CN106751737B - Thermoset polyurethane composite - Google Patents
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- CN106751737B CN106751737B CN201510815382.8A CN201510815382A CN106751737B CN 106751737 B CN106751737 B CN 106751737B CN 201510815382 A CN201510815382 A CN 201510815382A CN 106751737 B CN106751737 B CN 106751737B
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Abstract
The present invention relates to a thermoset polyurethane composite comprising: (I) a polyurethane matrix in an amount of 10 to 70 wt%, prepared from a polyurethane composition comprising a component a and a component B, wherein the component a is an organic polyisocyanate and/or an organic polyisocyanate prepolymer and the component B is an isocyanate-reactive component having a hydroxyl value of 300 to 600mgKOH/g, preferably 350 to 550 mgKOH/g; (II) a reinforcing material in an amount of 30 to 90 wt%. The composite has high mechanical property and good appearance.
Description
Technical Field
The present invention relates to a thermosetting polyurethane composite.
Background
Fiber reinforced polyurethane composites are composed of two or more different physical phases in which the fibers are dispersed in a continuous polyurethane resin matrix phase. Compared with the conventional materials, the fiber-reinforced polyurethane compound has the characteristics of light weight, corrosion resistance, high toughness and high construction efficiency. However, isocyanate is easy to react with water, and bubbles are easily generated during resin curing, so that the strength of the produced polyurethane composite is greatly reduced, and a large number of bubbles appear on the surface of a product, which affects the appearance of the product.
patent CN 104045806a discloses a glycerol-initiated polyether polyol based polyurethane resin composition for preparing polyurethane composites, comprising a polyisocyanate component and an isocyanate-reactive component, wherein the isocyanate component comprises 10-56% of 2,2 '-diphenylmethane diisocyanate and 2, 4' -diphenylmethane diisocyanate. The isocyanate reactive component comprises 30-100% of glycerol starting polyol, the viscosity is 50-450mPas, the hydroxyl value is 120-450mgKOH/g, and the glycerol starting polyol adopted by the patent is sensitive to moisture and is easy to generate foaming problem in the forming process, thereby influencing the mechanical property of the product.
Patent WO2002/083758 discloses an LPA hybrid comprising: a first component having at least one ethylenically unsaturated bond and an isocyanate-reactive group, a second component of ethylenically unsaturated monomers capable of reacting with the first component by free radical polymerization, and a third component of polyisocyanates having an average functionality of at least 1.75 when reacted with the first component by polyurethane, the free radical catalyst being a fourth component and 3-20% of a hybrid of a thermoplastic polymer having a molecular weight of at least 10000 daltons, which contains a significant amount of unsaturated monomers, is relatively volatile and is relatively brittle after curing.
Patent CN104277194A discloses a resin composition containing carbon dioxide polyether polyol, which comprises organic isocyanate, one or more polycarbonate polyols prepared by adding carbon dioxide and an alkylene oxide compound on an active hydrogen-containing initiator using a double metal cyanide catalyst. The resin composition can be used for preparing polyurethane composites by pultrusion, winding, vacuum infusion and other processes. This patent does not address the disadvantage of easy foaming of polyurethane composites.
Patent CN1401680 discloses a hard polyurethane casting material, which comprises A, R, F three components, wherein the component A is a semi-prepolymer synthesized by 65-90% of polyisocyanate with the functionality of 2-2.7 and 10-35% of polyether polyol with the molecular weight of 400-10000, and the content of free isocyanate group in the semi-prepolymer is 18-35%; the R component comprises 10-40% of chain extender, 30-60% of polyether polyol and 1-5% of auxiliary agent. The isocyanate component in the formula disclosed by the patent has high viscosity due to low isocyanate content, is only suitable for a polyurethane casting process and is not suitable for traditional composite material processes such as winding, pultrusion, vacuum infusion and the like, and the problem that the polyurethane composite material is easy to foam is not solved.
Disclosure of Invention
One of the objectives of the present invention is to provide a thermosetting polyurethane composite, which solves the problem of easy foaming of polyurethane composite materials, and has high mechanical properties and good appearance.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
A thermoset polyurethane composite comprising:
(I) A polyurethane matrix in an amount of 10 to 70 wt%, preferably 20 to 50 wt%, more preferably 30 to 45 wt%, based on the total weight of the thermoset polyurethane composite;
the polyurethane matrix is prepared from a polyurethane composition comprising:
a organic polyisocyanate and/or organic polyisocyanate prepolymer, NCO content 25-35 wt%;
B an isocyanate-reactive component having a hydroxyl value of from 300 to 600mgKOH/g, preferably from 350 to 500 mgKOH/g;
(II) a reinforcing material in an amount of 30 to 90 wt%, preferably 50 to 80 wt%, more preferably 55 to 70 wt%, based on the total weight of the thermosetting polyurethane composite.
In the present invention, the organic polyisocyanate prepolymer is prepared from 90 to 99.9% by weight, preferably 95 to 99.8% by weight, of polyisocyanate and 0.1 to 10% by weight, preferably 0.2 to 5% by weight, of polyol, based on the total weight of the organic polyisocyanate prepolymer.
In the present invention, the polyol used for preparing the organic polyisocyanate prepolymer is selected from organic polyols having a functionality of 2 to 4 and a molecular weight of 400 to 10000, examples of which include, but are not limited to, one or more of polyethylene glycol ether, polypropylene glycol ether, polypentaerythritol ether, polytetrahydrofuran ether glycol.
In the present invention, it is desirable to control the water content of the polyurethane composition to be less than 0.1 wt%, preferably free of water, mainly by controlling the water content of the raw materials in the composition. The density of the polyurethane matrix prepared from the polyurethane composition is 910-1500kg/m3The foaming degree of the polyurethane matrix is very slight, even no foaming, and the density of the polyurethane matrix resin with serious foaming degree is lower than the density range of the invention.
In the present invention, the organic polyisocyanate in the a component and the polyisocyanate used to prepare the organic polyisocyanate prepolymer may be any aliphatic, cycloaliphatic and aromatic isocyanate known to be used to prepare polyurethanes, examples of which 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, 4' -dicyclohexylmethane diisocyanate, isophorone diisocyanate (IPDI), p-phenylene diisocyanate (PPDI), p-phenylene diisocyanate (XDI), tetramethyldimethylene diisocyanate (TMXDI), and polymers thereof or combinations thereof; the polyisocyanates which can be used according to the invention preferably have a functionality of from 2.0 to 3.5, particularly preferably from 2.1 to 2.9; the isocyanate viscosity is preferably from 5 to 700 mPas, particularly preferably from 10 to 300 mPas, determined at 25 ℃ in accordance with DIN 53019-1-3.
When polyphenylmethane Polyisocyanate (PMDI) is used in the present invention, it may be selected from, but is not limited to, uretdione, trimer, tetramer, pentamer or combinations thereof.
Preferably, the a component in the present invention is selected from diphenylmethane diisocyanate (MDI), polyphenylmethane Polyisocyanate (PMDI), and polymers, prepolymers or combinations thereof.
In the present invention, the preparation method of the component A and each compound contained therein are well known to those skilled in the art.
in the invention, the component B comprises:
b1) one or more polyether polyols starting from pentaerythritol, the b1) component having an average hydroxyl value of from 200 to 650mg KOH/g, preferably from 350 to 500mg KOH/g, parts by weight of the b1 component being from 25 to 75, preferably from 40 to 70;
Wherein the polymerized monomer of the polyether polyol in b1) is preferably propylene oxide;
b2) At least one organic polyol having a functionality of from 2 to 6, preferably from 2 to 3, and a hydroxyl number of from 100 to 450mgKOH/g, preferably from 150 to 250mgKOH/g, the b2 component being present in parts by weight of from 20 to 60, preferably from 21 to 40.
By way of further explanation and preference, the b2) component comprises at least one organic polyol selected from one or more of polyether polyols, polyether carbonate polyols, polyester polyols, polycarbonate diols, vegetable oil based polyols.
By way of further explanation and explanation, when a polyether polyol is used in the b2) component of the present invention, the polyether polyol may be prepared by known processes, for example, by reacting an olefin oxide with an initiator in the presence of a catalyst; the catalyst is preferably, but not limited to, alkali hydroxide, alkali alkoxide, antimony pentachloride, boron fluoride diethyl ether or a mixture thereof. The alkylene oxide is preferably, but not limited to, tetrahydrofuran, ethylene oxide, propylene oxide, 1, 2-butylene oxide, 2, 3-butylene oxide, styrene oxide, or a mixture thereof, and ethylene oxide and/or propylene oxide is particularly preferred. The initiator is preferably, but not limited to, a polyol, preferably, but not limited to, water, ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, diethylene glycol, trimethylolpropane, glycerol, xylitol, sorbitol, sucrose, bisphenol a, bisphenol S, or mixtures thereof, or a polyamine, preferably, but not limited to, ethylenediamine, propylenediamine, butylenediamine, hexylenediamine, diethylenetriamine, tolylenediamine, or mixtures thereof.
By way of further explanation and illustration, when polyether carbonate polyols are used in the b2) component of the present invention, the polycarbonate polyols can be prepared by addition of carbon dioxide and alkylene oxides onto an active hydrogen-containing starter using double metal cyanide catalysts; the polycarbonate polyols preferably have a molecular weight of 500 to 6000, more preferably 1000 to 4000, and even more preferably 2000 to 3000.
By way of further explanation and illustration, when a polyester polyol is used in the b2) component of the present invention, the polyester polyol is prepared by reacting a dicarboxylic acid or dicarboxylic acid anhydride with a polyol; the dicarboxylic acid is preferably, but not limited to, an aliphatic carboxylic acid having 2 to 12 carbon atoms or an aromatic carboxylic acid having 6 to 12 carbon atoms, the aliphatic carboxylic acid having 2 to 12 carbon atoms or the aromatic carboxylic acid having 6 to 12 carbon atoms, and is preferably, but not limited to, succinic acid, malonic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecane carboxylic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, or a mixture thereof. The dicarboxylic acid anhydride is preferably, but not limited to, phthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride, or a mixture thereof. The polyhydric alcohol reacted with the dicarboxylic acid or dicarboxylic acid anhydride is preferably, but not limited to, ethylene glycol, diethylene glycol, 1, 2-propanediol, 1, 3-propanediol, dipropylene glycol, 1, 3-methylpropanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, neopentyl glycol, 1, 10-decanediol, glycerol, trimethylolpropane, or a mixture thereof; the polyester polyols preferably have a molecular weight of 100 to 1000 and a functionality of 2 to 6, preferably 2 to 4, more preferably 2 to 3. The polyester polyol also comprises polyester polyol prepared from lactone; the lactone is preferably, but not limited to, epsilon-caprolactone; preferably, the lactone-prepared polyester polyol has a molecular weight of 200 to 3000 and a functionality of 2 to 6, preferably 2 to 4, more preferably 2 to 3.
By way of further explanation and illustration, when a polycarbonate diol is used in the b2) component of the present invention, the polycarbonate diol may be prepared by reacting a diol with a dialkyl carbonate or a diol with a diaryl carbonate or a diol with phosgene; the dihydric alcohol 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, the dialkyl carbonate is preferably but not limited to dimethyl carbonate, and the diaryl carbonate is preferably but not limited to diphenyl carbonate.
By way of further explanation and illustration, when a vegetable oil-based polyol is used in the b2) component of the present invention, the vegetable oil-based polyol includes a vegetable oil, a vegetable oil polyol, or a modified product thereof; vegetable oils are compounds prepared from unsaturated fatty acids and glycerol or oils and fats extracted from fruits, seeds, germs of plants, preferably but not limited to peanut oil, soybean oil, linseed oil, castor oil, rapeseed oil, palm oil; the vegetable oil polyol is a polyol initiated by one or more vegetable oils; synthetic vegetable oil polyol starters include, but are not limited to, soybean oil, palm oil, peanut oil, canola oil, and castor oil; the vegetable oil polyol starter may be used to introduce hydroxyl groups by cleavage, oxidation, or transesterification, and the corresponding vegetable oil polyol may be prepared by processes well known to those skilled in the art for preparing organic polyols.
Further preferably, b2) comprises at least one organic polyol having a functionality of 2.1 to 3 and a viscosity of 20 to 2000 mPas, preferably 200 to 1000 mPas.
methods for measuring hydroxyl numbers are well known to the person skilled in the art, for example in HoubenWeyl, Methoden der Organischen Chemie, vol.XIV/2 Makromolekulare Stoffe, p.17, Georg Thieme Verlag; stuttgart 1963.
It is specifically noted that, when used in the present invention, unless otherwise indicated, the functionality and hydroxyl number of the polyol are both the average functionality and the average hydroxyl number.
the component for preparing the polyurethane matrix (I) can also comprise an additive, wherein the additive can be selected from one or more of fillers, internal release agents, flame retardants, smoke inhibitors, dyes, pigments, antistatic agents, antioxidants, UV stabilizers, diluents, antifoaming agents, coupling agents, surface wetting agents, flatting agents, water scavengers, catalysts, molecular sieves, thixotropic agents, plasticizers and chain extenders.
When necessary, the additive of the present invention comprises a catalyst for catalyzing the reaction of isocyanate groups (NCO) with hydroxyl groups (OH); suitable catalysts for the polyurethane reaction of the present invention are preferably, but not limited to, amine catalysts, organometallic catalysts, or mixtures thereof. The amine catalyst is preferably, but not limited to, triethylamine, tributylamine, triethylenediamine, N-ethylmorpholine, N, N, N ', N' -tetramethyl-ethylenediamine, pentamethyldiethylenetriamine, N, N-methylaniline, N, N-dimethylaniline, or a mixture thereof. The organometallic catalyst is preferably, but not limited to, organotin compounds, such as: tin (II) acetate, tin (II) octoate, tin ethylhexanoate, tin laurate, dibutyltin oxide, dibutyltin dichloride, dibutyltin diacetate, dibutyltin maleate, dioctyltin diacetate, or a mixture thereof; the catalysts are used in amounts of 0.001 to 10% by weight, based on the total weight of the isocyanate-reactive components.
Where necessary, the additive of the invention comprises a filler selected from: aluminum hydroxide, bentonite, fly ash, wollastonite, perlite powder, cenosphere, calcium carbonate, talcum powder, mica powder, porcelain clay, fumed silica, expandable microspheres, diatomite, volcanic ash, barium sulfate, calcium sulfate, glass microspheres, stone powder, wood powder, sawdust, bamboo powder, bamboo sawdust, rice grains, straw scraps, sorghum straw scraps, graphite powder, metal powder, thermosetting compound recovery powder, plastic particles or powder or a combination thereof; wherein the glass microspheres can be solid or hollow.
when necessary, the additive of the present invention contains an internal mold release agent, which may be any conventional mold release agent used for producing polyurethanes, and examples thereof include long-chain carboxylic acids, particularly fatty acids such as stearic acid, amines of long-chain carboxylic acids such as stearamide, fatty acid esters, metal salts of long-chain carboxylic acids such as zinc stearate, or polysiloxanes.
when necessary, the additive of the present invention comprises a flame retardant, and examples thereof include triaryl phosphate, trialkyl phosphate, triaryl phosphate or trialkyl phosphate with halogen, melamine resin, halogenated paraffin, red phosphorus, or a combination thereof.
where necessary, the additive of the present invention comprises a chain extender, examples of which include ethylene glycol, propylene glycol, 1, 4-butanediol, diethylene glycol, glycerol, trimethylolpropane, 1, 4-cyclohexanediol, hydrogenated bisphenol a, dimethylenephenyl glycol, hydroquinone bis- β -hydroxyethyl ether, resorcinol hydroxy ether, diethanolamine, triethanolamine, methyldiethanolamine, 3 '-dichloro-4, 4' -diphenylmethane, diethyltoluenediamine, 3, 5-dimethylthiotoluenediamine, α -glycerol allyl ether, glycidyl allyl ether dicumyl peroxide, sulfur or a combination thereof.
Where necessary, the additive according to the invention comprises further auxiliaries, in particular water scavengers, such as molecular sieves; defoamers, such as polydimethylsiloxane; coupling agents, such as monoepoxyethane or organic amine functional trialkoxysilane or combinations thereof. Coupling agents are particularly preferred for improving the adhesion of the resin matrix to the fibrous reinforcement. Finely particulate fillers, such as clays and fumed silicas, are commonly used as thixotropic agents.
The reinforcing material (II) is preferably one or more of glass fiber, carbon nano tube, carbon fiber, polyester fiber, natural fiber, aromatic polyamide fiber, nylon fiber, basalt fiber, boron fiber, silicon carbide fiber and asbestos fiber.
When used in the present invention, the fibrous reinforcement is not required in shape and size, and may be, for example, continuous fibers, a web formed by bonding, or a fabric.
the thermosetting polyurethane composite of the present invention is prepared by winding, vacuum infusion, resin transfer molding, hand lay-up, spray or continuous sheet processes and combinations thereof, preferably winding, vacuum infusion, hand lay-up or combinations thereof.
for a detailed description of the process, reference may be made to chapter 2 and chapter 6-9 of "composite materials Process and apparatus" (Liu Xiong Asia et al, 1994, published by Wuhan university of science).
The thermosetting polyurethane composite can be used for wind driven generator blades, yacht shells, window frames, door frames, ladder frames, telegraph pole cross arms, tent supports, solar frames, antenna covers, radar covers, highway guardrails, cable troughs, container floors, various winding pipelines, telegraph poles, engine covers, automobile trunks, trunk supports, golf clubs, net clubs, badminton clubs, bicycle frames, surfboards or skis. The polyurethane composite of the present invention is not limited to the above-mentioned uses.
the reasonable design of the formula in the polyurethane composition enables the foaming degree of a polyurethane matrix prepared from the polyurethane composition to be very slight, even not foamed, and the polyurethane matrix prepared from the polyurethane composition is used in the formula of the polyurethane composition, so that the problem that the polyurethane composition is easy to foam is solved, the appearance of the composition is improved, and the mechanical property of the composition is improved.
In addition, according to the formula of the polyurethane composition and the matching of the reinforcing material, the polyurethane composition and the reinforcing material can be combined with the preparation process disclosed by the invention to prepare a compound with good appearance and excellent performance.
Detailed Description
The present invention is further illustrated by the following examples, which will enable one skilled in the art to more fully understand the present invention, but which are not intended to limit the invention in any way.
Examples
Test methods in which specific conditions are not specified in the following examples are generally carried out under conventional conditions or under conditions recommended by the manufacturer. All percentages and parts are by weight unless otherwise indicated.
the raw materials used in the examples are as follows:
Isocyanate having an isocyanate group content of 31.4% by weight, an average functionality of 2.7 and a viscosity of 200 mPa.s at 25 ℃ from Vanhua chemical group, Inc.;
Isocyanate having an isocyanate group content of 33.5% by weight, an average functionality of 2.0 and a viscosity of 15 mPa.s at 25 ℃ from Vanhua chemical group, Inc.;
Polyether polyol 1: 3-functionality polyol prepared by taking glycerol as an initiator and propylene oxide as a main body of polymerization reaction, wherein the hydroxyl value is 168mgKOH/g, and the viscosity is 260mPa & s at 25 ℃;
Polyether polyol 2: 3-functionality polyol prepared by taking glycerol as an initiator and propylene oxide as a main body of polymerization reaction, wherein the hydroxyl value is 240mgKOH/g, and the viscosity is 290mPa & s at 25 ℃;
polyether polyol 3: the 3-functionality polyol prepared by taking glycerol as an initiator and propylene oxide as a main body of polymerization reaction has a hydroxyl value of 420mgKOH/g and viscosity of 350mPa & s at 25 ℃;
polyether polyol 4: the 3-functionality polyol prepared by taking glycerol as an initiator and propylene oxide as a main body of polymerization reaction has a hydroxyl value of 560mgKOH/g and a viscosity of 470mPa & s at 25 ℃;
polyether polyol 5: the 4.5 functionality degree polyalcohol is prepared by taking glycerol and sorbitol as initiator and propylene oxide as main body of polymerization reaction, the hydroxyl value is 500mgKOH/g, and the viscosity is 4000 mPa.s at 25 ℃;
Polyether polyol 6: pentaerythritol is taken as an initiator, and propylene oxide is taken as a main body of polymerization reaction to prepare 4-functionality polyol with a hydroxyl value of 725 mgKOH/g;
Polyether polyol 7: the hydroxyl value of the 4-functionality polyol prepared by taking pentaerythritol as an initiator and propylene oxide as a main body of polymerization reaction is 500 mgKOH/g;
Polyether polyol 8: the hydroxyl value of 4-functionality polyol prepared by taking pentaerythritol as an initiator and propylene oxide as a main body of polymerization reaction is 375 mgKOH/g;
Polyether polyol 9: the hydroxyl value of the 4-functionality polyol prepared by taking pentaerythritol as an initiator and propylene oxide as a main body of polymerization reaction is 170 mgKOH/g;
Ethylene glycol: hydroxyl number 1809, available from national chemical group, chemical reagents, ltd;
BAYLITH L-paste: molecular sieves, available from Shanghai Cyclosphere molecular sieves, Inc.;
uniaxial glass fiber cloth: 14EU970-01190, available from Satex Dongying Co., Ltd;
Detection standard of resin stretching: GB/T2568-1995;
Detection criteria for composite stretching: GB/T3354-1999;
Density test standard: GB/T1463-2005
in the following examples, the isocyanate indices are as follows:
X ═ mole number of isocyanate groups (NCO groups) in the a component)/(mole number of isocyanate group-reactive groups in the B component ]
Wherein the A component is an organic isocyanate component and the B component refers to all isocyanate-reactive components.
Isocyanate prepolymer a 1: adding 475gPM200 and 475g MDI-50 into a reaction kettle, stirring at a constant speed, heating to 80 ℃, dropwise adding polyether 50g polyether glycol 1 into the kettle, stirring while preserving heat, gradually heating to 85 +/-2 ℃ after dropwise adding, preserving heat for 3 hours, sampling, measuring the NCO content to reach a theoretical value, cooling and discharging to obtain the isocyanate-terminated prepolymer. Test by the di-n-butylamine method, isocyanate content of component A was 30.42 wt%, giving isocyanate prepolymer A1.
Comparative examples 1 to 4, examples 1 to 6
The polyurethane resin matrix according to the corresponding comparative ratio and the examples was obtained by placing the mold in an oven at 120 degrees celsius, degassing the components in a vacuum for 1 hour according to the weight ratio of the components listed in table 1, stirring the components at 500 rpm for 5 minutes, pouring the resin into the mold, and curing the resin at 120 degrees celsius for 60 minutes.
TABLE 1 polyurethane matrix formulation and Properties thereof
As can be seen from Table 1, the mechanical properties of the materials of examples 1-6 are higher than those of the comparative examples in the absence of the reinforcing material, which indicates that the polyurethane resin prepared from the composition of the present invention has better mechanical properties in the absence of the reinforcing material.
comparative examples 1 '-3' and examples 1 '-6'
the polyurethane matrix resins of comparative example 1 ', comparative example 2 ', comparative example 3 ' and example 1 ', example 2 ', example 3 ', example 4 ', example 5 ' and example 6 ' are prepared into polyurethane composites by a hand lay-up forming process by using the same formula as that of example 1 and example 1, respectively, and using the same formula as that of comparative example 1, comparative example 2, comparative example 3, example 1, example 2, example 3, example 4, example 5 and example 6, and the concrete operation steps are as follows:
Firstly, respectively degassing an isocyanate component A and an isocyanate reactive component B for one hour under a vacuum condition, then stirring for 5 minutes at room temperature by adopting a mechanical stirrer at the rotating speed of 500 revolutions per minute, pouring 2g of mixed resin onto a film, naturally spreading the mixed resin, observing the density of the film after the room temperature is solidified, then pouring the remaining resin onto the film coated with a release agent, preparing a hand-pasted plate of 2 layers of unidirectional glass fiber cloth according to a hand-pasting process, placing the hand-pasted plate into an oven after the preparation, solidifying at 120 ℃ for 60 minutes, cooling, preparing a sample and testing.
it is emphasized that the polyurethane matrix resin prepared in comparative example 4 was inferior in performance, and thus comparative testing of the composite was not performed.
TABLE 2 thermoset polyurethane composites and their Properties
in the case of adding the reinforcing material, the polyurethane compositions of the examples in table 2 were prepared according to the formulations of the examples in table 1, and from the results of the respective examples, the prepared composite had excellent mechanical properties while having a slight foaming and good appearance, while the mechanical properties of the materials of the comparative examples were lower than those of the examples, and some of the comparative examples had severe foaming and poor appearance.
Claims (16)
1. A thermoset polyurethane composite, comprising:
(I) a polyurethane matrix in an amount of 10 to 70 wt% based on the total weight of the thermoset polyurethane composite,
The polyurethane matrix is prepared from a polyurethane composition comprising:
a organic polyisocyanate and/or organic polyisocyanate prepolymer, NCO content 25-35 wt%;
B an isocyanate-reactive component having a hydroxyl value of from 300 to 600 mgKOH/g;
(II) a reinforcing material in an amount of 30 to 90 wt% based on the total weight of the thermoset polyurethane composite;
Said B isocyanate-reactive component comprising:
b1) One or more polyether polyols starting from pentaerythritol, the hydroxyl value of the b1) component being from 200 to 650mg KOH/g, parts by weight of the b1) component being from 25 to 75; the polymerized monomer of the b1) polyether polyol is propylene oxide;
b2) at least one organic polyol with the functionality of 2-6 and the hydroxyl value of 100-450mgKOH/g, wherein the b2) component accounts for 20-60 parts by weight, the b2) organic polyol is polyether polyol, and the polymerization monomer is propylene oxide.
2. The composite of claim 1, wherein the polyurethane matrix is present in an amount of 20 to 50 wt% and the reinforcing material is present in an amount of 50 to 80 wt%, based on the total weight of the thermoset polyurethane composite.
3. the composite of claim 2, wherein the polyurethane matrix is present in an amount of 30 to 45 wt% and the reinforcing material is present in an amount of 55 to 70 wt%, based on the total weight of the thermoset polyurethane composite.
4. A composite according to claim 1 wherein the B isocyanate-reactive component has a hydroxyl number of from 350 to 500 mgKOH/g.
5. The composite of claim 1, wherein said b1) component has a hydroxyl number of 350 to 500mgKOH/g, and wherein 40 to 70 parts by weight of said b1) component; the b2) organic polyol has the functionality of 2-3 and the hydroxyl value of 150-250mgKOH/g, and the b2) component accounts for 21-40 parts by weight.
6. The composite of claim 1, wherein the organic polyisocyanate prepolymer is prepared from 90 to 99.9 weight percent polyisocyanate and 0.1 to 10 weight percent polyol, based on the total weight of the organic polyisocyanate prepolymer.
7. A composite according to claim 6, wherein the organic polyisocyanate prepolymer is prepared from 95 to 99.8% by weight of polyisocyanate and 0.2 to 5% by weight of polyol, based on the total weight of the organic polyisocyanate prepolymer.
8. The composite according to claim 1, wherein the polyurethane composition has a water content of less than 0.1 wt.% and the polyurethane matrix (I) prepared from the polyurethane composition has a density of 910 to 1500kg/m3。
9. The composite of claim 8, wherein the polyurethane composition is free of water.
10. a composite according to claim 1, characterized in that said b2) comprises at least one organic polyol having a functionality of 2.1 to 3 and a viscosity of 20 to 2000 mPa-s at 25 ℃.
11. A composite according to claim 10, wherein the organic polyol has a viscosity of from 200 to 1000 mPa-s at 25 ℃.
12. the composite of claim 1 wherein said polyurethane composition has an isocyanate index of from 0.8 to 2.5.
13. the composite of claim 1, wherein the composite is prepared by winding, vacuum infusion, resin transfer molding, hand lay-up, spraying, continuous sheet processes, or combinations thereof.
14. The composite of claim 1, wherein the composite is prepared by a winding, vacuum infusion, hand lay-up process, or a combination thereof.
15. The composite of claim 1, wherein the reinforcing material is selected from one or more of glass fibers, carbon nanotubes, carbon fibers, polyester fibers, natural fibers, aramid fibers, nylon fibers, basalt fibers, boron fibers, silicon carbide fibers, and asbestos fibers.
16. Use of a composite according to any one of claims 1-15 for the preparation of wind turbine blades, yacht hulls, window frames, door frames, ladder frames, utility pole crossarms, tent frames, solar bezels, radomes, radar covers, highway barriers, cable troughs, container floors, wound pipes, utility poles, engine hoods, car trunks, trunk racks, golf clubs, tennis clubs, badminton clubs, bicycle frames, surfboards or skis.
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