CN108485279A - Ternary system resin and preparation method thereof, composite material and preparation method - Google Patents
Ternary system resin and preparation method thereof, composite material and preparation method Download PDFInfo
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- CN108485279A CN108485279A CN201810444541.1A CN201810444541A CN108485279A CN 108485279 A CN108485279 A CN 108485279A CN 201810444541 A CN201810444541 A CN 201810444541A CN 108485279 A CN108485279 A CN 108485279A
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- cyanate
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- benzoxazine
- propargyl ether
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
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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
- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
- C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
- C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
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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
- C08G73/0644—Poly(1,3,5)triazines
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2383/16—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers in which all the silicon atoms are connected by linkages other than oxygen atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2461/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2461/34—Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C08J2461/04, C08J2461/18, and C08J2461/20
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
- C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
Abstract
The invention discloses a kind of ternary system resin and preparation method thereof, composite material and preparation methods.The preparation method of ternary system resin includes the following steps：After siliceous aryl propargyl ether resin is dissolved as solution, it is uniformly mixed with cyanate and benzoxazine, vacuum rotary steam；It is in terms of 100% by the sum of addition of siliceous aryl propargyl ether resin, cyanate and benzoxazine, the sum of mass fraction of cyanate and benzoxazine is 10%~50%, and the mass fraction of siliceous aryl propargyl ether resin is 50%~90%.The present invention promotes the mechanical property of siliceous aryl propargyl ether modified resin by being blended with cyanate and benzoxazine, to provide the modified silicon-contained aryl propargyl ether resin that mechanical property is excellent, heat resistance is good, and is used to prepare carbon fibre reinforced composite.
Description
Technical field
The present invention relates to polymer chemistry, Polymer Physics and field of high polymer material modification, and in particular to a kind of
Ternary system resin and preparation method thereof, composite material and preparation method.
Background technology
Aerospace and the carrier speed of communications and transportation are getting faster, the frivolous small development of electronic product, it is desirable that material
It is heat-resisting it is high, light and intensity is good.The development of high new capability high molecular material can meet aerospace and electronic information to new material
Demand.
Composite material is in damp and hot ring caused by water imbibition (~5%) to overcome epoxy resin and bimaleimide resin
The decline of physical-mechanical properties under border, United States Patent (USP) (US4 885 403,1989) disclose a kind of bisphenols propargyl ether
Preparation.The monomer is easily prepared, and yield is high, and purity is high, and synthesis material is inexpensive, is suitble to industrial large-scale low-cost production.
Resin water suction prepared by such monomer is low, and thermal stability is excellent, and adhesion strength is good, and physical-mechanical properties and dielectric properties are excellent, can use
It, can be in composite material, adhesive, coating and electronic material as the low cost of epoxy resin in advanced polymer composite
Alternative materials.
United States Patent (USP) (US5 155 196,1992) discloses aryl propargyl ether stannous chloride in dichloro-benzenes and is catalyzed
The lower reaction that chromene (chromene sees below Formulas I) is formed through heat polymerization (resetting cyclization-addition), the polymerizate of chromene
There is significant bending property to improve, and to wet insensitive.
European patent (EP 0410547,1991) discloses bisphenol-A dipropargyl ether resin with two (triphenylphosphines) two
The dielectric constant and coefficient of thermal expansion of composite panel of the resin of palladium bichloride catalytic polymerization through glass fiber reinforcement are less than glass
The brominated epoxy resin composite material of enhancing, and the glass transition temperature of composite material is 175 DEG C, is higher than brominated epoxy resin
35 DEG C of based composites.
Chinese invention patent (application No. is 200910047842.1) is disclosed to be contained with the propargyl ether modified height of aryl is heat-resisting
The method of silicon aryne resin, modified siliceous aryne resin processability is good, and molten resin viscosity also reduces, and resin has with fiber
Excellent caking property, the siliceous aryne resin of bisphenol-A dipropargyl ether (DPBPA) modification of 50% mass fraction is through T300 carbon fibers
The composite material bending strength of dimension enhancing reaches 485MPa, and 66%, and glass are improved than pure siliceous aryne resin based composites
Glass transition temperature still has 486 DEG C.The patent has only used aryl propargyl ether small molecule monomer (such as bisphenol-A dipropargyl ether)
Siliceous aryne resin is modified.
Chinese invention patent (application No. is 201010195572.1) discloses a kind of preparation side of silicon-containing alkyne aryl ether resin
Method, by after the alkynes hydrogen grignard of aryl propargyl ether with dichlorosilane polycondensation and silicon-containing alkyne aryl ether resin, aryl propargyl ether
In aryl be bisphenol-A, hexafluoro bisphenol-A and isophthalic, dichlorosilane be dimethyldichlorosilane, hydrogen dimethyl dichlorosilane (DMCS) and first
Base hydridovinyldichlorosilane.Wherein bisphenol-A dipropargyl ether or hexafluoro bisphenol-A dipropargyl ether contract with dimethyldichlorosilane
Poly- resin, its glass transition temperature is respectively higher than 365 DEG C and 375 DEG C after curing at 280 DEG C, in nitrogen atmosphere, 5%
Weightless temperature is that decomposition residual rate is 70.8% and 79% at 432 DEG C and 440 DEG C, 800 DEG C, multiple with T300 carbon fiber-reinforced resins
The bending strength of condensation material is 275MPa and 271MPa, and bending modulus is 37.5GPa and 39.5GPa.The patent Grignard Reagent
The siliceous aryl propargyl ether resin that method is prepared by aryl propargyl ether and dimethyldichlorosilane polycondensation, Grignard Reagent method used
The process route for preparing resin is long, and the side reaction of Grignard Reagent reaction is more, and grignard reaction is tended to have in end product resin
By-product.
Document (Journal of Applied Polymer Science, 2012,127 (4):3178-3185.；High
Performance Polymers,2014,26(3):290-297.) report bisphenol-A, hexafluoro bisphenol-A and bisphenol S and phenyl
Monosilane (Ph-SiH3) reaction 20h can obtain siliceous aryl propargyl ether resin at 120 DEG C under the catalysis of lithium aluminium hydride reduction,
In siliceous bisphenol-A dipropargyl ether resin solidfied material glass transition temperature be 384 DEG C, 5% thermal weight loss temperature is in argon gas
437 DEG C, 900 DEG C of residues are 65%.And the glass transition temperature of siliceous bisphenol S dipropargyl ether resin solidfied material is 440
DEG C, 5% thermal weight loss temperature is 481 DEG C in argon gas, and 900 DEG C of residues are 70%.
Invention content
Technical problem to be solved by the present invention lies in overcome siliceous aryl propargyl ether resin in the prior art and its
The not high technical problem of the mechanical property of the composite material of preparation, and provide a kind of ternary system resin and preparation method thereof,
Composite material and preparation method.The present invention promotes siliceous aryl propargyl ether by being blended with cyanate and benzoxazine and changes
The mechanical property of property resin is used in combination to provide the modified silicon-contained aryl propargyl ether resin that mechanical property is excellent, heat resistance is good
In preparing carbon fibre reinforced composite.
It is an object of the present invention to provide a kind of preparation methods of ternary system resin comprising following steps：
After siliceous aryl propargyl ether resin is dissolved as solution, it is uniformly mixed with cyanate and benzoxazine, vacuum rotary steam；With
The sum of addition of siliceous aryl propargyl ether resin, cyanate and benzoxazine is 100% meter, cyanate and benzoxazine
The sum of mass fraction is 10%~50%, and the mass fraction of siliceous aryl propargyl ether resin is 50%~90%.
In the present invention, the solvent used that dissolves is common aprotic organic solvent.Described is non-proton organic molten
Agent is preferably comprised one or more in acetone, ethyl acetate, toluene, tetrahydrofuran and 1,4- dioxane.In the present invention,
The meaning for being dissolved as being completely dissolved generally uses the stirring and dissolving operation of this field routine to realize that the stirring is molten
Solution is preferably：At room temperature, resin is stirred 0.5~4.0 hour with the rotating speed of 300~500rpm in a solvent.
In the present invention, it is preferable that the ratio between addition of cyanate and benzoxazine is 1:1, which is mass ratio.To carry
Siliceous arylalkyne third is added using mass ratioes such as cyanate and benzoxazines in the mechanical property of high siliceous aryl propargyl ether resin
After being uniformly mixed in base ether resin solution, vacuum distillation can prepare modified siliceous aryl propargyl ether resin.
Wherein, cyanate is preferably bisphenol A cyanate ester, bisphenol E-type cyanate, bisphenol-f type cyanate, bis-phenol M type cyanogen
Any one in acid esters, Novolac Cyanate Eater Resin, dicyclopentadiene type ethylene rhodanate and tetramethyl bisphenol-f type cyanate or at least two
The mixture of kind, more preferably bisphenol A cyanate ester and/or bisphenol E-type cyanate.
Wherein, benzoxazine selects the benzene of phenol, formaldehyde and the functional group of base containing propynyloxy to the synthesis of propynyloxy base aniline
Bing oxazines (P-appe), and/or, the benzoxazine (P- of the functional group containing acetenyl of phenol, formaldehyde and acetylenylaniline synthesis
apa)。
Preferably, in terms of by the sum of addition of siliceous aryl propargyl ether resin, cyanate and benzoxazine for 100%,
The sum of mass fraction of cyanate and benzoxazine is 30%, and the mass fraction of siliceous aryl propargyl ether resin is 70%.
In the present invention, the number-average molecular weight of the siliceous aryl propargyl ether resin is preferably 900~1500, structural formula
As shown in Formula II：
Wherein, X includes any one of following 4 kinds of structures：
R1And R2Including any one of following 5 kinds combinations：
CH3, CH3；C6H5, C6H5；CH3, C6H5；H, C6H5；H, CH3
I.e. in the present invention, the preferred bisphenol-A diine of monomer aryl propargyl ether in the siliceous aryl propargyl ether resin
It is one or more in propyl ether, bisphenol AF dipropargyl ether, diphenyl ether dipropargyl ether and bisphenol fluorene dipropargyl ether.It is described
Monomer dihalide halosilanes in siliceous aryl propargyl ether resin preferably include dimethyldichlorosilane, diphenyl dichlorosilane,
It is one or more in dichloromethyl phenylsilane, phenyl hydrogen dichlorosilane and methyl hydrogen dichlorosilane.
In the present invention, the siliceous aryl propargyl ether resin can be obtained by this field conventional synthesis process, such as ethyl
Magnesium bromide Grignard Reagent method.
In one embodiment of the application, the technique of siliceous bisphenol-A propargyl ether resin is prepared according to Publication No.
The embodiment 3 of the Chinese patent of CN101857677A (application No. is 201010195572.1) is disclosed to prepare siliceous bisphenol-A alkynes
The method of propyl ether resin, referring specifically to the 98th section~107 sections of operating procedure of the Patent Publication.
Accordingly, in the embodiment, the structural formula of the siliceous bisphenol-A propargyl ether resin of preparation is as shown in formula III：
The second object of the present invention is, provides a kind of ternary system resin made from aforementioned preparation process.
In the present invention, it is modified by cyanate and benzoxazine, the mechanics of siliceous aryl propargyl ether resin can be promoted
Performance, and be used to prepare in high performance resin based composites as high-performance resin matrix.
The third object of the present invention is, provides a kind of preparation of modified silicon-contained aryl propargyl ether resin composite materials
Method comprising following steps：It is quality point by the siliceous aryl propargyl ether resin or the ternary system resin formulations
Number is 30%~42% maceration extract, carbon cloth is immersed in the maceration extract, or by unidirectional carbon in the dipping
Row's yarn is carried out in liquid, obtains prepreg, after part ＜ 1% to be evaporated, by prepreg overlay, and hot compression molding, you can.
In the present invention, the solvent in the maceration extract is common aprotic organic solvent.Described is non-proton organic molten
Agent is preferably comprised one or more in acetone, ethyl acetate, toluene, tetrahydrofuran and 1,4- dioxane.
In the present invention, the maceration extract is for impregnating T300 carbon cloths or carrying out row's yarn to T700 unidirectional carbons.
In the present invention, the equipment that above-mentioned hot compression molding uses is generally flat-bed press.The presser of hot compression molding
The forming process of skill is preferably：Pass through 210 DEG C/2h successively, 250 DEG C/2h, 300 DEG C/2h and 330 DEG C/4h is molded, briquetting pressure
For 3MPa.
The fourth object of the present invention is, provides a kind of aryl propargyl modified silicon-contained made from aforementioned preparation process
Ether resin composite material.
In the present invention, the gel content of the composite material is preferably 30%.
In above each scheme, the purpose of the vacuum rotary steam is to remove solvent, and condition is this field normal condition, example
If vacuum pressure is -0.09~-0.1MPa.The temperature of vacuum distillation according to selected solvent boiling point determine, generally 50 DEG C~
100 DEG C, such as when solvent is tetrahydrofuran in resin solution, the temperature for removing the corresponding vacuum distillation of tetrahydrofuran is 50
℃；When solvent is toluene, the temperature for removing the corresponding vacuum distillation of toluene is 90 DEG C；When solvent is ethyl acetate, remove
The temperature of the corresponding vacuum distillation of ethyl acetate is 60 DEG C；The mixed solvent of toluene and tetrahydrofuran in this way removes solvent and corresponds to
Vacuum distillation temperature be 90 DEG C.
In above each scheme, the room temperature has this field conventional sense, generally 15~40 DEG C.
On the basis of common knowledge of the art, above-mentioned each optimum condition can be combined arbitrarily to get each preferable reality of the present invention
Example.
The reagents and materials used in the present invention are commercially available.
The positive effect of the present invention is that：The present invention with cyanate and benzoxazine by being mixed to form binary polymerization
Object improves the mechanical property of siliceous aryl propargyl ether resin.Modified silicon-contained aryl propargyl ether resin produced by the present invention is
A kind of reisn base material having excellent heat resistance and mechanical property, is additionally operable to prepare polymer matrix composites, widen
The application prospect in the fields such as aerospace and electronic information.
Description of the drawings
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of siliceous bisphenol-A propargyl ether resin in embodiment 1；
Fig. 2 is the DSC spectrograms of siliceous bisphenol-A propargyl ether resin in embodiment 1；
Fig. 3 is the TGA spectrograms of siliceous bisphenol-A propargyl ether resin in embodiment 1.
Specific implementation mode
It is further illustrated the present invention below by the mode of embodiment, but does not therefore limit the present invention to the reality
It applies among a range.In the following examples, the experimental methods for specific conditions are not specified, according to conventional methods and conditions, or according to quotient
Product specification selects.
In embodiment 1, embodiment 2 and embodiment 3, cyanate raw material is purchased from Yangzhou apocalypse new material limited liability company,
Selection bisphenol A cyanate ester monomer, product type CE01MO, selection bisphenol E-type cyanate monomer, product type are
CE09MO。
The structure of data test part, resin is tested by hydrogen nuclear magnetic resonance instrument.The curing reaction temperature of resin can use differential
Scanning calorimeter (DSC) is tested, and the initial temperature (T of curing reaction can be obtainedi) and curing reaction peak temperature (Tp), it is solid
Change reaction end temp (Tf) and curing reaction heat release enthalpy (Δ H).It is true that the curing process of resin can refer to resin DSC test results
It is fixed.The thermal stability of resin through heat cure can be tested with thermal gravimetric analyzer (TGA) in nitrogen atmosphere, can be obtained 5%
Thermal weight loss temperature (Td5) and 800 DEG C of residual rate (Yr800℃), the thermal stability of resin is reflected with this.The composite material power of resin
Learning performance can newly think carefully that 4204 type microcomputer controlled electronic universal testers of material tests Co., Ltd SANS CMT are surveyed with Shenzhen
Examination.
It is total in 400 type superconduction Fourier transform nuclear-magnetisms of German BRUKER companies AVANCE after resin is dissolved with deuterochloroform
It is tested on vibration wave spectrometer.
In DSC test process, with U.S.'s TA companies Q2000 type differential scanning calorimeters, be from 40 DEG C of continuous warmings to
390 DEG C, heating rate control is 10K/min.
It is from 40 with I type thermal gravimetric analyzers of Switzerland Mettler Toledo company's Ts GA/DAC in TGA test process
To 900 DEG C, heating rate control is 10K/min for DEG C continuous warming.
The solidification process of resin is the process of ladder-like elevated cure, such as from 210 DEG C/2h to 250 DEG C/process of 2h can
It is split as following 3 step concrete operations：First, 2h is kept the temperature at 210 DEG C, 250 DEG C is then warming up to from 210 DEG C, then protect at 250 DEG C
Warm 2h.Other processes and so on.
Embodiment 1
Cyanate, the preparation of P-appe and siliceous bisphenol-A propargyl ether blending resin and the preparation of composite material
(1) preparation of siliceous bisphenol-A dipropargyl ether resin (PSAP-A)
Ethylmagnesium bromide method prepares siliceous bisphenol-A propargyl ether resin：
It is made according to the embodiment 3 of the Chinese patent of Publication No. CN101857677A (application No. is 201010195572.1)
Standby siliceous bisphenol-A propargyl ether resin (being denoted as PSPA-A resins), referring specifically to the 98th section~107 sections of the Patent Publication
Operating procedure.
Siliceous bisphenol-A propargyl ether resin (PSPA-A resins) is subjected to hydrogen nuclear magnetic resonance spectrogram analysis, it is as a result as follows：
1H NMR(DCCl3-d1)δ7.2-6.8(m,8H)；4.64(s,2H)；2.52(s,1H)；1.63(s,6H)；0.33
(s,6H).Polymerization degree n is 2.
For details, reference can be made to Fig. 1.
Dsc analysis also has been carried out to PSPA-A resins, has as a result seen Fig. 2 and table 1.It can be seen that the starting heat release temperature of PSAP-A resins
For degree at 244 DEG C or so, exothermic peak temperature reaches 291 DEG C and 316 DEG C.According to DSC data, PSAP-A is pressed into curing process 210
DEG C/2h, 250 DEG C/2h, 300 DEG C/2h, 330 DEG C/4h solidifications obtain the solidfied material of PSAP-A, TGA surveys are carried out in nitrogen atmosphere
Examination, is as a result shown in Fig. 3 and table 2.
The DSC data of 1 siliceous bisphenol-A propargyl ether resin of table
| Resin | Ti/℃ | Tp1/℃ | Tp2/℃ | ΔH/(J/g) |
| PSAP-A | 244 | 291 | 316 | 794 |
The TGA data of 2 siliceous bisphenol-A propargyl ether resin of table
| Resin | Td5(℃) | Yr800℃(%) |
| PSAP-A | 422 | 58.7 |
(2) preparation of ternary system resin and composite material
By bisphenol-A dicyanate (BADCy), benzoxazine (P-appe) and siliceous bisphenol-A dipropargyl ether resin
(PSAP-A) according to mass ratio 15:15:70 are dissolved in tetrahydrofuran solution, 30min are stirred, after mixing, by vacuum rotary steam
Postcooling, you can obtain modified ternary system resin.This resin is dissolved in acetone, be configured to mass fraction be 38% it is molten
Liquid impregnates carbon cloth (T300) through above-mentioned solution, acquisition prepreg, after part ＜ 1% to be evaporated, by prepreg overlay, and
The compression moulding on platen-press.Pressing process be 210 DEG C/2h, 250 DEG C/2h, 300 DEG C/2h and 330 DEG C/4h, briquetting pressure
For 3MPa, composite material gel content obtained is about 30%.The bending property of composite material is shown in Table 3, it can be seen that cyanic acid is added
After ester, benzoxazine P-appe, the bending strength of PSAP-A resins has rising, bending modulus to be more than 40GPa.
Composite material (enhancing of T300 carbon cloths) bend performance data prepared by 3 modified resin of table
Embodiment 2
Cyanate, the preparation of P-appe and siliceous bisphenol-A propargyl ether blending resin and the preparation of composite material
Bisphenol E-type dicyanate (BEDCy), benzoxazine (P-appe) and siliceous bisphenol-A dipropargyl ether resin is (real
Apply the PSAP-A resin raw materials that example 1 obtains) according to mass ratio 15:15:70 are dissolved in tetrahydrofuran solution, stir 30min, and mixing is equal
After even, by vacuum rotary steam postcooling, you can obtain modified ternary system resin.This resin is dissolved in acetone, is configured to
Carbon cloth (T300) is impregnated through above-mentioned solution, obtains prepreg, part ＜ 1% to be evaporated by the solution that mass fraction is 38%
Afterwards, by prepreg overlay, and the compression moulding on platen-press.Pressing process be 210 DEG C/2h, 250 DEG C/2h, 300 DEG C/2h and
330 DEG C/4h, briquetting pressure 3MPa, composite material gel content obtained is about 30%.The bending property of composite material is shown in Table 3,
It can be seen that being added after cyanate, benzoxazine P-appe, the bending strength of PSAP-A resins has rising, bending modulus big
In 40GPa.
Embodiment 3
The system of cyanate, the preparation of benzoxazine P-apa and siliceous bisphenol-A propargyl ether blending resin and composite material
It is standby
Bisphenol-A dicyanate (BADCy), benzoxazine (P-apa) and siliceous bisphenol-A dipropargyl ether resin is (real
Apply the PSAP-A raw materials that example 1 obtains) according to mass ratio 15:15:70 are dissolved in tetrahydrofuran solution, stir 30min, are uniformly mixed
Afterwards, by vacuum rotary steam postcooling, you can obtain modified ternary system resin.This resin is dissolved in acetone, matter is configured to
The solution that score is 38% is measured, carbon cloth (T300) is impregnated through above-mentioned solution, acquisition prepreg, after part ＜ 1% to be evaporated,
By prepreg overlay, and the compression moulding on platen-press.Pressing process be 210 DEG C/2h, 250 DEG C/2h, 300 DEG C/2h and 330
DEG C/4h, briquetting pressure 3MPa, composite material gel content obtained is about 30%.The bending property of composite material is shown in Table 3, can
After finding out addition cyanate, benzoxazine P-apa, the bending strength of PSAP-A resins has rising, bending modulus to be more than
40GPa。
The above is only a preferred embodiment of the present invention.It should be pointed out that for those skilled in the art, do not taking off
Under the premise of from present inventive concept, several improvements and modifications can also be made, these improvements and modifications also should be regarded as the present invention's
In protection domain.
Claims (10)
1. a kind of preparation method of ternary system resin, which is characterized in that it includes the following steps：By siliceous aryl propargyl ether
It after resin is dissolved as solution, is uniformly mixed with cyanate and benzoxazine, vacuum rotary steam；With siliceous aryl propargyl ether tree
The sum of addition of fat, cyanate and benzoxazine is counted for 100%, and the sum of mass fraction of cyanate and benzoxazine is 10%
~50%, the mass fraction of siliceous aryl propargyl ether resin is 50%~90%.
2. preparation method as described in claim 1, which is characterized in that the solvent used that dissolves includes acetone, acetic acid second
It is one or more in ester, toluene, tetrahydrofuran and 1,4- dioxane；The dissolving is operated using stirring and dissolving and is realized,
Preferably：At room temperature, resin is stirred 0.5~4.0 hour with the rotating speed of 300~500rpm in a solvent.
3. preparation method as described in claim 1, which is characterized in that the ratio between addition of cyanate and benzoxazine is 1:1,
The ratio is mass ratio；
And/or by the sum of addition of siliceous aryl propargyl ether resin, cyanate and benzoxazine be 100% in terms of, cyanate
It is 30% with the sum of the mass fraction of benzoxazine, the mass fraction of siliceous aryl propargyl ether resin is 70%.
4. preparation method as described in claim 1, which is characterized in that cyanate is bisphenol A cyanate ester, bisphenol E-type cyanic acid
Ester, bisphenol-f type cyanate, bis-phenol M types cyanate, Novolac Cyanate Eater Resin, dicyclopentadiene type ethylene rhodanate and tetramethyl bisphenol-f type
In cyanate any one or at least two mixture, preferably bisphenol A cyanate ester and/or bisphenol E-type cyanate；
And/or the Ben Bing Evil that benzoxazine is phenol, formaldehyde and the functional group of base containing propynyloxy to the synthesis of propynyloxy base aniline
Piperazine, and/or, it is the benzoxazine of the functional group containing acetenyl of phenol, formaldehyde and acetylenylaniline synthesis.
5. preparation method as described in claim 1, which is characterized in that the equal molecule of number of the siliceous aryl propargyl ether resin
Amount is 900~1500, and structural formula is as shown in Formula II：
Wherein, X includes any one of following 4 kinds of structures：
R1And R2Including any one of following 5 kinds combinations：
CH3, CH3；C6H5, C6H5；CH3, C6H5；H, C6H5；H, CH3。
6. a kind of ternary system resin made from preparation method as claimed in any one of claims 1 to 5, wherein.
7. a kind of preparation method of modified silicon-contained aryl propargyl ether resin composite materials, which is characterized in that it includes following step
Suddenly：It is the maceration extract that mass fraction is 30%~42% by ternary system resin formulations as claimed in claim 6, by carbon fiber
Cloth is immersed in the maceration extract, or unidirectional carbon is carried out row's yarn in the maceration extract, obtains prepreg, part ＜ to be evaporated
After 1%, by prepreg overlay, and hot compression molding, you can.
8. preparation method as claimed in claim 7, which is characterized in that the solvent in the maceration extract includes acetone, acetic acid second
It is one or more in ester, toluene, tetrahydrofuran and 1,4- dioxane.
9. preparation method as claimed in claim 7, which is characterized in that the equipment that the hot compression molding uses is tablet hot pressing
Machine；
And/or the compression moulding process of the hot compression molding is：Successively pass through 210 DEG C/2h, 250 DEG C/2h, 300 DEG C/2h and
330 DEG C/4h is molded, briquetting pressure 3MPa.
10. modified silicon-contained aryl propargyl ether tree made from a kind of preparation method by as described in claim 7~9 any one
Resin composite material.
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| CN109777123A (en) * | 2018-12-25 | 2019-05-21 | 广东生益科技股份有限公司 | Resin combination, preliminary-dip piece used for printed circuit and metal-coated laminated board |
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