CN112011027B - Preparation method of polyurethane composite material - Google Patents
Preparation method of polyurethane composite material Download PDFInfo
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- CN112011027B CN112011027B CN201910465930.7A CN201910465930A CN112011027B CN 112011027 B CN112011027 B CN 112011027B CN 201910465930 A CN201910465930 A CN 201910465930A CN 112011027 B CN112011027 B CN 112011027B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
- C08G18/6677—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
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Abstract
The invention discloses a preparation method of a polyurethane composite material, which controls the injection pressure of reactants and the vacuum degree of a mold, wherein the defined reactants have proper operation time and lower viscosity, and have the characteristics of low viscosity at the early stage, slow viscosity increase, extremely high curing speed at the later stage, short demolding time and the like in the high-temperature mold.
Description
Technical Field
The invention relates to a preparation method of a polyurethane composite material, in particular to a preparation method of a polyurethane composite material by adopting a high-pressure injection molding process.
Background
The high pressure resin transfer molding (HP-RTM) technology is a new technology for mass production of high performance composite material, and it adopts prefabricated member, steel film, vacuum auxiliary exhaust, and through high pressure injection, the resin liquid is quickly filled in the die cavity and solidified.
The resins commonly used in the HP-RTM process in the market at present are mainly epoxy resins and polyurethane resins, but have the following three disadvantages: (1) the resin is not ideal enough for impregnating the fiber, and the porosity of the product is high; (2) the matching between the operable time of the resin and the forming speed is poor, and the realization of the high quality and high production speed cooperation is difficult; (3) large area and complicated structure in the mold cavity, the prediction and control cannot be carried out, and the resin flow is not balanced.
Patent CN106232671A discloses a composite fiber part and its manufacture, the technical solution is a fiber composite part obtained by impregnating fibers with a polyurethane reactive resin mixture formed of polyisocyanate, polyol, two or more heat latent catalysts, etc., the resin molding speed is still slow, the glass transition temperature is only 110 ℃, and the heat resistance is not high enough; secondly, the flame retardant performance is not high enough under the condition of adding the flame retardant. The above properties still do not meet the requirements.
Therefore, it is necessary to provide a technical solution to the problems in the prior art.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a preparation method of a polyurethane composite material. The reactants adopted by the preparation method have proper operation time and lower viscosity, and have the characteristics of low early-stage viscosity, slow viscosity increase, extremely high later-stage curing speed, short demolding time and the like in a high-temperature mold.
A method of preparing a polyurethane composite, comprising: mixing an isocyanate component and an isocyanate reactive component, injecting the mixture into a die with a built-in reinforcing material under the pressure of 80-200 bar, preferably 100-160 bar, reacting, controlling the vacuum degree of the die to be-0.08-0.1 MPa, preferably-0.085-0.095 MPa in the injection process, and obtaining the composite material after the reaction is finished; wherein the isocyanate component comprises a polymethylene polyphenyl isocyanate and the isocyanate-reactive component comprises a polyether polyol, a catalyst.
Methods of controlling the pressure at which reactants are injected into a mold are well known in the art, such as adjusting the injection pressure via pressure valves on an HP-RTM apparatus, etc.; methods of controlling mold vacuum are well known in the art, such as by adjusting the mold gap or by vacuum systems, and the like.
Controlling the injection pressure of the reactant and the vacuum degree of the mold within the range of the invention can promote the rapid injection of the reactant into the mold, increase the wettability between the reactant and the built-in reinforcing material in the mold, improve the production efficiency and reduce the defects of poor glue or wrapped bubbles and the like in the product.
In a preferred embodiment, the isocyanate component and the isocyanate-reactive component have a viscosity of 30 to 300mp.s, preferably 50 to 200mp.s, at 50 ℃ within 30 seconds after mixing. Controlling the viscosity of the reaction mixture can facilitate the reactants to quickly infiltrate the reinforcement material in the mold, reducing defects in the article.
The polymethylene polyphenyl isocyanate refers to a mixture of isocyanate compounds with different functionalities, which are common in the field, and the obtained route can be prepared by adopting a method commonly used in the field or obtained by commercial purchase, and the commercial products include but are not limited to PM-100, PM-130, PM-200, PM-300, PM-400, PM-2010 and the like produced by Wanhua chemistry.
The isocyanate component also optionally includes organic isocyanate monomers, isocyanate prepolymers, other isocyanate-modified products, and the like, examples of which include, but are not limited to, Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI), Hexamethylene Diisocyanate (HDI), dicyclohexylmethane diisocyanate (HMDI), Naphthalene Diisocyanate (NDI), p-phenylene diisocyanate (PPDI), 1, 4-cyclohexane diisocyanate (CHDI), Xylylene Diisocyanate (XDI), cyclohexanedimethylene diisocyanate (HXDI), trimethyl-1, 6-hexamethylene diisocyanate (TMHDI), tetramethylm-xylylene diisocyanate (TMXDI), norbornane diisocyanate (NBDI), dimethylbiphenyl diisocyanate (TODI), and the like, Methylcyclohexyl diisocyanate (HTDI), and the like, and prepolymers, modified products, and the like of such monomers. Preferably, the isocyanate component has an NCO content of 27.5 to 33.5%, preferably 30 to 32%, and a viscosity of 5 to 300mp.s, preferably 100 to 250mp.s at 25 ℃.
In a preferred embodiment, the isocyanate component is a polymethylene polyphenyl isocyanate, free of other classes of isocyanate-based compounds. The isocyanate component only selects polymethylene polyphenyl isocyanate and is matched with other components for use, the effect which can be achieved by adopting the composite isocyanate component can be achieved within the limited range of the invention, the reaction raw materials are reduced, the process steps are simplified, and the production efficiency is further improved. Particularly, compared with the isocyanate prepolymer, the reaction activity is higher, the curing degree is higher under the condition of the same demolding time, the dimensional stability of the product is better, the product is more suitable for the HP-RTM process production needing rapid curing, and the mechanical strength, the heat resistance and the like of the product are higher than those of the product using the isocyanate prepolymer, so that the product with higher mechanical property requirements can be produced; in addition, the single raw material composition enables the quality stability of the raw materials to be higher, the performance of the product to be more stable, and the batch production of products with stable performance and high qualified rate to be easier to realize.
The polyether polyol refers to a class of compounds obtained by reacting a polyol as a starter, and an alkylene oxide as a polymerization monomer, examples of the starter including, but not limited to, ethylene glycol, propylene glycol, 1, 4-butanediol, 1, 3-butanediol, 1, 2-butanediol, 1 pentanediol, hexanediol, diethylene glycol, triethylene glycol, dipropylene glycol, diethylene glycol, neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, and the like, and examples of the alkylene oxide including, but not limited to, ethylene oxide, propylene oxide, butylene oxide, and the like.
Preferably, the viscosity of the polyether polyol at 25 ℃ is 30-1000 mp.s, preferably 50-500 mp.s. The viscosity of the polyether polyol needs to be within the range defined by the invention, the defects of insufficient fiber infiltration and the like can be caused when the viscosity is too high, the method is particularly obvious when large-size or thick products are prepared, and good products can be obtained only by ensuring that a resin system has low viscosity.
Preferably, the polyether polyol has a functionality of 3, is polymerized from propylene oxide, and has a hydroxyl value of 80 to 800mgKOH/g, preferably 180 to 750mgKOH/g, more preferably 300 to 600 mgKOH/g.
The isocyanate-reactive component also optionally includes polyester polyols, polycarbonate polyols, bio-based polyols, other classes of polyether polyols, and the like. In a preferred embodiment, the isocyanate-reactive component does not comprise a polyester polyol, a polycarbonate polyol, a biobased polyol.
The catalyst refers to a class of compounds having a catalytic effect on isocyanate groups and active hydrogen atoms, and examples thereof include, but are not limited to, organometallic catalysts, amine catalysts, and the like.
Preferably, the catalyst comprises at least one thermosensitive catalyst having an activation temperature of not less than 50 ℃.
The heat-sensitive catalyst refers to a type of catalyst having a significant catalytic activity at a specific temperature or temperature range, and examples thereof include, but are not limited to, blocked amine-based catalysts, blocked amidine-based catalysts, high steric-hindered organometallic catalysts, and the like, and more specific examples thereof include, but are not limited to, phenol-blocked 1, 8-diazabicyclo [5.4.0] undec-7-ene, formic acid-blocked triethylenediamine, triethylenediamine dicyanoacetate, formate or phenoxide or isooctanoate of dimethylcyclohexylamine, dioctyltin dithiolate, bis (dimethylaminoethyl) ether derivatives, and the like, and commercial products such as WANALYST KC110, WANALYST KC101, UL-32 of Michikuwa chemical, DABCO BL-17 of air chemical, and the like. In order to ensure the initial low viscosity of the reaction system, it is required that the reaction mass is maintained at 40 ℃ or above, and the viscosity increases slowly at the initial stage of injection, and has high fluidity for a relatively long time, so that the activation temperature of the catalyst is selected to be not lower than 50 ℃, the catalyst is prevented from being deactivated by deblocking before the injection of the reactant, and product defects such as poor fiber infiltration caused by rapid increase of the viscosity of the system due to rapid catalytic reaction at the initial stage of injection of the reactant are also prevented.
In a preferred embodiment, the catalyst comprises a heat-sensitive catalyst and at least one gel-type catalyst.
The gel-type catalyst is different from the thermosensitive catalyst, and refers to a catalyst capable of promoting rapid gelation of the mixed solution, and can rapidly catalyze the reaction between functional groups after being added into the reaction system, so as to improve the gel curing speed of the system, and examples thereof include, but are not limited to, tertiary amine catalysts such as aliphatic amine, alicyclic amine, aromatic amine and alcohol amine, and metal alkyl compounds such as bismuth, lead, tin, titanium, antimony, mercury and zinc.
In a preferred embodiment, the catalyst comprises only one heat-sensitive catalyst. The catalyst is only selected to be a thermosensitive catalyst and matched with other components of the invention for use, and within the limited range of the invention, the effect which can be achieved by a composite catalyst system can be achieved, reaction raw materials are reduced, the process steps are simplified, and the production efficiency is further improved; in addition, the use of a single catalyst can make the reaction system of the system simpler, thereby increasing the stability of the process.
The isocyanate reactive component also comprises micromolecular alcohol, and the functionality is 1-4, preferably 2-3; preferred examples include, but are not limited to, ethylene glycol, propylene glycol, 1, 4-butanediol, 1, 3-butanediol, 1, 2-butanediol, 1 pentanediol, hexanediol, diethylene glycol, triethylene glycol, dipropylene glycol, diethylene glycol, neopentyl glycol, glycerol, trimethylolpropane, etc., and such small molecular alcohols may be used alone or in combination. The small molecular alcohol can play roles in chain extension and crosslinking of polymer molecules, molecular weight improvement and the like. Further preferably, the small molecule alcohol is selected from one or more of ethylene glycol, propylene glycol, glycerol and trimethylolpropane.
The isocyanate-reactive component also contains a flame retardant capable of imparting flame retardant effect to the resulting composite material, and examples thereof include, but are not limited to, halogenated phosphate flame retardants, halogenated hydrocarbons and other halogen-containing flame retardants, melamine and salts thereof, reactive flame retardants, inorganic flame retardants, and the like, which may be used alone or in combination. Preferably, the flame retardant is selected from liquid flame retardants with viscosity of 40-800 mpa.s at 25 ℃; further preferably, the viscosity of the flame retardant is 60-400 mpa.s at 25 ℃; preferably, the flame retardant consists of a reactive flame retardant and a non-reactive flame retardant, and the mass ratio of the reactive flame retardant to the non-reactive flame retardant is 1-4: 1, preferably 1 to 3: 1. the reactive flame retardant means that the flame retardant itself can participate in the reaction, so that the polyurethane molecule obtained by the reaction has a flame retardant function and has small influence on the material performance, and examples of the reactive flame retardant include, but are not limited to, tris (dipropylene glycol) phosphite, diethyl N, N-bis (2-hydroxyethyl) aminomethylene phosphonate, dimethyl N, N-bis (2-hydroxyethyl) aminomethylphosphonate, and commercial products such as WANOLFR-130, WANOLFR-1830 and the like produced by Wanhua chemistry. The non-reactive flame retardant refers to a type of flame retardant that can exert a flame retardant effect without participating in a reaction, and examples thereof include, but are not limited to, tris (2-chloroethyl) phosphate, (2-chloropropyl) phosphate, bis (3-bromo-2, 2-dimethylpropyl) phosphate, dimethyl methyl phosphate, diethyl ethyl phosphate, dimethyl propyl phosphate, triethyl phosphate, triphenyl phosphate, tricresyl phosphate, and the like. The flame retardant is matched with other components and processes for use, so that the prepared composite material has a good flame retardant effect within the range defined by the invention, the flame retardance reaches V0 or V1 grade in UL94 standard, and meanwhile, the flame retardant has lower viscosity at room temperature, and the wettability of the polyurethane composition and the reinforced material is improved.
The isocyanate-reactive component further comprises an internal mold release agent, and the addition of the internal mold release agent can reduce the mold release time of the polyurethane material formed by the reaction and improve the production efficiency, and examples thereof include, but are not limited to, condensation products having an ester group, silicone compounds, higher fatty alcohols, higher fatty amines, zinc stearate, and the like, and such internal mold release agents can be used alone or in combination.
The isocyanate reactive component can also be optionally added with a dispersing agent, a dye, a defoaming agent, a leveling agent, an impregnating compound, a coupling agent, a water removing agent, an antioxidant, an anti-hydrolysis agent, an antistatic agent, a viscosity reducing agent, a filler and the like.
In a preferred embodiment, based on the total mass of the isocyanate-reactive components:
the using amount of the polyether polyol is 20-89.9%, preferably 45-84%;
the dosage of the catalyst is 0.1-0.7%, preferably 0.2-0.5%;
the dosage of the micromolecule alcohol is 0-30%, preferably 5-15%;
the amount of the flame retardant is 0-50%, preferably 10-40%.
The preparation method is suitable for a non-foaming system, namely reactants contain no water basically, and no other physical or chemical foaming agent, and all the raw materials used contain no water basically, or are dehydrated or dried by adding a drying agent. In general, the reactant may absorb a small amount of moisture in the air after contacting with the air, or a very small amount of water remains in the raw material, and the water content in the reactant should be controlled to be less than 0.1 wt%, preferably less than 0.05 wt%, without affecting the practice of the present invention.
In a preferred embodiment, the molar ratio of isocyanate groups in the isocyanate component to active hydrogen atoms in the isocyanate-reactive component is from 0.85 to 1.25: 1, preferably 1 to 1.2: 1.
the reinforcing material may be selected from materials commonly used in the art, examples of which include, but are not limited to, glass fibers, carbon fibers, metal fibers, natural fibers, aramid fibers, polyethylene fibers, and the like, and such reinforcing materials may be used alone or in combination. Preferably, the reinforcing material is selected from glass fibres and/or carbon fibres.
In a preferred embodiment, the reinforcing material is present in an amount of 10 to 90%, preferably 30 to 80%, based on the total mass of the composite material.
In a preferred embodiment, the preparation method employs a high pressure resin transfer molding process comprising the steps of:
respectively and uniformly mixing and stirring the isocyanate components at 10-60 ℃ for later use, and uniformly mixing and stirring the isocyanate reactive components for later use;
uniformly mixing the isocyanate component and the isocyanate reactive component at 10-60 ℃ by using a static mixer of a high-pressure resin transfer molding device, injecting the mixture into a mold which is provided with a reinforcing material in advance and has a vacuum degree of-0.08-0.1 MPa, preferably-0.09-0.095 MPa, wherein the injection pressure is 80-200 bar, preferably 100-160 bar, the temperature of the mold is controlled at 50-130 ℃ for reaction, and obtaining the composite material after the reaction is finished.
The invention has the beneficial effects that: because each reactant has proper operation time and lower viscosity at the temperature of the processing material, and has the advantages of low viscosity at the early stage, slow growth, extremely fast curing speed at the later stage and short demolding time in a high-temperature mold, the composite material prepared by the reactants has better impregnation of resin to a reinforcing material, and meanwhile, the product has good dimensional stability, high quality, and excellent mechanical property and heat resistance.
Detailed Description
The examples and comparative examples used the following starting materials:
isocyanate:
WANNATE PM200, NCO content 31.2 wt.%, viscosity 200mpa.s at 25 ℃, Wanhua chemistry,
WANNATE MDI50, NCO content 33.5% by weight, viscosity at 25 ℃ 10mpa.s, Vanhua Chemicals,
isocyanate prepolymer a having an NCO content of 29.5 wt%, a viscosity at 25 ℃ of 145mpa.s, obtainable by reacting an isocyanate compound which is a mixture of WANNATE PM200 and WANNATE MDI50, and a polyester polyol having a hydroxyl value of 56mgKOH/g and a functionality of 2;
polyether polyol 1, glycerol-initiated, hydroxyl value of 560mgKOH/g, propylene oxide polymerization, viscosity at 25 ℃ of 350 mpa.s;
polyether polyol 2, started by glycerol, with a hydroxyl value of 420mgKOH/g, polymerized by propylene oxide and with a viscosity of 380mpa.s at 25 ℃;
polyether polyol 3, started with glycerol and having a hydroxyl value of 336mgKOH/g, polymerized with propylene oxide and having a viscosity of 340mpa.s at 25 ℃;
polyether polyol 4, 1,2 propylene glycol, with a hydroxyl value of 515mgKOH/g, propylene oxide polymerization, viscosity at 25 ℃ of 70 mPas;
heat-sensitive catalysts: WANALYSTKC110 (activation temperature 60 ℃), Van Waals Chemicals;
heat-sensitive catalysts: BICAT 2536 (activation temperature 72 ℃), advanced chemistry;
gel type catalyst: BICAT8118, advanced chemistry;
reactive flame retardant: WANOL FR-130, Wanhua chemical, viscosity 500mpa.s at 25 ℃;
non-reactive flame retardant: LF11, Yake science and technology, Jiangsu, viscosity 71mpa.s at 25 ℃;
internal mold release agent: HB-650D, TECHNICK PRODUCTS;
glass fiber cloth: EWR400, china gigante gmbh.
The examples and comparative examples used the following test methods or standards:
the wettability testing method comprises the following steps: the wettability of the composite material is observed visually, and the good wettability indicates that the inner surface and the outer surface of a composite material product are smooth, have good gloss and no bubbles, the inner surface and the outer surface of resin are not provided with naked reinforcing materials, and the composite material plate is not layered, vacuoles, pores and the like; the poor infiltration condition indicates that the composite material product has unsmooth inner and outer surfaces, poor gloss, bubbles, partially exposed reinforcing materials on the inner and outer surfaces of resin, obvious layering, vacuole, pore and other phenomena in the composite material plate;
the viscosity test standard is: GB/T12008.8-92;
the flexural modulus test standard is: DIN ISO 527;
the flexural strength test criteria were: DIN ISO 527;
the impact strength test standard is as follows: GB/T1043-;
tensile strength test standards were: DIN ISO 527;
the elongation at break test standard is: DIN ISO 527;
the glass transition temperature test standard is as follows: JY/T014-;
the flame resistance test standards were: GB/T2408-2008/UL 94.
Testing the curing degree of the resin: DSC was used to measure the total amount of exotherm produced by mixing the isocyanate component and the isocyanate-reactive component to complete cure (denoted as Q)total(ii) a ) Taking a cured resin sample which is not subjected to any treatment after demolding, carrying out DSC test until the resin sample is completely cured, and recording the heat release as Qsample(ii) a The selected test conditions are kept consistent in all the test processes, and the curing degree is calculated according to the following formula:
the amounts of the components of the polyurethane compositions in the examples and comparative examples are shown in Table 1.
TABLE 1
The process conditions for the preparation of the polyurethane composites in the examples and comparative examples are shown in table 2.
TABLE 2
The composites of examples and comparative examples were prepared according to the raw materials listed in table 1 by high pressure resin transfer molding process with the glass fiber contents controlled to 55 wt%, 65 wt%, 80 wt%, respectively, and the process parameters listed in table 2, by the following steps:
respectively and uniformly mixing the isocyanate components for later use, and uniformly mixing the isocyanate reactive components for later use;
and (2) uniformly mixing the isocyanate component and the isocyanate reactive component through a static mixer of a high-pressure resin transfer molding device, injecting the mixture into a mold in which a reinforcing material is placed in advance for reaction, and demolding after curing time is reached to obtain the composite material.
The composite materials prepared by the high pressure resin transfer molding process were subjected to performance tests, and the test results are shown in table 3.
TABLE 3
What needs to be said is that: in the comparative example 2, when a sample is prepared, the injection pressure and the vacuum degree are not in the range defined by the invention, so that the wettability of the obtained composite material sample piece is poor, which shows that more glass fibers are exposed on the inner surface and the outer surface of a composite material product, and obvious vacuoles, pores and other phenomena exist in a composite material plate, so that a sample strip meeting the mechanical property test standard and the like cannot be prepared on the whole composite material sample piece, and the performance test cannot be carried out.
Claims (21)
1. A method for preparing a polyurethane composite, comprising: mixing an isocyanate component and an isocyanate reactive component, injecting the mixture into a mold with a built-in reinforcing material under the pressure of 80-200 bar for reaction, controlling the vacuum degree of the mold to be-0.08 to-0.1 MPa in the injection process, and obtaining a composite material after the reaction is finished; wherein the isocyanate component comprises a polymethylene polyphenyl isocyanate and the isocyanate-reactive component comprises a polyether polyol, a catalyst;
the catalyst comprises at least one thermosensitive catalyst, and the activation temperature of the thermosensitive catalyst is not lower than 50 ℃;
the isocyanate-reactive component further comprises a flame retardant selected from liquid flame retardants having a viscosity of 40-800 mpa.s at 25 ℃; the flame retardant consists of a reactive flame retardant and a non-reactive flame retardant, and the mass ratio of the reactive flame retardant to the non-reactive flame retardant is 1-4: 1.
2. the method according to claim 1, wherein the injection pressure is 100 to 160bar, and the vacuum degree of the mold during the injection process is-0.085 to-0.095 MPa.
3. A method according to claim 1, wherein the isocyanate component and the isocyanate-reactive component have a viscosity of 30 to 300mp.s at 50 ℃ within 30 seconds after mixing.
4. A method according to claim 3, wherein the isocyanate component and the isocyanate-reactive component have a viscosity of 50 to 200mp.s at 50 ℃ within 30 seconds after mixing.
5. The method of claim 1, wherein the isocyanate component has an NCO content of 27.5 to 33.5% and a viscosity of 5 to 300mp.s at 25 ℃.
6. The method of claim 5, wherein the isocyanate component has an NCO content of 30 to 32% and a viscosity of 100 to 250mp.s at 25 ℃.
7. The process according to claim 1, wherein the polyether polyol has a viscosity of 30 to 1000mp.s at 25 ℃.
8. The method according to claim 7, wherein the polyether polyol has a viscosity of 50 to 500mp.s at 25 ℃.
9. The process of claim 1, wherein the polyether polyol has a functionality of 3 and is polymerized from propylene oxide and has a hydroxyl number of from 80 to 800 mgKOH/g.
10. The process of claim 9, wherein the polyether polyol has a functionality of 3 and is polymerized from propylene oxide and has a hydroxyl number of from 180 to 750 mgKOH/g.
11. The process of claim 10, wherein the polyether polyol has a functionality of 3 and is polymerized from propylene oxide and has a hydroxyl number of from 300 to 600 mgKOH/g.
12. The method of claim 1,
the catalyst comprises a heat-sensitive catalyst and at least one gel-type catalyst.
13. The method of claim 1, wherein the catalyst comprises only one heat-sensitive catalyst.
14. The method of claim 1, wherein the isocyanate-reactive component further comprises a small molecule alcohol.
15. The method according to claim 14, characterized in that, based on the total mass of the isocyanate-reactive components:
the using amount of the polyether polyol is 20-89.9%;
the dosage of the catalyst is 0.1-0.7%;
the dosage of the micromolecular alcohol is 0-30%;
the dosage of the flame retardant is 0-50%.
16. The method of claim 15, characterized in that, based on the total mass of the isocyanate-reactive components:
the using amount of the polyether polyol is 45-84%;
the dosage of the catalyst is 0.2-0.5%;
the using amount of the micromolecular alcohol is 5-15%;
the dosage of the flame retardant is 10-40%.
17. The process of claim 1, wherein the molar ratio of isocyanate groups in the isocyanate component to active hydrogen atoms in the isocyanate-reactive component is from 0.85 to 1.25: 1.
18. a process according to claim 17, wherein the molar ratio of isocyanate groups in the isocyanate component to active hydrogen atoms in the isocyanate-reactive component is from 1 to 1.2: 1.
19. the method according to claim 1, wherein the reinforcing material comprises 10 to 90% by mass of the total mass of the composite material.
20. The method of claim 19, wherein the reinforcement material comprises 30-80% by mass of the total mass of the composite material.
21. The method of claim 1, wherein the manufacturing method uses a high pressure resin transfer molding process comprising the steps of:
respectively and uniformly mixing and stirring the isocyanate components at 10-60 ℃ for later use, and uniformly mixing and stirring the isocyanate reactive components for later use;
and (2) uniformly mixing the isocyanate component and the isocyanate reactive component through a static mixer of high-pressure resin transfer molding equipment at the temperature of 10-60 ℃, injecting the mixture into a mold in which a reinforcing material is placed in advance, controlling the temperature of the mold to react at the temperature of 50-130 ℃, and obtaining the composite material after the reaction is finished.
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