CN105111437A - Functionalized graphene oxide enhanced benzoxazine-based composite resin and preparation method thereof - Google Patents
Functionalized graphene oxide enhanced benzoxazine-based composite resin and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a functionalized graphene oxide enhanced benzoxazine-based composite resin and a preparation method thereof. The resin is prepared by: 1, preparing natural flake graphite into graphene oxide by a modified Hummers method; 2, chemically modifying the graphene oxide to obtain carboxylated graphene oxide or aminated graphene oxide; 3, physically mixing, by weight, 0.1-10% of the carboxylated graphene oxide or aminated graphene oxide with 90-99.9% of benzoxazine binary resin prepolymer or benzoxazine ternary resin prepolymer to obtain a mixed sample; 4, evacuating the mixed sample at 80-100 DEG C for 1-2h, and allowing curing reaction at 100-220 DEG C for 4-24h so as to obtain the functionalized graphene oxide enhanced benzoxazine-based composite resin. The prepared composite resin cures without shrinking and has good heat resistance, moisture resistance, mechanical performances and electrical performances.
Description
Technical field
The present invention relates to technical field of polymer materials, be specifically related to a class functional graphene oxide and strengthen benzoxazinyl compound resin and solvent-free in-site intercalation polymerization method thereof.
Background technology
The class being Material synthesis with phenols, aldehydes and primary amine compound is containing the intermediate-benzoxazine of heterocycle structure, ring-opening polymerization under heating and/or catalyst action, generate the nitrogenous and reticulated structure of similar resol, be called Polybenzoxazine or benzoxazine colophony (BOZ).As a kind of novel hot setting engineering resin, compared with traditional phenolic aldehyde, epoxy resin, it not only has good flame retardant effect and chemical resistance, and there is low-shrinkage, low-k and the advantage such as molecular designing flexibly, and can be heating and curing when catalyst-free, and release without small molecules.But benzoxazine colophony also exists some shortcomings, as cross-linking density is low; Curing reaction temperature is high, set time is long; Common benzoxazine resin after polymerization is more crisp; Thermal characteristics also needs to be improved further.
In recent years, the modification of inorganic nano material Dui benzoxazine colophony has become a kind of new way of benzoxazine colophony modification, and wherein, Graphene and graphene oxide gain a special interest.Zeng Ming etc. adopt in-situ intercalative polymerization to prepare graphite oxide benzoxazine nano-composite resin first, research shows that graphene oxide reduces resin cure temperature, improve thermostability (ZengM., Polymer, 2013 of resin, 54,3107), but there is nanoparticle and resin effect is little, compound resin cross-linking density is low, property is crisp, the problems such as poor heat resistance.
Summary of the invention
Technical problem to be solved by this invention is for above shortcomings in prior art, a kind of functional graphene oxide is provided to strengthen benzoxazinyl compound resin and preparation method thereof, this compound resin solidification ungauged regions, there is good thermotolerance, wet fastness, mechanical property and electric property, compared with existing benzoxazine colophony, reduce solidification value, accelerate solidification rate, improve second-order transition temperature, improve processing characteristics and physicals, and preparation process technique is simple, especially without the need to chemical solvents, there is the feature of environmental protection, make it in copper-clad plate, veneer sheet, spacecraft, friction materials, the fields such as resin transfer moulding (RTM) are with a wide range of applications.
For solving the problems of the technologies described above, technical scheme provided by the invention is:
There is provided a kind of functional graphene oxide to strengthen benzoxazinyl compound resin, it is prepared by following methods:
1) take natural flake graphite as raw material, obtain graphite oxide by the Hummers method improved;
2) by step 1) gained graphite oxide carries out chemical modification by chloroactic acid method to it, obtains carboxylated graphene oxide; Or
By step 1) gained graphite oxide adds in solvent dimethylformamide, the graphene oxide dispersion of 1 ~ 4mg/mL is obtained through ultrasonic disperse, then in this dispersion liquid, diamine monomer is added, wherein the mass ratio of diamine monomer and graphite oxide is 1.5 ~ 3:1, coupling agent is added after fully mixing, the mass ratio of coupling agent and graphite oxide is 5 ~ 8:100, and in 50 ~ 70 DEG C of back flow reaction 6 ~ 10h, reaction terminates rear products therefrom washing with alcohol, filtration, drying obtain amination graphene oxide;
3) in mass ratio, by 0.1 ~ 10 part of step 2) the carboxylated graphene oxide of gained or amination graphene oxide and 90 ~ 99.9 parts of benzoxazine binary resin prepolymers or benzoxazine ternary resin prepolymer carry out physical mixed, obtain biased sample, described benzoxazine binary resin prepolymer is benzoxazine/epoxy prepolymer or benzoxazine/phenolic aldehyde performed polymer, and described benzoxazine ternary resin prepolymer is benzoxazine/Epoxy Resin/Phenol aldehyde performed polymer;
4) by step 3) gained biased sample vacuumize degassing 1 ~ 2h at 80 ~ 100 DEG C, then in 100 ~ 220 DEG C of curing reaction 4 ~ 24h, obtain functional graphene oxide and strengthen benzoxazinyl compound resin.
Preferably, step 1) described natural flake graphite particle diameter is 20 ~ 50 μm.
Preferably, step 2) described ultrasonic disperse is ultrasonic 1 ~ 2h at 30 DEG C, ultrasonic power is 400 ~ 800W.
Preferably, step 2) described diamine monomer is quadrol or hexanediamine; Described coupling agent is 2-(7-azo benzotriazole)-N, N, N', N'-tetramethyl-urea phosphofluoric acid ester.
By such scheme, step 3) described physical mixed is blended for carrying out in high speed planetary ball mill instrument, and concrete technology be at 400rpm elder generation ball milling 3 ~ 5h, then at 500rpm ball milling 1 ~ 2h, the every continued running 20min of this process high speed planetary ball mill instrument, stall 5min.
By such scheme, step 3) described benzoxazine/epoxy prepolymer is the mixture that benzoxazine prepolymer and epoxy resin prepolymer are mixed to get in any proportion; Described benzoxazine/phenolic aldehyde performed polymer is the mixture of benzoxazine prepolymer and resol performed polymer, and wherein resol performed polymer quality is no more than 50% of benzoxazine/phenolic aldehyde performed polymer total mass; In described benzoxazine/Epoxy Resin/Phenol aldehyde performed polymer, the mass ratio of benzoxazine prepolymer, epoxy resin prepolymer and resol performed polymer is 4 ~ 8:1 ~ 5:1;
Described benzoxazine prepolymer comprises the monoamine of single functionality and single phenolic benzoxazine, the dihydroxyphenyl propane of difunctionality, Bisphenol F and two amine type benzoxazines, polyfunctionality benzoxazine, bis-phenol main chain and two amine type main chain benzoxazines and naphthalene system benzoxazine.
By such scheme, described resol performed polymer comprises the resin that phenol and homologue (as cresols, xylenol etc.) and formaldehyde condensation thereof obtain;
Described epoxy resin prepolymer comprises glycidyl ether type epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, linear aliphatic based epoxy resin, alicyclic based epoxy resin.
The present invention also provides above-mentioned functions graphene oxide to strengthen the preparation method of benzoxazinyl compound resin, and step is as follows:
1) take natural flake graphite as raw material, obtain graphite oxide by the Hummers method improved;
2) by step 1) gained graphite oxide carries out chemical modification by chloroactic acid method to it, obtains carboxylated graphene oxide; Or
By step 1) gained graphite oxide adds in solvent dimethylformamide, the graphene oxide dispersion of 1 ~ 4mg/mL is obtained through ultrasonic disperse, then in this dispersion liquid, diamine monomer is added, wherein the mass ratio of diamine monomer and graphite oxide is 1.5 ~ 3:1, coupling agent is added after fully mixing, the mass ratio of coupling agent and graphite oxide is 5 ~ 8:100, and in 50 ~ 70 DEG C of back flow reaction 6 ~ 10h, reaction terminates rear products therefrom washing with alcohol, filtration, drying obtain amination graphene oxide;
3) in mass ratio, by 0.1 ~ 10 part of step 2) the carboxylated graphene oxide of gained or amination graphene oxide and 90 ~ 99.9 parts of benzoxazine binary resin prepolymers or benzoxazine ternary resin prepolymer carry out physical mixed, obtain biased sample, described benzoxazine binary resin prepolymer is benzoxazine/epoxy prepolymer or benzoxazine/phenolic aldehyde performed polymer, and described benzoxazine ternary resin prepolymer is benzoxazine/Epoxy Resin/Phenol aldehyde performed polymer;
4) by step 3) gained biased sample vacuumize degassing 1 ~ 2h at 80 ~ 100 DEG C, then in 100 ~ 220 DEG C of curing reaction 4 ~ 24h, obtain functional graphene oxide and strengthen benzoxazinyl compound resin.
Principle of the present invention is: compared with graphene oxide, functional graphene oxide (carboxylated graphene oxide or amination graphene oxide) surface is containing a large amount of oxy radicals or amino group, not only can participate in the network structure of benzoxazine colophony in benzoxazine monomer ring opening polymerisation process, actively impact is produced on the chainpropagation of resin, thus improve the state of cure of matrix resin, also can produce intermolecular hydrogen bonding effect with the hydroxyl that produces after benzoxazine colophony ring-opening polymerization and tertiary amine groups, in the molecule strengthening resin network structure and Intermolecular Forces, thus improve the second-order transition temperature of matrix material, heat decomposition temperature, the thermal characteristicss such as Residual carbon.And the performance such as thermal conductivity, electrical insulating property that functional graphene oxide is good, also has an impact the electric property of p-poly-phenyl Bing oxazine resin, thermal property.
Epoxy resin and/or resol and benzoxazine colophony copolymerization form toughness and the cross-linking density that binary or ternary tree resin copolymer can improve benzoxazine colophony, and this multipolymer has the cross-linking density higher than benzoxazine homopolymer and second-order transition temperature.This is because the phenolic hydroxyl group that benzoxazine colophony open loop produces can react with epoxy resin, under the katalysis of tertiary amine, the homopolymerization of epoxy resin can be suppressed, thus epoxy-functional is participated in benzoxazine colophony network structure, adds the cross-linking density of benzoxazine colophony.Resol also can form Mannich bridge construction with the contraposition of novolac phenolic hydroxyl group as after the catalyzer Er Qie oxazine ring open loop of benzoxazine colophony, so by adding appropriate resol and benzoxazine carries out the solidification value that chemical blend can reduce benzoxazine colophony effectively.All each its performance of tool of often kind of resin in benzoxazine/epoxy resin/resol ternary resin, and interact, influence each other; benzoxazine colophony can give the better thermostability of material, lower water-intake rate, higher carbonization degree, strengthens mechanical property simultaneously.Epoxy resin effect is on the one hand equivalent to thinner, and reduce the viscosity of system, improve the processing performance of ternary tree resin system, on the other hand, epoxy resin can improve the cross-linking density of material, improves thermostability.And resol is the solidifying agent of epoxy resin, be also the catalyzer of benzoxazine colophony, improve the cross-linking density of epoxy resin while reducing system solidification value, thus improve electrical insulation capability further, reduce coefficient of thermal expansion.
To sum up, the present invention by introducing the solidification value that functional graphene oxide reduces benzoxazine colophony in benzoxazine colophony system, improve thermotolerance, also form the cross-linked network structure that binary or ternary tree resin copolymer improve benzoxazine colophony with epoxy resin and/or resol, maintain or improve excellent properties such as benzoxazine colophony solidification ungauged regions, wet fastness etc.
Beneficial effect of the present invention is: 1, simple, the raw material of preparation method of the present invention is easy to get, and does not use solvent, is conducive to environmental protection, 2, functional graphene oxide prepared by the present invention strengthens benzoxazinyl compound resin solidification ungauged regions, there is good thermotolerance, wet fastness, mechanical property and electric property, compared with existing benzoxazine colophony, solidification value reduces by 5 ~ 25 DEG C, second-order transition temperature improves 5 ~ 45 DEG C, accelerate solidification rate, improve processing characteristics and physicals, and preparation process technique is simple, especially without the need to chemical solvents, there is the feature of environmental protection, make it in copper-clad plate, veneer sheet, spacecraft, friction materials, the fields such as resin transfer moulding (RTM) are with a wide range of applications.
Accompanying drawing explanation
Fig. 1 is that the amination graphene oxide that carboxylated graphene oxide strengthens benzoxazine/resol (a), prepared by embodiment 5 prepared by the embodiment of the present invention 1 strengthens benzoxazine/epoxy resin (b), the carboxylated graphene oxide of embodiment 6 preparation strengthens the solidified sample photo of benzoxazine/Phenolic Resin with Epoxy Resin (c);
Fig. 2 is the dynamic thermomechanometry collection of illustrative plates of graphene oxide enhancing benzoxazine/epoxy bielement nano compound resin prepared by embodiment 4.
Embodiment
For making those skilled in the art understand technical scheme of the present invention better, below in conjunction with accompanying drawing, the present invention is described in further detail.
Preparation method is as follows for embodiment of the present invention functional graphene oxide used:
The preparation of carboxylated graphene oxide:
With particle diameter 50 μm of natural flake graphites for raw material, obtain graphite oxide by the Hummers method improved, the Hummers method of described improvement is joined by natural flake graphite in sulfuric acid/phosphoric acid mixed solution that volume ratio is 9:1, stirs, adds potassium permanganate; Specifically: by quality % ratio, natural flake graphite accounts for 3, sulfuric acid/phosphoric acid mixed solution accounts for 85, and potassium permanganate accounts for 12; Control temperature of reaction system in ice-water bath below 10 DEG C, after reaction 60min, be warming up to 40 DEG C, reaction 20h; Reaction product, by after centrifuge washing to sulfate radical-free ion, in 60 DEG C of oven dry, obtains graphite oxide.
By chloroactic acid method, chemical modification is carried out to graphite oxide again, obtain carboxylated graphene oxide: first by graphite oxide with addition of to enter in deionized water and ultrasonic disperse 2h obtains the graphene oxide dispersion that concentration is 4mg/mL, then sodium hydroxide and Mono Chloro Acetic Acid ultrasonic disperse 4h is added, by quality % ratio, wherein graphite oxide accounts for 0.5, sodium hydroxide 48.5, and Mono Chloro Acetic Acid accounts for 51, finally repeatedly be washed to solution in neutral with supercentrifuge, dry grinding at 60 DEG C and namely obtain carboxylated graphene oxide.
The preparation of amination graphene oxide:
With particle diameter 20 μm of natural flake graphites for raw material, graphite oxide is obtained by the Hummers method improved, the Hummers method of described improvement is joined by natural flake graphite in sulfuric acid/phosphoric acid mixed solution that volume fraction is 9:1, stirs, adds potassium permanganate; Specifically: by quality % ratio, natural flake graphite accounts for 1, sulfuric acid/phosphoric acid mixed solution accounts for 90, and potassium permanganate accounts for 9; Control temperature of reaction system in ice-water bath below 0 DEG C, after reaction 40min, be warming up to 40 DEG C, reaction 24h; Reaction product, by after centrifuge washing to sulfate radical-free ion, in 50 DEG C of oven dry, obtains graphite oxide.
Prepare amination graphene oxide by chemical modification again: first 200mg graphite oxide is added 400mL solvent dimethylformamide and ultrasonic 1h obtains the graphene oxide dispersion that concentration is 2mg/mL at 30 DEG C, add 300mg hexanediamine subsequently and ultrasonic and mechanical stirring 2h.Gained mixed solution is transferred to water bath device and adds 13mg2-(7-azo benzotriazole)-N, N, N', N'-tetramethyl-urea phosphofluoric acid ester coupling agent, condensing reflux reaction 10h at 60 DEG C, after having reacted, with washing with alcohol product 10 times, filtration product and at being placed in vacuum drying oven 50 DEG C dry 12h namely obtain amination graphene oxide.
Embodiment 1
Carboxylated Graphene strengthens the preparation of benzoxazine/phenolic aldehyde bielement nano compound resin:
By quality % ratio, by 1% carboxylated graphene oxide and 99% bisphenol A benzoxazine monomer (molecular formula C
22h
30N
2o
2molecular weight 354) mixture of/single order resol (phenol source is phenol, cresols, xylenol) performed polymer carries out blended, intercalation in high speed planetary ball mill instrument, and in wherein bisphenol A benzoxazine monomer/single order resol performed polymer, bisphenol A benzoxazine monomer and single order resol performed polymer mass ratio are 6:4.Concrete technology is by mixture at the first ball milling 3h of 400rpm, then at 500rpm ball milling 1h, and the every continued running 20min of this process high speed planetary ball mill instrument, stall 5min.
Gained biased sample vacuumize degassing 2h at 80 DEG C, to remove bubble, then in 220 DEG C of curing reaction 6h, is obtained carboxylated graphene oxide and strengthens benzoxazine/phenolic aldehyde bielement nano compound resin.Fig. 1 (a) is the photo of gained compound resin sample after the present embodiment solidification, and as seen from the figure, sample flat smooth, illustrates that carboxylated graphene oxide and benzoxazine/phenolic aldehyde binary resin matrix have good consistency.
The cure peak temperature adopting differential scanning calorimetric analysis instrument (DSC) to record this compound resin comparatively benzoxazine colophony reduces by 20 DEG C, and solidification rate is accelerated; Adopt dynamic thermomechanical analysis apparatus (DMA) to record Tg to compare benzoxazine colophony and improve 10 DEG C, thermotolerance is improved.
Embodiment 2
Amination Graphene strengthens the preparation of benzoxazine/phenolic aldehyde bielement nano compound resin:
By quality % ratio, by 1% amination graphene oxide and 97% Bisphenol F benzoxazine monomer (molecular formula C
30h
30n
2o
2molecular weight 450) mixture of/second order resol (phenol source is phenol) performed polymer carries out blended, intercalation, in wherein Bisphenol F benzoxazine monomer/second order resol performed polymer, Bisphenol F benzoxazine monomer and second order resol performed polymer mass ratio are 7:3, concrete technology is at the first ball milling 3h of 400rpm by mixture, then at 500rpm ball milling 1h, the every continued running 20min of this process high speed planetary ball mill instrument, stall 5min.
Biased sample vacuumize degassing 1h at 100 DEG C, to remove bubble, then in 200 DEG C of curing reaction 8h, is obtained amination graphene oxide and strengthens benzoxazine/phenolic aldehyde bielement nano compound resin.The cure peak temperature adopting the method identical with embodiment 1 to record this compound resin comparatively benzoxazine colophony reduces by 15 DEG C, and Tg compares benzoxazine colophony and improves 8 DEG C.
Embodiment 3
Amination Graphene strengthens the preparation of benzoxazine/phenolic aldehyde bielement nano compound resin:
By quality % ratio, by 5% amination graphene oxide and 95% diamines benzoxazine monomer (molecular formula C
32h
34n
2o
2, molecular weight 478) and the mixture of/resorcinol formaldehyde resin performed polymer carries out blended, intercalation, and wherein in diamines benzoxazine monomer/resorcinol formaldehyde resin performed polymer, diamines benzoxazine monomer and resorcinol formaldehyde resin performed polymer mass ratio are 8:2.Operating process is that mixture is carried out blended, intercalation in high speed planetary ball mill instrument, and operating process is mixture at the first ball milling 4h of 400rpm, then at 500rpm ball milling 2h, and the every continued running 20min of this process high speed planetary ball mill instrument, stall 5min.
Biased sample vacuumize degassing 2h at 90 DEG C, to remove bubble, then in 180 DEG C of curing reaction 10h, is obtained amination graphene oxide and strengthens benzoxazine/phenolic aldehyde bielement nano compound resin.Adopt the method identical with embodiment 1 record this compound resin cure peak temperature comparatively benzoxazine colophony reduce by 5 DEG C, Tg compares benzoxazine colophony and improves 6 DEG C.
Embodiment 4
Carboxylated Graphene strengthens the preparation of benzoxazine/epoxy bielement nano compound resin:
By quality % ratio, by 1% carboxylated graphene oxide and 99% polyetheramine benzoxazine monomer (molecular formula C
33h
50n
2o
4molecular weight 538) mixture of/propane type epoxy resin of di phenolic group performed polymer carries out blended, intercalation, and wherein in polyetheramine benzoxazine monomer/propane type epoxy resin of di phenolic group performed polymer, polyetheramine benzoxazine monomer and propane type epoxy resin of di phenolic group performed polymer mass ratio are 9:1.Operating process is mixture at the first ball milling 4h of 400rpm, then at 500rpm ball milling 2h, and the every continued running 20min of this process high speed planetary ball mill instrument, stall 5min.
Biased sample vacuumize degassing 2h at 80 DEG C, to remove bubble, then in 220 DEG C of curing reaction 6h, is obtained carboxylated graphene oxide and strengthens benzoxazine/epoxy bielement nano compound resin.Adopt the method identical with embodiment 1 record this compound resin cure peak temperature comparatively benzoxazine colophony reduce by 12 DEG C, be illustrated in figure 2 the dynamic thermomechanometry collection of illustrative plates of the compound resin prepared by the present embodiment, as figure shows, the Tg of this compound resin is 235 DEG C, and Tg compares pure benzoxazine colophony and improves 45 DEG C.
Embodiment 5
Amination graphene oxide strengthens the preparation of benzoxazine/epoxy bielement nano compound resin:
By quality % ratio, by 2% amination graphene oxide and 98% diamines benzoxazine monomer (molecular formula C
27h
26n
2o
2molecular weight 410) Keep agitation is until mix in high speed planetary ball mill instrument for the mixture of/Resorcinol type epoxy resin prepolymer, and in wherein diamines benzoxazine monomer/Resorcinol type epoxy resin prepolymer, diamines benzoxazine monomer and Resorcinol type epoxy resin prepolymer mass ratio are 8:2.Carry out blended in high speed planetary ball mill instrument, operating process is mixture at the first ball milling 3h of 400rpm, then at 500rpm ball milling 1h, and the every continued running 20min of this process high speed planetary ball mill instrument, stall 5min.
Biased sample vacuumize degassing 2h at 90 DEG C, to remove bubble, then in 200 DEG C of curing reaction 8h, is obtained amination graphene oxide and strengthens benzoxazine/epoxy bielement nano compound resin.Fig. 1 (b) is the photo of gained compound resin sample after the present embodiment solidification, and as seen from the figure, sample flat smooth, illustrates that amination graphene oxide and benzoxazine/epoxy binary resin matrix have good consistency.Adopt the method identical with embodiment 1 record this compound resin cure peak temperature comparatively benzoxazine colophony reduce by 18 DEG C, Tg Xiang improves 30 DEG C Bi oxazine resin.
Embodiment 6
Carboxylated graphene oxide strengthens the preparation of benzoxazine/Epoxy Resin/Phenol aldehyde ternary nano compound resin:
By quality % ratio, by 7% amination graphene oxide and 93% bisphenol A benzoxazine monomer (molecular formula C
22h
30N
2o
2molecular weight 354)/tetra-phenolic group ethane type epoxy resin prepolymers/resorcinol formaldehyde type resol performed polymer carries out blended, intercalation, and wherein in bisphenol A benzoxazine monomer/tetra-phenolic group ethane type epoxy resin prepolymer/resorcinol formaldehyde resin performed polymer, the mass ratio of bisphenol A benzoxazine monomer, four phenolic group ethane type epoxy resin prepolymers and resorcinol formaldehyde resin performed polymer is 6:3:1.Operating process is mixture at the first ball milling 3h of 400rpm, then at 500rpm ball milling 1h, and the every continued running 20min of this process high speed planetary ball mill instrument, stall 5min.
Biased sample vacuumize degassing 2h at 90 DEG C, to remove bubble, then in 180 DEG C of curing reaction 12h, is obtained carboxylated graphene oxide and strengthens benzoxazine/Epoxy Resin/Phenol aldehyde ternary nano compound resin.Fig. 1 (c) is the photo of gained compound resin sample after the present embodiment solidification, and as seen from the figure, sample flat smooth, illustrates that carboxylated graphene oxide and benzoxazine/Epoxy Resin/Phenol aldehyde ternary resin matrix have good consistency.
Adopt the method identical with embodiment 1 record this compound resin cure peak temperature comparatively benzoxazine colophony reduce by 22 DEG C, Tg Xiang improves 26 DEG C Bi oxazine resin.
Embodiment 7
Amination graphene oxide strengthens the preparation of benzoxazine/Epoxy Resin/Phenol aldehyde ternary nano compound resin:
By quality % ratio, by 10% amination graphene oxide and 90% Bisphenol F benzoxazine monomer (molecular formula C
30h
30n
2o
2molecular weight 450) Keep agitation is until mix in high speed planetary ball mill instrument for/tri-hydroxyphenyl methane type epoxy resin prepolymer/resorcinol formaldehyde resin performed polymers, and wherein in Bisphenol F benzoxazine monomer/tri-hydroxyphenyl methane type epoxy resin prepolymer/resorcinol formaldehyde resin performed polymer, the mass ratio of Bisphenol F benzoxazine monomer, three hydroxyphenyl methane type epoxy resin prepolymers and resorcinol formaldehyde resin performed polymer is 7:2:1.In high speed planetary ball mill instrument, carry out blending operations process is mixture at the first ball milling 3h of 400rpm, then at 500rpm ball milling 1h, and the every continued running 20min of this process high speed planetary ball mill instrument, stall 5min.
Biased sample vacuumize degassing 1h at 100 DEG C, to remove bubble, then in 140 DEG C of curing reaction 24h, is obtained amination graphene oxide and strengthens benzoxazine/Epoxy Resin/Phenol aldehyde ternary nano compound resin.Record this compound resin cure peak temperature comparatively benzoxazine colophony reduce by 14 DEG C, Tg Xiang improves 33 DEG C Bi oxazine resin.
Claims (7)
1. functional graphene oxide strengthens a benzoxazinyl compound resin, and it is characterized in that, it is prepared by following methods:
1) take natural flake graphite as raw material, obtain graphite oxide by the Hummers method improved;
2) by step 1) gained graphite oxide carries out chemical modification by chloroactic acid method to it, obtains carboxylated graphene oxide; Or
By step 1) gained graphite oxide adds in solvent dimethylformamide, the graphene oxide dispersion of 1 ~ 4mg/mL is obtained through ultrasonic disperse, then in this dispersion liquid, diamine monomer is added, wherein the mass ratio of diamine monomer and graphite oxide is 1.5 ~ 3:1, coupling agent is added after fully mixing, the mass ratio of coupling agent and graphite oxide is 5 ~ 8:100, and in 50 ~ 70 DEG C of back flow reaction 6 ~ 10h, reaction terminates rear products therefrom washing with alcohol, filtration, drying obtain amination graphene oxide;
3) in mass ratio, by 0.1 ~ 10 part of step 2) the carboxylated graphene oxide of gained or amination graphene oxide and 90 ~ 99.9 parts of benzoxazine binary resin prepolymers or benzoxazine ternary resin prepolymer carry out physical mixed, obtain biased sample, described benzoxazine binary resin prepolymer is benzoxazine/epoxy prepolymer or benzoxazine/phenolic aldehyde performed polymer, and described benzoxazine ternary resin prepolymer is benzoxazine/Epoxy Resin/Phenol aldehyde performed polymer;
4) by step 3) gained biased sample vacuumize degassing 1 ~ 2h at 80 ~ 100 DEG C, then in 100 ~ 220 DEG C of curing reaction 4 ~ 24h, obtain functional graphene oxide and strengthen benzoxazinyl compound resin.
2. functional graphene oxide according to claim 1 strengthens benzoxazinyl compound resin, it is characterized in that: step 1) described natural flake graphite particle diameter is 20 ~ 50 μm.
3. functional graphene oxide according to claim 1 strengthens benzoxazinyl compound resin, it is characterized in that: step 2) described diamine monomer is quadrol or hexanediamine; Described coupling agent is 2-(7-azo benzotriazole)-N, N, N', N'-tetramethyl-urea phosphofluoric acid ester.
4. functional graphene oxide according to claim 1 strengthens benzoxazinyl compound resin, it is characterized in that: step 3) described physical mixed for carry out in high speed planetary ball mill instrument blended, concrete technology is at the first ball milling 3 ~ 5h of 400rpm, then at 500rpm ball milling 1 ~ 2h, the every continued running 20min of this process high speed planetary ball mill instrument, stall 5min.
5. functional graphene oxide according to claim 1 strengthens benzoxazinyl compound resin, it is characterized in that: step 3) described benzoxazine/epoxy prepolymer is the mixture that benzoxazine prepolymer and epoxy resin prepolymer are mixed to get in any proportion; Described benzoxazine/phenolic aldehyde performed polymer is the mixture of benzoxazine prepolymer and resol performed polymer, and wherein resol performed polymer quality is no more than 50% of benzoxazine/phenolic aldehyde performed polymer total mass; In described benzoxazine/Epoxy Resin/Phenol aldehyde performed polymer, the mass ratio of benzoxazine prepolymer, epoxy resin prepolymer and resol performed polymer is 4 ~ 8:1 ~ 5:1;
Described benzoxazine prepolymer comprises the monoamine of single functionality and single phenolic benzoxazine, the dihydroxyphenyl propane of difunctionality, Bisphenol F and two amine type benzoxazines, polyfunctionality benzoxazine, bis-phenol main chain and two amine type main chain benzoxazines and naphthalene system benzoxazine.
6. functional graphene oxide according to claim 5 strengthens benzoxazinyl compound resin, it is characterized in that: described resol performed polymer is the resin that phenol and homologue thereof and formaldehyde condensation obtain; Described epoxy resin prepolymer is glycidyl ether type epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, linear aliphatic based epoxy resin or alicyclic based epoxy resin.
7. the arbitrary described functional graphene oxide of claim 1 ~ 6 strengthens a preparation method for benzoxazinyl compound resin, it is characterized in that step is as follows:
1) take natural flake graphite as raw material, obtain graphite oxide by the Hummers method improved;
2) by step 1) gained graphite oxide carries out chemical modification by chloroactic acid method to it, obtains carboxylated graphene oxide; Or
By step 1) gained graphite oxide is dissolved in dimethyl formamide, the graphene oxide dispersion of 1 ~ 4mg/mL is obtained through ultrasonic disperse, then in this dispersion liquid, diamine monomer is added, wherein the mass ratio of diamine monomer and graphite oxide is 1.5 ~ 3:1, coupling agent is added after fully mixing, the mass ratio of coupling agent and graphite oxide is 5 ~ 8:100, and in 50 ~ 70 DEG C of back flow reaction 6 ~ 10h, reaction terminates rear products therefrom washing with alcohol, filtration, drying obtain amination graphene oxide;
3) in mass ratio, by 0.1 ~ 10 part of step 2) the carboxylated graphene oxide of gained or amination graphene oxide and 90 ~ 99.9 parts of benzoxazine binary resin prepolymers or benzoxazine ternary resin prepolymer carry out physical mixed, obtain biased sample, described benzoxazine binary resin prepolymer is benzoxazine/epoxy prepolymer or benzoxazine/phenolic aldehyde performed polymer, and described benzoxazine ternary resin prepolymer is benzoxazine/Epoxy Resin/Phenol aldehyde performed polymer;
4) by step 3) gained biased sample vacuumize degassing 1 ~ 2h at 80 ~ 100 DEG C, then in 100 ~ 220 DEG C of curing reaction 4 ~ 24h, obtain functional graphene oxide and strengthen benzoxazinyl compound resin.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106519522A (en) * | 2016-11-10 | 2017-03-22 | 无锡市明盛强力风机有限公司 | Broadband electromagnetic shielding material |
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| CN113201109A (en) * | 2021-05-08 | 2021-08-03 | 中北大学 | Method for preparing benzoxazine resin based composite material by in-situ dispersion of carbon material |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106519522A (en) * | 2016-11-10 | 2017-03-22 | 无锡市明盛强力风机有限公司 | Broadband electromagnetic shielding material |
| CN108003564B (en) * | 2017-11-08 | 2021-04-13 | 淮北绿洲新材料有限责任公司 | High-frequency low-dielectric-property functionalized graphene/main chain benzoxazine composite resin and preparation method of in-situ intercalation solution thereof |
| CN107987471A (en) * | 2017-11-08 | 2018-05-04 | 淮北绿洲新材料有限责任公司 | A kind of high frequency low-dielectric main chain benzoxazine compound resin, preparation method and applications |
| CN108003564A (en) * | 2017-11-08 | 2018-05-08 | 淮北绿洲新材料有限责任公司 | High frequency low-dielectric functionalization graphene/main chain benzoxazine compound resin and its in-situ inserted solution preparation method |
| CN107987471B (en) * | 2017-11-08 | 2021-04-13 | 淮北绿洲新材料有限责任公司 | High-frequency low-dielectric-property main chain benzoxazine composite resin, preparation method and application thereof |
| CN108559016A (en) * | 2018-05-30 | 2018-09-21 | 邢月军 | A kind of amination graphene oxide bromobutyl acceptable packaging material and preparation method thereof |
| CN109054288A (en) * | 2018-07-04 | 2018-12-21 | 山东非金属材料研究所 | A kind of Wet Winding Process benzoxazine resin system |
| CN111100291A (en) * | 2018-10-25 | 2020-05-05 | 中国科学院上海硅酸盐研究所 | Preparation method of polybenzoxazine-reinforced three-dimensional graphene foam |
| CN111100291B (en) * | 2018-10-25 | 2021-08-31 | 中国科学院上海硅酸盐研究所 | Preparation method of polybenzoxazine-reinforced three-dimensional graphene foam |
| CN113150493A (en) * | 2021-01-06 | 2021-07-23 | 成都科宜高分子科技有限公司 | High-conductivity and high-toughness benzoxazine composite material and preparation method thereof |
| CN113201109A (en) * | 2021-05-08 | 2021-08-03 | 中北大学 | Method for preparing benzoxazine resin based composite material by in-situ dispersion of carbon material |
| CN113201109B (en) * | 2021-05-08 | 2022-05-24 | 中北大学 | Method for preparing benzoxazine resin based composite material by in-situ dispersion of carbon material |
| CN113355062A (en) * | 2021-06-22 | 2021-09-07 | 西南石油大学 | Elastic graphite strong-adsorption plugging agent and oil-based drilling fluid |
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