CN113527767A - Magnetic internal mold release agent and preparation method thereof, polyurethane composition and preparation method of polyurethane HP-RTM composite material - Google Patents
Magnetic internal mold release agent and preparation method thereof, polyurethane composition and preparation method of polyurethane HP-RTM composite material Download PDFInfo
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Abstract
The invention provides a magnetic internal mold release agent and a preparation method thereof, a polyurethane composition and a preparation method of a polyurethane HP-RTM composite material, wherein the polyurethane composition is obtained by reacting an isocyanate component and an isocyanate reactive component, and the isocyanate reactive component comprises: polyether polyol 1, polyether polyol 2, a chain extender, a cross-linking agent, a catalyst, a flame retardant, a dispersing agent and a magnetic internal release agent. The polyurethane composition can be used for preparing a polyurethane high-pressure resin transfer molding (HP-RTM) composite material, has excellent continuous demolding performance and excellent mechanical property, and can greatly improve the production efficiency of the composite material.
Description
Technical Field
The invention relates to the field of polyurethane materials, in particular to a polyurethane composition for a polyurethane composite material for high-pressure resin transfer molding, a HP-RTM composite material containing the polyurethane and a preparation method thereof.
Background
The high-pressure resin transfer moulding (HP-RTM) technology is a new technology which is introduced in recent years and aims at producing high-performance composite materials in large scale, and adopts prefabricated parts, steel films and vacuum-assisted exhaust, and makes resin liquid quickly fill a mould cavity and be solidified through high-pressure injection.
HP-RTM refers to a molding process for obtaining a composite material product by performing resin flow mold filling, impregnation, curing and demolding on resin which is subjected to opposite-punch mixing by using high pressure and is injected into a vacuum closed mold paved with a fiber reinforced material and a preset insert in advance. The HP-RTM adopts a process of performing piece, steel mould, vacuum assistance, high-pressure mixing injection and high-pressure resin impregnation and solidification, belonging to the technical field of non-foaming resin. Compared with the traditional polyurethane foaming composite material process, the method is two completely different technical routes. The former is impregnation and solidification under negative pressure, and the latter is foaming infiltration and solidification under pressure maintaining. And the former has higher density and is used for structural parts with higher requirements on strength.
Resins commonly used in HP-RTM technology in the market at present are mainly epoxy resin and polyurethane resin, and the polyurethane resin shows the advantages of light weight, quick curing, high flame retardance, high heat resistance and the like in HP-RTM products, so that the resin is more and more widely applied. In addition, the forming temperature of the polyurethane HP-RTM process is higher than that of other polyurethane composite material processes, and many products are required to be more than or equal to 150 ℃ and even reach 200 ℃. And the mechanical strength of the composite material is improved due to the reduction of bubbles due to the special advantages of the process.
Along with the application and popularization of the polyurethane HP-RTM, the call for improving the production efficiency in the industry is higher and higher. At present, even if high parts of common internal mold release agents are added in the industry, the expectation is still not achieved, the external mold release agents are sprayed for 1 time every 10-20 molds on average, and mold cleaning equipment after mold sticking has great influence on production efficiency. It is therefore highly desirable in the industry to be able to greatly improve the continuous demolding ability.
Patent CN 110922554 a discloses a polyurethane system and a composite material preparation method for VARTM and HPRTM processes. The technical scheme has low viscosity at the early stage and quick solidification at the later stage, improves the wettability and the mechanical property of the fiber, but still can not achieve the continuous demoulding time expectation in the current industry.
Patent CN 111019089 a discloses a polyurethane system for HPRTM process and a method for preparing composite material. The technical scheme improves the wettability, the mechanical property and the heat resistance of the fiber, but the continuous demolding frequency can not reach the expectation in the current industry.
Therefore, a technical scheme is needed to solve the problems that in the prior art, the number of continuous demolding is small, and the production efficiency needs to be improved.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a magnetic internal mold release agent which can be used in a polyurethane composition and is beneficial to improving the continuous mold release performance and the production efficiency.
The invention also aims to provide a preparation method of the magnetic internal release agent.
It is a further object of the present invention to provide a polyurethane composition containing the aforementioned magnetic internal mold release agent, which is useful for the preparation of polyurethane HP-RTM composites, having very excellent continuous mold release properties and excellent mechanical properties.
The invention further aims to provide a preparation method of the polyurethane HPRTM composite material.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a preparation method of a magnetic internal release agent comprises the following steps:
1) preparing magnetic material particles: preferably the magnetic material is a ferrite magnetic material; more preferably gamma-Fe having a particle size of 20 to 80nm2O3Particles;
2) preparing an amino modified magnetic material: adding the magnetic material particles into a mixed solution of distilled water and ethanol, performing full ultrasonic dispersion, dropwise adding a compound with amino and alkoxy under the protection of nitrogen, fully stirring until the reaction is finished, cooling the solution to room temperature, washing the solution for multiple times by using absolute ethanol, and performing freeze drying to obtain the amino modified magnetic material;
3) preparing a magnetic internal release agent: adding the amino modified magnetic material into absolute ethyl alcohol, performing full ultrasonic dispersion, adding an activating agent, fully stirring, dropwise adding a hydroxyl-terminated polysiloxane release agent graft under stirring, stirring until the reaction is finished, washing with absolute ethyl alcohol for multiple times, adding distilled water, and performing freeze drying to obtain the magnetic internal release agent.
In a preferred embodiment, the volume ratio of distilled water to ethanol in the mixed solution in the step 2) is 1:1, the ultrasonic dispersion time is 30-60 min, the compound with amino and alkoxy is selected from one or more of gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane and N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane, the reaction temperature is 30-60 ℃, the stirring speed is 500-1500 r/min, the stirring time is 1-5 h, the washing times of the absolute ethanol are 5-20 times, the freeze drying vacuum degree is 4-5 Pa, the temperature is-50-60 ℃, and the time is 20-30 h;
the ultrasonic dispersion time in the step 3) is 30-60 min, the activating agent is N, N '-carbonyldiimidazole, the stirring speed is 500-1500 r/min, the stirring time is 1-5 h after the N, N' -carbonyldiimidazole is added, the reaction conditions of adding the release agent graft are that the reaction temperature is 50-70 ℃, the stirring time is 2-6 h, the absolute ethyl alcohol is washed for 5-20 times, the freeze drying vacuum degree is 4-5 Pa, the temperature is-50-60 ℃, and the time is 20-30 h; the hydroxyl-terminated polysiloxane release agent graft is selected from one or two of hydroxyl-terminated polydimethylsiloxane and hydroxyl-terminated polyvinyl siloxane; further preferably, the hydroxyl-terminated polydimethylsiloxane is of weight average molecular weight 1000-; the hydroxyl-terminated polyvinyl siloxane has a weight-average molecular weight of 1000-10000 and a vinyl content of 0.1-3 wt%.
In another aspect of the invention, the magnetic internal mold release agent is prepared by the preparation method of the magnetic internal mold release agent.
In yet another aspect of the present invention, a polyurethane composition is obtained from a reaction comprising an isocyanate component and an isocyanate-reactive component, the isocyanate-reactive component comprising: polyether polyol 1, polyether polyol 2, a chain extender, a cross-linking agent, a catalyst, a flame retardant, a dispersing agent and a magnetic internal release agent; wherein the magnetic internal release agent is prepared by the method or the magnetic internal release agent.
In a specific embodiment, the polyether polyol 1 in the isocyanate reactive component has an average functionality of 2 to 4, preferably 2 to 3, and a hydroxyl value of 15 to 50mgKOH/g, preferably 20 to 45mgKOH/g, and is obtained by reacting ethylene oxide and propylene oxide, wherein the ethylene oxide content is 5 to 50 wt%, preferably 10 to 35 wt%; the polyether polyol 2 has an average functionality of 2.5 to 8, preferably 3 to 5, more preferably 4, and a hydroxyl value of 50 to 200mgKOH/g, preferably 55 to 180 mgKOH/g.
In a specific embodiment, the isocyanate component is a mixture of monomeric diphenylmethane diisocyanate and homologues of diphenylmethane diisocyanate having more rings.
In a specific embodiment, the molar ratio of isocyanate groups in the isocyanate component to active hydrogen atoms in the isocyanate-reactive component is from 90 to 120: 100, preferably 100 to 110: 100.
in a particular embodiment, the isocyanate-reactive component comprises, based on the total mass of the isocyanate-reactive component:
the using amount of the polyether polyol 1 is 5-10%;
the using amount of the polyether polyol 2 is 50-70%;
the using amount of the chain extender is 7-15%;
the dosage of the cross-linking agent is 7-15%;
the dosage of the catalyst is 0.3-0.5%;
the using amount of the flame retardant is 5-20%;
the dosage of the dispersant is 0.2-0.5%;
the dosage of the magnetic internal release agent is 0.1-0.5%.
In a further aspect of the invention, a process for the preparation of a polyurethane HPRTM composite from the aforementioned polyurethane composition comprises the steps of:
1) 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;
2) 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 of a magnetic field injection machine in which a reinforcing material is placed in advance, reacting, curing and molding, and demolding to obtain the polyurethane HP-RTM composite material.
In a specific embodiment, the vacuum degree in the step 2) is-0.08 to-0.1 MPa, preferably-0.09 to-0.095 MPa, the injection pressure is 80 to 200bar, preferably 100 to 160bar, the mold temperature is preferably 50 to 200 ℃, the dwell time is preferably 1 to 10 minutes, and the mold magnetic field strength is 5000-.
Compared with the prior art, the invention has the beneficial effects that:
1) the invention provides a magnetic internal mold release agent and a polyurethane composition containing the same, wherein the polyurethane composition can be used for preparing a polyurethane HP-RTM composite material, has very excellent continuous mold release performance and excellent mechanical properties, and can be used for producing and manufacturing diversified and complex-structure products such as automobile bodies, new energy battery cases, plate springs, hubs and the like. Because the continuous demolding performance is very excellent, the production efficiency is greatly improved.
2) The polyurethane non-foaming system has higher density and lower shrinkage rate, so the demoulding difficulty is higher than that of the traditional foaming system under the same condition. Compared with the conventional means that more parts of release agent are required to be added to improve the release efficiency, the magnetic internal release agent disclosed by the invention is matched with a mold with a magnetic field injection machine for use, and the high magnetism of nano-scale magnetic particles is utilized to drive release agent molecules to directionally migrate to the surface of a part along the direction of a magnetic field, so that the release agent is enriched on the surface of the part, the utilization rate of the release agent is increased, the use amount of the release agent is reduced, and the cost is saved; and the main chain siloxane structure of the magnetic internal release agent endows the release agent with more excellent high temperature resistance, can still fully play a role under the molding process condition that the temperature of the polyurethane HP-RTM is up to 200 ℃, and endows the release agent with higher production efficiency at high temperature.
Detailed Description
The following examples will further illustrate the method provided by the present invention in order to better understand the technical solution of the present invention, but the present invention is not limited to the listed examples, and should also include any other known modifications within the scope of the claims of the present invention.
A polyurethane composition includes an isocyanate component and an isocyanate-reactive component. Wherein the isocyanate-reactive component comprises: polyether polyol 1, polyether polyol 2, a chain extender, a cross-linking agent, a catalyst, a flame retardant, a dispersing agent and a magnetic internal release agent.
In a preferred embodiment, the isocyanate-reactive component comprises, based on the total mass of the isocyanate-reactive component:
wherein the polyether polyol 1 has an average functionality of 2-4, preferably 2-3, a hydroxyl value of 15-50 mgKOH/g, preferably 20-45 mgKOH/g, and is obtained by reacting ethylene oxide and propylene oxide, wherein the ethylene oxide content is 5-50 wt%, preferably 10-35 wt%; examples of the initiator of the polyether polyol 1 include, but are not limited to, ethylene glycol, propylene glycol, 1, 4-butanediol, dipropylene glycol, diethylene glycol, triethylene glycol, bisphenol a, glycerin, trimethylolpropane, diethanolamine, triethanolamine, ethylenediamine, tolylenediamine, pentaerythritol, sorbitol, xylitol, sucrose, or a mixture thereof, and ethylene oxide and propylene oxide react by block addition or random addition, but block addition is preferred, propylene oxide polymerization is further preferred, and ethylene oxide block addition is performed terminally. For example, glycerol-initiated, propylene oxide polymerization, ethylene oxide end block addition, ethylene oxide content 10 wt%, hydroxyl value 20mgKOH/g (example polyether polyol 1-1).
The polyether polyol 2 has an average functionality of 2.5-8, preferably 3-5, more preferably 4, and a hydroxyl value of 50-200 mgKOH/g, preferably 55-180 mgKOH/g; the starter of the polyether polyol 2 may be selected from small molecule alcohols having a molecular weight not exceeding 400, which meet the limits of average functionality. Preferred starters are one or more of ethylene glycol, propylene glycol, diethylene glycol, glycerol, trimethylolpropane, pentaerythritol, xylitol, sorbitol and sucrose, and the most preferred starter is pentaerythritol. The polymerization monomer of the polyether polyol 2 may be selected from polymerization monomers commonly used in the art, examples of which include, but are not limited to, ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide, and the like, and such polymerization monomers may be used alone or in combination. The polyether polyol 2 is preferably a propylene oxide homopolymer, or an ethylene oxide homopolymer, or a copolymer of ethylene oxide and propylene oxide, most preferably a propylene oxide homopolymer. For example pentaerythritol starting, propylene oxide homopolymerization, hydroxyl value 150mgKOH/g (example polyether polyol 2-1).
The chain extender, the crosslinking agent, the catalyst, the flame retardant and the dispersant are not particularly limited, and may be a chain extender, a crosslinking agent, a catalyst, a flame retardant and a dispersant which are commonly used in the art, for example, the chain extender may be a chain extender which is commonly used in the art, and examples thereof include, but are not limited to, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, butanediol, cyclohexanediol, hydrogenated bisphenol a and the like, and such chain extenders may be used alone or in combination. Preferably, the chain extender can be one or more selected from ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol and butanediol.
The crosslinking agent may be one commonly used in the art, and examples thereof include, but are not limited to, trimethylolpropane, glycerol, diethanolamine, triethanolamine, ethylenediamine, sorbitol, etc., and such crosslinking agents may be used alone or in combination.
The catalyst refers to a class of compounds having catalytic activity to isocyanate and active hydrogen atoms, and examples thereof include, but are not limited to, amine-based catalysts, organometallic-based catalysts, and the like, which may be used alone or in combination. Preferably, the catalyst is selected from the group consisting of heat-sensitive catalysts, which refers to a class of catalysts having significant catalytic activity at a particular temperature or temperature range, examples include, but are not limited to, blocked amine catalysts, blocked amidine catalysts, high steric hindered organometallic catalysts, and the like, more specific examples 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 isooctoate of dimethylcyclohexylamine, dioctyltin dithiolate, bis (dimethylaminoethyl) ether derivatives, and the like, commercial products such as WANALYST KC110, WANALYST KC101, UL-32 of Michigan, DABCO BL-17 of air chemistry, and the like.
Examples of the flame retardant 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 1-3: 1, preferably 2: 1. the reactive flame retardant refers to a flame retardant which can participate in a reaction to enable polyurethane molecules obtained by the reaction to have a flame retardant function and have small influence on material properties, 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, FR212 (manufactured by wawa chemical company) and the like. 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 disclosed by the invention enables the polyurethane composition to have a good flame retardant effect, and meanwhile, the polyurethane composition has lower viscosity at room temperature, and the moldability of the polyurethane composition and a reinforcing material is improved.
The dispersant may be one commonly used in the art, and examples thereof include, but are not limited to, anionic, cationic, nonionic, amphoteric, electroneutral and the like, and such dispersants may be used alone or in combination.
Wherein the isocyanate component refers to a class of compounds having isocyanate groups, 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), methylcyclohexyl diisocyanate (HTDI), and the like, and prepolymers, modified products, polymers and the like of such monomers, and such isocyanate compounds may be used alone or in combination. The isocyanate component is preferably a mixture of monomeric diphenylmethane diisocyanate and homologues of diphenylmethane diisocyanate having more than one ring (polymethylene polyphenyl isocyanates).
Another key to the invention is a magnetic internal mold release agent suitable for the HP-TRM process, which can be added to polyurethane compositions for the preparation of polyurethane HPRTM composites, which replaces the internal mold release agents currently on the market, for example the traditional corning company G40 internal mold release agent. The magnetic internal release agent is obtained by reacting amino modified magnetic material particles with hydroxyl-terminated polysiloxane release agent grafts. When the polyurethane HPRTM composite material is prepared, the polyurethane composition containing the magnetic internal release agent is matched with a mold with a magnetic field injection machine for use, and the high magnetism of nano-scale magnetic particles is utilized to drive release agent molecules to directionally migrate to the surface of a component along the direction of a magnetic field, so that the release agent is enriched on the surface of the component, the use amount of the release agent is greatly reduced, the continuous release times of the component are greatly improved, and the production efficiency is greatly improved.
Meanwhile, the main chain siloxane structure of the magnetic internal mold release agent endows the mold release agent with more excellent high temperature resistance, can still fully play a role under the molding process condition that the temperature of the polyurethane HP-RTM is up to 200 ℃, and endows the mold release agent with higher production efficiency at high temperature. .
The magnetic internal release agent is prepared by the following method:
1) preparing magnetic material particles: preferably the magnetic material is a ferrite magnetic material, which may be, for example, Fe3O4Or gamma-Fe2O3(ii) a More preferably gamma-Fe having a particle size of 20 to 80nm2O3Particles;
2) preparing an amino modified magnetic material: adding the magnetic material particles into a mixed solution of distilled water and ethanol, performing full ultrasonic dispersion, dropwise adding a compound with amino and alkoxy under the protection of nitrogen, fully stirring until the reaction is finished, cooling the solution to room temperature, washing the solution for multiple times by using absolute ethanol, and performing freeze drying to obtain the amino modified magnetic material; preferably, the volume ratio of distilled water to ethanol in the mixed solution is 1:1, the ultrasonic dispersion time is 30-60 min, the compound with amino and alkoxy is selected from one or more of gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane and N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane, the reaction temperature is 30-60 ℃, the stirring speed is 500-1500 r/min, the stirring time is 1-5 h, the washing times of anhydrous ethanol are 5-20 times, the freeze drying vacuum degree is 4-5 Pa, the temperature is-50-60 ℃, and the time is 20-30 h;
3) preparing a magnetic internal release agent: adding the amino modified magnetic material into absolute ethyl alcohol, performing full ultrasonic dispersion, adding an activating agent, fully stirring, dropwise adding a hydroxyl-terminated polysiloxane release agent graft under stirring, stirring until the reaction is finished, washing with absolute ethyl alcohol for multiple times, adding distilled water, and performing freeze drying to obtain the magnetic internal release agent; preferably, the ultrasonic dispersion time is 30-60 min, the activating agent is N, N '-carbonyldiimidazole, the stirring speed is 500-1500 r/min, the stirring time is 1-5 h after the N, N' -carbonyldiimidazole is added, the reaction conditions of adding the release agent graft are that the reaction temperature is 50-70 ℃, the stirring time is 2-6 h, the absolute ethyl alcohol is washed for 5-20 times, the freeze drying vacuum degree is 4-5 Pa, the temperature is-50-60 ℃, and the time is 20-30 h; the hydroxyl-terminated polysiloxane type release agent graft is selected from hydroxyl-terminated polysiloxane, more preferably any one or two of hydroxyl-terminated polydimethylsiloxane and hydroxyl-terminated polyvinyl siloxane. The hydroxyl-terminated polydimethylsiloxane is 1000-10000 in weight average molecular weight; the hydroxyl-terminated polyvinyl siloxane has a weight-average molecular weight of 1000-10000 and a vinyl content of 0.1-3 wt%.
It will be appreciated by those skilled in the art that the isocyanate-reactive component may also contain other additives commonly used in the art, such as coupling agents, fillers, smoke suppressants, dyes, pigments, defoamers, water scavengers, antistatic agents, antioxidants, UV stabilizers, diluents, surface wetting agents, leveling agents, viscosity reducers, plasticizers, and the like, to improve processability of the composite, and the like.
In the polyurethane composition of the present invention, the molar ratio of isocyanate groups in the isocyanate component to active hydrogen atoms in the isocyanate-reactive component is 90 to 120: 100, preferably 100 to 110: 100.
the preparation method of the invention is applicable to non-foaming systems, namely, reactants contain no water basically, and other physical or chemical foaming agents, and the used raw materials contain no water basically, or are dried by dehydration treatment or addition of drying agents. This is significantly different from foaming systems, including significant differences in polyurethane composition formulation, processing temperature, and mechanical properties of the final product. 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.
On the other hand, the preparation method of the polyurethane HP-RTM composite material adopts a high-pressure resin transfer molding process and comprises the following steps:
1) 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;
2) 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 of a magnetic field injection machine in which a reinforcing material is placed in advance, reacting, curing and molding, and demolding to obtain the polyurethane HPRTM composite material. In the step, the vacuum degree is-0.08 to-0.1 MPa, preferably-0.09 to-0.095 MPa, the injection pressure is 80 to 200bar, preferably 100 to 160bar, the mold temperature is preferably 50 to 200 ℃, the pressure maintaining time is preferably 1 to 10 minutes, and the magnetic field strength of the mold is 5000-8000Oe, preferably 6000-6500 Oe.
Among them, 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 50 to 80%, based on the total mass of the composite material.
With respect to the specific components involved in the polyurethane composition of the present invention, such as polyols, auxiliaries and the like, may be used alone or in combination, except as specifically mentioned. In addition, raw materials, processes, methods, parameters and the like required for preparing the components can refer to the techniques which are commonly used in the field in the unexplained or unrecited part, and the implementation of the invention, such as the preparation of polyether polyol, the preparation of catalyst and the like, is not influenced.
The "hydroxyl value" appearing in the present invention means an average hydroxyl value of the component unless otherwise specified.
Some examples are listed below to provide the public with a better understanding of the technical aspects of the present invention.
The examples and comparative examples used the following starting materials:
an isocyanate component 1, polymethylene polyphenyl isocyanate WANNATE PM-8219, the NCO content is 32.2%, the viscosity is 55mPa & s at 25 ℃, and the chemical property is Wanhua;
isocyanate component 2, polymethylene polyphenyl polyisocyanate WANNATE PM-200, NCO content 31.4%, viscosity 200 mPa.s at 25 ℃, Wanhua chemistry;
1-1 of polyether polyol, starting with glycerol, polymerizing propylene oxide, and performing addition on an ethylene oxide terminal block, wherein the ethylene oxide content is 10 wt%, and the hydroxyl value is 20 mgKOH/g;
1-2 parts of polyether polyol, beginning with diethylene glycol, polymerizing propylene oxide, and performing addition on ethylene oxide terminal blocks, wherein the ethylene oxide content is 35 wt%, and the hydroxyl value is 45 mgKOH/g;
1-3 parts of polyether polyol, starting with trimethylolpropane, polymerizing propylene oxide, and performing addition on an ethylene oxide terminal block, wherein the ethylene oxide content is 20 wt%, and the hydroxyl value is 34 mgKOH/g;
2-1 parts of polyether polyol, initiated by pentaerythritol, homopolymerized by propylene oxide and with a hydroxyl value of 150 mgKOH/g;
2-2 parts of polyether polyol, initiated by pentaerythritol, homopolymerized by propylene oxide and with a hydroxyl value of 55 mgKOH/g;
2-3 parts of polyether polyol, initiated pentaerythritol and homopolymerized propylene oxide, wherein the hydroxyl value is 180 mgKOH/g;
chain extender 1, ethylene glycol;
chain extender 2, 1, 4-butanediol;
crosslinker 1, trimethylolpropane;
crosslinker 2, glycerol;
catalyst 1, WANALYST KC110 (heat sensitive, activation temperature 60 ℃), Wanhua chemistry;
catalyst 2: BICAT8118, advanced chemistry;
flame retardant 1: FR212, wanhua chemistry;
flame retardant 2: a710 new material of grass wood;
dispersing agent: BYK9076, BYK chemical;
internal mold release agent 3, G40, corning corporation;
internal mold release agent 4, BYK9912, birk chemical.
The preparation method of the internal release agent 1 comprises the following steps:
2 parts by weight of gamma-Fe with the grain diameter of 20nm2O3Adding particles into a mixed solution (volume ratio is 1:2) of 50 parts by weight of distilled water and ethanol, performing ultrasonic dispersion for 30min, dropwise adding 8 parts by weight of gamma-aminopropyltriethoxysilane under the protection of nitrogen, stirring for 1h at the rotation speed of 800r/min at 30 ℃, washing for 5 times by absolute ethanol after the solution is cooled to room temperature, performing freeze drying for 20h at 4Pa and 50 ℃, adding 40 parts by weight of absolute ethanol, performing ultrasonic dispersion for 30min, adding 0.5 part by weight of N, N' -carbonyldiimidazole, stirring for 1h at the stirring rotation speed of 500r/min, dropwise adding 8 parts by weight of hydroxyl-terminated polyvinyl siloxane with the weight average molecular weight of 5000 and the vinyl content of 1 wt%, stirring for 2h at 50 ℃, washing for 5 times by using absolute ethanol, adding 90 parts by weight of distilled water, performing freeze drying for 20h at 4Pa and 50 ℃, the internal mold release agent 1 can be obtained.
The preparation method of the internal release agent 2 comprises the following steps:
taking 6 parts by weight of gamma-Fe with the particle diameter of 80nm2O3Adding particles into 100 parts by weight of mixed solution (volume ratio is 1:2) of distilled water and ethanol, performing ultrasonic dispersion for 80min, dropwise adding 12 parts by weight of N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane under the protection of nitrogen, stirring for 5h at the rotation speed of 1500r/min at 70 ℃, after the solution is cooled to room temperature, washing for 20 times by using absolute ethyl alcohol, performing freeze drying for 30h at 5Pa and-60 ℃, adding 80 parts by weight of absolute ethyl alcohol, performing ultrasonic dispersion for 60min, adding 2 parts by weight of N, N' -carbonyldiimidazole, stirring for 5h at the stirring rotation speed of 1500r/min, dropwise adding 12 parts by weight of hydroxyl-terminated polyvinyl siloxane with the weight average molecular weight of 5000 and the vinyl content of 2 wt%, stirring for 6h at 70 ℃, and then washing for 20 times by using absolute ethyl alcoholThen 180 parts by weight of distilled water is added, and the mixture is frozen and dried for 30 hours at the temperature of 5Pa and 60 ℃ below zero to obtain the internal mold release agent 2.
The preparation method of the internal release agent 5 comprises the following steps:
taking 5 parts by weight of FeCl3And 2 parts by weight of FeCl2Dissolving the components in 50 weight parts of distilled water, stirring the mixed solution at 30 ℃ for 10min at a speed of 500r/min, and continuously introducing nitrogen during stirring. Then heating to 80 ℃, dropwise adding 10 parts by weight of concentrated ammonia water under the condition of continuously introducing nitrogen, and stirring at 500r/min for reaction for 1 h. Washing the solid product with ethanol and distilled water alternately to neutrality, adding 50 weight parts of mixed solution of distilled water and ethanol (volume ratio of distilled water to ethanol is 1:1), and ultrasonic dispersing for 30 min. Under the protection of nitrogen, 10 weight parts of gamma-aminopropyl triethoxysilane is added drop by drop and stirred for 1h at the temperature of 30 ℃ at the speed of 500 r/min. After the solution is cooled to room temperature, washing the solution with absolute ethyl alcohol for 5 times, then freeze-drying the solution at 5Pa and-50 ℃ for 20h, adding 50 parts by weight of ethyl alcohol, ultrasonically dispersing the solution for 30min, adding 1 part by weight of N, N' -carbonyldiimidazole, stirring the solution at 50 ℃ for 1h at 500r/min, then dropwise adding 10 parts by weight of lauric acid while stirring, continuously stirring the solution for reaction for 2h, washing the solution for 5 times with absolute ethyl alcohol, then adding 100 parts by weight of distilled water, and freeze-drying the solution at 5Pa and-50 ℃ for 20h to obtain the internal mold release agent 5.
Examples and comparative example 4 preparation of polyurethane HPRTM composite:
step one, respectively mixing and stirring the isocyanate components uniformly at 30 ℃ for later use, and mixing and stirring the isocyanate reactive components uniformly for later use;
and step two, 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 30 ℃, injecting the mixture into a mold of a magnetic field injection machine in which a glass fiber mat is placed in advance, reacting, curing and molding, and demolding to obtain the polyurethane HPRTM composite material. The vacuum degree is-0.093 MPa, the injection pressure is 130bar, the mold temperature is 180 ℃, the pressure maintaining time is 1.5 minutes, and the mold magnetic field strength is 6500 Oe. Areal density of the glass fiber mat was 400g/m2。
Comparative examples 1-3 preparation of polyurethane HPRTM composites:
step one, respectively mixing and stirring the isocyanate components uniformly at 30 ℃ for later use, and mixing and stirring the isocyanate reactive components uniformly for later use;
and step two, 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 30 ℃, injecting the mixture into a mold with a glass fiber mat placed in advance, reacting, curing and molding, and demolding to obtain the polyurethane HPRTM composite material. The vacuum degree is-0.093 MPa, the injection pressure is 130bar, the mold temperature is 180 ℃, and the pressure maintaining time is 1.5 minutes. Areal density of the glass fiber mat was 400g/m2。
The raw materials used in the examples and comparative examples are shown in Table 1.
TABLE 1 raw material data table (parts by mass) for examples and comparative examples
The tests were carried out on samples of polyurethane HPRTM composite obtained in the examples and comparative examples, using the test standards and methods:
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 flame retardant rating test standard is: UL-94 (vertical burn);
continuous demolding performance test standard: before each test, the same gram of external release agent is sprayed on the upper die and the lower die of the die. When the preparation of the polyurethane HPRTM composite material was carried out according to the preparation method, the number of complete demolds was tested.
The test results are shown in Table 2 below.
TABLE 2 tables of the respective performance data of examples and comparative examples
The comparison of the performances of the examples and the comparative examples shows that the examples have excellent bending performance, impact performance and tensile performance and better comprehensive mechanical properties. When the using amount of the internal mold release agent is within 0.5 wt%, the continuous mold release can be carried out for at least more than 70 times in the test of the continuous mold release performance with high glass fiber content, the production efficiency can be greatly improved, the excellent continuous mold release performance is shown, and the low-cost and high-efficiency production is realized.
While the present invention has been described in detail with reference to the preferred embodiments, it should be understood that the above description should not be taken as limiting the invention. It will be appreciated by those skilled in the art that modifications or adaptations to the invention may be made in light of the teachings of the present specification. Such modifications or adaptations are intended to be within the scope of the present invention as defined in the claims.
Claims (10)
1. A preparation method of a magnetic internal release agent comprises the following steps:
1) preparing magnetic material particles: preferably the magnetic material is a ferrite magnetic material; more preferably gamma-Fe having a particle size of 20 to 80nm2O3Particles;
2) preparing an amino modified magnetic material: adding the magnetic material particles into a mixed solution of distilled water and ethanol, performing full ultrasonic dispersion, dropwise adding a compound with amino and alkoxy under the protection of nitrogen, fully stirring until the reaction is finished, cooling the solution to room temperature, washing the solution for multiple times by using absolute ethanol, and performing freeze drying to obtain the amino modified magnetic material;
3) preparing a magnetic internal release agent: adding the amino modified magnetic material into absolute ethyl alcohol, performing full ultrasonic dispersion, adding an activating agent, fully stirring, dropwise adding a hydroxyl-terminated polysiloxane release agent graft under stirring, stirring until the reaction is finished, washing with absolute ethyl alcohol for multiple times, adding distilled water, and performing freeze drying to obtain the magnetic internal release agent.
2. The method for preparing the magnetic internal mold release agent according to claim 1, wherein the volume ratio of distilled water to ethanol in the mixed solution in the step 2) is 1:1, the ultrasonic dispersion time is 30-60 min, the compound having an amino group and an alkoxy group is one or more selected from the group consisting of γ -aminopropyltriethoxysilane, γ -aminopropyltrimethoxysilane, N- (β -aminoethyl) - γ -aminopropyltrimethoxysilane, and N- (β -aminoethyl) - γ -aminopropylmethyldimethoxysilane, the reaction temperature is 30-60 ℃, the stirring speed is 500-1500 r/min, the stirring time is 1-5 h, the number of washing times of the anhydrous ethanol is 5-20, the degree of vacuum of freeze drying is 4-5 Pa, the temperature is-50 ℃ to-60 ℃, the time is 20-30 h;
the ultrasonic dispersion time in the step 3) is 30-60 min, the activating agent is N, N '-carbonyldiimidazole, the stirring speed is 500-1500 r/min, the stirring time is 1-5 h after the N, N' -carbonyldiimidazole is added, the reaction conditions of adding the release agent graft are that the reaction temperature is 50-70 ℃, the stirring time is 2-6 h, the absolute ethyl alcohol is washed for 5-20 times, the freeze drying vacuum degree is 4-5 Pa, the temperature is-50-60 ℃, and the time is 20-30 h; the hydroxyl-terminated polysiloxane release agent graft is selected from one or two of hydroxyl-terminated polydimethylsiloxane and hydroxyl-terminated polyvinyl siloxane; preferably, the hydroxyl-terminated polydimethylsiloxane is of weight average molecular weight 1000-10000; the hydroxyl-terminated polyvinyl siloxane has a weight-average molecular weight of 1000-10000 and a vinyl content of 0.1-3 wt%.
3. A magnetic internal mold release agent produced by the production method for a magnetic internal mold release agent according to claim 1.
4. A polyurethane composition resulting from a reaction comprising an isocyanate component and an isocyanate-reactive component, wherein the isocyanate-reactive component comprises: polyether polyol 1, polyether polyol 2, a chain extender, a cross-linking agent, a catalyst, a flame retardant, a dispersing agent and a magnetic internal release agent; wherein the magnetic internal mold release agent is prepared by the method of claim 1 or 2 or the magnetic internal mold release agent of claim 3.
5. A polyurethane composition according to claim 4, characterised in that the polyether polyol 1 of the isocyanate reactive component has an average functionality of 2 to 4, preferably 2 to 3, and a hydroxyl number of 15 to 50mgKOH/g, preferably 20 to 45mgKOH/g, obtained from the reaction of ethylene oxide and propylene oxide, the ethylene oxide content being 5 to 50 wt.%, preferably 10 to 35 wt.%; the polyether polyol 2 has an average functionality of 2.5 to 8, preferably 3 to 5, more preferably 4, and a hydroxyl value of 50 to 200mgKOH/g, preferably 55 to 180 mgKOH/g.
6. A polyurethane composition according to claim 4 or 5, wherein the isocyanate component is a mixture of monomeric diphenylmethane diisocyanate and homologues of diphenylmethane diisocyanates having more rings.
7. A polyurethane composition as claimed in any one of claims 4 to 6 wherein the molar ratio of isocyanate groups in the isocyanate component to active hydrogen atoms in the isocyanate-reactive component is from 90 to 120: 100, preferably 100 to 110: 100.
8. a polyurethane composition as claimed in any one of claims 4 to 7 wherein the isocyanate-reactive component comprises, based on the total mass of the isocyanate-reactive component:
the using amount of the polyether polyol 1 is 5-10%;
the using amount of the polyether polyol 2 is 50-70%;
the using amount of the chain extender is 7-15%;
the dosage of the cross-linking agent is 7-15%;
the dosage of the catalyst is 0.3-0.5%;
the using amount of the flame retardant is 5-20%;
the dosage of the dispersant is 0.2-0.5%;
the dosage of the magnetic internal release agent is 0.1-0.5%.
9. A process for the preparation of a polyurethane HP-RTM composite comprising the steps of:
1) 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;
2) 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 of a magnetic field injection machine in which a reinforcing material is placed in advance, reacting, curing and molding, and demolding to obtain the polyurethane HP-RTM composite material.
10. The method according to claim 9, wherein the vacuum degree in step 2) is-0.08 to-0.1 MPa, preferably-0.09 to-0.095 MPa, the injection pressure is 80 to 200bar, preferably 100 to 160bar, the mold temperature is preferably 50 to 200 ℃, the dwell time is preferably 1 to 10 minutes, and the mold magnetic field strength is 5000-8000Oe, preferably 6000-6500 Oe.
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