CN116333309A - Preparation method of high-modulus high-temperature-resistant modified cyanate resin - Google Patents
Preparation method of high-modulus high-temperature-resistant modified cyanate resin Download PDFInfo
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- CN116333309A CN116333309A CN202310249608.7A CN202310249608A CN116333309A CN 116333309 A CN116333309 A CN 116333309A CN 202310249608 A CN202310249608 A CN 202310249608A CN 116333309 A CN116333309 A CN 116333309A
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- 229920005989 resin Polymers 0.000 title claims abstract description 74
- 239000011347 resin Substances 0.000 title claims abstract description 74
- 150000001913 cyanates Chemical class 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000003822 epoxy resin Substances 0.000 claims abstract description 43
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 43
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims abstract description 37
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000012948 isocyanate Substances 0.000 claims abstract description 12
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 12
- 229920000642 polymer Polymers 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 239000004643 cyanate ester Substances 0.000 claims description 24
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 17
- 239000000178 monomer Substances 0.000 claims description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 238000001723 curing Methods 0.000 claims description 12
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 6
- 125000003700 epoxy group Chemical group 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 238000002390 rotary evaporation Methods 0.000 claims description 6
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- HCNHNBLSNVSJTJ-UHFFFAOYSA-N 1,1-Bis(4-hydroxyphenyl)ethane Chemical compound C=1C=C(O)C=CC=1C(C)C1=CC=C(O)C=C1 HCNHNBLSNVSJTJ-UHFFFAOYSA-N 0.000 claims description 4
- 229930185605 Bisphenol Natural products 0.000 claims description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 4
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 4
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 claims description 3
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 3
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 3
- 238000013007 heat curing Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000004593 Epoxy Substances 0.000 claims description 2
- 230000009477 glass transition Effects 0.000 abstract description 9
- 239000000725 suspension Substances 0.000 abstract description 7
- 230000000452 restraining effect Effects 0.000 abstract description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 6
- 239000004917 carbon fiber Substances 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000002131 composite material Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- -1 anhydride compound Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 238000010125 resin casting Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
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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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
- C08G73/065—Preparatory processes
-
- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
- C08G73/0644—Poly(1,3,5)triazines
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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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)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses a preparation method of high-modulus high-temperature-resistant modified cyanate resin, which comprises the steps of heating monoepoxy cage-type oligomeric silsesquioxane and isocyanate in a reaction kettle, and reacting to obtain isocyanate-terminated cage-type oligomeric silsesquioxane; the cage-type oligomeric silsesquioxane with terminal isocyanate groups and bisphenol-type epoxy resin are subjected to further grafting reaction to prepare epoxy resin grafted with the cage-type oligomeric silsesquioxane; uniformly stirring epoxy resin containing cage-type oligomeric silsesquioxane and cyanate, performing prepolymerization reaction, and then performing vacuum defoamation and curing to obtain high-modulus high-temperature-resistant cyanate resin. According to the invention, the suspension state size and the distribution of the cage-type oligomeric silsesquioxane in the cyanate resin are optimized by controlling the reaction conditions, so that the monoepoxy cage-type oligomeric silsesquioxane plays a role in restraining the movement of a polymer chain segment, the rigidity of a resin system is improved, and the tensile modulus and the glass transition temperature of the resin are obviously improved.
Description
Technical Field
The invention relates to the technical field of polymer composite materials, in particular to a preparation method of high-modulus high-temperature-resistant modified cyanate resin.
Background
The cyanate resin is a thermosetting resin with excellent mechanical property, high thermal stability, excellent dielectric property, good dimensional stability and excellent space resistance, can be compounded with high-modulus carbon fiber to form a high-modulus carbon fiber resin matrix composite material, and has wide application prospect in the field of aerospace.
The cyanate monomer is polymerized to generate a compact triazine ring network, so that the cyanate resin has poor manufacturability, and the heat resistance of the cyanate is often reduced when the cyanate is modified to improve the manufacturability. Meanwhile, the modulus value of the cyanate resin is insufficient to be matched with the high-modulus carbon fiber so as to fully exert the mechanical property advantage of the high-modulus carbon fiber, so that the mechanical property of the formed high-modulus carbon fiber resin matrix composite material is weakened, and the problem to be solved is to improve the modulus of the cyanate resin. For example, patent application number CN201310442784.9 discloses a cyanate modification method for introducing an anhydride compound into a cyanate/bismaleimide/bisoxazoline/epoxy system, which improves the modulus of the resin system, but the viscosity of the resin system is high, and the resin system can be used for forming a composite material only after being dissolved in a solvent, so that the environmental pollution is high. It is therefore necessary to develop high modulus, high temperature resistant modified cyanate ester resins to meet the needs of the aerospace field.
Disclosure of Invention
The invention aims to provide a preparation method of high-modulus high-temperature-resistant modified cyanate resin with obviously improved tensile modulus and glass transition temperature, which solves the problem that the existing cyanate resin cannot fully exert the mechanical property advantage of high-modulus carbon fiber.
In order to achieve the above purpose, the present invention provides the following technical solutions:
a preparation method of high-modulus high-temperature-resistant modified cyanate ester resin comprises the following steps:
s1: dissolving isocyanate and monoepoxy cage type oligomeric silsesquioxane in N, N-dimethylacetamide, heating to 140-160 ℃ under the protection of nitrogen with the isocyanate group of epoxy group= (2-1.2): 1, reacting for 3-5h, and removing the organic solvent by rotary evaporation after the reaction is finished to obtain the cage type oligomeric silsesquioxane with the isocyanate group;
s2: mixing the cage-type oligomeric silsesquioxane with the isocyanate groups and bisphenol-type epoxy resin obtained in the step S1, dissolving the mixture in acetone, and further carrying out a grafting reaction at 70-90 ℃ to prepare the epoxy resin grafted with the cage-type oligomeric silsesquioxane;
s3: uniformly stirring cyanate monomer and epoxy resin grafted with cage-type oligomeric silsesquioxane obtained in the step S2 at 100-120 ℃ and performing a prepolymerization reaction to obtain a modified cyanate resin prepolymer;
s4: pouring the modified cyanate ester resin prepolymer obtained in the step S3 into a mould, removing bubbles in the system in vacuum, and finally, carrying out vacuum curing in an oven to obtain the high-modulus high-temperature-resistant modified cyanate ester resin system.
Further, the isocyanate selected in S1 is one or more of toluene diisocyanate, p-phenylene diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate and isophorone diisocyanate.
Further, the bisphenol type epoxy resin in S2 is one or more of bisphenol A type epoxy resin, bisphenol S type epoxy resin, bisphenol F type epoxy resin and hydrogenated bisphenol A type epoxy resin.
Further, the cyanate monomer in S3 is any one of bisphenol a type cyanate monomer, bisphenol E type cyanate monomer, dicyclopentadiene type cyanate monomer, or a prepolymer thereof.
Further, the epoxy resin grafted with the cage-type oligomeric silsesquioxane accounts for 20-30% of the total modified cyanate resin by mass.
Further, the cage-type oligomeric silsesquioxane of the terminal isocyanate groups accounts for 1-3% of the total modified cyanate resin by mass.
Further, the resin curing treatment in S4 adopts a heat curing method, wherein the resin is cured at 150 ℃ for 2 hours, 180 ℃ for 3 hours, and 200 ℃ for 2 hours.
Furthermore, in S1-S3, the monoepoxy cage type oligomeric silsesquioxane is introduced into a cyanate resin system in a suspension state, and the suspension state size and the distribution of the cage type oligomeric silsesquioxane in the cyanate resin are optimized by controlling the reaction conditions, so as to restrict the movement of a polymer chain segment.
Compared with the prior art, the invention has the beneficial effects that:
according to the preparation method of the high-modulus high-temperature-resistant modified cyanate resin, the monoepoxy cage-type oligomeric silsesquioxane is subjected to grafting reaction with epoxy resin, and after the monoepoxy cage-type oligomeric silsesquioxane is copolymerized with a cyanate ester system, the monoepoxy cage-type oligomeric silsesquioxane is introduced into the cyanate ester resin system in a suspension state, and the suspension state size of the cage-type oligomeric silsesquioxane and the distribution of the monoepoxy cage-type oligomeric silsesquioxane in the cyanate ester resin are optimized by controlling reaction conditions, so that the monoepoxy cage-type oligomeric silsesquioxane plays a role of restraining the movement of a polymer chain segment, the rigidity of the resin system is improved, and the tensile modulus and the glass transition temperature of the resin are obviously improved, so that the requirements of the aerospace field are met.
Drawings
FIG. 1 is a graph of tensile modulus of a casting of different resin systems according to an embodiment of the present invention;
FIG. 2 is a graph of glass transition temperatures of different resin system casts of an embodiment of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The embodiment of the invention provides a preparation method of high-modulus high-temperature-resistant modified cyanate resin, which comprises the following steps:
s1: dissolving isocyanate and monoepoxy cage type oligomeric silsesquioxane in N, N-dimethylacetamide, heating to 140-160 ℃ under the protection of nitrogen with the mass ratio of isocyanate groups to epoxy groups= (2-1.2): 1, reacting for 3-5h, and removing the organic solvent by rotary evaporation after the reaction is finished to obtain isocyanate group-terminated cage type oligomeric silsesquioxane, wherein the mass ratio of the isocyanate group-terminated cage type oligomeric silsesquioxane to the total modified cyanate resin is 1% -3%; wherein the selected isocyanate is one or more of toluene diisocyanate, p-phenylene diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate and isophorone diisocyanate;
s2: mixing and dissolving the cage-type oligomeric silsesquioxane with the isocyanate groups obtained in the step S1 and bisphenol type epoxy resin into acetone, and further carrying out a grafting reaction at 70-90 ℃ to prepare epoxy resin grafted with the cage-type oligomeric silsesquioxane, wherein the epoxy resin grafted with the cage-type oligomeric silsesquioxane accounts for 20-30% of the mass of the total modified cyanate resin; the bisphenol type epoxy resin is one or more of bisphenol A type epoxy resin, bisphenol S type epoxy resin, bisphenol F type epoxy resin and hydrogenated bisphenol A type epoxy resin;
s3: uniformly stirring cyanate monomer and epoxy resin grafted with cage-type oligomeric silsesquioxane obtained in the step S2 at 100-120 ℃ and performing a prepolymerization reaction to obtain a modified cyanate resin prepolymer; wherein the cyanate monomer is any one of bisphenol A type cyanate monomer, bisphenol E type cyanate monomer and dicyclopentadiene type cyanate monomer, or prepolymer thereof;
s4: pouring the modified cyanate ester resin prepolymer obtained in the step S3 into a mold, removing bubbles in the system in vacuum, and finally, carrying out vacuum curing in an oven to obtain a high-modulus high-temperature-resistant modified cyanate ester resin system, wherein the resin curing treatment adopts a heat curing method, and is cured for 2 hours at 150 ℃ at first, cured for 3 hours at 180 ℃ at last, and cured for 2 hours at 200 ℃.
For further better explanation of the present invention, the following specific examples are provided for illustration:
example 1:
reacting hexamethylene diisocyanate with monoepoxy oligomeric silsesquioxane in the molar ratio of isocyanate groups to epoxy groups=1.5:1 in N, N-dimethylacetamide at 160 ℃ for 3 hours, and removing the organic solvent by rotary evaporation to obtain isocyanate group-terminated cage oligomeric silsesquioxane; reacting 0.6g of the isocyanate-terminated cage-type oligomeric silsesquioxane with 8g of bisphenol-type epoxy resin after drying in acetone at 90 ℃ for 12 hours to obtain the epoxy resin grafted with the cage-type oligomeric silsesquioxane; 8g of the epoxy resin grafted with the cage-type oligomeric silsesquioxane and 22g of dicyclopentadiene cyanate ester are uniformly stirred at 110 ℃ and are prepolymerized, defoaming treatment is carried out under vacuum, then the mixture is poured into a mould, the mixture is cured for 2 hours at 150 ℃, the temperature is 180 ℃ and the mixture is cured for 2 hours at 200 ℃ to obtain a resin casting body.
The tensile modulus was measured to be 3.72GPa and the glass transition temperature was measured to be 250℃by the DMA method.
Example 2:
reacting isophorone diisocyanate with monoepoxy oligomeric silsesquioxane in the molar ratio of isocyanate group to epoxy group=1.2:1 in N, N-dimethylacetamide at 150 ℃ for 4 hours, and removing the organic solvent by rotary evaporation to obtain isocyanate group-terminated cage oligomeric silsesquioxane; reacting 0.3g of the isocyanate-terminated cage-type oligomeric silsesquioxane with 9g of bisphenol-type epoxy resin after drying in acetone at 90 ℃ for 12 hours to obtain the epoxy resin grafted with the cage-type oligomeric silsesquioxane; 9g of the epoxy resin grafted with the cage-type oligomeric silsesquioxane and 21g of bisphenol E cyanate were uniformly stirred at 100 ℃ and prepolymerized, and the defoaming treatment was carried out under vacuum, and the curing process of the resin was the same as in example 1.
The tensile modulus was measured to be 3.80GPa and the glass transition temperature was 261℃by the DMA method.
Example 3:
toluene diisocyanate and monoepoxy oligomeric silsesquioxane are reacted in N, N-dimethylacetamide for 5 hours at 140 ℃ according to the molar ratio of isocyanate groups to epoxy groups=2:1, and organic solvent is removed by rotary evaporation to obtain isocyanate group-terminated cage oligomeric silsesquioxane; reacting 0.9g of the isocyanate-terminated cage-type oligomeric silsesquioxane with 6g of bisphenol-type epoxy resin after drying in acetone at 90 ℃ for 12 hours to obtain the epoxy resin grafted with the cage-type oligomeric silsesquioxane; 6g of the epoxy resin grafted with the cage-type oligomeric silsesquioxane and 24g of bisphenol A cyanate were uniformly stirred at 120 ℃ and prepolymerized, and the defoaming treatment was carried out under vacuum, and the curing process of the resin was the same as in example 1.
The tensile modulus was measured to be 4.03GPa and the glass transition temperature was 275℃by the DMA method.
Comparative example:
9g of bisphenol A type epoxy resin and 21g of dicyclopentadiene type cyanate resin are uniformly mixed at 100 ℃, 500ppm of dibutyltin dilaurate catalyst is added for prepolymerization, defoaming treatment is carried out under vacuum condition, and the curing process of the resin is the same as in example 1.
The tensile modulus was measured to be 3.25GPa and the glass transition temperature was 229℃by the DMA method.
As shown in fig. 1-2: as shown by the above examples 1-3 and test comparative examples: epoxy resin modified cyanate resin system grafted with monoepoxy cage type oligomeric silsesquioxane, and its tensile modulus and glass transition temperature (T) g ) In addition, the monoepoxy cage-type oligomeric silsesquioxane can also play a role in catalyzing a cyanate resin system, so that the curing temperature of the resin is reduced, and the curing at an excessive temperature is avoided. Finally, the introduction of the monoepoxy cage-type oligomeric silsesquioxane has development prospect in improving the dielectric property and flame retardance of the modified cyanate resin system.
To sum up: according to the preparation method of the high-modulus high-temperature-resistant modified cyanate resin, the monoepoxy cage-type oligomeric silsesquioxane is subjected to grafting reaction with epoxy resin, and after the monoepoxy cage-type oligomeric silsesquioxane is copolymerized with a cyanate resin system, the monoepoxy cage-type oligomeric silsesquioxane is introduced into the cyanate resin system in a suspension state, and the suspension state size of the cage-type oligomeric silsesquioxane and the distribution of the monoepoxy cage-type oligomeric silsesquioxane in the cyanate resin are optimized by controlling reaction conditions, so that the monoepoxy cage-type oligomeric silsesquioxane plays a role in restraining the movement of a polymer chain segment, and the rigidity of the resin system is improved.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should be covered by the protection scope of the present invention by making equivalents and modifications to the technical solution and the inventive concept thereof.
Claims (8)
1. The preparation method of the high-modulus high-temperature-resistant modified cyanate ester resin is characterized by comprising the following steps of:
s1: dissolving isocyanate and monoepoxy cage type oligomeric silsesquioxane in N, N-dimethylacetamide, heating to 140-160 ℃ under the protection of nitrogen with the isocyanate group of epoxy group= (2-1.2): 1, reacting for 3-5h, and removing the organic solvent by rotary evaporation after the reaction is finished to obtain the cage type oligomeric silsesquioxane with the isocyanate group;
s2: mixing the cage-type oligomeric silsesquioxane with the isocyanate groups and bisphenol-type epoxy resin obtained in the step S1, dissolving the mixture in acetone, and further carrying out a grafting reaction at 70-90 ℃ to prepare the epoxy resin grafted with the cage-type oligomeric silsesquioxane;
s3: uniformly stirring cyanate monomer and epoxy resin grafted with cage-type oligomeric silsesquioxane obtained in the step S2 at 100-120 ℃ and performing a prepolymerization reaction to obtain a modified cyanate resin prepolymer;
s4: pouring the modified cyanate ester resin prepolymer obtained in the step S3 into a mould, removing bubbles in the system in vacuum, and finally, carrying out vacuum curing in an oven to obtain the high-modulus high-temperature-resistant modified cyanate ester resin system.
2. The method for preparing the high-modulus and high-temperature-resistant modified cyanate ester resin according to claim 1, which is characterized in that: the isocyanate selected in the S1 is one or more of toluene diisocyanate, p-phenylene diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate and isophorone diisocyanate.
3. The method for preparing the high-modulus and high-temperature-resistant modified cyanate ester resin according to claim 1, which is characterized in that: the bisphenol type epoxy resin in S2 is one or more of bisphenol A type epoxy resin, bisphenol S type epoxy resin, bisphenol F type epoxy resin and hydrogenated bisphenol A type epoxy resin.
4. The method for preparing the high-modulus and high-temperature-resistant modified cyanate ester resin according to claim 1, which is characterized in that: the cyanate monomer in S3 is any one of bisphenol A type cyanate monomer, bisphenol E type cyanate monomer and dicyclopentadiene type cyanate monomer, or prepolymer thereof.
5. The method for preparing the high-modulus and high-temperature-resistant modified cyanate ester resin as claimed in claim 1, wherein the epoxy resin grafted with the cage-type oligomeric silsesquioxane accounts for 20-30% of the total modified cyanate ester resin by mass.
6. The method for preparing the high-modulus and high-temperature-resistant modified cyanate ester resin as claimed in claim 1, wherein the cage-type oligomeric silsesquioxane with terminal isocyanate groups accounts for 1-3% of the total mass of the modified cyanate ester resin.
7. The method for preparing a high modulus, high temperature resistant modified cyanate ester resin as claimed in claim 1, wherein the resin curing treatment in S4 is a heat curing method, wherein the curing is performed at 150 ℃ for 2 hours, at 180 ℃ for 3 hours, and at 200 ℃ for 2 hours.
8. The method for preparing a high modulus, high temperature resistant modified cyanate ester resin according to claim 1, wherein the mono-epoxy cage type oligomeric silsesquioxane is introduced into the cyanate ester resin system in a pendant state in S1-S3, and the pendant state size of the cage type oligomeric silsesquioxane and the distribution in the cyanate ester resin are optimized by controlling the reaction conditions for binding the movement of the polymer chain segment.
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| CN202310249608.7A CN116333309A (en) | 2023-03-15 | 2023-03-15 | Preparation method of high-modulus high-temperature-resistant modified cyanate resin |
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| CN202310249608.7A CN116333309A (en) | 2023-03-15 | 2023-03-15 | Preparation method of high-modulus high-temperature-resistant modified cyanate resin |
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| CN202310249608.7A Pending CN116333309A (en) | 2023-03-15 | 2023-03-15 | Preparation method of high-modulus high-temperature-resistant modified cyanate resin |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2012134231A (en) * | 2011-12-13 | 2014-02-20 | Институт химии высокомолекулярных соединений НАН Украины | METHOD FOR PRODUCING POLICE |
| CN105367793A (en) * | 2015-11-27 | 2016-03-02 | 北京卫星制造厂 | Cyanate ester resin prepolymer with excellent space environment property, and prepreg, preparation method and application thereof |
| CN107033805A (en) * | 2017-04-25 | 2017-08-11 | 晶锋集团股份有限公司 | A kind of composite heat-conducting high-temperature insulation pressure-sensitive band of polyacrylate glass fabric and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2012134231A (en) * | 2011-12-13 | 2014-02-20 | Институт химии высокомолекулярных соединений НАН Украины | METHOD FOR PRODUCING POLICE |
| CN105367793A (en) * | 2015-11-27 | 2016-03-02 | 北京卫星制造厂 | Cyanate ester resin prepolymer with excellent space environment property, and prepreg, preparation method and application thereof |
| CN107033805A (en) * | 2017-04-25 | 2017-08-11 | 晶锋集团股份有限公司 | A kind of composite heat-conducting high-temperature insulation pressure-sensitive band of polyacrylate glass fabric and preparation method thereof |
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