CN116589682B - Preparation method and application of silicone resin suitable for hot-melt presoaking - Google Patents
Preparation method and application of silicone resin suitable for hot-melt presoaking Download PDFInfo
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- CN116589682B CN116589682B CN202310854301.XA CN202310854301A CN116589682B CN 116589682 B CN116589682 B CN 116589682B CN 202310854301 A CN202310854301 A CN 202310854301A CN 116589682 B CN116589682 B CN 116589682B
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- 229920002050 silicone resin Polymers 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000012943 hotmelt Substances 0.000 title claims abstract description 18
- 239000000835 fiber Substances 0.000 claims abstract description 42
- 229920005989 resin Polymers 0.000 claims abstract description 38
- 239000011347 resin Substances 0.000 claims abstract description 38
- 239000004744 fabric Substances 0.000 claims abstract description 32
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 31
- 239000010703 silicon Substances 0.000 claims abstract description 31
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000008367 deionised water Substances 0.000 claims abstract description 23
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 23
- 229910000077 silane Inorganic materials 0.000 claims abstract description 16
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 238000005470 impregnation Methods 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 238000007598 dipping method Methods 0.000 claims abstract description 10
- 238000002844 melting Methods 0.000 claims abstract description 8
- 230000008018 melting Effects 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 150000001298 alcohols Chemical class 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 230000007062 hydrolysis Effects 0.000 claims abstract description 7
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 7
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000010453 quartz Substances 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000003365 glass fiber Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- 229920006231 aramid fiber Polymers 0.000 claims description 6
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 claims description 6
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 claims description 6
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 claims description 5
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- ZZNQQQWFKKTOSD-UHFFFAOYSA-N diethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OCC)(OCC)C1=CC=CC=C1 ZZNQQQWFKKTOSD-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 claims description 4
- NLSXASIDNWDYMI-UHFFFAOYSA-N triphenylsilanol Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(O)C1=CC=CC=C1 NLSXASIDNWDYMI-UHFFFAOYSA-N 0.000 claims description 4
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002131 composite material Substances 0.000 abstract description 10
- 230000007547 defect Effects 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000001816 cooling Methods 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 239000007787 solid Substances 0.000 description 3
- 239000004760 aramid Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- -1 alkoxy silane Chemical compound 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
- C08G77/08—Preparatory processes characterised by the catalysts used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2383/04—Polysiloxanes
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
A preparation method and application of silicone resin suitable for hot melt prepreg belong to the technical field of composite material preparation. The specific scheme comprises the following steps: uniformly mixing silane, a catalyst and water, heating to 45-65 ℃ and reacting for 2-12 hours; adding deionized water into a reaction container after the reaction is finished, standing for more than 6 hours, taking out a lower layer mixture, distilling under reduced pressure to remove deionized water and alcohols generated by silane hydrolysis, and then adding a structure auxiliary agent to rapidly stir for 5-10 minutes to obtain viscous solvent-free silicone resin; and heating and melting the silicon resin at 120-150 ℃, uniformly dipping the molten silicon resin on the surface of the fiber cloth, and pre-curing for 5-20 min at 150-220 ℃ to obtain the continuous fiber prepreg. The prepreg prepared by the invention has uniform impregnation and few defects; the preparation process is completely solvent-free, does not pollute the environment, and is suitable for large-scale industrial production.
Description
Technical Field
The invention belongs to the technical field of composite material preparation, and particularly relates to a preparation method and application of silicone resin suitable for hot melt prepreg.
Background
In recent years, people have been paying more attention to organic high-temperature-resistant composite materials, and because of the excellent combination property of resin matrix and reinforcing fiber, the composite materials are used as strategic key materials essential in national defense and national economic construction, and are applied to the fields of aerospace, industrial manufacturing, rail transit, clean energy and the like, and have very broad development prospects. The organic high-temperature resistant material mainly takes a fiber reinforced resin matrix composite material as a source, and the composite material taking phenolic resin and polyimide resin as a matrix has higher use temperature, but the organic resin has obviously inferior heat resistance compared with an inorganic material due to self elements and structural characteristics. So in the practical application in the aerospace field, researchers focus on the organic-inorganic property-combined organic-silicon resin-based composite material. The silicon resin has an Si-O-Si inorganic main chain structure, and the bond energy of Si-O is very high, so that the temperature resistance of the silicon resin is much higher than that of other carbon chain polymers, and the organic side chains of the silicon resin such as methyl and phenyl also endow the silicon resin with processability. The fiber reinforced silicone resin can be used for preparing a structural composite material with high temperature resistance and wave transmission performance.
The prepreg is a composition of a resin matrix and a fiber reinforcement, is an important intermediate material in the process of forming a resin/reinforced fiber composite material, and is prepared by impregnating fibers or fabrics with the resin matrix under strictly controlled conditions. The prepreg has a certain mechanical structure, so the properties of the prepreg can greatly influence the overall performance of the composite material. While the preparation of the silicone resin/fiber prepreg at present uses a large amount of organic solvents (such as ZL201410828666.6 and ZL 201410829372.5) which are not friendly to the environment and harmful to human bodies, the preparation methods need to be improved.
Disclosure of Invention
In order to solve the problems of environmental pollution caused by solvent volatilization and low control precision of resin content in a silicone resin prepreg hot-melt process, the invention adopts the silicone resin which is solid at room temperature and has excellent fluidity in the temperature range of 120-150 ℃, and adopts a hot-melt impregnation method to prepare the fiber/silicone resin prepreg with uniform resin distribution. The pre-cured composite material of the prepreg has excellent high temperature resistance and mechanical properties.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a preparation method of silicone resin suitable for hot-melt presoaking comprises the following steps:
uniformly mixing 50-100 parts of silane, 0.1-1 part of catalyst and 5-50 parts of deionized water, and heating to 45-65 ℃ to react for 2-12 hours, wherein the catalyst and the deionized water are respectively added in a small amount for many times; adding 50-200 parts of deionized water into a reaction container after the reaction is finished, stirring until the reaction system is milky, standing for more than 6 hours, preferably 6-24 hours, taking a lower-layer high-viscosity mixture, removing alcohols generated by hydrolysis of deionized water and silane by reduced pressure distillation, adding a structural additive capable of reacting with a silicone resin prepolymer, rapidly stirring for 5-10 minutes, uniformly mixing, and cooling to room temperature to obtain viscous solvent-free silicone resin, namely, normal-temperature solid, high-temperature low-viscosity silicone resin suitable for hot melting prepreg; the silane comprises one or more of methyltriethoxysilane, phenyltrimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, and dimethyldimethoxysilane.
Further, the catalyst comprises one or a combination of more of hydrochloric acid, sulfuric acid and nitric acid.
Further, the structure auxiliary agent comprises one or a combination of more of diphenyl diethoxy silane, diphenyl dimethoxy silane, triphenyl silanol and phenyl triethoxy silane.
Further, the mass of the added structure auxiliary agent is 1% -10% of the total mass of the silane.
The preparation method comprises the steps of heating and melting the silicon resin at 120-150 ℃, uniformly dipping the melted silicon resin on the surface of continuous fiber cloth, and pre-curing for 5-20 min at 150-220 ℃ to obtain the fiber prepreg.
Further, in the continuous fiber prepreg, the silicone resin content accounts for 25-40% of the mass of the prepreg.
Further, the molar mass of the silicone resin is 2000-8000 g/mol, and the viscosity of the silicone resin at 120-150 ℃ is 100-800 mPa.s.
Further, the fiber cloth includes one of a glass fiber cloth, a quartz fiber cloth, an aramid fiber cloth, a mixed woven cloth woven from glass fibers, quartz fibers and aramid fibers, a mixed woven cloth woven from glass fibers and aramid fibers, a mixed woven cloth woven from quartz fibers and polysulfonamides fibers, and a mixed woven cloth woven from glass fibers and polysulfonamides fibers.
Further, the impregnation method includes blade coating impregnation, coater coating impregnation or prepreg machine impregnation.
Further, the prepreg pre-curing includes atmospheric pre-curing, pressurized pre-curing or vacuum pre-curing.
Compared with the prior art, the invention has the beneficial effects that:
the invention mainly solves the problem of environmental pollution caused by using a large amount of harmful and toxic solvents in the preparation of the prior silicone resin continuous fiber prepreg. The invention adopts the alkoxy silane as the raw material to prepare the silicon resin prepolymer which is solid at room temperature and has good heating fluidity by a hydrolysis-condensation method, and the change of the viscosity is small when the silicon resin prepolymer is heated for a long time at 120 ℃. And then presoaking is carried out in a molten state by methods such as blade coating, coating or prepreg in a dipping machine, and finally, the silicone resin/continuous fiber prepreg is obtained through presoaking treatment. The prepreg prepared by the invention has uniform impregnation and few defects; the preparation process is completely solvent-free, does not pollute the environment, and is suitable for large-scale industrial production. The invention is applied to the field of prepreg preparation.
Drawings
FIG. 1 is a plot of viscosity versus time at 150℃for the silicone resin prepared in example 1;
FIG. 2 is a graph showing the viscosity of the silicone resin prepared in example 2 as a function of temperature;
FIG. 3 is a graph showing the results of a chromatography test on a silicone gel prepared in example 2;
FIG. 4 is a graph of the microtopography of the prepreg prepared in example 2.
Description of the embodiments
The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings and examples, and it is apparent that the described examples are only some, but not all, of the examples of the invention, and all other examples obtained by those skilled in the art without making any inventive effort are within the scope of the present invention.
Examples
A preparation method and application of silicone resin suitable for hot-melt presoaking comprise the following steps: adding methyltriethoxysilane 436 g, phenyltrimethoxysilane g and dimethyldiethoxysilane 145 g into a reactor, stirring for 5 minutes, taking 168 g of deionized water, slowly adding 12 g mol/L hydrochloric acid into the reactor, stirring for 30 minutes at room temperature after the addition is finished, heating to 45 ℃ for reaction for 8 hours, cooling to room temperature after the reaction is finished, adding deionized water 1500 g, standing for more than 6 hours, removing deionized water and alcohols generated by silane hydrolysis by reduced pressure distillation of a lower layer high-viscosity liquid to obtain silicon resin, adding 17 g of phenyltriethoxysilane and triphenylsilanol respectively after the deionized water and alcohols generated by silane hydrolysis are completely removed, rapidly stirring for 5 minutes, cooling to room temperature, and obtaining the silicon resin suitable for hot melt prepreg. The viscosity change curve of the silicone resin in the range of 50-80 ℃ along with the temperature is shown in figure 1, the viscosity of the silicone resin is gradually reduced along with the temperature rise, the viscosity of the silicone resin is 210 mPas when the temperature is 120 ℃, and the viscosity meets the requirement of preparing the prepreg by a hot melting method. The viscosity of the silicon resin changes with time at 150 ℃ as shown in figure 2, the viscosity of the silicon resin does not change obviously when the silicon resin is continuously heated for 4 hours at 150 ℃, and the surface silicon resin has enough impregnation time when being prepared into prepreg through melt impregnation, so that good fiber infiltration of the silicon resin can be ensured.
The silicone resin prepared above was heated in an oven at 150℃until the silicone resin temperature reached 150℃and then the silicone resin was transferred to a thickness of 0.2mm and an areal density of 160g/m 2 And then a coating scraper is adopted to rapidly coat the silicon resin on the surface of the high silicon fiber cloth uniformly, then the high silicon fiber cloth which is dipped uniformly is subjected to heat preservation for 15 minutes at 180 ℃ in a vacuum oven with the vacuum degree of-0.05 MPa, and finally the high silicon fiber cloth/silicon resin prepreg is obtained after cooling to room temperature.
Examples
A preparation method and application of silicone resin suitable for hot-melt presoaking comprise the following steps: adding methyltriethoxysilane 526 and g, phenyltrimethoxysilane 255 and g and dimethyldiethoxysilane 231 and g into a reactor, stirring for 5 minutes, taking 172 g of deionized water, 7 g mol/L of hydrochloric acid and 8g of 2 mol/L of nitric acid, slowly adding into the reactor, stirring for 30 minutes at room temperature after the addition is finished, heating to 65 ℃ for reaction for 6 hours, cooling to room temperature after the reaction is finished, adding 1800 and g of deionized water, standing for more than 8 hours, taking out the lower-layer high-viscosity liquid, and distilling at 150 ℃ under reduced pressure until no distillate is distilled out, thus obtaining the silicone resin. The silicone GPC test results are shown in FIG. 3, with the silicone molar mass being 2228g/mol.
And (3) adding 5 parts of diphenyl dimethoxy silane, 10 parts of diphenyl diethoxy silane and 5 parts of triphenyl silanol into 250 parts of the silicon resin synthesized by the method, rapidly stirring for 5 minutes, uniformly mixing, and finally naturally cooling to room temperature to obtain the silicon resin for hot melting prepreg.
The prepared silicon resin is heated for 1 hour at 120 ℃ to obtain the molten silicon resin with good fluidity. The thickness is 0.18mm, and the surface density is 150g/m 2 And (3) placing the quartz fiber cloth on a heatable scraper type coater and heating to 120 ℃, then transferring the molten silicon resin to the surface of the quartz fiber cloth, fully soaking the quartz fiber cloth by a coating scraper, hot-pressing and pre-curing the fully soaked quartz fiber cloth at 220 ℃ under the pressure of 2 MPa for 5 minutes, and cooling to room temperature to obtain the prepreg. Prepregs with different resin contents are prepared by controlling the resin content of the prepreg through adjusting the height of the scraper.
Examples
A preparation method and application of silicone resin suitable for hot-melt presoaking comprise the following steps: methyl triethoxysilane 1260 g, phenyl trimethoxysilane 872, 872 g and dimethyl diethoxysilane 645, 645 g are added into a reactor and stirred for 10 minutes, 320 g of deionized water and 30 g of 1 mol/L sulfuric acid are slowly added into the reactor, the mixture is stirred for 60 minutes at room temperature after the addition is finished, the temperature is raised to 60 ℃ for 8 hours, the temperature is reduced to room temperature after the reaction is finished, deionized water 3000, 3000 g is added, the mixture is left for more than 8 hours, the lower layer high-viscosity liquid is distilled at 120 ℃ under reduced pressure to remove alcohols generated by the hydrolysis of the deionized water and the silane until no fraction is distilled out, 50g of phenyl triethoxysilane g and 45g of diphenyl dimethoxysilane are added, and the mixture is rapidly stirred for 5 minutes and uniformly mixed, so that the silicone resin is obtained. Transferring the obtained silicone resin while it is hot to a dipping machine for addingHeating at 120deg.C in a hot tank to a thickness of 0.1mm and an areal density of 110g/m 2 The quartz fiber cloth of (2) is taken as a reinforcing material, is presoaked by a dipping machine and presoaked for 10 minutes at 200 ℃, and is cooled to room temperature to obtain the quartz fiber cloth/silicone resin presoaked material. The microcosmic appearance chart of the prepared prepreg is shown in figure 4, the silicone resin in the prepreg is distributed uniformly on the surface of the quartz fiber cloth, the wettability is good, and the prepreg is free of bubbles and impurities, so that the prepared prepreg is uniform in resin distribution and free of bubbles.
Examples
A preparation method and application of silicone resin suitable for hot-melt presoaking comprise the following steps: 1982.9g of phenyl trimethoxy silane is added into a reactor, evenly mixed with 308g of deionized water, 15g of 2 mol/L hydrochloric acid, 10g of 1 mol/L sulfuric acid and 10g of 2 mol/L nitric acid, then slowly added into the reactor, stirred at room temperature for 30min after the addition is completed, heated to 65 ℃ for reaction for 10 hours, cooled to room temperature after the reaction is completed, then added with 2000 g of deionized water, left stand for more than 8 hours, the lower layer of high viscosity liquid is distilled at 150 ℃ under reduced pressure to remove alcohols generated by the hydrolysis of deionized water and silane until no fraction is distilled out, and then 80 g of diphenyl diethoxy silane is added, and the mixture is quickly stirred for 10 minutes and evenly mixed to obtain the silicone resin. Transferring the obtained silicone resin while it is hot into a heating tank of a dipping machine, heating at 120deg.C to a thickness of 0.12mm and an areal density of 120g/m 2 The glass fiber and polysulfonamide fiber woven mixed woven cloth is used as a reinforcing material, is presoaked by a dipping machine, presoaked for 10 minutes at 220 ℃ and normal pressure, and is cooled to room temperature to obtain the glass fiber and polysulfonamide fiber woven mixed woven cloth/silicone resin presoaked material.
TABLE 1 Properties of the Silicone prepregs obtained in examples 1-4
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.
Claims (6)
1. The preparation method of the silicone resin suitable for hot melt prepreg is characterized by comprising the following steps of:
uniformly mixing silane, a catalyst and deionized water, heating to 45-65 ℃ and reacting for 2-12 hours; adding deionized water into a reaction container after the reaction is finished, stirring until the reaction system is milky, standing for more than 6 hours, taking out a lower layer mixture, distilling under reduced pressure to remove deionized water and alcohols generated by hydrolysis of silane, adding a structural auxiliary agent capable of reacting with silicone resin, and rapidly stirring and uniformly mixing to obtain the silicone resin suitable for hot melting presoaking; the silane comprises one or more of methyltriethoxysilane, phenyltrimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane and dimethyldimethoxysilane, the structural auxiliary agent capable of reacting with the silicon resin comprises a combination of more of diphenyldiethoxysilane, diphenyldimethoxysilane, triphenylsilanol and phenyltriethoxysilane, and the mass ratio of the silane to the catalyst to the deionized water added for the first time to the deionized water added for the second time is 50-100:0.1-1:5-50:50-200, wherein the catalyst comprises one or a combination of more of hydrochloric acid, sulfuric acid and nitric acid, the mass of the added structure auxiliary agent is 1-10% of the total mass of silane, the molar mass of the silicone resin suitable for hot-melt prepreg is 2000-8000 g/mol, and the viscosity of the silicone resin suitable for hot-melt prepreg at 120-150 ℃ is 100-800 mPa.s.
2. Use of a silicone resin suitable for hot melt prepregs prepared by the method of claim 1, characterized in that: and heating and melting the silicon resin suitable for hot-melt pre-dipping, uniformly dipping the melted silicon resin on the surface of the fiber cloth, and pre-curing to obtain the continuous fiber pre-dipping material.
3. The use according to claim 2, characterized in that: the temperature of heating and melting is 120-150 ℃; the pre-curing temperature is 150-220 ℃ and the pre-curing time is 5-20 min.
4. The use according to claim 2, characterized in that: in the continuous fiber prepreg, the content of the silicone resin suitable for hot melt prepreg accounts for 25-40% of the mass of the prepreg.
5. The use according to claim 2, characterized in that: the fiber cloth comprises one of glass fiber cloth, quartz fiber cloth, aramid fiber cloth, mixed woven cloth woven by glass fiber, quartz fiber and aramid fiber, mixed woven cloth woven by glass fiber and aramid fiber, mixed woven cloth woven by quartz fiber and polysulfonamide fiber, and mixed woven cloth woven by glass fiber and polysulfonamide fiber.
6. The use according to claim 2, characterized in that: the method for impregnation comprises blade coating impregnation, coating impregnation by a coating machine or prepreg impregnation; the pre-curing of the prepreg includes atmospheric pre-curing, pressurized pre-curing or vacuum pre-curing.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202310854301.XA CN116589682B (en) | 2023-07-13 | 2023-07-13 | Preparation method and application of silicone resin suitable for hot-melt presoaking |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202310854301.XA CN116589682B (en) | 2023-07-13 | 2023-07-13 | Preparation method and application of silicone resin suitable for hot-melt presoaking |
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| Publication Number | Publication Date |
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| CN116589682A CN116589682A (en) | 2023-08-15 |
| CN116589682B true CN116589682B (en) | 2023-10-03 |
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