CN108003564B - High-frequency low-dielectric-property functionalized graphene/main chain benzoxazine composite resin and preparation method of in-situ intercalation solution thereof - Google Patents
High-frequency low-dielectric-property functionalized graphene/main chain benzoxazine composite resin and preparation method of in-situ intercalation solution thereof Download PDFInfo
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- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 title claims abstract description 151
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 148
- 239000000805 composite resin Substances 0.000 title claims abstract description 37
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 22
- 238000009830 intercalation Methods 0.000 title claims abstract description 21
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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
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- 229920005989 resin Polymers 0.000 claims abstract description 90
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- 238000006116 polymerization reaction Methods 0.000 claims description 7
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 7
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 6
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims description 5
- 229940106681 chloroacetic acid Drugs 0.000 claims description 5
- 239000007822 coupling agent Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
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- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical group N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 claims description 4
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 claims description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
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- 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 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 2
- 239000004713 Cyclic olefin copolymer Substances 0.000 claims description 2
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- 239000002174 Styrene-butadiene Substances 0.000 claims description 2
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- 239000004842 bisphenol F epoxy resin Substances 0.000 claims description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 2
- 229920001971 elastomer Polymers 0.000 claims description 2
- 239000005457 ice water Substances 0.000 claims description 2
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- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 4
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- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 239000011206 ternary composite Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
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- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
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- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- 235000010344 sodium nitrate Nutrition 0.000 description 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- BYVSMDBDTBXASR-UHFFFAOYSA-N 5,6-dihydro-4h-oxazine Chemical group C1CON=CC1 BYVSMDBDTBXASR-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- UFZOLVFGAOAEHD-UHFFFAOYSA-N benzaldehyde;phenol Chemical compound OC1=CC=CC=C1.O=CC1=CC=CC=C1 UFZOLVFGAOAEHD-UHFFFAOYSA-N 0.000 description 1
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- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 1
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- 125000000623 heterocyclic group Chemical group 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/34—Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C08L61/04, C08L61/18 and C08L61/20
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a high-frequency low-dielectric-property functionalized graphene/main chain benzoxazine composite resin and a preparation method of an in-situ intercalation solution thereof. The preparation method comprises the following steps: dispersing the functionalized graphene oxide in an organic solvent by an ultrasonic dispersion method to obtain 0.1-10 g/L functionalized graphene oxide uniform dispersion liquid; dissolving a main chain benzoxazine binary or ternary resin prepolymer in a corresponding organic solvent to obtain a prepolymer solution with the mass concentration of 10-30%; blending the functionalized graphene oxide dispersion liquid and the prepolymer solution to obtain a uniform mixed liquid, wherein the mass ratio of the graphene oxide or the functionalized graphene oxide to the main chain benzoxazine binary or ternary resin prepolymer in the mixed liquid is 0.1-1: 99 to 99.9; reacting the obtained mixed solution at 80-140 ℃ for 2-8 h, and then carrying out curing reaction at 100-220 ℃ for 4-24 h. The composite resin has the advantages of short curing time, no shrinkage during curing, good nano particle dispersibility, low dielectric constant, low dielectric loss, good heat resistance, moisture resistance and mechanical properties.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to functionalized graphene oxide reinforced main chain benzoxazine composite resin and a preparation method of an in-situ intercalation solution thereof.
Background
Benzoxazine is a high molecular monomer containing a heterocyclic ring structure synthesized by taking phenols, aldehydes and primary amine compounds as raw materials, and is subjected to ring opening polymerization under the action of heating and/or a catalyst to generate a nitrogen-containing network structure similar to phenolic resin, namely polybenzoxazine or benzoxazine resin. The benzoxazine resin not only has good flame retardant effect and chemical resistance, but also has the advantages of low shrinkage, low dielectric constant, flexible molecular design and the like, can be heated and cured without a catalyst, and does not release small molecules. However, benzoxazine resins also have some disadvantages in practical applications, such as low crosslinking density; the curing reaction temperature is high, and the curing time is long; the resin after the polymerization of the common benzoxazine is brittle; thermal performance is yet to be further improved, etc.
Recently, a main chain type benzoxazine resin with a novel structure has attracted much attention, i.e., the main chain of its synthetic monomer, the main chain of homopolymer and its copolymer contains oxazine ring or its ring-opening product. Main chain type benzoxazine (main chain benzoxazine) is a novel benzoxazine resin developed for two thousand years, and has fundamental differences from the aspects of chemical structure design and application performance compared with the traditional single-functionality benzoxazine resin and the traditional double-functionality benzoxazine resin. The traditional monofunctional and bifunctional benzoxazine monomers have only 1 or 2 oxazine rings, and the main chain benzoxazine monomer contains 2n oxazine rings. Therefore, the main chain benzoxazine monomer tends to be crosslinked to obtain high molecular weight and excellent toughness, and the benzoxazine monomer can be dissolved in a solvent and can also be processed in a molten state, and the material after being heated and cured is still a thermosetting polymer. The main chain type benzoxazine resin has the advantages of both thermosetting resin and thermoplastic resin, has good application prospect, and can be used as electronic packaging, printed circuit boards, aviation and film materials. In order to meet the requirements of the prior art on materials with higher requirements on comprehensive properties such as low dielectric constant, low dielectric loss, high heat resistance, high flame resistance, flexibility and the like, the construction of binary and ternary copolymer resin systems and the composite modification research have very important significance.
Disclosure of Invention
The invention aims to solve the technical problem of providing a high-frequency low-dielectric-property functionalized graphene oxide reinforced main chain benzoxazine composite resin and a preparation method of an in-situ intercalation solution thereof aiming at the defects in the prior art.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
the functionalized graphene oxide reinforced main chain benzoxazine composite resin is functionalized graphene oxide modified main chain benzoxazine/hydrocarbon resin binary resin or functionalized graphene oxide modified main chain benzoxazine/epoxy resin/hydrocarbon resin ternary resin, 0.1-5 parts of functionalized graphene oxide is calculated according to parts by weight, and 5-99.9 parts of main chain benzoxazine/hydrocarbon resin binary resin or main chain benzoxazine/epoxy resin/hydrocarbon resin ternary resin is calculated according to parts by weight; the functionalized graphene oxide is carboxylated graphene oxide or aminated graphene oxide;
the main chain benzoxazine/hydrocarbon resin binary resin is obtained by curing a main chain benzoxazine/hydrocarbon resin binary prepolymer obtained by cross-linking and polymerizing 50-90 parts by weight of main chain benzoxazine and 10-50 parts by weight of hydrocarbon resin; the main chain benzoxazine/epoxy resin/hydrocarbon resin ternary resin is prepared from 50-80 parts by weight of main chain benzoxazine; 10-20 parts by weight of epoxy resin; 10-30 parts by weight of hydrocarbon resin, and curing the obtained benzoxazine/epoxy resin/hydrocarbon resin ternary copolymer system.
According to the scheme, the main chain benzoxazine has the following structure:
or
Is ODA type main chain benzoxazine.
Wherein n is 2.5 to 20.
According to the scheme, the epoxy resin is one or the combination of the following components: bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, novolac epoxy resin, bisphenol A novolac epoxy resin, bisphenol F novolac epoxy resin, o-cresol epoxy resin, trifunctional epoxy resin, tetrafunctional group epoxy resin, polyfunctional group epoxy resin, dicyclopentadiene epoxy resin, p-xylene epoxy resin, naphthalene type epoxy resin, biphenol aldehyde epoxy resin, isocyanate modified epoxy resin and phenol benzaldehyde epoxy resin.
According to the scheme, the hydrocarbon resin is one or the combination of the following components: polybutadiene resin, styrene-butadiene resin, styrene-maleic anhydride, styrene-butadiene copolymer, cyclic olefin copolymer, styrene-isoprene copolymer, polyisoprene rubber, styrene-butadiene-divinylbenzene copolymer, hydrogenated diene-butadiene-styrene copolymer.
According to the scheme, the preparation method of the main chain benzoxazine composite resin comprises the following steps: adding 50-80 parts by weight of main chain benzoxazine into a reaction container; 10-20 parts by weight of epoxy resin; 10-30 parts by weight of hydrocarbon resin, dispersing the hydrocarbon resin in an organic solvent, reacting at 80-110 ℃ for 1-6 hours to obtain a main chain benzoxazine composite resin prepolymer with a solid content of 30-70 wt%, placing the obtained resin prepolymer in an oven for temperature programming and curing, and curing to obtain a main chain benzoxazine/epoxy resin/hydrocarbon resin ternary composite resin;
adding 50-90 parts by weight of main chain benzoxazine into a reaction container; 10-50 parts by weight of hydrocarbon resin; and dispersing the benzoxazine resin in an organic solvent, reacting for 1-6 h at 80-110 ℃ to obtain a main chain benzoxazine composite resin prepolymer with the solid content of 30-70 wt%, placing the obtained resin prepolymer into an oven for temperature programming and curing, and curing to obtain the main chain benzoxazine/hydrocarbon resin binary composite resin.
According to the scheme, the organic solvent is any one or a mixture of more of acetone, toluene, xylene, ethanol, chloroform, dimethylformamide and 1, 4-dioxane.
According to the scheme, the carboxylated graphene oxide is obtained by ultrasonically dispersing graphite oxide in an ethanol solvent to obtain an effectively stripped graphene oxide solution, and chemically modifying the graphene oxide solution by a chloroacetic acid method; the ultrasonic dispersion is ultrasonic for 10-30 min under the ice-water bath condition, and the ultrasonic power is 400-800W;
the amination graphene oxide is prepared by adding graphene oxide into a dimethylformamide solvent, performing ultrasonic dispersion to obtain 1-4 mg/mL graphene oxide dispersion liquid, and then adding a diamine monomer into the dispersion liquid, wherein the mass ratio of the diamine monomer to the graphite oxide is 1.5-3: 1, fully and uniformly mixing, adding a coupling agent, wherein the mass ratio of the coupling agent to graphite oxide is 5-8: 100, carrying out reflux reaction at 50-70 ℃ for 6-10 hours, and washing, filtering and drying an obtained product after the reaction is finished by using ethanol to obtain the product;
according to the scheme, the graphene oxide is prepared by taking natural crystalline flake graphite as a raw material through an improved Hummers method. The particle size of the natural crystalline flake graphite is 30-40 mu m.
According to the scheme, the preparation method of the in-situ intercalation solution of the functionalized graphene oxide reinforced main chain benzoxazine composite resin comprises the following steps: dispersing the functionalized graphene oxide in an organic solvent by an ultrasonic dispersion method to obtain 0.1-10 g/L functionalized graphene oxide uniform dispersion liquid; dissolving a main chain benzoxazine binary or ternary resin prepolymer in a corresponding organic solvent to obtain a prepolymer solution with the mass concentration of 10-30%;
blending the functionalized graphene oxide dispersion liquid and the prepolymer solution to obtain a uniform mixed liquid, wherein the mass ratio of the graphene oxide or the functionalized graphene oxide to the main chain benzoxazine binary or ternary resin prepolymer in the mixed liquid is 0.1-1: 99 to 99.9;
and reacting the obtained mixed solution at 80-140 ℃ for 2-8 h, and then curing and reacting at 100-220 ℃ for 4-24 h to obtain the functionalized graphene oxide reinforced main chain benzoxazine composite resin.
In the invention: the main chain benzoxazine monomer contains 2n oxazine rings, reaction sites of the cross-linking reaction generated by ring opening of the main chain benzoxazine monomer are increased remarkably, and more chemical bonding effects can be generated with carboxyl functional groups and the like contained in other resins in a binary or ternary system, so that the chemical cross-linking effect of the binary or ternary composite resin system is enhanced based on the increase of the unique structure and the copolymerization reaction of the main chain benzoxazine, the cross-linking density of the composite resin is greatly improved, and the thermal performance and the dielectric performance can be further improved based on the synergistic effect of the main chain benzoxazine monomer and the carboxyl functional groups.
Specifically, a binary system is constructed by adopting a main chain benzoxazine monomer and hydrocarbon resin, or a ternary system is constructed by adopting the main chain benzoxazine monomer, epoxy resin and hydrocarbon resin, and by regulating and controlling the proportioning amount, on one hand, the main chain benzoxazine monomer, the epoxy resin and the hydrocarbon resin are subjected to a cross-linking reaction to obtain a composite resin system which takes the main chain benzoxazine as a main body and has an interpenetrating network (IPN) structure.
According to the invention, the hydrocarbon resin is creatively introduced into the main chain type benzoxazine resin, and the hydrocarbon resin can complete self-polymerization in the polymerization and curing process of the main chain benzoxazine resin to form an interpenetrating network (IPN) structure with the benzoxazine resin, so that the crosslinking density and the high temperature resistance of the composite resin are effectively improved. The hydrocarbon resin has a regular structure and a low-polarity long carbon chain chemical structure, and the introduction of the hydrocarbon resin can improve the dielectric property of the whole composite resin system. In addition, the carbonyl functional group contained in the hydrocarbon resin can react with the phenolic hydroxyl group of the benzoxazine to generate aromatic ester, so that a chemical crosslinking structure is formed, the crosslinking density of the copolymer resin is further improved, and the thermal property and the mechanical property of the composite resin are greatly improved. Meanwhile, the reduction of the polar phenolic hydroxyl functional groups of the main chain type benzoxazine resin is also beneficial to the improvement of the dielectric property of the composite resin. The epoxy resin has the characteristics of good flexibility, high crosslinking density and the like, and the toughness and the crosslinking density of the main chain benzoxazine resin can be improved by copolymerizing the epoxy resin and the main chain benzoxazine resin. The phenolic hydroxyl generated by the ring opening of the main chain benzoxazine resin can react with the epoxy resin, and the homopolymerization reaction of the epoxy resin can be inhibited under the catalytic action of tertiary amine, so that an epoxy functional group participates in a main chain benzoxazine resin network structure, and the crosslinking density of the main chain benzoxazine resin is increased. In addition, polar phenolic hydroxyl generated by polymerization of the main chain type benzoxazine resin is consumed in the copolymerization process, and the dielectric constant and the dielectric loss of the copolymerized resin are favorably reduced.
In conclusion, each resin in the main chain type benzoxazine/epoxy resin/hydrocarbon resin ternary resin has the performance and interaction and mutual influence. Except the reaction of the main chain type benzoxazine resin with the epoxy resin and the hydrocarbon resin respectively, the epoxy resin is equivalent to a diluent in the ternary resin, so that the viscosity of the system can be reduced, and the technological property of the ternary resin system can be improved. The hydrocarbon resin is not only a curing agent of the epoxy resin, but also a catalyst of the main chain benzoxazine resin, can effectively reduce the curing temperature of a system, improves the processing performance and simultaneously improves the crosslinking density of the composite resin, thereby further improving the thermal performance and the dielectric performance. Therefore, the combination and proportion regulation of the components in the ternary resin system provided by the invention have great influence on the structure and performance of the composite resin.
Furthermore, the surfaces of the functionalized graphene oxides (carboxylated graphene oxide and aminated graphene oxide) contain a large amount of oxygen-containing groups or amino groups, which not only participate in the network structure of the main chain benzoxazine resin in the ring-opening polymerization process of the main chain benzoxazine monomer, has positive influence on the chain growth of the resin, thereby improving the curing degree of the matrix resin, generating intermolecular hydrogen bond action with hydroxyl and tertiary amine groups generated after ring-opening polymerization of the main chain benzoxazine resin, enhancing the intramolecular and intermolecular action force of a resin network structure, thereby improving the thermal properties of the composite material such as glass transition temperature, thermal decomposition temperature, carbon residue rate and the like, meanwhile, the introduction of the functionalized graphene oxide can consume polar phenolic hydroxyl generated by polymerization of the main chain type benzoxazine resin, and is favorable for reducing the dielectric constant and dielectric loss of the copolymer resin. And due to the introduction of a proper amount of functionalized graphene oxide nanosheets and the like, a hole structure can be formed in the composite resin system, so that the dielectric property of the whole composite resin system can be improved by utilizing the low dielectric constant of air, and the nano composite resin has lower dielectric constant (1.2-2.4) and dielectric loss (0.001-0.005) under the condition of high-frequency electromagnetic wave (10 GHZ).
The invention has the beneficial effects that:
1. the functionalized graphene oxide reinforced main chain benzoxazine composite resin prepared by the invention obviously reduces the curing temperature, accelerates the curing speed, has no shrinkage during curing, improves the glass transition temperature, and has low dielectric constant, low dielectric loss, good heat resistance, moisture resistance, mechanical property and electrical property. Particularly, in view of the synergistic effect of the main chain benzoxazine and the composite resin and the contribution of the functionalized graphene to the dielectric property, the nano composite resin has lower dielectric constant (1.2-2.4) and dielectric loss (0.001-0.005) under the condition of high-frequency electromagnetic waves, so that the nano composite resin has application prospects in emerging fields such as microwave communication and the like. The curing temperature of the functionalized graphene oxide reinforced main chain benzoxazine composite resin is 210-240 ℃, the glass transition temperature is 285-350 ℃, the tensile strength is 145-190 MPa, the dielectric constant under 10GHz is 1.2-2.4, and the dielectric loss is 0.001-0.005;
2. the functionalized graphene oxide reinforced main chain benzoxazine composite resin is prepared by an in-situ solution preparation method, the graphene oxide is easy to disperse, and the preparation method is suitable for preparing a functionalized graphene oxide reinforced main chain benzoxazine composite resin material with high graphene oxide mixing amount. Moreover, the resin is easy to disperse in a resin matrix, chemical and physical interaction is easier to generate, and the resin prepared in a solvent state is good in compatibility. The preparation method has simple process and easily obtained raw materials.
Drawings
Fig. 1 is a DSC curve of a functionalized graphene oxide reinforced main chain benzoxazine/epoxy/hydrocarbon composite resin prepared according to an embodiment of the present invention. Wherein a is a cured DSC curve of a main chain benzoxazine/epoxy/hydrocarbon composite resin to which no carboxylated graphene oxide is added, and a 'and b' are cured DSC curves of a carboxylated graphene oxide reinforced main chain benzoxazine/epoxy/hydrocarbon composite resin prepared in examples 4 and 5, respectively. As shown in the figure, after the carboxylated graphene is added, the curing peak temperature of the ternary composite resin is reduced by about 20 ℃, which shows that the carboxylated graphene oxide can effectively promote the curing of the main chain benzoxazine ternary resin, so that the curing temperature is reduced, and the curing degree is improved.
Detailed Description
In order to make the technical solutions of the present invention better understood by those skilled in the art, the present invention is further described in detail with reference to the following examples.
Preparing graphene oxide:
taking natural crystalline flake graphite with the particle size of 48 mu m as a raw material, and preparing graphite oxide by an improved Hummers method, namely adding the natural crystalline flake graphite into concentrated sulfuric acid, stirring, and adding sodium nitrate and potassium permanganate; specifically, the natural crystalline flake graphite accounts for 2 mass percent, the sodium nitrate accounts for 1 mass percent, the potassium permanganate accounts for 7 mass percent, and the concentrated sulfuric acid with the concentration of 98 percent accounts for 90 mass percent; controlling the temperature of concentrated sulfuric acid to be 4 ℃, and reacting for 60 min; heating to 32 ℃, and reacting for 30 min; reacting at 100 deg.C for 30 min; and (3) centrifugally washing the reaction product until sulfate ions are not generated, and drying at 40 ℃ to obtain the graphite oxide. And dispersing graphite oxide in an ethanol solvent, and carrying out ultrasonic treatment on the solution at the power of 500W for 1h to obtain the effectively stripped graphene oxide solution.
Preparation of carboxylated graphene oxide:
preparing graphite oxide according to the method, and chemically modifying the graphite oxide by a chloroacetic acid method to obtain carboxylated graphene oxide: firstly, adding graphite oxide into deionized water, performing ultrasonic dispersion for 2 hours to obtain graphene oxide dispersion liquid with the concentration of 4mg/mL, then adding sodium hydroxide and chloroacetic acid, performing ultrasonic dispersion for 4 hours, wherein the graphite oxide accounts for 0.5, the sodium hydroxide accounts for 48.5 and the chloroacetic acid accounts for 51 in percentage by mass, finally washing the solution for multiple times by using a high-speed centrifuge until the solution is neutral, and drying and grinding the solution at the temperature of 60 ℃ to obtain the carboxylated graphene oxide.
Preparation of aminated graphene oxide:
preparing graphite oxide according to the method, and preparing aminated graphene oxide through chemical modification: firstly, 200mg of graphite oxide is added into 400mL of dimethylformamide solvent and is subjected to ultrasonic sound for 1h at 30 ℃ to obtain graphene oxide dispersion liquid with the concentration of 2mg/mL, and then 300mg of hexamethylenediamine is added and is subjected to ultrasonic sound and mechanical stirring for 2 h. And transferring the obtained mixed solution to a water bath device, adding 13mg of 2- (7-azobenzotriazol) -N, N, N ', N' -tetramethylurea hexafluorophosphate coupling agent, carrying out condensation reflux reaction for 10 hours at the temperature of 60 ℃, washing the product for 10 times by using ethanol after the reaction is finished, filtering the product, and drying the product in a vacuum drying oven for 12 hours at the temperature of 50 ℃ to obtain the aminated graphene oxide.
Example 1
Preparing a carboxylated graphene oxide reinforced main chain benzoxazine/hydrocarbon resin binary nano composite resin by an in-situ intercalation solution method:
dispersing the prepared carboxylated graphene oxide in a dimethylformamide solvent, and carrying out ultrasonic treatment for 30min at the power of 600W to obtain 0.5g/L carboxylated graphene oxide solution. According to the mass parts, 15 parts of DDM type main chain benzoxazine prepolymer and 5 parts of polybutadiene resin are dissolved in 80 parts of dimethylformamide solvent and fully stirred and dissolved to obtain a main chain benzoxazine/hydrocarbon resin prepolymer solution. Blending the carboxylated graphene oxide solution and the main chain benzoxazine/hydrocarbon resin prepolymer solution to obtain a mixed solution, wherein the mass ratio of the carboxylated graphene oxide to the main chain benzoxazine/hydrocarbon resin prepolymer in the mixed solution is 3: 97.
And reacting the mixed solution at 120 ℃ for 6h by adopting an in-situ intercalation solution polymerization method, and then curing and reacting at 220 ℃ for 10h to prepare the carboxylated graphene oxide reinforced main chain benzoxazine/hydrocarbon resin binary nano composite resin. The curing temperature is 235 ℃, the glass transition temperature is 290 ℃, the tensile strength is 168MPa, the dielectric constant under 10GHz is 2.3, and the dielectric loss is 0.004.
Example 2
Preparing a graphene oxide reinforced main chain benzoxazine/hydrocarbon resin binary nano composite resin by an in-situ intercalation solution method:
dispersing the prepared graphene oxide in a 1, 4-dioxane solvent, and carrying out ultrasonic treatment with the power of 800W for 30min to obtain a 1g/L graphene oxide solution. Dissolving 15 parts by mass of ODA type main chain benzoxazine prepolymer and 5 parts by mass of styrene-maleic anhydride in 80 parts by mass of 1, 4-dioxane solvent, and fully stirring and dissolving to obtain a main chain benzoxazine/hydrocarbon resin prepolymer solution. Blending the aminated graphene oxide solution and the main chain benzoxazine/hydrocarbon resin prepolymer solution to obtain a mixed solution, wherein the mass ratio of the graphene oxide to the main chain benzoxazine/hydrocarbon resin prepolymer in the mixed solution is 5: 95.
And (3) reacting the mixed solution at 90 ℃ for 8h by adopting an in-situ intercalation solution polymerization method, and then curing and reacting at 180 ℃ for 24h to prepare the graphene oxide reinforced main chain benzoxazine/hydrocarbon resin binary nano composite resin. The curing temperature is 225 ℃, the glass transition temperature is 295 ℃, the tensile strength is 175MPa, the dielectric constant is 2.3 at 10GHz, and the dielectric loss is 0.005.
Example 3
Preparing an aminated graphene oxide reinforced main chain benzoxazine/epoxy/hydrocarbon resin ternary nano composite resin by an in-situ intercalation solution method:
dispersing the prepared aminated graphene oxide in a dimethylformamide solvent, and carrying out ultrasonic treatment with the power of 800W for 10min to obtain 2g/L of ammonia oxidation graphene solution. Dissolving 5 parts by mass of ODA type main chain benzoxazine, 2 parts by mass of bisphenol A novolac epoxy resin and 3 parts by mass of styrene-butadiene copolymer in 90 parts by mass of dimethylformamide solvent, fully stirring and dissolving to obtain a main chain benzoxazine/epoxy/hydrocarbon resin prepolymer solution, blending the aminated graphene oxide solution and the main chain benzoxazine/epoxy/hydrocarbon resin prepolymer solution to obtain a mixed solution, and enabling the mass ratio of the aminated graphene oxide and the main chain benzoxazine/epoxy/hydrocarbon resin prepolymer in the mixed solution to be 1:99 according to the mass percent ratio.
And (3) reacting the mixed solution at 140 ℃ for 2h by adopting an in-situ intercalation solution polymerization method, and then curing and reacting at 220 ℃ for 10h to prepare the aminated graphene oxide reinforced main chain benzoxazine/epoxy/hydrocarbon resin ternary nano composite resin. The curing temperature is 225 ℃, the glass transition temperature is 312 ℃, the tensile strength is 185MPa, the dielectric constant is 2.2 at 10GHz, and the dielectric loss is 0.003.
Example 4
Preparing a carboxylated graphene oxide reinforced main chain benzoxazine/epoxy/hydrocarbon resin ternary nano composite resin by an in-situ intercalation solution method:
dispersing the prepared carboxylated graphene oxide in a toluene solvent, and carrying out ultrasonic treatment for 30min at the power of 400W to obtain 3g/L carboxylated graphene oxide solution. According to the mass parts, 8 parts of DDM type main chain benzoxazine, 1 part of dicyclopentadiene epoxy resin and 1 part of styrene-butadiene copolymer are dissolved in 90 parts of toluene solvent and fully stirred and dissolved to obtain a main chain benzoxazine/epoxy/hydrocarbon resin prepolymer solution. Blending the carboxylated graphene oxide solution with the main chain benzoxazine/epoxy/hydrocarbon resin prepolymer solution to obtain a mixed solution, wherein the mass ratio of the carboxylated graphene oxide to the main chain benzoxazine/epoxy/hydrocarbon resin prepolymer in the mixed solution is 1: 99.
And reacting the mixed solution at 110 ℃ for 6h by adopting an in-situ intercalation solution polymerization method, and then curing and reacting at 180 ℃ for 22h to prepare the carboxylated graphene oxide reinforced main chain benzoxazine/epoxy/hydrocarbon resin ternary nano composite resin. The curing temperature is 235 ℃, the glass transition temperature is 325 ℃, the tensile strength is 178MPa, the dielectric constant is 2.1 under 10GHz, and the dielectric loss is 0.002.
Example 5
Preparing a carboxylated graphene oxide reinforced main chain benzoxazine/epoxy/hydrocarbon resin ternary nano composite resin by an in-situ intercalation solution method:
dispersing the prepared carboxylated graphene oxide in a toluene/ethanol solvent (the volume ratio of toluene to ethanol is 1:2), and carrying out ultrasonic treatment at the power of 400W for 30min to obtain a 3g/L carboxylated graphene oxide solution. According to the mass parts, 15 parts of ODA type main chain benzoxazine, 2 parts of bisphenol A epoxy resin, 3 parts of glycidyl ester type epoxy resin and 10 parts of styrene-isoprene copolymer are dissolved in 70 parts of toluene/ethanol solvent (the volume ratio of toluene to ethanol is 1:2) and fully stirred and dissolved to obtain a main chain benzoxazine/epoxy/hydrocarbon resin prepolymer solution. Blending the carboxylated graphene oxide solution with the main chain benzoxazine/epoxy/hydrocarbon resin prepolymer solution to obtain a mixed solution, wherein the mass ratio of the carboxylated graphene oxide to the main chain benzoxazine/epoxy/hydrocarbon resin prepolymer is 3: 97.
And reacting the mixed solution at 90 ℃ for 8h by adopting an in-situ intercalation solution polymerization method, and then curing and reacting at 170 ℃ for 24h to prepare the carboxylated graphene oxide reinforced main chain benzoxazine/epoxy/hydrocarbon resin ternary nano composite resin. The curing temperature is 227 ℃, the glass transition temperature is 350 ℃, the tensile strength is 188MPa, the dielectric constant is 1.2 at 10GHz, and the dielectric loss is 0.001.
Example 6
Preparing a carboxylated graphene oxide reinforced main chain benzoxazine/epoxy/hydrocarbon resin ternary nano composite resin by an in-situ intercalation solution method:
dispersing the prepared carboxylated graphene oxide in a toluene/ethanol solvent (the volume ratio of toluene to ethanol is 2:1), and carrying out ultrasonic treatment at the power of 400W for 30min to obtain a 3g/L carboxylated graphene oxide solution. According to the mass parts, 15 parts of DDM main chain benzoxazine prepolymer, 5 parts of p-xylene epoxy resin, 2 parts of styrene-maleic anhydride, 4 parts of styrene-butadiene copolymer and 4 parts of polybutadiene resin are dissolved in 70 parts of toluene/ethanol solvent (the volume ratio of toluene to ethanol is 2:1) and fully stirred and dissolved to obtain a main chain benzoxazine/epoxy/hydrocarbon resin prepolymer solution. Blending the carboxylated graphene oxide solution with the main chain benzoxazine/epoxy/hydrocarbon resin prepolymer solution to obtain a mixed solution, wherein the mass ratio of the carboxylated graphene oxide to the main chain benzoxazine/epoxy/hydrocarbon resin prepolymer in the mixed solution is 5: 95.
And reacting the mixed solution at 80 ℃ for 6h by adopting an in-situ intercalation solution polymerization method, and then curing and reacting at 220 ℃ for 10h to prepare the carboxylated graphene oxide reinforced main chain benzoxazine/epoxy/hydrocarbon resin ternary nano composite resin. The curing temperature is 228 ℃, the glass transition temperature is 325 ℃, the tensile strength is 190MPa, the dielectric constant is 1.6 under 10GHz, and the dielectric loss is 0.002.
Example 7
Preparing an aminated graphene oxide reinforced main chain benzoxazine/epoxy/hydrocarbon resin ternary nano composite resin by an in-situ intercalation solution method:
dispersing the prepared aminated graphene oxide in a chloroform solvent, and carrying out ultrasonic treatment for 30min at the power of 600W to obtain a 10g/L aminated graphene oxide solution. According to the mass parts, 6 parts of ODA type main chain benzoxazine, 2 parts of dicyclopentadiene epoxy resin and 2 parts of styrene-isoprene copolymer are dissolved in 90 parts of chloroform solvent and fully stirred and dissolved, so that main chain benzoxazine/epoxy/hydrocarbon resin prepolymer solution is obtained. Blending the aminated graphene oxide solution and the main chain benzoxazine/epoxy/hydrocarbon resin prepolymer solution to obtain a mixed solution, wherein the mass ratio of the aminated graphene oxide to the main chain benzoxazine/epoxy/hydrocarbon resin prepolymer in the mixed solution is 5: 90.
And reacting the mixed solution at 80 ℃ for 7h by adopting an in-situ intercalation solution polymerization method, and then curing and reacting at 220 ℃ for 10h to prepare the aminated graphene oxide reinforced main chain benzoxazine/epoxy/hydrocarbon resin ternary nano composite resin. The curing temperature is 226 ℃, the glass transition temperature is 345 ℃, the tensile strength is 189MPa, the dielectric constant is 1.8 under 10GHz, and the dielectric loss is 0.002.
Claims (7)
1. The functional graphene oxide reinforced main chain benzoxazine composite resin is characterized in that: the composite material is functionalized graphene oxide modified main chain benzoxazine/hydrocarbon resin binary resin or functionalized graphene oxide modified main chain benzoxazine/epoxy resin/hydrocarbon resin ternary resin, wherein the functionalized graphene oxide is 1-5 parts by weight, and the main chain benzoxazine/hydrocarbon resin binary resin or the main chain benzoxazine/epoxy resin/hydrocarbon resin ternary resin is 95-99 parts by weight; the functionalized graphene oxide is carboxylated graphene oxide or aminated graphene oxide, and the hydrocarbon resin is one or the combination of the following: polybutadiene resin, styrene-butadiene resin, styrene-maleic anhydride, a styrene-butadiene copolymer, a cyclic olefin copolymer, a styrene-isoprene copolymer, polyisoprene rubber, a styrene-butadiene-divinylbenzene copolymer and a hydrogenated diene-butadiene-styrene copolymer, wherein a main chain benzoxazine monomer contains 2n oxazine rings, n is 2.5-20, and hydrocarbon resin completes self-polymerization in the polymerization and curing process of the main chain benzoxazine resin and forms an interpenetrating network (IPN) structure with the benzoxazine resin;
the main chain benzoxazine/hydrocarbon resin binary resin is obtained by curing a main chain benzoxazine/hydrocarbon resin binary prepolymer obtained by cross-linking and polymerizing 50-90 parts by weight of main chain benzoxazine and 10-50 parts by weight of hydrocarbon resin; the main chain benzoxazine/epoxy resin/hydrocarbon resin ternary resin is prepared from 50-80 parts by weight of main chain benzoxazine; 10-20 parts by weight of epoxy resin; 10-30 parts by weight of hydrocarbon resin, and curing the obtained benzoxazine/epoxy resin/hydrocarbon resin ternary copolymer system.
2. The functionalized graphene oxide reinforced backbone benzoxazine composite resin according to claim 1, wherein: the backbone benzoxazine has the following structure:
or
Is an ODA type main chain benzoxazine,
wherein n is 2.5 to 20.
3. The functionalized graphene oxide reinforced backbone benzoxazine composite resin according to claim 1, wherein: the epoxy resin is one or the combination of the following: bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, novolac epoxy resin, polyfunctional group epoxy resin, dicyclopentadiene epoxy resin, p-xylene epoxy resin, naphthalene epoxy resin and isocyanate modified epoxy resin.
4. The functionalized graphene oxide reinforced backbone benzoxazine composite resin according to claim 1, wherein: the carboxylated graphene oxide is obtained by ultrasonically dispersing graphite oxide in an ethanol solvent to obtain an effectively stripped graphene oxide solution, and chemically modifying the graphene oxide solution by a chloroacetic acid method; the ultrasonic dispersion is ultrasonic for 10-30 min under the ice-water bath condition, and the ultrasonic power is 400-800W;
the amination graphene oxide is prepared by adding graphene oxide into a dimethylformamide solvent, performing ultrasonic dispersion to obtain 1-4 mg/mL graphene oxide dispersion liquid, and then adding a diamine monomer into the dispersion liquid, wherein the mass ratio of the diamine monomer to the graphite oxide is 1.5-3: 1, fully and uniformly mixing, adding a coupling agent, wherein the mass ratio of the coupling agent to graphite oxide is 5-8: 100, carrying out reflux reaction at 50-70 ℃ for 6-10 hours, and washing, filtering and drying an obtained product after the reaction is finished by using ethanol to obtain the product; the graphene oxide is prepared by taking natural crystalline flake graphite as a raw material through an improved Hummers method, wherein the particle size of the natural crystalline flake graphite is 30-40 mu m.
5. The method for preparing the functionalized graphene oxide reinforced main chain benzoxazine composite resin according to claim 1, wherein the method comprises the following steps: the in-situ intercalation solution preparation method comprises the following steps: dispersing the functionalized graphene oxide in an organic solvent by an ultrasonic dispersion method to obtain 0.1-10 g/L functionalized graphene oxide uniform dispersion liquid; dissolving a main chain benzoxazine binary or ternary resin prepolymer in a corresponding organic solvent to obtain a prepolymer solution with the mass concentration of 10-30%;
blending the functionalized graphene oxide dispersion liquid and the prepolymer solution to obtain a uniform mixed liquid, wherein the mass ratio of the functionalized graphene oxide to the main chain benzoxazine binary or ternary resin prepolymer in the mixed liquid is 1-5: 95-99;
and reacting the obtained mixed solution at 80-140 ℃ for 2-8 h, and then curing and reacting at 100-220 ℃ for 4-24 h to obtain the functionalized graphene oxide reinforced main chain benzoxazine composite resin.
6. The method of claim 5, wherein: the organic solvent is any one or a mixture of more of acetone, toluene, xylene, ethanol, chloroform, dimethylformamide and 1, 4-dioxane.
7. The use of the functionalized graphene oxide reinforced backbone benzoxazine composite resin according to claim 1 as a low dielectric low loss material under high frequency electromagnetic wave conditions.
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