 3-35 parts, the solvent is 3-55 parts, the catalyst is 0.05-1 part, and the polymerization inhibitor is 0.03-0.5 parts.

In some embodiments, the acrylic substance is mixed with at least one organic polyol, a solvent, a catalyst, etc. under the condition of ice bath and stirring, and then the esterification reaction is carried out under ice bath for 3-8 hours.

Specifically, in terms of parts by mass, the at least one organic polyol is 60-90 parts, the acrylic substance is 20-60 parts, the solvent is 200-500 parts, the auxiliary agent is 30-150 parts, and the polymerization inhibition The quality of the agent is 0.03-0.45 parts.

Embodiments provide several reactive components, and the reactive components used in different embodiments are combined from at least one of the several reactive components.

In some specific examples, each reactive component among the several reactive components is abbreviated as B-P1-1, B-P1-2, B-P2-1, B-P2-2, B -P3-1 and B-P4-1.

Each molecule of B-P1-1 contains 2 methacrylates and 1 hydroxyl group. The preparation method is as follows: polyether polyol P1 and hydroquinone, the masses are 71.6g and 0.1g respectively, and hydroquinone is used as Inhibitor; methacrylic acid is an acrylic substance with a mass of 20.7g; 30g of cyclohexane is a solvent with a mass of 30g; p-toluenesulfonic acid is a catalyst with a mass of 0.8g; the above mixture is reacted at 80°C until water separation When the water in the vessel is no longer produced, the reaction is finished, and the solvent is removed by vacuum rotation, and the resulting mixture can be purified to obtain the product B-P1-1.

Each molecular structure of B-P1-2 contains 1 methacrylate and 2 hydroxyl groups. The preparation method is as follows: polyether polyol P1 is 71.6g, methacrylic acid is 10.3g, 15g cyclohexane, 0.4g P-toluenesulfonic acid and 0.08g of hydroquinone are mixed and reacted at 80°C until water in the water separator no longer occurs, then the reaction is completed, the solvent is removed by vacuum rotation, and the obtained mixture is purified to obtain the product B-P1-2.

Each molecular structure of B-P2-1 contains 2 acrylates and 1 hydroxyl group. The preparation method is as follows: 51g of polyether polyol P2, 17.3g of acrylic acid, 22g of cyclohexane, 0.8g of p-toluenesulfonic acid and 0.1g of hydroquinone was reacted at 80°C until the water in the water separator was no longer produced, then the reaction was completed, the solvent was removed by vacuum rotation, and the obtained mixture was purified to obtain the product B-P2-1.

Each molecular structure of B-P2-2 contains 1 acrylate and 2 hydroxyl groups. The preparation method is as follows: 51g of polyether polyol P2, 8.7g of acrylic acid, 11g of cyclohexane, 0.4g of p-toluenesulfonic acid and 0.08g of hydroquinone is reacted at 80°C until the water in the water separator is no longer produced, then the reaction is complete, the solvent is removed by vacuum rotation, and the obtained mixture is purified to obtain the product B-P2-2.

Each molecular structure of B-P3-1 contains 2 acrylates and 2 hydroxyl groups. The preparation method is as follows: 50g of polyether polyol P3, 17.3g of acrylic acid, 22g of cyclohexane, 0.8g of p-toluenesulfonic acid and 0.1g of hydroquinone is reacted at 80°C until the water in the water separator no longer produces, then the reaction is completed, the solvent is removed by vacuum rotation, and the obtained mixture is purified to obtain the product B-P3-1.

Each molecular structure of B-P4-1 contains 5 acrylates and 1 hydroxyl group. The preparation method is as follows: slowly add 42.5ml of acryloyl chloride dropwise to 78.3 g polyether polyol P4, 0.2 g of hydroquinone and 100 g of triethylamine in dichloromethane 350 ml solution, the dropwise addition was completed in 60 minutes, and triethylamine was used as an auxiliary agent. The reaction was continued for another 5 hours under ice-bath conditions. Stop stirring and let stand overnight. After standing overnight, the reaction was terminated, and unreacted products and other impurities were removed by washing successively with water, 1M hydrochloric acid, and 1M NaOH solution. The solvent was spun off in vacuo, and the resulting mixture was purified to obtain the product B-P4-1.

The test methods for which specific conditions are not indicated in the following examples are generally in accordance with conventional conditions, or in accordance with the conditions suggested by the manufacturer. All percentages and parts are by weight unless otherwise indicated.

Example 1-5

First, put the mold of the casting body in an oven at 150°C to keep the temperature constant, then prepare the components listed in Table 1 into a resin mixed liquid in proportion, and after uniform mixing, quickly pour the resin liquid into the mold, and heat it at 150°C Leave on for 25 minutes. Then the heating of the oven was stopped to lower the temperature slowly, and after cooling to room temperature, the cured sample could be taken out to obtain the thermosetting polyurethane resin matrix of Comparative Examples 1-4 and Examples 1-5. The specific test results are shown in Table 1.

Table 1

It can be seen from the data analysis of comparative examples 1-4 and examples 1-5 in the above table 1 that the introduction of reactive components containing (meth)acrylate and hydroxyl functional groups can not only make the gel time Significantly extended, can also further improve the mechanical properties of the cured resin. The long gel time is beneficial to the production needs of the composite material industry. For example, in the pultrusion production process, when the equipment fails and needs to be shut down for repairs, if the gel time is not long enough, the injection box and the mold will usually be blocked by the cured resin, resulting in a blocked production accident. At this time, it is necessary to disassemble the injection box and mold for cleaning. Not only waste time, reduce production efficiency, but also generate a lot of glass fiber and resin solid waste. Another example is that when large-scale products such as blades and yachts are prepared by the vacuum introduction process, it takes a long time for resin introduction. If the gel time is less than 150 minutes, it is far from enough. Therefore, the comparative examples 1-3 based on the traditional polyurethane system do not meet the requirements of many kinds of composite material production processes. Comparative Example 4 shows that even with the addition of partially reactive component (B), the requirements are not met. However, Examples 1-5 show that the gel time is significantly prolonged, all above 200 minutes, far higher than the requirement of 150 minutes, so it can better adapt to the time operation requirements of many composite material production processes; and its mechanical properties be greatly improved. The improvement of mechanical properties helps to further reduce the weight of the composite material based on this thermosetting resin on the premise of meeting the requirements of actual use, so that it can meet the requirements of lighter weight. In Example 5, the shrinkage rate of the resin after curing was too large, resulting in brittleness and cracking of the resin plate sample, and a satisfactory test sample could not be obtained. The reason is that the content of acrylate is too high, resulting in too high free radical polymerization crosslinking density of active double bonds, so that the cured resin shrinkage rate is too large and internal cracking occurs. Therefore, although the use of the reactive component (B) will bring advantages such as long gel time and excellent mechanical properties, the average number of (meth)acrylate functional groups in its molecular structure should have a preferred range; If it is low, the gel time and mechanical properties cannot be significantly prolonged, but if it is too high, adverse effects such as shrinkage and cracking will occur.

Example 6

According to the ratio in Table 2, polyol, isocyanate component (A), reactive component (B), free radical initiator (C) and other additives are made into resin mixed liquid, and stirred under vacuum condition Breathe for 5 minutes. Then put the resin mixed liquid into the casting body mold that has been kept in a constant temperature oven at 35°C, and keep the constant temperature for 2 hours, then raise the temperature of the oven to 80°C and keep it for 4 hours, and then turn off the heating. After cooling to room temperature, the cured sample can be taken out to obtain the thermosetting polyurethane resin matrix of Comparative Example 5 and Example 6. The specific test results are shown in Table 2.

Table 2

From the comparison of the data of Comparative Example 5 and Example 6 listed in Table 2 above, it shows that the introduction of the reactive component (B) can significantly improve the gel time and mechanical properties of the resin. By comparing Example 5 and Example 6, it is shown that the thermosetting polyurethane resin matrix introduced with the reactive component (B) has better comprehensive properties than ordinary polyurethane resins.

Example 7

The polyurethane composite material in this embodiment, the resin is based on the polyurethane compositions of comparative example 6, comparative example 7 and embodiment 7 in table 3, prepared by hand lay-up process in the laboratory, to be used to compare the process of its actual operation properties and observe its cured effect including composite quality.

The operation is carried out on glass plates: place four layers of uniaxial glass fiber cloth (Hengshi, E61200, UD, ~1200g/m2) on the upper surfaces of three glass plates sprayed with release agent respectively, at 25°C and 50% Place in a relative humidity environment for 24 hours for temperature and humidity balance. According to the components and proportions in Table 3, after preparing the three types of resins, slowly pour them on the upper surface of their respective glass fiber cloths, so that the liquid resins naturally penetrate into the glass fiber cloths from top to bottom, and wait for 6 minutes to fully absorb them. Soak the glass fiber, then cover the upper surface of the glass fiber cloth with a layer of transparent plastic film, and then use a hand lay-up roller to squeeze out all the air in the soaked glass fiber cloth. (During the actual operation, it was found that because the viscosity of the resin in Comparative Example 7 was too low, it was easy to flow, and the resin could not be effectively absorbed by the glass fiber cloth, resulting in resin loss and the lack of glue in the glass fiber cloth. The fiber cloth leaves a lot of pores, and after curing, the final composite product will contain many holes and cause product defects; while the resins in Comparative Example 6 and Example 7 have moderate viscosity and can be effectively absorbed by the glass fiber cloth without producing Lack of glue. If the viscosity of the resin is too low, it is not suitable for hand lay-up, winding and other processes, because problems such as dripping and lack of glue will occur. This is also the consensus of the composite material industry, and Comparative Example 7 also verifies this A little.) Then put the whole in an oven at 80°C and cure for 3 hours. Stop the oven heating, let the temperature drop to room temperature slowly, and then take out three cured composite sheets respectively. After observation, the sheet quality based on comparative example 6 resin-impregnated glass fiber cloth is unqualified, because the foaming problem is very serious, indicating that its water sensitivity is high; the sheet quality based on comparative example 7 resin-impregnated glass fiber cloth is not up to standard Qualified, because although its foaming problem has declined to some extent, it is still obvious, indicating that although the components are adjusted in Comparative Example 7, the water-sensitive foaming problem cannot be completely avoided; The sheets of cloth are of good quality, uniform and complete, and there is no foaming problem. The experimental results are listed in Table 3. The tensile modulus and tensile strength are the modulus and strength measured in the 90° direction, which mainly reflect the resin strength and the bonding strength of the resin and fiber interface.

table 3

From the comparison of the data of comparative example 6, comparative example 7 and embodiment 7 listed in the above table 3, it is shown that the introduction of reactive component (B) can significantly reduce the water sensitivity of the resin, under 50% humidity It can even be applied to the hand lay-up process to prepare composite products. Based on the mechanical property test of the composite material, it can also be seen that due to the high water sensitivity of Comparative Example 6 and Comparative Example 7, the sheet contains many bubbles, which significantly reduces the mechanical properties of the sheet. Through a comprehensive comparison of Comparative Example 6, Comparative Example 7 and Example 7, it is shown that the thermosetting polyurethane resin matrix introduced with reactive component (B) has better operability in composite material technology than ordinary polyurethane resin and other modified Polyurethane can be used to prepare hand lay-up products.

Example 8

The polyurethane composite material of this example is based on the polyurethane resin compositions of Comparative Example 5 and Example 6 in Table 2, respectively, and the composite product is prepared through a vacuum introduction process, and its properties are tested. (the composite material of comparative example 8 uses the resin of comparative example 5; the composite material of embodiment 8 uses the resin of embodiment 6)

The operation is carried out on the glass plate: place the Hengshi uniaxial glass fiber cloth (E61200, UD, ~1200g/m2) on the upper surface of the glass plate sprayed with the release agent, and then put the release cloth and the flow guide on it in turn. Netting and vacuum bags. The front position of this device is connected to the vacuum, and the rear position is connected to the liquid resin through the guide tube. After all these are set up, bend and block the tube of the guide tube, then put the whole device into an oven heated to 60°C, connect the tube connected to the vacuum to the vacuum pump, and heat and dehumidify under vacuum for 2 hours , in order to remove the moisture on auxiliary materials such as glass fiber and guide net as much as possible, and then turn off the oven to heat, so that the whole device will naturally drop to room temperature while maintaining a vacuum state.

Then mix the isocyanate component (A), reactive component (B), free radical starter (C) and other additives according to the proportioning in Table 2, and stir and degas under vacuum for 6 minutes, immediately This resin mixed liquid is introduced into the glass fiber cloth of the above-mentioned device under vacuum condition. After the glass fiber cloth is fully soaked, bend the guide tube and the tube connected to the vacuum to block, so that the whole system soaked by all the liquid resin is still kept in a vacuum state; then start to gradually increase the temperature within 1 hour. 80°C, then keep at 80°C for 2 hours, accelerate the curing of the resin by heating at a high temperature, then turn off the heating, and cool down to room temperature naturally, then demould the cured product to obtain a polyurethane composite material reinforced with glass fiber cloth. The performance parameters of the obtained polyurethane composite materials are shown in Table 4.

The properties of the polyurethane composite material of the present invention are shown in Table 4. The tensile modulus and tensile strength shown in Table 4 are the modulus and strength measured under the tensile condition of 0° direction.

Table 4

By comparing the mechanical properties of Comparative Example 8 and Example 8 listed in Table 4, it is shown that the composite material prepared by introducing the thermosetting polyurethane resin matrix after the reactive component (B) has better mechanical properties than the existing common polyurethane Composite materials made of resin. The above results show that the thermosetting polyurethane resin matrix containing the reactive component (B) is suitable for the composite material process and prepares qualified composite products.

Example 9 and Example 10

In order to further verify that the introduction of the reactive component (B) helps to significantly reduce the water sensitivity of the thermosetting polyurethane resin composition and is superior to other types of modified polyurethane resins, we made some adjustments to the vacuum introduction process. Compared with Example 8, the process of vacuum heating and dehumidification was directly skipped to verify the sensitivity of several resins to water vapor.

The operation is carried out on the glass plate: place the Hengshi uniaxial glass fiber cloth (E61200, UD, ~1200g/m2) on the upper surface of the glass plate sprayed with the release agent, and then put the release cloth and the flow guide on it in turn. Netting and vacuum bags. The front position of this device is connected to the vacuum, and the rear position is connected to the liquid resin through the guide tube. After all these are set, the tube of the draft tube is bent and blocked, and then the tube connected to the vacuum is connected to the vacuum pump, so that the whole setup is kept in a vacuum state.

Then immediately mix the isocyanate component (A), reactive component (B), free radical initiator (C) and other additives according to the ratio in Table 5, and stir and degas under vacuum for 6 minutes. Next, the resin mixed liquid is introduced into the glass fiber cloth of the above-mentioned device under vacuum condition. After the glass fiber cloth is fully soaked, bend the guide tube and the tube connected to the vacuum to block, so that the whole system soaked by all the liquid resin is still kept in a vacuum state; then start to gradually increase the temperature within 1 hour. 80°C, then keep at 80°C for 2 hours, accelerate the curing of the resin by heating at high temperature, and then turn off the heat. After naturally cooling down to room temperature, the cured product is demolded to obtain a polyurethane composite material reinforced with glass fiber cloth. It can be observed that the composite board of Comparative Example 9 still has a small amount of bubbles, and the glass fiber has white silk phenomenon; this is caused by the resin being sensitive to water vapor. And embodiment 9 and 10 do not have this kind of bubble and white silk phenomenon, illustrate that corresponding resin has effectively overcome the problem of water sensitivity under this condition. The specific results and test data are shown in Table 5 below. Tensile modulus and tensile strength are the modulus and strength measured in the 90° direction.

table 5

By comprehensively comparing the curing effect and mechanical property data of Comparative Example 9 and Examples 9 and 10 listed in Table 5, it is shown that the water sensitivity of the thermosetting polyurethane resin after introducing the reactive component (B) is better than that of other methods Improved polyurethane resin, and its mechanical properties are also superior to composite materials prepared by other improved polyurethane resins. The above results show that this thermosetting polyurethane resin matrix containing reactive component (B) is suitable for the composite process and can be used to prepare qualified composite products.

Although the embodiments of the present invention have been described in detail above, it will be apparent to those skilled in the art that various modifications and changes can be made to the embodiments. However, it should be understood that such modifications and changes are within the scope and spirit of the present invention described in the claims. Furthermore, the invention described herein is capable of other embodiments and of being practiced or carried out in various ways.

Claims (17)

1. A resin composition, characterized in that, comprising an isocyanate component, a reactive component and a free radical initiator;

   The isocyanate component comprises at least one organic isocyanate;

   Among the reactive components:

   On average, each molecule contains at least one acrylate double bond, which is a double bond on an acrylic group or a methacrylic acid group, for free-radical polymerization to occur under the action of said free-radical initiator the double bond on the group;

   comprising on average at least one active hydrogen per molecule for addition polymerization with said at least one organic isocyanate;

   The average sum of the number of acrylate double bonds and active hydrogen contained in each molecule is not less than 2.1.
2. The resin composition according to claim 1, wherein the reactive component comprises 1-4 acrylate groups per molecule on average, and each of the acrylate groups comprises the acrylic acid ester double bond.
3. The resin composition according to claim 1, wherein the reactive component contains 1.1-4.9 hydroxyl groups on average per molecule, and each of the hydroxyl groups contains the active hydrogen.
4. The resin composition according to claim 1, wherein the reactive component comprises an ester product obtained by esterification reaction of at least one organic polyol and an acrylic substance, and the at least one organic polyol has an average of at least 2.1 of said active hydrogens per molecule.
5. The resin composition according to claim 4, wherein said at least one organic polyol comprises at least one polyether polyol comprising said active hydrogen.
6. The resin composition according to claim 5, characterized in that, the average functionality of the at least one polyether polyol is 2.1-6, and the hydroxyl value is 25-1100 mg potassium hydroxide/g.
7. The resin composition according to claim 1, characterized in that, based on the mass percentage of the reactive components, the content of the free radical initiator is 0.01%-7%.
8. Resin composition according to claim 1, is characterized in that, also comprises catalyst, to accelerate the cross-linking reaction that generates carbamate group, accounts for the mass percent of described reactive component, and the mass percent of described catalyst The content is greater than 0 and less than or equal to 5%, and the urethane group is obtained by the addition polymerization reaction of the active hydrogen and the at least one organic isocyanate.
9. The resin composition according to claim 1, characterized in that, it also comprises several auxiliary agents to facilitate the regulation and control of the physical and chemical properties of the polyurethane material prepared by the resin composition.
10. The resin composition according to claim 1, wherein the average functionality of the at least one organic isocyanate is 2.0-3.6.
11. The resin composition according to claim 1, characterized in that the at least one organic isocyanate has a viscosity of 4-2500 mPa.s at 25° C. as measured according to DIN 53019-1-3.
12. A polyurethane material, characterized in that it comprises a polyurethane matrix prepared from the resin composition according to any one of claims 1-11.
13. A method for preparing a polyurethane material, characterized in that it comprises:

    Resin composition as described in any one of claim 1-11 is provided, and described resin composition comprises reactive component, radical initiator and at least one organic isocyanate, and the average of each of described reactive component The molecule contains at least one acrylate double bond and at least one active hydrogen;

    The free radical polymerization reaction of the at least one acrylate double bond is initiated by the free radical initiator, and the at least one active hydrogen undergoes an addition polymerization reaction with the at least one organic isocyanate.
14. The method for preparing a polyurethane material according to claim 13, wherein the resin composition further comprises a catalyst, and the mass percentage of the catalyst in the reactive component is controlled to be greater than 0 and less than or equal to 5%, so as to accelerate the process by The active hydrogen reacts with the at least one organic isocyanate to undergo a cross-linking reaction of urethane groups obtained by the addition polymerization reaction.
15. A polyurethane composite material, characterized in that it comprises a reinforcing material and the polyurethane material according to claim 12.
16. The polyurethane composite material according to claim 15, characterized in that the reinforcing material accounts for 1-91% by mass of the polyurethane composite material.
17. A method for preparing a polyurethane composite material, characterized in that, using the reinforcing material and the polyurethane material described in claim 12 as raw materials, through a vacuum introduction process, a pultrusion process, a winding process, a resin transfer process, a hand lay-up process, It is prepared by at least one of a compression molding process and an injection molding process.