Resin intermediate containing active hydrogen, chain-extended resin intermediate and thermosetting polyurethane resin and composite material thereof

Abstract

The invention discloses an active hydrogen-containing resin intermediate, a chain-extended resin intermediate and thermosetting polyurethane resin and a composite material thereof, which are prepared by the following steps: step 1, carrying out degradation reaction on initial polyurethane and a degradation agent with active groups, breaking at least one part of molecular chains of the initial polyurethane, preparing an active hydrogen-containing resin intermediate containing the initial polyurethane molecular fragment; the active groups comprise hydroxyl and / or amido; and step 2, changing the active hydrogen-containing resin intermediate into the chain-extended resin intermediate through a grafting reaction. Mixing the resin intermediate and other active components to form an isocyanate reaction component B; the component B is mixed with the isocyanate component A and other components, the mixture is cured to obtain a novel thermosetting polyurethane resin material, and the double-component polyurethane resin has good strength and toughness, can be used as a polyurethane foaming material, and can be combined with a reinforcing material to generate various composite materials.

Description

Technical Field

[0001] This patent relates to the field of polymer material technology, and involves an active hydrogen-containing resin intermediate, a chain extension resin intermediate, a thermosetting polyurethane resin and a composite material. Background Art

[0002] Alcohol hydrolysis recovery of polyurethane solid materials is one of the most commonly used chemical recycling methods for polyurethane degradation and recycling. Polyurethane solid materials include polyurethane solid waste, scraps generated during the production of polyurethane products, retired polyurethane materials (refrigerator container insulation rigid foam, mattress sofa soft foam, sole materials, polyurethane elastomers, polyurethane semi-rigid foam, polyurethane adhesives, etc.) and polyurethane composite materials (window frames, beams, solar frames, sleepers, cable boxes, battery shells, sucker rods, brackets, etc.) and other solid alcoholysis.

[0003] But the alcoholysis of these solid polyurethanes, including the alcoholysis of various polyurethane solid wastes (soft foam, hard foam, semi-hard foam, elastomer, adhesive, cast body, composite material, etc.), is routinely thoroughly depolymerized to obtain the polyol component that is completely dissociated, then further separation and purification of this polyol component, then the polyol component after this type of purification is by a certain proportion in common polyol (i.e. conventional industrialization according to the polyol obtained by ring-opening such as ethylene oxide, propane or butane, or polyester polyol, etc.) component back-mixing mode, re-prepare various types of polyurethane products, such as foam, elastomer, adhesive, etc. This recycling mode is only focused on the polyol product obtained by the complete degradation of polyurethane and other components related to isocyanate are not further studied and effectively utilized, and new waste can be generated again in the purification process of the degraded polyol product. Therefore, the recycled product of this recycling mode accounts for a low useful ratio of solid waste, and the economic value is limited, and the purposes are also limited, which is unfavorable for the economic and efficient recycling of polyurethane solid waste.

[0004] This reaction provides a new type of alcoholysis chemical recovery method for polyurethane solid materials, which can avoid the above-mentioned problems and instead degrade and fully recycle the polyurethane solid waste as a whole material, thereby further reducing the cost of the entire process, improving efficiency and increasing the overall recycling rate of solid waste. Summary of the invention

[0005] The purpose of the present invention is to provide a resin intermediate obtained by recycling and processing polyurethane solid materials and a manufacturing method thereof, as well as the use of the resin intermediate in the preparation of a novel two-component thermosetting polyurethane resin matrix by directly adding a resin composition, which not only achieves the purpose of improving the recycling rate of polyurethane solid waste, but also simplifies the entire polyurethane solid material recycling process and improves its economic benefits and value.

[0006] In a first aspect, the present invention provides an active hydrogen-containing resin intermediate, which is prepared by the following steps: Step A1: subjecting an initial polyurethane to a degradation reaction with a degradation agent having an active group to break at least a portion of the molecular chain of the initial polyurethane to obtain the active hydrogen-containing resin intermediate containing the initial polyurethane molecular fragment, wherein the active group comprises a hydroxyl group and / or an amine group.

[0007] Further, in step A1: the degradation reaction is an alcoholysis reaction; the degradation agent includes a polyol, and the polyol includes a diol and / or a high-functionality polyol; the diol includes a low molecular weight C2-C6 diol; the low molecular weight C2-C6 diol includes one or more combinations of ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, monoethylene glycol, monopropylene glycol or neopentyl glycol; the high-functionality polyol includes glycerol , trimethylolethane, trimethylolpropane, pentaerythritol, sucrose polyol, sorbitol or polyether polyol; the temperature of the alcoholysis reaction is 110-150°C, 150-170°C, 170-180°C, 180-200°C, 200-220°C or 220-250°C; the time of the alcoholysis reaction is 0.5-2h, 2-3h, 3-6h, 6-12h, 12-24h, 24-48h or 48-64h.

[0008] In a second aspect, the present invention provides a chain extension resin intermediate, which is prepared by the following steps: Step A1: subjecting an initial polyurethane to a degradation reaction with a degradation agent having an active group to break at least a portion of the molecular chain of the initial polyurethane to obtain an active hydrogen-containing resin intermediate containing molecular fragments of the initial polyurethane; the active group comprises a hydroxyl group and / or an amine group; Step A2: converting the active hydrogen-containing resin intermediate into the chain extension resin intermediate through a grafting reaction.

[0009] Further, in step A1: the degradation reaction is an alcoholysis reaction; the degradation agent includes a polyol, and the polyol includes a diol and / or a high-functionality polyol; the diol includes a low molecular weight C2-C6 diol; the low molecular weight C2-C6 diol includes one or more combinations of ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, monoethylene glycol, monopropylene glycol or neopentyl glycol; the high-functionality polyol includes glycerol, trimethylolethane, trimethylolpropane, pentaerythritol, sucrose polyol, sorbitol or polyether polyol; the temperature of the alcoholysis reaction is 110-150°C, 150-170°C, 170-180°C, 180-200°C, 200-220°C or 220-250°C; the alcoholysis reaction time is 0.5-2h, 2-3h, 3-6h, 6-12h, 12-24h, 24-48h or 48-64h; in the step A2: the grafting reaction includes a ring-opening reaction of the active hydrogen of the active hydrogen-containing resin intermediate and the cyclic acid anhydride; the cyclic acid anhydride includes one or more combinations of monofunctional acid anhydride, difunctional acid anhydride or free acid anhydride; the cyclic acid anhydride includes one or more combinations of succinic anhydride, maleic anhydride, phthalic anhydride, nadic anhydride, methylhexahydrophthalic anhydride, chlorendic anhydride, pyromellitic anhydride or trimellitic anhydride.

[0010] In a third aspect, the present invention provides a thermosetting polyurethane resin, which is obtained by mixing a thermosetting polyurethane prepolymer mixture under reaction conditions in which a free radical polymerization reaction and an addition polymerization reaction of an isocyanate group and an active hydrogen group exist simultaneously, wherein the thermosetting polyurethane prepolymer mixture comprises: component A: an isocyanate component, wherein the isocyanate component comprises one or more organic polyisocyanates; component B: an isocyanate-reactive component, wherein the isocyanate-reactive component comprises a resin intermediate, wherein the resin intermediate is composed of the above-mentioned active hydrogen-containing resin intermediate and / or the above-mentioned chain extension resin intermediate.

[0011] Further, the isocyanate reactive component accounts for 21-60wt.% of the thermosetting polyurethane prepolymer mixture; the isocyanate reactive component also includes: component B1: organic polyol, the organic polyol accounts for 0-50wt.% of the thermosetting polyurethane prepolymer mixture; component B3: a compound containing both active double bonds and hydroxyl groups, the compound containing active double bonds and hydroxyl groups accounts for 0-30wt.% of the thermosetting polyurethane prepolymer mixture; the active double bonds are acrylate, methacrylate or styrene-containing structure; the resin intermediate as component B2 accounts for 2-30wt.% of the thermosetting polyurethane prepolymer mixture; the thermosetting polyurethane prepolymer mixture also includes: component C: active diluent, the active diluent is a compound containing active The present invention relates to a compound having a reactive double bond but no hydroxyl group, wherein the reactive diluent accounts for 0-30wt.% of the thermosetting polyurethane prepolymer mixture; the reactive double bond is an acrylate, a methacrylate or a styrene-containing structure; component D is a free radical initiator, wherein the free radical initiator accounts for 0.05-0.10wt.%, 0.10-0.15wt.%, 0.15-0.50wt.%, 0.50-1.00wt.%, 1.00-2.00wt.%, 2.00-3.00wt.% or 3.00-4.00wt.% of the thermosetting polyurethane prepolymer mixture; component E is a catalyst, wherein the catalyst is used to accelerate the urethane reaction and / or the catalyst for accelerating the free radical polymerization reaction; and / or component F is an auxiliary agent and / or an additive.

[0012] In a fourth aspect, the present invention provides a thermosetting polyurethane resin composite material, which is obtained by mixing a thermosetting polyurethane prepolymer mixture with a reinforcing material under reaction conditions in which a free radical polymerization reaction and an addition polymerization reaction of an isocyanate group and an active hydrogen group exist simultaneously, wherein the thermosetting polyurethane prepolymer mixture comprises: component A: an isocyanate component, wherein the isocyanate component comprises one or more organic polyisocyanates; component B: an isocyanate-reactive component, wherein the isocyanate-reactive component comprises: component B2: a resin intermediate, wherein the resin intermediate is composed of the active hydrogen-containing resin intermediate as described in claim 1 and / or the chain-extended resin intermediate as described in claim 3.

[0013] Furthermore, the isocyanate reactive component accounts for 21-60wt.% of the thermosetting polyurethane prepolymer mixture; the isocyanate reactive component also includes: component B1: organic polyol, the organic polyol accounts for 0-50wt.% of the thermosetting polyurethane prepolymer mixture; component B3: a compound containing both active double bonds and hydroxyl groups, the compound containing active double bonds and hydroxyl groups accounts for 0-30wt.% of the thermosetting polyurethane prepolymer mixture; the active double bonds are acrylate, methacrylate or styrene-containing structure; the resin intermediate as component B2 accounts for 2-30wt.% of the thermosetting polyurethane prepolymer mixture; the thermosetting polyurethane prepolymer mixture also includes: component C: active diluent, the active diluent is a compound containing active The present invention relates to a compound having a reactive double bond but no hydroxyl group, wherein the reactive diluent accounts for 0-30wt.% of the thermosetting polyurethane prepolymer mixture; the reactive double bond is an acrylate, a methacrylate or a styrene-containing structure; component D is a free radical initiator, wherein the free radical initiator accounts for 0.05-0.10wt.%, 0.10-0.15wt.%, 0.15-0.50wt.%, 0.50-1.00wt.%, 1.00-2.00wt.%, 2.00-3.00wt.% or 3.00-4.00wt.% of the thermosetting polyurethane prepolymer mixture; component E is a catalyst, wherein the catalyst is used to accelerate the urethane reaction and / or the catalyst for accelerating the free radical polymerization reaction; and / or component F is an auxiliary agent and / or an additive.

[0014] Furthermore, the thermosetting polyurethane resin composite material is obtained by a process selected from one or more combinations of infusion, pultrusion, winding, spraying, RTM, hand lay-up, prepreg, SMC / BMC.

[0015] Furthermore, the reinforcing material is one or more combinations selected from glass fiber, carbon fiber, carbon nanotube, polyester fiber, aromatic polyamide fiber, nylon fiber, natural fiber, basalt fiber, silicon carbide fiber, boron fiber, asbestos fiber, whisker, hard particles, and metal fiber.

[0016] Alcoholysis reaction in the present invention is to add alcohol degradation agent (middle and long chain polyol, small molecule polyol etc.) to the polyurethane solid material, and then degrade or partially degrade the macromolecular chain in it by heating to depolymerize it into liquid polyol substances containing polyhydroxyl and / or amino groups, which are polyol substances containing active hydrogen with initial polyurethane molecular fragments. These liquid polyol substances are specially referred to as resin intermediates containing active hydrogen in this patent, which can be first separated, purified and classified further, such as deamination, removal of particles, etc., and directly used as a part of a two-component system to participate in the preparation of novel thermosetting polyurethane resins, and can also continue to carry out grafting reaction before this to make this resin intermediate containing active hydrogen further become a resin intermediate containing initial polyurethane molecular fragments with chain extension groups. Actual alcoholysis process can add a certain amount of co-alcoholization agent and / or catalyst etc. according to specific needs, such as one or more combinations in amines, phosphates, alcoholamines, carboxylates of alkali metals and alkaline earth metals and hydroxides or other metal salts (tin, titanium etc.).

[0017] The grafting reaction includes a ring-opening reaction between the active hydrogen-containing resin intermediate and the cyclic acid anhydride, that is, the active hydrogen-containing resin intermediate obtained by the alcoholysis reaction is further transformed into a resin intermediate containing an initial polyurethane molecular fragment with a chain extension group through a grafting reaction.

[0018] The grafting reaction includes a ring-opening reaction between active hydrogen of the resin intermediate and a cyclic acid anhydride, wherein the cyclic acid anhydride includes one or more combinations of monofunctional acid anhydride, difunctional acid anhydride or free acid anhydride.

[0019] Further, in step A, the cyclic anhydride includes one or more combinations of succinic anhydride, maleic anhydride, phthalic anhydride, nadic anhydride, methylhexahydrophthalic anhydride, chlorendic anhydride, pyromellitic anhydride or trimellitic anhydride;

[0020] Wherein, component A-isocyanate includes any aliphatic, alicyclic or aromatic isocyanate or prepolymer or combination thereof known for preparing polyurethane. Examples thereof include, but are not limited to: toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polyphenylmethane polyisocyanate (pMDI), 1,5-naphthalene diisocyanate (NDI), hexamethylene diisocyanate (HDI), methylcyclohexyl diisocyanate (TDI), 4,4,-dicyclohexylmethane diisocyanate, isophorone diisocyanate (IPDI), p-phenylene diisocyanate (PPDI), p-phenylene diisocyanate (XDI), tetramethyl dimethylene diisocyanate (TMXDI) and polymers thereof or combinations thereof. The functionality of the isocyanate that can be used in the present invention is preferably 2.0-3.5, particularly preferably 2.1-2.9, and the viscosity of the isocyanate is preferably 5-700 mPa.s, particularly preferably 10-300 mPa.s, measured at 25° C. according to DIN 53019-1-3. When used in the present invention, the isocyanate component also includes isocyanate dimers, trimers, tetramers, pentamers or combinations thereof.

[0021] Component B1-organic polyol, including organic polyols that can be organic polyols commonly used in the art for preparing polyurethanes, including but not limited to: polyether polyols, polyether carbonate polyols, polyester polyols, polycarbonate diols, polymer polyols, plant oil-based polyols or combinations thereof.

[0022] The above-mentioned polyether polyol can be prepared by a known process, for example, by reacting an olefin oxide with an initiator in the presence of a catalyst. The catalyst is preferably, but not limited to, an alkaline hydroxide, an alkaline alcohol salt, boron fluoride etherate, or a mixture thereof. The olefin oxide is preferably, but not limited to, tetrahydrofuran, ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, styrene oxide, or a mixture thereof, and ethylene oxide and / or propylene oxide are particularly preferred. The initiator is preferably, but not limited to, a polyhydroxy compound or a polyamine compound, and the polyhydroxy compound is preferably, but not limited to, water, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, diethylene glycol, trimethylolpropane, glycerol, bisphenol A, bisphenol S, or a mixture thereof, and the polyamine compound is preferably, but not limited to, ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, diethylenetriamine, toluenediamine, or a mixture thereof.

[0023] The above-mentioned polyether carbonate polyols can also be used in the present invention, and the polyether carbonate polyols can be prepared by adding carbon dioxide and an alkylene oxide to a starter containing active hydrogen using a bimetallic catalyst.

[0024] The polyester polyol is prepared by reacting a dicarboxylic acid or a dibasic acid anhydride with a polyol. The dicarboxylic acid is preferably, but not limited to, an aliphatic carboxylic acid containing 2 to 12 carbon atoms, and the aliphatic carboxylic acid containing 2 to 12 carbon atoms is preferably, but not limited to, succinic acid, malonic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecyl phthalic acid, maleic acid, fumaric acid, phthalic acid, terephthalic acid, or a mixture thereof. The dibasic acid anhydride is preferably, but not limited to, phthalic anhydride, tetrachlorobenzoic anhydride, maleic anhydride, or a mixture thereof. The polyols reacted with dicarboxylic acids or dibasic anhydrides are preferably, but not limited to, ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, 1,3-methylpropanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,10-decanediol, glycerol, trimethylolpropane, or mixtures thereof. The polyester polyols also include polyester polyols prepared from lactones. The polyester polyols prepared from lactones are preferably, but not limited to, caprolactone. Preferably, the molecular weight of the polyester polyol is 200-3000, and the functionality is 2-6, preferably 2-4, and more preferably 2-3.

[0025] The polycarbonate diol can be prepared by reacting a diol with a dialkyl carbonate or a diaryl carbonate or phosgene. The diol is preferably, but not limited to, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, trioxymethylene glycol, or a mixture thereof. The dialkyl carbonate or diaryl carbonate is preferably, but not limited to, diphenyl carbonate.

[0026] The above-mentioned polymer polyol can be a polymer-modified polyether polyol, preferably a grafted polyether polyol, a polyether polyol dispersion. The grafted polyether polyol is preferably a grafted polyether polyol based on styrene and / or acrylonitrile; the styrene and / or acrylonitrile can be formed by in-situ polymerization of styrene, acrylonitrile, or a mixture of styrene and acrylonitrile; in the mixture of styrene and acrylonitrile, the ratio of styrene to acrylonitrile is 90:10-10:90, preferably 70:30-30:70. The polymer polyol of the present invention can also be a bio-based polyol such as castor oil and linseed oil. The polymer polyether polyol dispersion includes a dispersed phase, for example, an inorganic filler, or a polyurethane of melamine. The amount of the dispersed phase is 1-50wt.%, preferably 1-45wt.%, based on 100wt.% of the weight of the polymer polyether polyol. Preferably, the polymer solid content in the polymer polyether polyol is 20% to 25%, based on 100% weight of the polymer polyether, and the hydroxyl value is 20-50 mgKOH / g.

[0027] When used in the present invention, the polyol based on vegetable oil includes vegetable oil, vegetable oil polyol or its modified product. Vegetable oil is a compound prepared from unsaturated fatty acids and glycerol or oil extracted from the fruit, seed, germ of the plant, preferably but not limited to peanut oil, soybean oil, linseed oil, castor oil, rapeseed oil, palm oil. The vegetable oil polyol is a polyol initiated by one or more vegetable oils. The initiator of the synthetic vegetable oil polyol includes but is not limited to soybean oil, palm oil, peanut oil, canola oil and castor oil. The initiator of the vegetable oil polyol can introduce hydroxyl groups through processes such as cracking, oxidation or transesterification, and then prepare the corresponding vegetable oil polyol through the process of preparing organic polyols well known to those skilled in the art. For the above related knowledge, reference can also be made to the document "Handbook of Polyurethane Raw Materials and Additives" (Second Edition, Edited by Liu Yijun, 2013, Chemical Industry Press), and the entire contents disclosed in this document are incorporated herein by reference.

[0028] The isocyanate reactive component B also contains component B3-compounds containing both active double bonds and hydroxyl groups, and the total number of double bond groups and hydroxyl groups in one compound structure is ≥2; its typical compound representatives include but are not limited to hydroxypropyl acrylate, hydroxyethyl acrylate, pentaerythritol diacrylate, glycerol diacrylate, hydroxypropyl methacrylate, hydroxyethyl methacrylate, dipropylene glycol monomethacrylate and the like. The content of component B3 is 0-30wt.%, based on 100wt.% of the total weight of the polyurethane composition.

[0029] The thermosetting polyurethane prepolymer mixture further comprises a component C-active diluent, which is a compound containing an active double bond but no hydroxyl group, and the double bond group is ≥1 in a structure of the active diluent compound; its typical compound representatives include but are not limited to isobornyl methacrylate, styrene, methyl methacrylate, isooctyl acrylate (IOA), ethylene glycol diacrylate (EGDA), dipropylene glycol dimethacrylate, bisphenol A diallyl ether, hydroxybutyl acrylate, glycidyl methacrylate, glycerol triacrylate, trimethylolpropane acrylate, etc., and the content of the component C is 0-30wt.%, based on the total weight of the polyurethane composition as 100wt.%;

[0030] The thermosetting polyurethane prepolymer mixture also contains component D - free radical initiator, including thermosensitive free radical initiator and photosensitive free radical initiator. The thermosensitive free radical initiator includes peroxide, persulfide, peroxycarbonate, peroxyboric acid, azo compound or other suitable free radical initiator that can initiate the curing of double bond-containing compounds.

[0031] More preferably, the free radical initiator includes tert-butyl peroxyisopropyl carbonate, methyl ethyl ketone peroxide, potassium persulfate, cumene hydroperoxide, dibenzoyl peroxide, tert-butyl perbenzoate or 2,4-di-tert-butyl peroxide isopropylbenzene.

[0032] The thermosetting polyurethane prepolymer mixture further comprises component E, which is a catalyst optionally used to accelerate the urethane reaction and / or accelerate the free radical polymerization reaction. Useful catalyst E includes conventional types of polyurethane catalysts and / or accelerators for free radical polymerization reactions. Catalyst E can be used, for example, as a catalyst or catalyst composition in an amount of 0 to 6%, particularly 0.001 to 2.5%, based on the weight of component (B). Component (E) includes, for example, 2,3-dimethyl-3,4,5,6-tetrahydropyrimidine; tertiary amines such as triethylamine, tributylamine, dimethylbenzylamine (BDMA), N-methylmorpholine, N-ethylmorpholine, N-cyclohexylmorpholine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylbutanediamine, N,N,N',N'-tetramethylhexanediamine, pentamethyldiethylenetriamine, tetramethyldiaminoethyl ether, bis(dimethylaminopropyl)urea, dimethylpiperazine, 1,2-dimethylimidazole, 1-azabicyclo(3,3,0)octane, preferably 1,4-diazabicyclo(2,2,2)octane and alkanolamine compounds such as triethanolamine, triisopropanolamine, N-methyldiethanolamine and N-ethyldiethanolamine and dimethylethanolamine. Also useful are organometallic compounds, preferably organotin compounds, such as tin (II) salts of organic carboxylic acids, such as tin (II) acetate, tin (II) octanoate, tin (II) ethylhexanoate, tin (II) laurate; and dialkyltin (IV) salts of organic carboxylic acids, such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate and dioctyltin diacetate; and organometallic bismuth salt compounds or mixtures thereof. The organometallic compound can be used alone or preferably in combination with a strong alkaline amine. The organometallic compound also includes at least one of an organobismuth salt, an organocobalt salt and an organocuproic salt. In some specific embodiments, the organometallic compound is at least one of bismuth neodecanoate, bismuth 2-ethylhexanoate and bismuth octanoate, cobalt naphthoate, cobalt octanoate and copper acetate. In other embodiments, a chelating agent may also be added to the organometallic compound to promote the stability of the organometallic compound. In some specific embodiments, the chelating agent includes at least one of an EDTA-type structure and a dicarbonyl compound. The dicarbonyl compounds include but are not limited to 1,3-dicarbonyl compounds, 2,4-pentanedione and various substituents thereof. The chelating agent is a common compound in the art and will not be described in detail herein. The dicarbonyl compounds can be pre-mixed with component A, or pre-mixed with component B, or can be pre-mixed in both A and B. Available catalysts E also include conventional free radical promoters, such as some anilines, substituted anilines or other organic amines, reducing agents in redox systems, etc. These components can be optionally included in the isocyanate component A and / or the reactive component B. These components can also be stored independently as component E.

[0033] The thermosetting polyurethane prepolymer mixture further comprises component F, and optionally other auxiliary agents and additives, including but not limited to: fillers, internal mold release agents, flame retardants, smoke suppressants, dyes, pigments, antistatic agents, antioxidants, UV stabilizers, diluents, defoamers, coupling agents, surface wetting agents, leveling agents, dewatering agents, catalysts, molecular sieves, thixotropic agents, plasticizers, free radical reaction inhibitors or combinations thereof, which may be optionally included in the isocyanate component A and / or the reactive component B. These components may also be stored independently as component F.

[0034] The inventors of the present invention unexpectedly found that the polyurethane material obtained based on the above-mentioned reactions and components, whether it is a foamed material, a non-foamed material, or a composite material based on a non-foamed material, shows excellent properties relative to traditional polyurethanes, especially in terms of its strength and toughness. DETAILED DESCRIPTION

[0035] The detailed features and advantages of this patent are described in detail in the specific implementation method below, and the content is sufficient to enable any technical personnel in this field to understand the technical content of this patent and implement it accordingly. According to the description and claims disclosed in this specification, the technical personnel in this field can easily understand the relevant purposes and advantages of this patent.

[0036] In order to make the purpose, technical solutions and advantages of this patent clearer, the implementation method of this patent will be further described in detail below.

[0037] The raw materials used in this embodiment can be purchased on the market:

[0038] Among them, cobalt water accelerator HL-88B and methyl ethyl ketone peroxide MEKP were purchased from Guangzhou Hongli Chemical.

[0039] Diphenylmethane diisocyanate (PMDI): trade name 44V20L, purchased from Covestro; polyols DC-635C, NJ-303, NJ-204, DC-210, NJ-305, NJ301, etc. were purchased from Jurong Ningwu New Materials Company; tert-butyl peroxybenzoate TBPB: purchased from Nouryon; benzoyl peroxide BPO: purchased from Nouryon; isooctyl acrylate (IOA), ethylene glycol diacrylate (EGDA ) and hydroxypropyl methacrylate (HPMA) were purchased from Sinopharm Group; the glass fiber for pultrusion was direct roving E6-332, which was 332 direct yarn from Jushi Fiberglass Company; surfactant AK8860, catalyst PC-8 and UL29, flame retardant TCPP, release agent 550D, foaming agent 141b, defoamer 066N, polyurethane catalyst UL-29, dimethylbenzylamine BDMA, and flame retardant TCPP were all commonly used additives, purchased from Alibaba.com.

[0040] The hydroxyl value is determined according to GB / T 12008.3-2009; the foam density is determined based on GB / T 6343-2008, the compressive strength is determined based on GB / T 8813-2008, and the thermal conductivity K value is determined based on GB / T 10294-2008; the tensile mechanical properties test of the resin board is carried out based on ASTM D638 standard.

[0041] The present invention provides a method for preparing a resin intermediate based on the degradation and grafting reaction of initial polyurethane. The resin intermediate is obtained by degradation of polyurethane solid material (referred to as "initial polyurethane" in this patent) and further grafting reaction. For the greatest economic and social value, the degraded polyurethane solid material raw material is usually preferably polyurethane solid waste. It is characterized in that it specifically includes the following steps:

[0042] Step A1: subjecting the initial polyurethane to a degradation reaction with a degradation agent having an active group, thereby breaking at least a portion of the molecular chain of the initial polyurethane, and obtaining a resin intermediate M1 containing active hydrogen and containing molecular fragments of the initial polyurethane;

[0043] Step A2: The active hydrogen-containing resin intermediate M1 is further transformed into a resin intermediate M2 containing an initial polyurethane molecular fragment with a chain extension group through a grafting reaction;

[0044] Intermediate Preparation Example M1

[0045] 200 grams of the first polyurethane waste (post-consumer refrigerator hard foam) and 60 grams of the second polyurethane waste (post-consumer polyurethane mattress foam material) were poured into a round-bottom flask, mixed with 200 grams of diethylene glycol, and mechanically stirred until the polyurethane solid was completely dissolved for degradation reaction, wherein the temperature was kept in the range of 230°C (220°C-240°C) for 2 hours to obtain a degradation reaction liquid. After cooling to 120°C, the undegraded solid residue was removed by filtration and separation, and the filtrate was decompressed and distilled to remove excess diethylene glycol to obtain a resin intermediate M1 containing active hydrogen, and its hydroxyl value was tested to be 390.

[0046] Intermediate Preparation Example M2:

[0047] Step 1: Take 40 grams of the third polyurethane waste (post-consumer polyurethane soft foam material), 200 grams of the fourth polyurethane waste (post-consumer container rigid foam) and 700 grams of ethylene glycol, add 0.1 grams of catalyst tetrabutyl titanate, and then heat and stir until the polyurethane solid is dissolved to perform a degradation reaction, wherein the temperature is maintained in the range of 190°C (160°C-210°C) to obtain a degradation reaction liquid.

[0048] Step 2: Cool the degradation reaction liquid to 50°C, add 15g of phthalic anhydride and 40g of maleic anhydride to the obtained filtrate, stir for 3 hours, then gradually raise the temperature to 165°C and maintain for 1 hour while continuing to stir; after stopping the reaction, reduce the temperature to 120°C, and filter and separate to remove the undegraded solid residue. Transfer the reaction mixture and remove the excess ethylene glycol by vacuum distillation to obtain the resin intermediate M2 after the grafting reaction, and its hydroxyl value is 330 when tested.

[0049] Example 1-3: Resin intermediate + component A two-component resin

[0050] Based on the above-mentioned resin intermediates M1 and / or M2, a resin composition is directly formed with other components. This resin composition can be combined with the isocyanate component A to form a two-component resin to prepare the novel thermosetting polyurethane resin of the present invention. Therefore, the thermosetting polyurethane resin matrix can be prepared by the above-mentioned resin composition.

[0051] The detailed test process and results of the polyurethane foam material comparative example 1 and embodiments 1-3 are given below for exemplary description:

[0052] Preparation process: Add the components according to Table 1 (the proportions in the table are weight ratios), mix them with a high-speed mixer (2000 rpm, stirring for 15 seconds), pour them into a metal box mold preheated to 40°C, then cover and lock the mold and wait for 10 minutes. Open the box and take out the foam for testing. The performance is shown in Table 1.

[0053] Table 1: Components and properties of polyurethane foams in Examples 1 to 3 and Comparative Example 1

[0054]

[0055]

[0056] It can be seen from Table 1 that after the resin intermediate prepared by the present invention is added to the resin composition, the thermal conductivity of the foam remains almost unchanged, but the strength is further improved, and the overall performance is better than that of traditional polyurethane foam materials, showing obvious advantages.

[0057] Example 4-8: Preparation of thermosetting polyurethane from resin composition

[0058] The present invention further provides a method for preparing a thermosetting polyurethane with better performance by using a resin composition containing such a resin intermediate, comprising the following steps:

[0059] First, according to Table 2 (all proportions in the table are weight ratios), the raw materials of the resin composition are added together and mixed uniformly to obtain a mixture; then the mixture is poured into a flat mold and then placed in an oven preheated to 80°C, and then heated to raise the oven temperature to 135°C for 1 hour and maintained for 1 hour; then the oven heating is turned off, and the cured resin plate is allowed to naturally cool to room temperature in the mold, and then the oven is opened to take out the cured resin plate.

[0060] The detailed test process and results of Examples 4 to 8 and Comparative Example 2 are given below for exemplary description, and the performance is shown in Table 2:

[0061] Table 2: Properties of Cured Polyurethane Resins in Examples 4 to 8 and Comparative Example 2

[0062]

[0063]

[0064] It can be seen from Table 2 that, after the resin intermediate prepared by the present invention is added to the resin composition, the mechanical strength of the cured resin is further improved, and from the perspective of elongation at break, the toughness of the resin is also improved. Therefore, the overall performance of the thermosetting polyurethane resin material of the present invention is better than that of the traditional polyurethane resin, showing obvious advantages.

[0065] Examples 9-10: Preparation of thermal composite materials from resin compositions

[0066] The present invention further provides a method for preparing a composite material product by a composite material production process based on a resin composition thermosetting polyurethane resin containing such a resin intermediate. Taking the commonly used pultrusion process as an example, the method comprises the following steps:

[0067] First, the raw materials of the resin composition are added together and mixed evenly. The obtained resin mixture is put on the pultrusion line for pultrusion and sample preparation. A glue injection box and a flat mold are used. The temperature settings of the three zones of the mold heating zone from the back to the front are: 100°C for zone 1, 170°C for zone 2, and 180°C for zone 3. The pultrusion speed is about 0.6m / min. The glass fiber is Jushi 332 direct yarn (direct untwisted roving E6-332 for pultrusion). The products prepared by this pultrusion process are shown in the following for example by the detailed proportions and test results of Examples 9 to 10 and Comparative Example 3. The performance is shown in Table 3.

[0068] Table 3: Composite material properties of Examples 9-10 and Comparative Example 3

[0069]

[0070]

[0071] As can be seen from Table 3, after the resin intermediate prepared by the present invention is added to the resin composition, the mechanical strength of the composite material obtained by the thermosetting polyurethane resin and the reinforcing material based on the resin composition is significantly improved, and the improvement can reach more than 30%. Therefore, the overall performance of the thermosetting polyurethane resin material of the present invention is better than that of the traditional polyurethane resin, showing obvious advantages, and can be used to prepare a composite material with better performance.

[0072] The terms and expressions used herein are for descriptive purposes only, and the patent shall not be limited to these terms and expressions. The use of these terms and expressions does not mean to exclude any equivalent features of the illustrations and descriptions (or parts thereof), and it should be recognized that various modifications that may exist should also be included in the scope of the claims. Other modifications, changes and substitutions may also exist. Accordingly, the claims should be deemed to cover all such equivalents.

[0073] Similarly, it should be pointed out that although this patent has been described with reference to the current specific embodiments, ordinary technicians in this technical field should realize that the above embodiments are only used to illustrate this patent, and various equivalent changes or substitutions can be made without departing from the spirit of this patent. Therefore, as long as the changes and modifications to the above embodiments are within the essential spirit of this patent, they will fall within the scope of the claims of this patent.

Claims

1. An active hydrogen-containing resin intermediate, characterized in that: Prepared by the following steps: Step A1: subjecting the initial polyurethane to a degradation reaction with a degradation agent having an active group, breaking at least a portion of the molecular chain of the initial polyurethane, and obtaining the active hydrogen-containing resin intermediate containing the initial polyurethane molecular fragment, wherein the active group comprises a hydroxyl group and / or an amine group.

2. The active hydrogen-containing resin intermediate according to claim 1, characterized in that: In the step A1: The degradation reaction is an alcoholysis reaction; The degradation agent includes a polyol, and the polyol includes a diol and / or a high-functionality polyol; The diols include low molecular weight C2-C6 diols; The low molecular weight C2-C6 diol includes one or more combinations of ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, ethylene glycol acetal, propylene glycol acetal or neopentyl glycol; The high-functionality polyol includes glycerol, trimethylolethane, trimethylolpropane, pentaerythritol, sucrose polyol, sorbitol or polyether polyol; The temperature of the alcoholysis reaction is 110-150°C, 150-170°C, 170-180°C, 180-200°C, 200-220°C or 220-250°C; The alcoholysis reaction time is 0.5 to 2 hours, 2 to 3 hours, 3 to 6 hours, 6 to 12 hours, 12 to 24 hours, 24 to 48 hours or 48 to 64 hours.

3. A chain extension resin intermediate, characterized in that: Prepared by the following steps: Step A1: subjecting the initial polyurethane to a degradation reaction with a degradation agent having an active group, thereby breaking at least a portion of the molecular chain of the initial polyurethane to obtain an active hydrogen-containing resin intermediate containing molecular fragments of the initial polyurethane; the active group comprises a hydroxyl group and / or an amine group; Step A2: converting the active hydrogen-containing resin intermediate into the chain-extended resin intermediate through a grafting reaction.

4. The active hydrogen-containing resin intermediate according to claim 3, characterized in that: In the step A1: The degradation reaction is an alcoholysis reaction; The degradation agent includes a polyol, and the polyol includes a diol and / or a high-functionality polyol; The diols include low molecular weight C2-C6 diols; The low molecular weight C2-C6 diol includes one or more combinations of ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, ethylene glycol acetal, propylene glycol acetal or neopentyl glycol; The high-functionality polyol includes glycerol, trimethylolethane, trimethylolpropane, pentaerythritol, sucrose polyol, sorbitol or polyether polyol; The temperature of the alcoholysis reaction is 110-150°C, 150-170°C, 170-180°C, 180-200°C, 200-220°C or 220-250°C; The alcoholysis reaction time is 0.5 to 2 hours, 2 to 3 hours, 3 to 6 hours, 6 to 12 hours, 12 to 24 hours, 24 to 48 hours or 48 to 64 hours; In the step A2: The grafting reaction includes a ring-opening reaction between active hydrogen of the active hydrogen-containing resin intermediate and a cyclic acid anhydride; The cyclic anhydride includes one or more combinations of monofunctional anhydride, difunctional anhydride or free acid anhydride; The cyclic anhydride includes one or more combinations of succinic anhydride, maleic anhydride, phthalic anhydride, nadic anhydride, methylhexahydrophthalic anhydride, chlorendic anhydride, pyromellitic anhydride or trimellitic anhydride.

5. A thermosetting polyurethane resin, characterized in that: The thermosetting polyurethane resin is obtained by mixing a thermosetting polyurethane prepolymer mixture under reaction conditions in which a free radical polymerization reaction and an addition polymerization reaction of an isocyanate group and an active hydrogen group exist simultaneously. The thermosetting polyurethane prepolymer mixture comprises: Component A: an isocyanate component, wherein the isocyanate component comprises one or more organic polyisocyanates; Component B: an isocyanate reactive component, wherein the isocyanate reactive component comprises a resin intermediate B2, wherein the resin intermediate B2 is composed of the active hydrogen-containing resin intermediate as claimed in claim 1 and / or the chain-extended resin intermediate as claimed in claim 3.

6. The thermosetting polyurethane resin according to claim 5, characterized in that: The isocyanate reactive component accounts for 21-60wt.% of the thermosetting polyurethane prepolymer mixture; The isocyanate reactive component also includes: Component B1: organic polyol, the organic polyol accounts for 0-50wt.% of the thermosetting polyurethane prepolymer mixture; Component B3: a compound containing both active double bonds and hydroxyl groups, wherein the compound containing active double bonds and hydroxyl groups accounts for 0-30wt.% of the thermosetting polyurethane prepolymer mixture; the active double bonds are acrylate, methacrylate or styrene-containing structures; The resin intermediate as the component B2 accounts for 2-30wt.% of the thermosetting polyurethane prepolymer mixture; The thermosetting polyurethane prepolymer mixture also includes: Component C: a reactive diluent, wherein the reactive diluent is a compound containing reactive double bonds but no hydroxyl group, and the reactive diluent accounts for 0-30wt.% of the thermosetting polyurethane prepolymer mixture; the reactive double bonds are acrylate, methacrylate or styrene-containing structures; Component D: a free radical initiator, wherein the free radical initiator accounts for 0.05-0.10wt.%, 0.10-0.15wt.%, 0.15-0.50wt.%, 0.50-1.00wt.%, 1.00-2.00wt.%, 2.00-3.00wt.% or 3.00-4.00wt.% of the thermosetting polyurethane prepolymer mixture; Component E: a catalyst, the catalyst being used to accelerate a urethane reaction and / or a catalyst for accelerating a free radical polymerization reaction; and / or Component F: auxiliaries and / or additives.

7. A thermosetting polyurethane resin composite material, characterized in that: The thermosetting polyurethane resin composite material is obtained by mixing a thermosetting polyurethane prepolymer mixture with a reinforcing material under reaction conditions in which a free radical polymerization reaction and an addition polymerization reaction of an isocyanate group and an active hydrogen group exist simultaneously. The thermosetting polyurethane prepolymer mixture comprises: Component A: an isocyanate component, wherein the isocyanate component comprises one or more organic polyisocyanates; Component B: an isocyanate-reactive component, the isocyanate-reactive component comprising: Component B2: a resin intermediate, wherein the resin intermediate is composed of the active hydrogen-containing resin intermediate according to claim 1 and / or the chain-extended resin intermediate according to claim 3.

8. The thermosetting polyurethane resin composite material according to claim 7, characterized in that: The isocyanate reactive component accounts for 21-60wt.% of the thermosetting polyurethane prepolymer mixture; The isocyanate reactive component also includes: Component B1: organic polyol, the organic polyol accounts for 0-50wt.% of the thermosetting polyurethane prepolymer mixture; Component B3: a compound containing both active double bonds and hydroxyl groups, wherein the compound containing active double bonds and hydroxyl groups accounts for 0-30wt.% of the thermosetting polyurethane prepolymer mixture; the active double bonds are acrylate, methacrylate or styrene-containing structures; The resin intermediate as the component B2 accounts for 2-30wt.% of the thermosetting polyurethane prepolymer mixture; The thermosetting polyurethane prepolymer mixture also includes: Component C: a reactive diluent, wherein the reactive diluent is a compound containing reactive double bonds but no hydroxyl group, and the reactive diluent accounts for 0-30wt.% of the thermosetting polyurethane prepolymer mixture; the reactive double bonds are acrylate, methacrylate or styrene-containing structures; Component D: a free radical initiator, wherein the free radical initiator accounts for 0.05-0.10wt.%, 0.10-0.15wt.%, 0.15-0.50wt.%, 0.50-1.00wt.%, 1.00-2.00wt.%, 2.00-3.00wt.% or 3.00-4.00wt.% of the thermosetting polyurethane prepolymer mixture; Component E: a catalyst, the catalyst being used to accelerate a urethane reaction and / or a catalyst for accelerating a free radical polymerization reaction; and / or Component F: auxiliaries and / or additives.

9. The thermosetting polyurethane resin composite material according to claim 7, characterized in that: The thermosetting polyurethane resin composite material is obtained by one or more process methods selected from the group consisting of infusion, pultrusion, winding, spraying, RTM, hand lay-up, prepreg, and SMC / BMC.

10. The thermosetting polyurethane resin composite material according to claim 7, characterized in that: The reinforcing material is selected from one or more combinations of glass fiber, carbon fiber, carbon nanotube, polyester fiber, aromatic polyamide fiber, nylon fiber, natural fiber, basalt fiber, silicon carbide fiber, boron fiber, asbestos fiber, whisker, hard particles, and metal fiber.

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