Resin composition for preparing thermoplastic polymer matrix

Abstract

The invention relates to a resin composition for preparing a thermoplastic polymer matrix, the thermoplastic polymer matrix prepared from the resin composition, a thermoplastic composite material containing the thermoplastic polymer matrix, a preparation method and application of the thermoplastic composite material, a mechanical or structured part or product containing the thermoplastic composite material and application of the mechanical or structured part or product. The resin composition comprises polyisocyanate of which the isocyanate group functionality is 2.10 to 2.84, an isocyanate reactive component of which the isocyanate reactive group functionality is less than 2.2, and an additive, the molar ratio of the isocyanate group to the isocyanate reactive group of the resin composition is 0.5: 1 to 2: 1. The resin composition disclosed by the invention is good in high-temperature fluidity and adjustable in hardness.

Description

Technical Field

[0001] The present invention relates to a resin composition for preparing a thermoplastic polymer matrix and the prepared thermoplastic polymer matrix, a thermoplastic composite material comprising the thermoplastic polymer matrix, a preparation method and use thereof, and a mechanical or structural part or product comprising the thermoplastic composite material and use thereof. Background Art

[0002] Composite materials refer to materials that are composed of two or more different substances in different ways. They can give full play to the advantages of various materials, overcome the defects of single materials, and expand the application range of materials. Composite materials have gradually replaced wood and metal alloys and are widely used in aerospace, automobile, electronic and electrical, construction, sports equipment and other fields due to their light weight, high strength, convenient processing and molding, excellent elasticity, chemical corrosion resistance and good weather resistance.

[0003] In commercial applications, the most important category is composites with an organic matrix, in which the matrix material is generally a polymer. According to the different matrix resins, polymer-based composite materials can be divided into thermosetting polymer-based composite materials and thermoplastic polymer-based composite materials. Among them, thermosetting polymers are composed of a three-dimensional structure with a high degree of crosslinking. The crosslinking is generally obtained by the curing reaction of a liquid resin. The polymer chains after the reaction are generally permanently crosslinked and hardened. Resin materials commonly used in thermosetting polymers include unsaturated polyesters, vinyl esters, epoxy resins or phenolic resins. Although thermosetting polymer-based composite materials have been widely used, there are still many problems that need to be solved, such as long curing time, high VOC emissions, low impact resistance and damage resistance. At present, the world is extremely concerned about waste and the increasingly serious pollution problems caused to the environment. Various countries have begun to require composite material manufacturers to recycle thermosetting composite waste and limit the emission of harmful gases during the molding process of thermosetting composites.

[0004] Thermoplastic composites have received extensive attention in the composite material field due to their unique advantages such as short molding time and recyclable waste. Currently, the main manufacturing methods of thermoplastic composites are the hot melt method or the solvent method. The hot melt method mainly melts the thermoplastic resin into a viscous liquid by heating and then impregnates the fibers. However, thermoplastic resin melts all have relatively high melt viscosities and melting temperatures, which pose difficulties for fiber impregnation in thermoplastic composites. To reduce the viscosity, it is usually necessary to increase the processing temperature. Generally, the continuous working temperature of thermoplastic resins is higher than 200 °C, which means high energy costs and directly affects the economy of the composite material process. In addition, if the temperature is very high, thermoplastic resins tend to degrade, especially for semi-crystalline thermoplastic resins with high melting points, thus bringing the risk of reduced molecular weight and mechanical properties of the manufactured thermoplastic composites. The other solvent method is to dissolve the resin into a solution by an appropriate solvent and then impregnate the fibers, and then heat and evaporate the solvent to remove it. Using a large amount of solvent has environmental problems.

[0005] CN111438966 discloses a composite material prepared by in-situ polymerization of a thermoplastic (meth)acrylic resin, a polymer composite material obtained by in-situ polymerization of a thermoplastic (meth)acrylic resin and a fiber material containing long fibers and its uses, a method for preparing such a composite material, and a mechanical or structured part or article manufactured including the polymer composite material. The polymerization selects a (meth)acrylic polymer, a (meth)acrylic monomer, and at least one initiator or initiator system for initiating the polymerization of the (meth)acrylic monomer. The initiator or initiator system is activated by heating. This system uses a large amount of methyl methacrylate monomer as a solvent, and at the same time, this system also requires high temperature or initiates free radical polymerization by absorbing radiation to cure.

[0006] WO2014 / 174098 discloses a low-temperature polymerization initiation system based on the above-mentioned liquid (meth)acrylic resin, which includes at least one accelerator, an organic aldehyde, a peracid, and a liquid peroxide. The composition of this initiation system is complex, and it takes at least 40 minutes to reach the reaction peak at 25 °C.

[0007] CN10836829 discloses a manufacturing method by using an in-situ polymerizable thermoplastic epoxy resin as a matrix resin and preparing an in-situ polymerizable thermoplastic prepreg. This system contains an in-situ polymerizable thermoplastic epoxy resin composition, which is maintained at 20 - 40 °C for 50 - 240 hours while undergoing first-stage polymerization and curing to a prepolymer with a weight-average molecular weight of 6000 or less. This prepolymer is coated on a release paper to make a resin film, impregnated into reinforcing fibers to prepare a continuous fiber-reinforced prepreg, and multiple layers of prepreg sheets are stacked and then heated and pressed for curing until the weight-average molecular weight of the thermoplastic epoxy resin is 30000 or more. In this system, the first-stage reaction time is relatively long, and the prepared prepreg still has reactive activity, so it needs to be stored at -10 °C before use, and there are also requirements for the storage period (24 hours - 720 hours).

[0008] CN109467884 discloses a thermoplastic polymer matrix composite material and a preparation method thereof. The thermoplastic polymer matrix composite material is made by impregnating a reinforcing material with a mixture or oligomer of an epoxy resin, a bismaleimide resin, and a difunctional amine and in-situ polymerizing. The epoxy resin and the bismaleimide resin are heated to 60 - 150 °C for mixing, cooled to room temperature, and then a difunctional amine is added in proportion, and then the fiber is impregnated, and then heated to initiate in-situ polymerization to form a thermoplastic composite material.

[0009] In view of the problems of existing thermoplastic resins, such as slow polymerization rate at room temperature, inability to achieve one-step reaction curing, and the resin system containing volatile monomers, a thermoplastic resin that can fully infiltrate the reinforcing material, has low energy consumption, and high yield is needed. Summary of the Invention

[0010] The present invention relates to a resin composition for preparing a thermoplastic polymer matrix, a thermoplastic polymer matrix prepared therefrom, a thermoplastic composite material containing the thermoplastic polymer matrix and its preparation method and uses, and a mechanical or structured part or article containing the thermoplastic composite material and its uses.

[0011] A resin composition for preparing a thermoplastic polymer matrix according to the present invention comprises:

[0012] a) a polyisocyanate with an isocyanate group functionality of 2.10 - 2.84;

[0013] b) an isocyanate-reactive component with an isocyanate-reactive group functionality of less than 2.2, comprising an aspartate ester conforming to the structure of formula I and 0 - 50 wt% of other isocyanate-reactive compounds; the isocyanate-reactive component exists in a liquid form at 5 °C - 25 °C, and the aspartate ester conforming to the structure of formula I is:

[0014]

[0015] wherein, X is an aliphatic residue, R 1 and R 2 are each independently an organic group that does not react with isocyanate groups under normal pressure and at a temperature less than or equal to 100 °C, and n ≥ 2;

[0016] The isocyanate-reactive groups of the other isocyanate-reactive compounds are one or more of the following: primary amino groups, secondary amino groups, and hydroxyl groups containing active hydrogen; and

[0017] c) additives;

[0018] The molar ratio of the isocyanate groups to the isocyanate-reactive groups of the resin composition is 0.5:1 - 2:1.

[0019] According to one aspect of the present invention, there is provided a polymer composite material comprising a thermoplastic polymer matrix and a reinforcing material, wherein the thermoplastic polymer matrix is prepared from the resin composition provided by the present invention.

[0020] According to another aspect of the present invention, there is provided a thermoplastic polymer matrix which is prepared from the resin composition provided by the present invention.

[0021] According to another aspect of the present invention, there is provided a method for preparing a thermoplastic composite material, wherein a reinforcing material is impregnated with the resin composition provided by the present invention and polymerized to obtain a thermoplastic composite material.

[0022] According to another aspect of the present invention, there is provided the use of the thermoplastic composite material provided by the present invention for preparing mechanical or structural parts or articles.

[0023] According to another aspect of the present invention, there is provided a mechanical or structural part or article comprising the thermoplastic composite material provided by the present invention.

[0024] According to another aspect of the present invention, there is provided the use of the thermoplastic composite material provided by the present invention in automotive applications, marine applications, railway applications, sports, aerospace and aviation applications, photovoltaic applications, computer-related applications, telecommunications applications, construction applications, building applications, or wind energy applications.

[0025] The thermoplastic polymer matrix of the present invention has good high-temperature fluidity, adjustable softness and hardness, and the thermoplastic polymer matrix can be processed by thermoforming or recycled repeatedly. The resin composition of the present invention can fully infiltrate the substrate, has low energy consumption, and high yield. Detailed Embodiments

[0026] The present invention provides a resin composition for preparing a thermoplastic polymer matrix, comprising:

[0027] a) a polyisocyanate having an isocyanate group functionality of 2.10 - 2.84; b) an isocyanate-reactive component having an isocyanate-reactive group functionality of less than 2.2, comprising an aspartate ester conforming to the structure of formula I and 0 - 50% by weight of other isocyanate-reactive compounds; the isocyanate-reactive component is in a liquid form at 5°C - 25°C, and the aspartate ester conforming to the structure of formula I is:

[0028]

[0029] wherein X is an aliphatic residue, R 1 and R 2 are each independently an organic group that does not react with the isocyanate group under normal pressure and at a temperature less than or equal to 100°C, and n ≥ 2; the isocyanate-reactive groups of the other isocyanate-reactive compounds are one or more of the following: a primary amino group, a secondary amino group, and a hydroxyl group containing active hydrogen; and c) an additive; the molar ratio of the isocyanate groups to the isocyanate-reactive groups in the resin composition is 0.5:1 - 2:1.

[0030] The present invention also provides a thermoplastic polymer matrix prepared from the resin composition, a thermoplastic composite material comprising the thermoplastic polymer matrix, and its preparation method and uses, as well as a mechanical or structured part or article comprising the thermoplastic composite material and its uses.

[0031] The thermoplastic polymer matrix herein can be melted and be in a plastic state after heating, and becomes solid after cooling, and the above process can be repeated.

[0032] The term "isocyanate-reactive component" used herein refers to a component containing a group that is reactive with the isocyanate group, that is, a component containing a Zerevitinov-active hydrogen group. The definition of Zerevitinov-active hydrogen refers to Rompp’s Chemical Dictionary (Rommp Chemie Lexikon), 10th ed., Georg Thieme Verlag Stuttgart, 1996. Generally, a group containing Zerevitinov-active hydrogen is understood in the art to refer to a hydroxyl group (OH), an amino group (NH x ) and a thiol group (SH).

[0033] The molar ratio of the isocyanate groups to the isocyanate-reactive groups in the resin composition is preferably 0.8:1 - 2:1, more preferably 0.8:1 - 1.5:1, and most preferably 1:1 - 1.2:1.

[0034] In a preferred embodiment of the present invention, the polyisocyanate, the polyisocyanate-reactive component and the additive account for at least 80% by weight, preferably at least 90% by weight, of the total weight of the resin.

[0035] The viscosity of the resin composition is preferably 10 mPa·s - 10000 mPa·s, and the viscosity is measured at 23°C using a Brookfield DV-II+Pro viscometer in accordance with the DIN EN ISO 3219 standard.

[0036] The heat flow temperature of the thermoplastic polymer matrix is measured by the hot stage method with a glass slide: Take two glass slides, place an appropriate amount (not more than 0.1 g) of the cured thermoplastic polymer matrix on one glass slide, cover it with the other glass slide, gently press it, and then place it in the center of the hot stage. Set the hot stage temperature in advance and maintain it at 220°C. Observe the melting process of the thermoplastic polymer matrix using a microscope. If it completely melts into a liquid at 220°C, the heat flow temperature of the thermoplastic polymer matrix is not more than 220°C. If it remains unmelted after 1 hour at 220°C, the heat flow temperature of the thermoplastic polymer matrix is greater than 220°C.

[0037] Component a) Polyisocyanate

[0038] When the component a) polyisocyanate is a mixture of isocyanate compounds, the isocyanate group functionality of the polyisocyanate refers to the average functionality of the isocyanate groups of the plurality of isocyanate compounds.

[0039] The polyisocyanate refers to any organic compound having two or more reactive isocyanate groups in a single molecule, such as diisocyanates, triisocyanates, tetraisocyanates, etc., and mixtures thereof. Cyclic and / or linear polyisocyanates can be advantageously used.

[0040] The isocyanate monomer content of the polyisocyanate is preferably less than 1% by weight, based on the total weight of the polyisocyanate.

[0041] The polyisocyanate is preferably one or more of the following: aliphatic polyisocyanates, cycloaliphatic polyisocyanates, aromatic polyisocyanates, and polymerization homologues and isocyanurates of the above isocyanates.

[0042] In a preferred embodiment of the present invention, based on the total weight of the polyisocyanate, the polyisocyanate consists of at least 80% by weight, preferably 90% by weight, more preferably at least 95% by weight, and most preferably at least 98% by weight of aliphatic and / or cycloaliphatic polyisocyanates. It is particularly preferred that the polyisocyanate in this embodiment consists of aliphatic and / or cycloaliphatic polyisocyanates.

[0043] In a more preferred embodiment of the present invention, based on the total weight of the polyisocyanate, the polyisocyanate consists of at least 80% by weight, preferably 90% by weight, more preferably at least 95% by weight, and most preferably at least 98% by weight of aliphatic polyisocyanates. Particularly preferably, the polyisocyanate in this embodiment consists of aliphatic polyisocyanates.

[0044] The aliphatic polyisocyanate is preferably one or more of the following: hexane diisocyanate (hexamethylene-1,6-diisocyanate, HDI), pentane-1,5-diisocyanate, butane-1,4-diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), 3,5,5-trimethyl-1-isocyanato-3-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 4-isocyanatomethyl-1,8-octane diisocyanate, 1,3-bis(isocyanatomethyl)benzene (XDI), hydrogenated xylylene diisocyanate, and hydrogenated toluene diisocyanate.

[0045] The aromatic polyisocyanate is preferably one or more of the following: toluene 2,4-diisocyanate, toluene 2,6-diisocyanate, diphenylmethane 4,4'-diisocyanate, diphenylmethane 2,4'-diisocyanate, p-phenylene diisocyanate, biphenyl diisocyanate, 3,3'-dimethyl-4,4'-diphenylene diisocyanate, hexahydro-phenylene 1,3-diisocyanate, and their derivatives having iminooxadiazinedione, isocyanurate, uretdione, carbamate, urethane, biuret, urea, oxadiazinetrione, oxazolidone, acylurea, and / or carbodiimide groups.

[0046] The functionality of the isocyanate groups of the component a) polyisocyanate is preferably 2.10 - 2.80, most preferably 2.30 - 2.80. The functionality of the isocyanate groups is calculated from the isocyanate group content and the molecular weight of the polyisocyanate, and the molecular weight is determined by gel permeation chromatography (GPC).

[0047] The isocyanate group content of the polyisocyanate is preferably 5.0 - 40% by weight, based on the total weight of the polyisocyanate.

[0048] The viscosity of the component a) polyisocyanate is preferably 100 mPa·s - 30000 mPa·s, most preferably 100 mPa·s - 3000 mPa·s, and the viscosity is measured at 23 °C according to DIN EN ISO 3219.

[0049] Component b) Isocyanate-reactive component

[0050] When the component b) isocyanate-reactive component is a mixture of isocyanate-reactive compounds, the functionality of the isocyanate-reactive groups of the isocyanate-reactive component refers to the average functionality of the isocyanate-reactive groups of the plurality of isocyanate-reactive compounds.

[0051] The functionality of the isocyanate-reactive groups is calculated from the isocyanate group content and the molecular weight of the isocyanate-reactive component, and the molecular weight is determined by gel permeation chromatography (GPC).

[0052] The functionality of the isocyanate-reactive groups of the isocyanate-reactive component is preferably from 1.7 to 3.2, more preferably from 1.9 to 3.0, even more preferably from 2.1 to 2.84, and most preferably from 2 to 2.05.

[0053] Aspartate ester conforming to the structure of formula I

[0054] The amount of the polyaspartate is preferably 50% to 100% by weight, based on 100% by weight of the component b) isocyanate-reactive component.

[0055] The aliphatic residue is preferably one or more of the following: straight-chain alkyl residue, branched alkyl residue, and cycloalkyl residue, and most preferably cycloalkyl residue.

[0056] The aliphatic residue herein is preferably obtained from an alcohol compound, and the alcohol compound is preferably one or more of the following: ethylene glycol, 1,2-dihydroxypropane, 1,4-dihydroxybutane, 1,6-dihydroxyhexane, 2,2,4- and / or 2,4,4-trimethyl-1,6-dihydroxyhexane, 1-hydroxy-3,3,5-trimethyl-5-hydroxymethylcyclohexane, 4,4'-dihydroxybicyclohexylmethane, 3,3'-dimethyl-4',4'-dihydroxybicyclohexylmethane, 1,5-dihydroxy-2-methylpentane, 1,1,1-trimethylolpropane, and 2,2-bis(hydroxymethyl)1,3-propanediol (pentaerythritol).

[0057] The R 1 and R 2 are each independently preferably an alkyl residue having 1 to 10 carbon atoms, and most preferably one or more of the following: methyl, ethyl, and butyl.

[0058] The n is 2.

[0059] When n of the aspartate is 2, it is preferably obtained by the reaction of a polyamine containing the following formula and a maleate and / or fumarate of the following formula:

[0060]

[0061] The polyamine is preferably one or more of the following: ethylenediamine, 1,2-diaminopropane, 1,4-diaminobutane, 1,3-diaminopentane, 1,6-diaminohexane, 2,5-diamino-2,5-dimethylhexane, 2,2,4-trimethyl-1,6-diaminohexane, 2,4,4-trimethyl-1,6-diaminohexane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,3-cyclohexanediamine and 1,4-cyclohexanediamine, aminomethyl-3,3,5-trimethyl-5-aminomethylcyclohexane, 2,4-hexahydrotoluenediamine, 2,6-hexahydrotoluenediamine, 2,4'-diamino-dicyclohexylmethane, 4,4'-diamino-dicyclohexylmethane, 3,3'-dialkyl-4,4'-diaminodicyclohexylmethane, 2,4,4'-triamino-5-methyldicyclohexylmethane, 2-methyl-1,5-pentanediamine, 1,3-xylylenediamine and 1,4-xylylenediamine, more preferably one or more of the following: 1,4-diaminobutane, 1,6-diaminohexane, 2,2,4-trimethyl-1,6-diaminohexane, 2,4,4-trimethyl-1,6-diaminohexane, aminomethyl-3,3,5-trimethyl-5-aminomethylcyclohexane, 4,4'-diamino-dicyclohexylmethane, 3,3'-dialkyl-4,4'-diaminodicyclohexylmethane and 2-methyl-1,5-pentanediamine, and most preferably one or more of the following: 2-methyl-1,5-pentanediamine, aminomethyl-3,3,5-trimethyl-5-aminomethylcyclohexane, 2,4'-diamino-dicyclohexylmethane, 4,4'-diamino-dicyclohexylmethane and 3,3'-dialkyl-4,4'-diaminodicyclohexylmethane.

[0062] The maleate and / or fumarate is preferably one or more of the following: dimethyl maleate, diethyl maleate, dibutyl maleate, dimethyl fumarate, diethyl fumarate and dibutyl fumarate.

[0063] The temperature of the reaction is preferably 0°C - 100°C.

[0064] The weight ratio of the maleate and / or fumarate to the polyamine is preferably 2:1.

[0065] The weight ratio of the olefin double bond of the maleate and / or fumarate to the primary amino group of the polyamine is preferably 1:1.

[0066] The product obtained from the reaction is preferably purified by distillation.

[0067] The components of the reaction may or may not contain a solvent, and preferably contain a solvent.

[0068] The solvent is preferably one or more of the following: methanol, ethanol, propanol and dioxane.

[0069] The equivalent weight of the amino group of the aspartic acid ester is preferably 200-500.

[0070] The viscosity of the aspartic acid ester is preferably 100-4000 mPa·s.

[0071] The aspartic acid ester conforming to the formula I structure is most preferably one or more of the following: isocyanate-reactive components described in US512617, US523674, US5489704, US5243012, US5736604, US6458293, US6833424, US7169876 or US2006 / 0247371, Desmophen NH1420, Desmophen NH1520, Desmophen NH1220, Desmophen NH1723LF, Desmophen NH2885, Desmophen NH1722, Desmophen NH2886, Desmophen NH1720, Desmophen NH1422 and Desmophen NH1423LF, which are commercially available from Covestro.

[0072] Other isocyanate-reactive compounds

[0073] The amount of the other isocyanate-reactive compound is preferably not more than 50% by weight, most preferably not more than 20% by weight, based on 100% by weight of the isocyanate-reactive component of component b).

[0075] In a preferred embodiment of the present invention, the amount of the other isocyanate-reactive compound is preferably 1 to 50% by weight, most preferably 1 to 20% by weight, based on 100% by weight of the isocyanate-reactive component of component b).

[0076] The viscosity of the other isocyanate-reactive compound is preferably 10 mPa·s - 100000 mPa·s, most preferably 10 mPa·s - 5000 mPa·s, and the viscosity is measured according to DIN EN ISO 3219 at 23°C.

[0077] The other isocyanate-reactive compound is preferably one or more of the following: polyhydroxy compounds, organic polyols and organic polyamines, most preferably one or more of the following: organic polyols and organic polyamines.

[0078] The polyhydroxy compound is preferably one or more of the following: ethylene glycol, 1,2-propanediol, 1,3-propanediol, diethylene glycol, trimethylolpropane, glycerol, bisphenol A and bisphenol S.

[0079] The organic polyol is preferably one or more of the following: polyether polyol, polyester polyol, polyether carbonate polyol, polycarbonate diol, polymer polyol, bio-based polyol, and vegetable oil-based polyol.

[0080] The organic polyamine is preferably a compound having at least two amine groups, and the amine groups contain at least one active hydrogen (N-H) group selected from primary amine or secondary amine. The organic amine is most preferably one or more of the following: ethylenediamine, isophorone diamine, tetramethylene diamine, hexamethylene diamine, dodecamethylene diamine, m-xylene diamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, polyether-modified polyamine resin, epoxy-modified polyamine resin, carbonyl compound-modified polyamine resin, phenolic-modified polyamine resin, and polyether aspartate polyamine resin.

[0081] Component c) Additive

[0082] The additive is preferably one or more of the following: light stabilizer, antioxidant, mold release agent, flame retardant, filler, pigment, defoaming agent, leveling agent, wetting agent, coupling agent, water remover, thixotropic agent, chelating agent, free radical reaction inhibitor, and other additives well-known to those skilled in the art that can be added to the resin composition for the application of the composite material.

[0083] The additive may optionally be included in component a) polyisocyanate and / or component b) isocyanate-reactive component. The additive can also be stored independently, and when used to prepare the thermoplastic polymer matrix of the thermoplastic composite material, the additive is first mixed with component a) polyisocyanate and / or component b) isocyanate-reactive component and then prepared.

[0084] The filler is preferably one or more of the following: aluminum hydroxide, bentonite, fly ash, wollastonite, perlite powder, cenosphere, calcium carbonate, talc powder, mica powder, kaolin, fumed silica, expandable microspheres, diatomite, volcanic ash, barium sulfate, calcium sulfate, glass microspheres, stone powder, wood powder, wood chips, bamboo powder, bamboo chips, rice grains, straw debris, sorghum stalk debris, graphite powder, metal powder, recycled powder of thermosetting composite material, plastic particles, and plastic powder. The glass microspheres can be solid or hollow.

[0085] The mold release agent can be any conventional mold release agent for producing polymers, preferably one or more of the following: long-chain carboxylic acid, amine of long-chain carboxylic acid, metal salt of long-chain carboxylic acid, and polysiloxane. The long-chain carboxylic acid is preferably fatty acid, and most preferably stearic acid. The amine of long-chain carboxylic acid is preferably one or more of the following: stearamide and fatty acid ester. The metal salt of long-chain carboxylic acid is preferably zinc stearate.

[0086] The flame retardant is preferably one or more of the following: triaryl phosphate, trialkyl phosphate, halogenated triaryl phosphate, halogenated trialkyl phosphate, melamine, melamine resin, halogenated paraffin, and red phosphorus.

[0087] The water remover is preferably molecular sieve.

[0088] The defoamer is preferably polydimethylsiloxane.

[0089] The coupling agent is used to improve the adhesion between the thermoplastic polymer matrix formed by the resin composition and the reinforcing material, and is preferably one or more of the following: monoethylene oxide and organoamine-functionalized trialkoxysilane.

[0090] The thixotropic agent is preferably fine particle filler, and most preferably one or more of the following: clay and fumed silica.

[0091] The chelating agent is preferably one or more of the following: acetylacetone, benzoylacetone, trichloroacetylacetone, and ethyl acetoacetate.

[0092] The radical reaction inhibitor is preferably one or more of the following: polymerization inhibitor and retarder, and further preferably one or more of the following: phenolic compound, quinone compound, and hindered amine compound, and most preferably one or more of the following: methylhydroquinone, p-methoxyphenol, benzoquinone, polymethylpiperidine derivative, and cuprous ion.

[0093] The amount of the additive is not limited as long as it does not affect the performance of the resin composition of the present invention.

[0094] Thermoplastic composite

[0095] The amount of the thermoplastic polymer matrix is preferably 20% to 80% by weight based on the total weight of the thermoplastic composite.

[0096] In a preferred embodiment of the present invention, the size of the thermoplastic composite is at least 5 mm x 5 mm x 50 mm, preferably 5 mm x 10 mm x 50 mm, and most preferably 10 mm x 10 mm x 200 mm. Particularly preferably, in such a thermoplastic composite, the amount of the polymer matrix is 20% to 80% by weight based on the total weight of the thermoplastic composite.

[0097] The reinforcing material is preferably reinforcing fiber material, and most preferably one or more of the following: plant fiber, wood fiber, animal fiber, mineral fiber, synthetic polymer fiber, glass fiber, and carbon fiber.

[0098] The reinforcing material preferably exists in one or more of the following forms: fiber mats, non-woven forms of woven fibers, woven roving forms of woven fibers, and forms of woven fiber bundles.

[0099] In a preferred embodiment of the present invention, the thermoplastic composite material is a product selected from the following: profiles, carriers, reinforcing struts, automotive parts, marine parts, train parts, sports products, aircraft or helicopter parts, spacecraft or rocket parts, photovoltaic module parts, wind turbine parts, furniture parts, building parts, structural parts, telephone parts, mobile phone parts, computer parts, television parts, printing press parts, and photocopier parts. Particularly preferably, the aforementioned products have the dimensions listed above.

[0100] Preferably, the thermoplastic polymer matrix is obtained by polymerizing a resin composition. Most preferably, the thermoplastic polymer matrix is prepared under reaction conditions in which a free radical polymerization reaction and an addition polymerization reaction of an isocyanate group with a hydroxyl group are simultaneously present in the resin composition.

[0101] The addition polymerization reaction of the isocyanate group with the hydroxyl group, wherein the isocyanate group can be the isocyanate group contained in component a) polyisocyanate, or can be the isocyanate group contained in the intermediate product of the reaction of component a) polyisocyanate with component b) isocyanate-reactive component; wherein the hydroxyl group can be the hydroxyl group contained in component b) isocyanate-reactive component, or can be the hydroxyl group contained in the intermediate product of the reaction of component a) polyisocyanate with component b) isocyanate-reactive component.

[0102] The free radical polymerization reaction is an addition polymerization reaction of an olefinic bond, wherein the olefinic bond can be the olefinic bond contained in component b) isocyanate-reactive component, or can be the olefinic bond contained in the intermediate product of the reaction of component b) isocyanate-reactive component with component a) polyisocyanate.

[0103] The addition polymerization reaction (i.e., the addition polymerization reaction of the isocyanate group with the hydroxyl group) and the free radical polymerization reaction are simultaneously present.

[0104] The thermoplastic composite material is preferably prepared by one or more of the following processes: pultrusion, filament winding, hand lay-up, spray-up, vacuum infusion, prepreg molding, and resin transfer molding, and most preferably by vacuum infusion.

[0105] Method for preparing a thermoplastic composite

[0106] It is well-known to those skilled in the art that the addition polymerization reaction of isocyanate groups and hydroxyl groups can be promoted by using tin-based or amine-based catalysts, the free radical polymerization reaction can be accelerated by using heating or promoters such as aniline compounds, and the addition polymerization reaction and the free radical polymerization reaction can be promoted simultaneously by using promoters such as cobalt salts. Therefore, those skilled in the art can select appropriate conditions to enable the simultaneous presence of free radical polymerization reaction and the addition polymerization reaction of isocyanate groups and hydroxyl groups in the resin composition.

[0107] The content of the reinforcing material is preferably 1% by weight to 90% by weight, more preferably 30% by weight to 85% by weight, and most preferably 50% by weight to 80% by weight, based on the total weight of the thermoplastic composite material.

[0108] Those skilled in the art are familiar with the operation method of the vacuum infusion process, such as the content described in Patent CN1954995A, and the entire content of this disclosure is incorporated herein by reference.

[0109] In the vacuum infusion process, one or more core materials are arranged in the mold, and the core material is optionally entirely or partially covered with a reinforcing material. Then, a negative pressure is formed in the mold to enable the resin composition to be infused into the mold; before curing, the resin composition will completely infiltrate the reinforcing material, and the core material will also be entirely or partially infiltrated by the resin composition. Then, appropriate conditions are adopted to enable the resin composition to simultaneously undergo polymer addition polymerization reaction and free radical polymerization reaction, so that the resin composition cures to form a thermoplastic polymer matrix. In the above vacuum infusion process, the mold can be a commonly used mold in the art, and those skilled in the art can select a suitable mold according to the required performance and size of the final product. When using the vacuum infusion process to prepare large objects, in order to ensure sufficient operation time, it is necessary to keep the viscosity of the resin composition low enough during the infusion process to maintain good fluidity.

[0110] The core material is used together with the thermoplastic polymer matrix and the reinforcing material, which is beneficial to the molding of the thermoplastic composite material and reduces the weight of the thermoplastic composite material. The thermoplastic composite material of the present invention can use commonly used core materials in the art, including but not limited to polystyrene foam such as foam; polyester PET foam; polyimide PMI foam; polyvinyl chloride foam; metal foam such as the metal foam available from Mitsubishi Corporation; balsa wood, etc.

[0111] The thermoplastic composite material of the present invention can also be prepared by pultrusion process, filament winding process, hand lay-up process, spray-up process or a combination thereof. For a detailed description of these processes, reference can be made to Chapters 2 and 6-9 of "Composite Materials Technology and Equipment" (Liu Xiongya et al., 1994, published by Wuhan University of Technology). The entire above-disclosed content is incorporated herein by reference.

[0112] Use

[0113] The mechanical or structural parts or articles are preferably selected from profiles, carriers, structural parts of reinforcing struts or lightweight structural parts, and most preferably from automotive parts, marine parts, train parts, sports articles, aircraft or helicopter parts, spacecraft or rocket parts, photovoltaic module parts, wind turbine parts, furniture parts, construction or building parts, telephone or mobile phone parts, computer or television parts, printing press and photocopier parts.

[0114] Examples

[0115] Unless otherwise defined, 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. When the definitions of terms in this specification conflict with the commonly understood meanings of those skilled in the art to which this invention belongs, the definitions set forth herein shall prevail.

[0116] Unless otherwise indicated, all numerical values expressing amounts of ingredients, reaction conditions, etc. used in the specification and claims are understood to be modified by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth herein are approximations that can vary depending upon the desired properties sought to be obtained.

[0117] Unless otherwise indicated, the articles "a", "an", "the" and "said" used in this specification are intended to include "at least one" or "one or more". For example, "a component" means one or more components, and thus more than one component may be contemplated and may be employed or used in the practice of the described embodiments.

[0118] As used herein, "and / or" refers to one or all of the recited elements.

[0119] As used herein, "comprises" and "comprising" cover the case where only the recited elements are present and the case where there are also other unrecited elements in addition to the recited elements.

[0120] All percentages in the present invention are weight percentages, unless otherwise specified.

[0121] The analytical measurements of the present invention are carried out at 23 ± 2 °C and 50 ± 5% humidity, unless otherwise specified.

[0122] The content of isocyanate groups (NCO) is determined according to DIN-EN ISO 11909∶2007-05, and the measured data includes the free and potentially free NCO content.

[0123] The viscosity of the polyisocyanate is measured at 23 °C using a Brookfield DV-II+Pro viscometer according to the DIN EN ISO3219 standard.

[0124] High-temperature fluidity: The melting state of the thermoplastic polymer matrix at high temperature is tested using a glass slide (hot stage method). Take two glass slides, place an appropriate amount of the cured thermoplastic polymer matrix (not more than 0.1 g) on one glass slide, cover it with the other glass slide, gently press it, and then place it in the center of the hot stage. Set the hot stage temperature in advance and keep it at 220 °C. Observe the melting process of the thermoplastic polymer matrix using a microscope. If it completely melts into a liquid at 220 °C, it is recorded as O (qualified); if it remains unmelted after 1 hour at 220 °C, it is recorded as X (unqualified).

[0125] Shore hardness: The cured thermoplastic polymer matrix is tested according to the DIN EN ISO 868 standard at room temperature.

[0126] The viscosity of the resin composition: The composition mixed with a Speedmixer is tested at 23 °C using a Brookfield DV-II+Pro viscometer according to the DIN EN ISO 3219 standard.

[0127] The glass transition temperature (Tg) of the thermoplastic composite: It is tested using dynamic mechanical analysis (DMA) according to the GB / T40396 standard.

[0128] The flexural strength and flexural modulus of the thermoplastic composite: They are tested using a universal material testing machine according to the ISO 14125 standard.

[0129] Raw materials and reagents

[0130] Desmodur N3400: An aliphatic uretdione polyisocyanate based on hexamethylene diisocyanate, with 100% solid content, an isocyanate group (NCO) content of 21.8 wt.%, a viscosity of about 150 mPa·s (23 °C), and an isocyanate group functionality of 2.5, purchased from Covestro;

[0131] Desmodur NZ 300: An aliphatic uretdione / trimer based on hexamethylene diisocyanate / isophorone diisocyanate, with 100% solid content, an NCO content of 21.0 wt.%, a viscosity of about 3000 mPa·s (23 °C), and an isocyanate group functionality of 2.8, purchased from Covestro;

[0132] Desmodur N 31100: An aliphatic urethane based on hexamethylene diisocyanate, 100% solids content by weight, NCO content is 20.0 wt.%, viscosity is about 500 mPa·s (23 °C), functionality of isocyanate groups is 2.3, purchased from Covestro;

[0133] Desmodur N 3300: An aliphatic trimer based on hexamethylene diisocyanate, 100% solids content by weight, NCO content is 21.8 wt.%, viscosity is about 3000 mPa·s (23 °C), functionality of isocyanate groups is 3.5, purchased from Covestro;

[0134] Desmodur N 3900: An aliphatic trimer based on hexamethylene diisocyanate, 100% solids content by weight, NCO content is 23.5 wt.%, viscosity is about 730 mPa·s (23 °C), functionality of isocyanate groups is 3.3, purchased from Covestro;

[0135] Desmodur NZ 200: An aliphatic trimer based on hexamethylene diisocyanate / isophorone diisocyanate, 100% solids content by weight, NCO content is 21.0 wt.%, viscosity is about 22500 mPa·s (23 °C), functionality of isocyanate groups is 3.2, purchased from Covestro;

[0136] Desmodur N 3200: An aliphatic biuret based on hexamethylene diisocyanate, 100% solids content by weight, NCO content is 23.0 wt.%, viscosity is about 2500 mPa·s (23 °C), functionality of isocyanate groups is 3.5, purchased from Covestro;

[0137] Desmodur XP 2599: An aliphatic prepolymer based on hexamethylene diisocyanate and containing ether groups, 100% solids content by weight, NCO content is 6 wt.%, viscosity is about 3000 mPa·s (23 °C), functionality of isocyanate groups is 4, purchased from Covestro;

[0138] Desmodur N 3500: An aliphatic urethane / trimer based on hexamethylene diisocyanate, 100% solids content by weight, NCO content is 19.5 wt.%, viscosity is about 35000 mPa·s (23 °C), functionality of isocyanate groups is 4.5, purchased from Covestro;

[0139] Desmocomp AP200: An aliphatic isocyanate, 100% solids content by weight, NCO content is 23 wt.%, viscosity is about 1300 mPa·s (23 °C), functionality of isocyanate groups is 3, purchased from Covestro;

[0140] Desmodur Eco N 7300: An aliphatic trimer based on pentamethylene diisocyanate, with a solids content of 100 wt%, an NCO content of 21.5 wt.%, a viscosity of approximately 9500 mPa·s (23 °C), an isocyanate group functionality of 3.7, available from Covestro;

[0141] Desmophen NH 1420: With an amino group functionality of 2.0, 279 equivalents of amino groups, a viscosity of 850 - 1800 mPa·s (23 °C), available from Covestro;

[0142] Desmophen NH 1520: With an amino group functionality of 2.0, 290 equivalents of amino groups, a viscosity of 800 - 2000 mPa·s (23 °C), available from Covestro;

[0143] Desmophen NH 1720: With an amino group functionality of 2.0, 295 equivalents of amino groups, a viscosity ≥ 80 mPa·s (23 °C), available from Covestro;

[0144] Desmophen NH 1220: With an amino group functionality of 2.0, 234 equivalents of amino groups, a viscosity < 100 mPa·s (23 °C), available from Covestro;

[0145] Butanediol BDO: With a hydroxyl group functionality of 2.0, a purity > 99.0%, available from Sinopharm Reagent;

[0146] Glycerol: With a hydroxyl group functionality of 2.0, a purity > 99.0%, available from Sinopharm Reagent;

[0147] 4,4′-Methylenebis(2-ethyl-6-methylaniline) MCDEA: With an amino group functionality of 2.0, a solid at room temperature, a purity of 98%, available from Adamas Reagent;

[0148] BYK-P9920: A wetting and dispersing agent, available from BYK;

[0149] Carbon fiber cloth: Using a carbon fiber twill woven cloth, model TC42S-12K, available from Taili.

[0150] Table 1 lists the composition of the resin compositions of the examples and the performance test results of the thermoplastic polymer matrix. Table 2 lists the composition of the resin compositions of the comparative examples and the performance test results of the thermoplastic polymer matrix.

[0151] Method for preparing the thermoplastic polymer matrix of the examples and comparative examples

[0152] At 23°C and 55%-65% humidity, a mixture was prepared according to the composition of the resin composition listed in Table 1 or Table 2. Then, the mixture was placed in a Speedmixer DAC150.1FVZ from Hauschild and mixed at 2750 revolutions per minute for 1 minute. Subsequently, the mixture was poured into a suitable mold and left at room temperature for 24 hours to obtain the thermoplastic polymer matrices of the examples and comparative examples.

[0153] As can be seen from Table 1, the thermoplastic polymer matrices cured from the resin compositions of Examples 1-21 have good high-temperature fluidity, are thermoplastic, and the softness and hardness of the thermoplastic polymer matrices can be adjusted.

[0154] When the isocyanate functionality of the polyisocyanate in the comparative resin compositions of Comparative Examples 1-5 is less than 2.10 or greater than 2.84, the high-temperature fluidity of the thermoplastic polymer matrices cured from the resin compositions is unqualified, there is no fluidity when heated at 220°C, and the polymer matrix is prone to thermal decomposition at higher temperatures and has poor strength.

[0155] Comparing Example 21 and Comparative Example 6, when the functionality of the isocyanate-reactive groups of the isocyanate-reactive components in the comparative resin composition is 2.2, the high-temperature fluidity of the thermoplastic polymer matrix cured from the resin composition is unqualified, there is no fluidity when heated at 220°C, and the polymer matrix is prone to thermal decomposition at higher temperatures and has poor strength.

[0156] The MCDEA contained in the comparative resin composition of Comparative Example 7 is an aromatic amine that is solid at room temperature. The high-temperature fluidity of the thermoplastic polymer matrix cured from the resin composition is unqualified, there is no fluidity when heated at 220°C, the polymer matrix is prone to thermal decomposition at higher temperatures and has poor strength, and the composition cures rapidly at room temperature and has a short pot life.

[0157] Preparation of the thermoplastic composite of Example 22

[0158] The resin composition was mixed according to the ratio of Example 2 in Table 1, and 0.5 wt% BKY-P9920 (based on the total weight of the resin composition of Example 2) was added and mixed evenly to obtain a mixture with a viscosity of 480 mPa·s;

[0159] Cut a 15 cm × 15 cm carbon fiber cloth and lay it flat on a silicone-coated release paper. The above mixture was evenly coated on the carbon fiber cloth with a brush and pressed with a roller to make the resin fully penetrate the carbon fiber cloth. The impregnated carbon fiber cloth was first placed at room temperature for 24 hours, and then put into an oven at 40°C for 20 minutes for in-situ polymerization to make a thermoplastic composite prepreg. The prepreg made above can be stored at room temperature for a long time;

[0160] Stack two pieces of composite material prepregs together, first heat them outside the mold at 170°C for 4 minutes, then put them into a hot press. The mold temperature is 80°C - 85°C, the pressure is 4000 KN, and after hot pressing for 1 minute, open the mold and cool to make a thermoplastic composite material.

[0161] The glass transition temperature of the above-mentioned thermoplastic composite material is tested to be 104°C; the flexural modulus is 22 GPa, and the flexural strength is 350 MPa. In the above preparation method, the liquid viscosity of the mixture is low at room temperature, it is easy to fully infiltrate the fibers, there is no need for high-temperature molten liquid, the energy consumption is low, and the obtained thermoplastic composite material can be formed at 170 degrees, and the processability is good.

[0162] Those skilled in the art will readily appreciate that the present invention is not limited to the foregoing specific details, and without departing from the spirit or main characteristics of the present invention, the present invention can be implemented in other specific forms. Therefore, in any sense, the described embodiments should be regarded as illustrative rather than restrictive, and the scope of the present invention should be pointed out by the claims rather than the foregoing description; and thus any change, as long as it falls within the meaning and scope of the equivalents of the claims, should be regarded as belonging to the present invention.

[0163]

[0164]

[0165]

Claims

1. A resin composition for preparing a thermoplastic polymer matrix, comprising: a) a polyisocyanate having an isocyanate group functionality of 1.7 - 3.0; b) an isocyanate-reactive component having an isocyanate-reactive group functionality of less than 2.2, comprising an aspartate ester conforming to the structure of Formula I and 0 - 50% by weight of other isocyanate-reactive compounds; the isocyanate-reactive component is in a liquid form at 5°C - 25°C, and the aspartate ester conforming to the structure of Formula I is: Wherein, X is an aliphatic residue, R 1 and R 2 are each independently an organic group that does not react with isocyanate groups under normal pressure and at a temperature less than or equal to 100 °C, and n ≥ 2; The isocyanate-reactive groups of the other isocyanate-reactive compounds are one or more of the following: primary amino groups, secondary amino groups, and hydroxyl groups containing active hydrogen; and c) an additive; The molar ratio of the isocyanate groups to the isocyanate-reactive groups in the resin composition is 0.5:1 - 2:

1.

2. The resin composition according to claim 1, wherein, The molar ratio of the isocyanate groups to the isocyanate-reactive groups in the resin composition is 0.8:1 - 2:1, more preferably 0.8:1 - 1.5:1, and most preferably 1:1 - 1.2:

1.

3. The resin composition according to claim 1 or 2, wherein, The polyisocyanate, the polyisocyanate-reactive component, and the additive account for at least 80% by weight.

4. The resin composition according to any one of claims 1 - 3, wherein, The amount of the other isocyanate-reactive compounds is 0 - 20% by weight, based on the total weight of the isocyanate-reactive component of component b).

5. The resin composition according to any one of claims 1 - 4, wherein, The viscosity of the resin composition is 10 mPa·s - 10000 mPa·s, and the viscosity is measured at 23°C according to DIN EN ISO 3219.

6. The resin composition according to any one of claims 1 - 5, wherein, Based on the total weight of the polyisocyanate, the polyisocyanate consists of at least 80% by weight of aliphatic and / or cycloaliphatic polyisocyanates.

7. A thermoplastic polymer matrix prepared by the resin composition according to any one of claims 1 - 5.

8. The resin composition according to claim 7, wherein, The heat distortion temperature of the thermoplastic polymer matrix is not greater than 220°C, and the heat distortion temperature is measured by the hot stage method, and the Shore hardness D is 10 - 90, and the Shore hardness D is tested according to the DINEN ISO 868 standard.

9. A thermoplastic composite material comprising a thermoplastic polymer matrix and a reinforcing material, wherein the thermoplastic polymer matrix is prepared by the resin composition according to any one of claims 1 - 6.

10. The thermoplastic composite material according to claim 9, wherein, Its size is at least 5 mm x 5 mm x 50 mm.

11. The thermoplastic composite material according to claim 9 or 10, wherein, The reinforcing material is a reinforcing fiber material, and most preferably one or more of the following: plant fiber, wood fiber, animal fiber, mineral fiber, synthetic polymer fiber, glass fiber, and carbon fiber.

12. The thermoplastic composite material according to any one of claims 9-11, wherein, the reinforcing material exists in one or more of the following forms: fiber mat, non-woven form of woven fibers, woven roving form of woven fibers, and form of fiber bundles of woven fibers.

13. The thermoplastic composite material according to any one of claims 9-12, wherein, the thermoplastic composite material is prepared by one or more of the following processes: pultrusion, filament winding, hand lay-up, spray-up, vacuum infusion, prepreg molding, and resin transfer molding.

14. The thermoplastic composite material according to any one of claims 9-13, wherein, the thermoplastic composite material is a product selected from the following: profiles, carriers, reinforcing struts, automotive parts, marine parts, train parts, sports products, aircraft or helicopter parts, spacecraft or rocket parts, photovoltaic module parts, wind turbine parts, furniture parts, building parts, structural parts, telephone parts, mobile phone parts, computer parts, television parts, printing press parts, and photocopier parts.

15. A method for preparing a thermoplastic composite material, wherein a resin composition according to any one of claims 1-6 is impregnated into a reinforcing material and polymerized to obtain a thermoplastic composite material.

16. Use of the thermoplastic composite material according to any one of claims 9-13 for preparing mechanical or structural parts or articles.

17. The use according to claim 16, wherein, the mechanical or structural parts or articles are selected from structural parts or lightweight structural parts of profiles, carriers, and reinforcing struts, and most preferably from automotive parts, marine parts, train parts, sports products, aircraft or helicopter parts, spacecraft or rocket parts, photovoltaic module parts, wind turbine parts, furniture parts, structural or building parts, telephone or mobile phone parts, computer or television parts, printing presses, and photocopier parts.

18. A mechanical or structural part or article comprising the thermoplastic composite material according to any one of claims 9-13.

19. Use of the thermoplastic composite material according to any one of claims 9-13 in automotive applications, marine applications, railway applications, sports, aerospace and aviation applications, photovoltaic applications, computer-related applications, telecommunications applications, structural applications, building applications, or wind energy applications.

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