CN110527300A - A kind of high-strength epoxy with inierpeneirating network structure-silicon rubber modified material - Google Patents
A kind of high-strength epoxy with inierpeneirating network structure-silicon rubber modified material Download PDFInfo
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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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
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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
- C08L83/00—Compositions 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; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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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
- C08L2205/02—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
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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
- C08L2205/04—Polymer mixtures characterised by other features containing interpenetrating networks
Abstract
The high-strength epoxy with inierpeneirating network structure-silicon rubber modified material that the present invention provides a kind of, it is prepared by the raw material of following portions by weight: 100.00 parts of silicon rubber, 5.00~15.00 parts of epoxy resin, 10.00~15.00 parts of epoxy hardener, 8.00~20.00 parts of containing hydrogen silicone oil, 0.05~1.00 part of rubber additive, wherein the epoxy hardener is the acid anhydride type curing agent with more vinyl structures.The present invention also provides the preparation methods of the material.Epoxy of the present invention-silicon rubber modified material is interpenetrating polymer networks structure, function admirable, when the epoxy resin especially added in system is graft modification epoxy resin, epoxy hardener is tung oil acid anhydride, the mechanical property of material significantly improves, the strength of materials, toughness and adhesive property are promoted simultaneously, especially the tensile strength of material promotes amplitude highly significant, and interpenetrating polymer networks stable structure, system can keep homogeneous state for a long time, phenomena such as will not being layered, performance is very good.It can be applied to aerospace, electronic information, the high-temperaure coating of mechanical equipment field, adhesive, casting glue, rubber and flexible ablation resistant material matrix etc., greatly widened the application field of silastic material.
Description
Technical field
The invention belongs to field of polymer composite material, and in particular to a kind of with the high-strength of polymer interpenetration network structure
Spend epoxy-silicon rubber modified material.
Background technique
Silicon rubber is that the one of the organic groups such as methyl, ethyl, phenyl are connected on Si atom using Si-O inorganic structure as main chain
Half inorganic polymer of kind.Due to structure and the particularity of composition, the characteristic and function of silastic material collection inorganic matter and organic matter
, the excellent properties that cannot be provided simultaneously with many other materials, such as brilliant resistant of high or low temperature, excellent is resistance to
Oil, solvent resistant, resistance to ultraviolet, radiation resistance, good resistance to ag(e)ing, excellent electrical insulating property and chemical stability and physiology
The advantages that inertia, be widely used at present Aeronautics and Astronautics, additive, electromagnetic shielding, membrane material, electric, medicine,
The fields such as daily necessities.However, intermolecular force is low since silicone rubber matrix lacks polar group, cohesive strength is low, in external force
Destruction is easily deformed under effect, causes its tensile strength low, and elongation at break is low, and adhesive property is bad, heat resistance
It is poor, significantly limit its application.Silicon rubber is modified to improve the performances such as its intensity, toughness, becomes the heat of research
Point.
In the prior art, the common method of modifying of silicon rubber has modified filler enhancing, matrix surface modification, addition third group
Divide adhesion promoters and matrix chemical modification etc..Filler modified is that silica is added into silicone rubber matrix, carbon fiber etc.
Filler, but filler introduces meeting so that the viscosity of matrix increases fairly obvious, is unfavorable for practice of construction and uses, while filler grain
A degree of aggregation can occur for son, also result in the intensity decline of material；The modified such as plasma-treated surface of matrix surface is smelly
Oxidation processes, surface etch etc. improve its adhesive property although this can improve the surface texture of silicon rubber, and surface changes
Property can only improve the character on silicone rubber matrix surface, cannot improve the performance of silicone rubber matrix, such as tensile strength, elongation at break
Deng, also, surface it is modified there is a problem of it is unstable；The adhesive property that adhesion promoters are able to ascend material is additionally incorporated, but
It is unstable to have mixed system, small molecule material be precipitated the problems such as.
Matrix chemical modification is by Molecular Design, and using grafting, the chemical modes such as block carry out modified silicon rubber material
Material, it is with good stability, the comprehensive performance of material can be obviously improved.Epoxy resin is as a kind of excellent high-intensitive thermosetting
Property resin, active group is had on molecule, can be formed highly cross-linked with amine, anhydride, polamides crosslinking curing
Space three-dimensional reticular structure, the rigidity having and polar group can effectively promote the cohesive strength of silicon rubber, synchronous
Improve its adhesive property.The promotion of adhesive strength significantly improves the interfacial adhesion of composite material, increase with functional stuffing,
The interface cohesion of reinforcing fiber, this is conducive to the composite material for preparing higher performance.Therefore, it is with epoxy resin modification silicon rubber
A kind of effective ways improving Mechanical Properties of Silicone Rubber and interfacial adhesion developed in recent years.
Guo Feige, " preparation and performance of the modified S-1 silicone rubber coating of epoxy E-51 ", aerospace material technique, 2014-06-
15 disclose a kind of method of epoxy-modified silicon rubber, are specifically modified S-1 silicon rubber, phase using using bisphenol A epoxide resin
Than non-modified silicon rubber, the tensile strength of modified silicon rubber, elongation at break have promotion, wherein tensile strength
Highest can be improved 49.4%, and elongation at break highest can be improved 23.1%.Further experiment shows epoxy-modified silicon rubber
It can be used as the basis material of the outer thermal protective coating of solid propellant rocket.But the raising width of its tensile strength, elongation at break
It spends limited, is unable to satisfy certain application demands.
As application No. is 201810897419.X, entitled " a kind of novel epoxy modified heat resistant liquid silastic
Recorded in the patent application of purposes ", the present inventor use epoxy graft modification silicon rubber, effectively increase silicon rubber intensity,
Toughness, adhesive property, wherein tensile strength is up to 0.83MPa, improves 162% compared with pure sample；Shear strength 0.81MPa, compared with pure sample
Improve 160%；Elongation at break reaches 268%, improves about 2 times compared with pure sample.This method effectively extends the application of silicon rubber
Range, but its tensile strength, the performance boosts amplitude such as shear strength need to be improved.If can further be promoted epoxy-modified
The tensile strength and shear strength of silicon rubber will have the field that the strength of materials requires in aerospace, electric mechanical etc.
Broader practice prospect.
Summary of the invention
The object of the present invention is to provide a kind of modified materials of the excellent epoxy of tensile property and adhesive property-silicon rubber
Material.
The present invention provides a kind of epoxy-silicon rubber modified materials, it is prepared by the raw material of following portions by weight:
100.00 parts of silicon rubber, 5.00~15.00 parts of epoxy resin, 10.00~15.00 parts of epoxy hardener, Silicon Containing Hydrogen
8.00~20.00 parts of oil, wherein, the epoxy hardener is acid anhydride type curing agent to 0.05~1.00 part of rubber additive.
Further, the composite material is prepared by the raw material of following portions by weight: 100.00 parts of silicon rubber, ring
10.00 parts of oxygen resin, 13.00 parts of epoxy hardener, 14.34~15.62 parts of containing hydrogen silicone oil, 0.35 part of rubber additive.
Further, the epoxy hardener is the acid anhydride type curing agent with more vinyl structures, preferably eleostearic acid
Acid anhydride；The containing hydrogen silicone oil is the mixing of Methyl Hydrogen Polysiloxane Fluid, phenyl hydrogen-containing silicon oil or Methyl Hydrogen Polysiloxane Fluid and phenyl hydrogen-containing silicon oil
Object, the mass ratio of Methyl Hydrogen Polysiloxane Fluid and phenyl hydrogen-containing silicon oil is preferably (1~4) in the mixture: 1；
It is highly preferred that the containing hydrogen silicone oil is Methyl Hydrogen Polysiloxane Fluid.
Further, the epoxy resin is unmodified epoxy resin or modified epoxy, wherein modified epoxy tree
The structure of rouge are as follows:
Wherein,Respectively remove remaining group after a H atom for bisphenol-A or two terminal hydroxy group of polyalcohol；
m1And m2For the degree of polymerization, m1For 0.18~2.4, m2It is 1~10；
R is C1~C3Alkyl.
Further, the structure of the modified epoxy are as follows:
m1、m2, R such as
It is upper described.
Further, the rubber additive is platinum catalyst, the mixture for being catalyzed delayed-action activator and Epoxy curing accelerators.
Further, the ratio between parts by weight of the platinum catalyst, catalysis delayed-action activator and Epoxy curing accelerators are 4:1:
2。
Further, the catalysis delayed-action activator is alkynol delayed-action activator, preferably -3 crotonylene alcohol of 2- methyl；The epoxy is solid
Change promotor is DMP-30.
Further, the composite material is interpenetrating polymer networks structure.
Prepare above-mentioned epoxy-silicon rubber modified material method the present invention also provides a kind of, the method includes with
Lower step:
(1) epoxy resin is added in silicone rubber matrix according to raw material weight number, the heating stirring at 90-110 DEG C
0.5-2h obtains uniformly mixed sizing material；
(2) containing hydrogen silicone oil, epoxy hardener, rubber is added into sizing material obtained by step (1) according to raw material weight number to add
Add agent, stirs 0.5-2h at normal temperature；
(3) after mixing evenly, solidify to get.
Further, in step (1), the epoxy resin is E44；Or the epoxy resin is modified epoxy, it should
Modified epoxy is prepared by following methods: by the E44 of equimolar metering proportion and methoxybenzene based polysiloxane 90
It is stirred at DEG C -110 DEG C, in nitrogen atmosphere, adds the catalyst tetraisopropyl titanate of 0.5wt%, after reacting 6~8h, stopped
Stirring is to get modified epoxy；
And/or in step (3), the condition of cure are as follows: successively at 90 DEG C at 2 hours, 120 DEG C at 2 hours, 140 DEG C
2 hours at 2 hours, 180 DEG C.
The experimental results showed that epoxy of the present invention-silicon rubber modified material, tensile strength are up to 2.07Mpa, pure sample is compared
567%, shear strength 1.34MPa are improved, improves 458% compared with pure sample, elongation at break compares pure sample up to 251%
Improve 90%.Compared with the epoxy-modified silicon rubber disclosed in the prior art, the tensile strength of the epoxy-modified silicon rubber of the present invention
It increases substantially, while elongation at break, adhesive property are also obviously improved.
A kind of high-strength epoxy with inierpeneirating network structure-silicon rubber modified material of the present invention is interpenetrating polymer net
Network structure, when the epoxy resin added in function admirable, especially system is the epoxy resin of graft modification, material mechanical performance
It significantly improves, intensity, toughness and adhesive property are promoted simultaneously, the wherein promotion highly significant of tensile strength of material, and interpenetrating
Polymer network structure is more stable, the presence that curing system can be stable, and phenomena such as will not be layered, performance is very excellent
It is good, it can be applied to aerospace, electronic information, the high-temperaure coating of mechanical equipment field, adhesive, casting glue and flexibility
Ablation resistant material matrix etc. has greatly widened the application field of silastic material.
" R C herein1~C3Alkyl " refer to R can selected from it is any include 1,2 or 3 carbon atom alkyl.
Obviously, above content according to the present invention is not being departed from according to the ordinary technical knowledge and customary means of this field
Under the premise of the above-mentioned basic fundamental thought of the present invention, the modification, replacement or change of other diversified forms can also be made.
The specific embodiment of form by the following examples remakes further specifically above content of the invention
It is bright.But the range that this should not be interpreted as to the above-mentioned theme of the present invention is only limitted to example below.It is all to be based on above content of the present invention
The technology realized all belongs to the scope of the present invention.
Detailed description of the invention
Fig. 1 is the Fourier transform infrared of epoxy prepolymer (the ES prepolymer i.e. in figure) prepared by the embodiment of the present invention 1
Spectrogram.
Fig. 2 is the nucleus magnetic hydrogen spectrum figure of epoxy prepolymer (prepolymer i.e. in figure) prepared by the embodiment of the present invention 1.
Fig. 3 is that the SEM of each sample quenches disconnected test chart.
Fig. 4 is the stretching and adhesive property test result of each sample.
Fig. 5 is the bond failure face shape appearance figure of each sample.
Fig. 6 is the thermogravimetic analysis (TGA) figure of each sample.
Specific embodiment
The raw materials used in the present invention and equipment are known product, as obtained by purchase commercial product.
Wherein, E44 epoxy resin (epoxide number 0.41-0.47ep/100g)；Methoxybenzene based polysiloxane is (in organosilicon
Mesosome DC3074)；Silicon rubber (vinyl silicone oil, viscosity 6000-10000cst, contents of ethylene 0.08-0.14Wt%)；Methyl
Containing hydrogen silicone oil (HS, hydrogen content 0.35mol/100g), phenyl hydrogen-containing silicon oil (UC233, hydrogen content 0.26mol/100g, viscosity
4800mPa·s)。
The structural formula of part material is as follows:
Silicone intermediate
Vinyl silicone oil
Methyl Hydrogen Polysiloxane Fluid
Phenyl hydrogen-containing silicon oil
Epoxy resin
Embodiment 1, the preparation of epoxy of the present invention-silicon rubber modified material
1, the preparation of epoxy prepolymer (ES): by the E44 of equimolar metering proportion and silicone intermediate methoxyphenyl
Polysiloxanes stirs at 100 DEG C, in nitrogen atmosphere, adds 0.5% catalyst TPT, after reacting 7h, stops stirring, i.e.,
Obtain epoxy prepolymer.
Epoxy prepolymer ES
Wherein, m1And m2For the degree of polymerization, m1For 0.18~2.4, m2It is 1~10；R is C1~C3Alkyl.
2, the epoxy-silicon rubber modified material preparation invented
According to feed ratio shown in table 1, epoxy-silicon rubber modified material of invention is prepared.Steps are as follows:
(1) according to feed ratio, epoxy prepolymer (ES) is added in silicone rubber matrix, in 90-110 DEG C of heating stirring
0.5-2h obtains uniformly mixed sizing material；
(2) then according to feed ratio, addition containing hydrogen silicone oil (Methyl Hydrogen Polysiloxane Fluid and/or phenyl hydrogen-containing silicon oil), epoxy are solid
Agent tung oil acid anhydride TOA, platinum catalyst, catalysis -3 crotonylene alcohol of delayed-action activator 2- methyl, Epoxy curing accelerators DMP-30, normal
Temperature is lower to stir 0.5-2h；
(3) after mixing evenly, successively solidify under the following conditions: at 90 DEG C at 2 hours, 120 DEG C 2 at 2 hours, 140 DEG C
Hour, at 180 DEG C 2 hours to get epoxy of the invention-silicon rubber modified material.
The epoxy of the present invention of table 1.-silicon rubber modified material feed ratio
The preparation of reference examples 1, control sample
According to feed ratio shown in table 1, control sample is prepared: Pure-HS-silicone, Pure-UC233-silicone.
Hereinafter, proving beneficial effects of the present invention by experimental example.
The structural characterization of experimental example 1, epoxy prepolymer
It carries out infrared, nucleus magnetic hydrogen spectrum to epoxy prepolymer made from embodiment 1 respectively to characterize, as a result such as Fig. 1 and Fig. 2 institute
Show.In Fig. 1 infrared spectroscopy, epoxy resin is in 3479cm-1There is hydroxyl appearance at place, and silicone intermediate is in 2846cm-1There is methoxy at place
Base appearance, and hydroxyl peak disappears substantially in epoxy prepolymer (prepolymer i.e. in figure), methoxy base peak also disappears at 2846cm-1
It loses, illustrates that the hydroxyl on epoxy resin is reacted with counter given birth to of the methoxyl group on silicone intermediate；In Fig. 2 nucleus magnetic hydrogen spectrum, epoxy
Prepolymer, without appearance, illustrates that methoxyl group appearance disappears in system, this is mutually confirmed with infrared spectrum at 3.47ppm.Illustrate this
Epoxy prepolymer (ES) has successfully been made in invention.
Experimental example 2, SEM, which quench to break, to be tested
1, experimental method
Solidification sample is obtained under 10 kilovolts of acceleration voltages with scanning electron microscope (SEM, JSM-5900, Japanese Jie Er)
The cross-sectional structure of product.All samples impregnate 12 hours or more in liquid nitrogen, plane of disruption metal spraying.
2, experimental result
As shown in figure 3, quenching disconnected figure as can be seen that utilizing the cured pure silicone rubber of phenyl hydrogen-containing silicon oil from scanning electron microscope
(Pure-UC233-silicone) section of quenching also shows island phase separating resulting, rather than smooth section, this be because
For the phenyl hydrogen-containing silicon oil phenyl of side group containing polarized, cause with vinyl silicone oil poor compatibility.And add in Methyl Hydrogen Polysiloxane Fluid
The phenyl hydrogen-containing silicon oil for entering different content, with the increase of phenyl hydrogen-containing silicon oil content, the dispersed phase size of system starts to become smaller.
Experimental example 3, Mechanics Performance Testing
1, experimental method
(1) tensile strength and elongation at break: according to ISO 37:2011 standard, using Instron (Instron 5567,
Instron, the U.S.) universal tensile testing machine is with the tensile strength and extension at break of the velocity test solidified sample of 500mm/min
Rate.
(2) adhesive property is tested: according to iso standard 4587:2003, with Instron 5567 with the rate pair of 5mm/min
Solidified sample carries out adhesion test.Five samples of all result average out to.
2, experimental result
Test result is as shown in Fig. 4, table 2, it can be seen that compared with control sample, the present invention is using tung oil acid anhydride as epoxy
Epoxy made from the curing agent-tensile property of silicon rubber modified material, adhesive property, toughness significantly improve, comprehensive mechanical property
It can significantly improve, this is because the more vinyl structures being had in tung oil acid anhydride, so that caused by system crosslink density rises.This
Outside, with the addition of phenyl hydrogen-containing silicon oil, the epoxy of the present invention-tensile strength of silicon rubber modified material, shear strength, fracture are stretched
There is increased trend after first reducing in long rate.Wherein, HS14.34-UC2330The tensile strength of-IPN is up to 2.07MPa, than
Pure-HS-silicone improves 5.7 times；HS14.34-UC2330The shear strength of-IPN is up to 1.34MPa, compares Pure-HS-
Silicone improves 4.6 times；HS14.34-UC2330The elongation at break of-IPN is up to 251.16%, compares Pure-HS-
Silicone improves 0.9 times.
Tensile strength, elongation at break, the shear strength of each sample of table 2
Experimental example 4, bond failure face pattern test
1, experimental method
According to ISO 4587:2003 standard, solidified sample is bonded with the speed of 5mm/min by Instron 5567
Test.5 samples of all result average out to.After carrying out failure by shear test, the pattern of failure mechanics is directly shot.
2, experimental result
Test results are shown in figure 5, it can be seen that the bond failure interface of control sample Pure-HS-silicone is smooth
Smooth, no removing；And epoxy of the present invention-silicon rubber modified material bond failure face pattern shows mixing and destroys formation,
It has cohesional failure and the removing from interface concurrently, is conducive to the adhesive property for improving composite material, improve Interface adhesive strength, and it is upper
Adhesive property test result is stated to be consistent.
Experimental example 5, thermogravimetic analysis (TGA) (TGA)
1, experimental method
Using thermogravimetric analyzer (TG 209F1 IRIS, German Nai Chi company) under a dry nitrogen atmosphere to solidified sample
Thermal stability be tested.Gas flow rate is 60 ml/mins, and heating speed is 10 degrees celsius/minutes, and temperature range is
50 to 800 degrees Celsius.
2, experimental result
Test result is as shown in Fig. 6 and table 3, it can be seen from the figure that and HS12-UC2333.03-IPN、HS10-
UC2335.63- IPN is compared, HS14.34-UC2330The thermal stability of-IPN is more preferable.
The TGA test result of each sample of table 3
To sum up, a kind of high-strength epoxy with inierpeneirating network structure-silicon rubber modified material of the present invention polymerize for interpenetrating
Object network structure, when the epoxy resin added in function admirable, especially system is the epoxy resin of graft modification, the mechanics of materials
Performance significantly improves, and intensity, toughness and adhesive property are promoted simultaneously, wherein the promotion of tensile strength clearly, and interpenetrating
Phenomena such as polymer network structure is stablized, and system can keep homogeneous state for a long time, will not be layered, performance is very good,
It can be applied to aerospace, electronic information, the high-temperaure coating of mechanical equipment field, adhesive, casting glue, rubber and soft
Property ablation resistant material matrix etc., has greatly widened the application field of silastic material.
Claims (10)
1. a kind of epoxy-silicon rubber modified material, it is characterised in that: it is prepared by the raw material of following portions by weight:
100.00 parts of silicon rubber, 5.00~15.00 parts of epoxy resin, 10.00~15.00 parts of epoxy hardener, containing hydrogen silicone oil
8.00~20.00 parts, wherein, the epoxy hardener is acid anhydride type curing agent to 0.05~1.00 part of rubber additive.
2. epoxy according to claim 1-silicon rubber modified material, it is characterised in that: the composite material is by following
The raw material of parts by weight is prepared: 100.00 parts of silicon rubber, 10.00 parts of epoxy resin, 13.00 parts of epoxy hardener, hydrogeneous
14.34~15.62 parts of silicone oil, 0.35 part of rubber additive.
3. epoxy according to claim 1 or 2-silicon rubber modified material, it is characterised in that: the epoxy hardener is band
There are the acid anhydride type curing agent of more vinyl structures, preferably tung oil acid anhydride；The containing hydrogen silicone oil is Methyl Hydrogen Polysiloxane Fluid, phenyl contains
The mixture of hydrogen silicone oil or Methyl Hydrogen Polysiloxane Fluid and phenyl hydrogen-containing silicon oil, Methyl Hydrogen Polysiloxane Fluid contains with phenyl in the mixture
The mass ratio of hydrogen silicone oil is preferably (1~4): 1；It is highly preferred that the containing hydrogen silicone oil is Methyl Hydrogen Polysiloxane Fluid.
4. epoxy according to claim 1-3-silicon rubber modified material, it is characterised in that: the epoxy resin
For unmodified epoxy resin or modified epoxy, the wherein structure of modified epoxy are as follows:
Wherein,Respectively remove remaining group after a H atom for bisphenol-A or two terminal hydroxy group of polyalcohol；
m1And m2For the degree of polymerization, m1For 0.18~2.4, m2It is 1~10；
R is C1~C3Alkyl.
5. epoxy according to claim 4-silicon rubber modified material, it is characterised in that: the knot of the modified epoxy
Structure are as follows:
m1、m2, R such as
Described in claim 4.
6. epoxy according to claim 1-5-silicon rubber modified material, it is characterised in that: the rubber addition
Agent is platinum catalyst, the mixture for being catalyzed delayed-action activator and Epoxy curing accelerators；
Preferably, the ratio between parts by weight of the platinum catalyst, catalysis delayed-action activator and Epoxy curing accelerators are 4:1:2.
7. epoxy according to claim 6-silicon rubber modified material, it is characterised in that: the catalysis delayed-action activator is alkynol
Delayed-action activator, preferably -3 crotonylene alcohol of 2- methyl；The Epoxy curing accelerators are DMP-30.
8. epoxy according to claim 1-7-silicon rubber modified material, it is characterised in that: the composite material
For interpenetrating polymer networks structure.
9. a kind of prepare the described in any item epoxies of claim 1-8-silicon rubber modified material method, it is characterised in that: institute
State method the following steps are included:
(1) epoxy resin is added in silicone rubber matrix according to raw material weight number, the heating stirring 0.5- at 90-110 DEG C
2h obtains uniformly mixed sizing material；
(2) containing hydrogen silicone oil, epoxy hardener, rubber additive are added into sizing material obtained by step (1) according to raw material weight number,
0.5-2h is stirred at normal temperature；
(3) after mixing evenly, solidify to get.
10. according to the method described in claim 9, it is characterized by: the epoxy resin is E44；Or the epoxy resin is
Modified epoxy, the modified epoxy are prepared by following methods: by the E44 and methoxybenzene of equimolar metering proportion
Based polysiloxane stirs at 90 DEG C -110 DEG C, in nitrogen atmosphere, adds the catalyst tetraisopropyl titanate of 0.5wt%, instead
After answering 6~8h, stop stirring to get modified epoxy；
And/or in step (3), the condition of cure are as follows: successively 2 small at 2 hours, 140 DEG C at 2 hours, 120 DEG C at 90 DEG C
When, 2 hours at 180 DEG C.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112063117A (en) * | 2020-09-23 | 2020-12-11 | 四川大学 | Ablation-resistant organic silicon modified epoxy resin-based carbon fiber composite material and preparation method thereof |
| CN113968973A (en) * | 2021-12-06 | 2022-01-25 | 四川大学 | Epoxy siloxane, epoxy polysiloxane-silicon rubber compound, preparation method and application thereof |
| CN114058017A (en) * | 2021-12-06 | 2022-02-18 | 四川大学 | Application of epoxy siloxane |
| CN117162543A (en) * | 2023-11-01 | 2023-12-05 | 上海材料研究所有限公司 | Elastic composite material resistant to instantaneous gas flow impact and preparation method and application thereof |
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| CN112063117B (en) * | 2020-09-23 | 2021-10-19 | 四川大学 | Ablation-resistant organic silicon modified epoxy resin-based carbon fiber composite material and preparation method thereof |
| CN113968973A (en) * | 2021-12-06 | 2022-01-25 | 四川大学 | Epoxy siloxane, epoxy polysiloxane-silicon rubber compound, preparation method and application thereof |
| CN114058017A (en) * | 2021-12-06 | 2022-02-18 | 四川大学 | Application of epoxy siloxane |
| CN113968973B (en) * | 2021-12-06 | 2022-11-04 | 四川大学 | Epoxy siloxane, epoxy polysiloxane-silicon rubber compound, preparation method and application thereof |
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| CN117162543A (en) * | 2023-11-01 | 2023-12-05 | 上海材料研究所有限公司 | Elastic composite material resistant to instantaneous gas flow impact and preparation method and application thereof |
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