CN103965583B - A kind of shape memory epoxy resin by using liquid crystal-glass fibre-silicon dioxide composite material and preparation method thereof - Google Patents
A kind of shape memory epoxy resin by using liquid crystal-glass fibre-silicon dioxide composite material and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to matrix material and preparation field thereof, disclose a kind of shape memory epoxy resin by using liquid crystal-glass fibre-silicon dioxide composite material and preparation method thereof.The preparation method of described shape memory epoxy resin by using liquid crystal-glass fibre-silicon dioxide composite material is: be dissolved in acetone by epoxy resin by using liquid crystal and solidifying agent, then the silicon-dioxide added after silane coupling agent surface treatment obtains composite material mixture, gained composite material mixture is poured into reaction solidification in the mould of the glass fibre after being covered with surface treatment, obtain the epoxy resin by using liquid crystal-glass fibre-silicon dioxide composite material with shape-memory properties.Resulting materials has excellent mechanical property and shape-memory properties, can be applicable to the science and technology field such as bio-medical, aerospace.
Description
Technical field
The invention belongs to matrix material and preparation field thereof, be specifically related to a kind of shape memory epoxy resin by using liquid crystal-glass fibre-silicon dioxide composite material and preparation method thereof.
Background technology
The appearance of shape-memory material is the great leap in Materials science history in this century, it discloses the special essence of material inherence, for the innovation of material processing technique and the exploitation of product innovation provide brand-new approach.Since finding Ni-Ti shape memory alloy from 1964, shape-memory material has caused countries in the world to pay close attention to widely and has achieved huge progress.Since the eighties, the shape memory high molecule material of sudden emergence has become a kind of noticeable active material with the over-all properties of its excellence.Compared with shape memory alloy, shape memory high molecule material has that lightweight, corrosion-resistant, easy formed machining, memory recovery temperature wide ranges, deformation quantity are large, insulation and the advantage such as good insulation preformance, low price.Therefore it has potential using value and application prospect widely in a lot of field, be used widely in the fields such as medical treatment, manufacture, packaging, building and AGRICULTURAL ENERGY as steel tubing in different shapes grafting material, surgical operation immobilization material, cushioning material, wrapping material, fire alarm equipment and coating etc. at present and developed, its economic benefit and social effect significantly, are research and develop field the most active in current shape-memory material.
In recent years, mesomorphic unit is incorporated in shape-memory material especially noticeable.The introducing of mesomorphic unit improves the recovery stress of shape-memory polymer, improves reply effect, is expected to obtain potential application in aerospace and bio-medical field.PattrickT.Mather etc. have synthesized a kind of smectic C type liquid crystal elastic body with shape memory effect first.Hiraoka etc. report the twin shaft shape memory effect of the liquid crystal elastic body of single domain chiral smectic phase.At home, Li Deli, Zhou Qifeng etc. have studied the shape memory effect of crust type liquid crystal polymer fibre.Application number be 201110305569.5 Chinese invention patent and application number be 201010203910.1 Chinese invention patent application disclose branched epoxy resin by using liquid crystal and biphenyl type epoxy resin by using liquid crystal and have studied its shape memory effect, its product has better thermomechanical property and shape-memory properties, but shape-memory material of the prior art can not meet the requirement of cost and performance simultaneously.
Summary of the invention
In order to solve the shortcoming and defect part of prior art, primary and foremost purpose of the present invention is the preparation method providing a kind of shape memory epoxy resin by using liquid crystal-glass fibre-silicon dioxide composite material.
Another object of the present invention is to provide a kind of shape memory epoxy resin by using liquid crystal-glass fibre-silicon dioxide composite material prepared by above-mentioned preparation method.
The object of the invention is achieved through the following technical solutions:
A preparation method for shape memory epoxy resin by using liquid crystal-glass fibre-silicon dioxide composite material, concrete operation step is as follows:
(1) silicon-dioxide and fiberglass surfacing process: get dried silicon-dioxide and anhydrous propanone mixing, under ultrasonic state, dropwise add the acetone soln (solubility of acetone soln is for making silicon-dioxide dispersed) of silane coupling agent, suction filtration after the ultrasonic 30min of solution, be placed in vacuum drying oven to dry, obtain the silicon-dioxide after surface treatment; Get glass fibre washing by soaking 24h in acetone soln (herein acetone soln energy submergence glasscloth), take out room temperature and dry, obtain the glass fibre after surface treatment;
(2) composite material mixture preparation: epoxy resin by using liquid crystal and solidifying agent are dissolved in acetone (herein acetone its epoxy resin by using liquid crystal and solidifying agent can be made to dissolve and silicon-dioxide dispersed), obtain mixed solution, add the silicon-dioxide after surface treatment in step (1) again, ultrasonic vibration makes silicon-dioxide dispersed in mixed solution, obtains composite material mixture;
(3) curing molding: the composite material mixture that step (2) obtains is poured in the mould of the glass fibre in the step (1) being covered with size and mating with die size after surface treatment, 30min is flooded under normal temperature, vacuum extracts solvent, die sinking after solidification, obtains shape memory epoxy resin by using liquid crystal-glass fibre-silicon dioxide composite material.
Described in step (1), silicon-dioxide preferable particle size is 20nm, and purity is the nano silicon of 99.9%; The preferred γ-aminopropyl triethoxysilane of described silane coupling agent (KH550), at least one in γ-(2,3-glycidoxy) propyl trimethoxy silicane (KH560) or γ-(methacryloxypropyl) propyl trimethoxy silicane (KH570); Described glass fibre preferred thickness is 0.1mm, and grammes per square metre is 300g/m
2alkali-free glass fiber cloth.
Described in step (1), the add-on of silane coupling agent is 0.5% ~ 1% of silicon-dioxide quality.
Described in step (2), epoxy resin by using liquid crystal preferably has the branched epoxy resin by using liquid crystal shown in formula 1,
Formula 1
Wherein, n is the integer of 1 ~ 12.
The preferred amine curing agent of solidifying agent described in step (2), more preferably, described amine curing agent is 4,4-diaminodiphenyl-methane (DDM), 4-aminophenyiamino sulfone (SAA), 4, at least one in 4-diaminodiphenyl oxide (DDE), 4,4-diamino-phenyl sulfoxides (DDS), methylresorcinol diamines (DAT) or quadrol.
Described in step (2), the mol ratio of epoxy resin by using liquid crystal and solidifying agent add-on is preferably 2:1.
The add-on of the silicon-dioxide after surface treatment described in step (2) is preferably 1% ~ 3% of the silicon-dioxide total mass after epoxy resin by using liquid crystal, solidifying agent and surface treatment.
The paving of glass fibre described in step (3) enter amount be preferably epoxy resin by using liquid crystal, solidifying agent, surface treatment after silicon-dioxide and spread into glass fibre total mass 20% ~ 40%.
Step (3) described solidification is solidification 12 ~ 16h under the condition of 5 ~ 10 DEG C more than epoxy resin by using liquid crystal fusing point preferably, then at 150 ~ 170 DEG C, solidifies 5 ~ 7h, finally at 200 DEG C, solidifies 1h.
A kind of shape memory epoxy resin by using liquid crystal-glass fibre-silicon dioxide composite material, obtains prepared by above-mentioned preparation method.
Principle of the present invention is: by adding glass fibre and nano silicon to strengthen the thermomechanical property of epoxy resin by using liquid crystal, by the surface treatment of silicon-dioxide, the interface cohesive force of glasscloth, silicon-dioxide and epoxy resin by using liquid crystal can be improved, make matrix material have better thermomechanical property and shape-memory properties.
Had the following advantages and beneficial effect by preparation method of the present invention and the product tool that obtains:
(1) the present invention uses glass fibre and nano-silicon dioxide modified epoxy resin by using liquid crystal, improves the thermomechanical property of material while reducing costs;
(2) the present invention carries out surface treatment to silicon-dioxide, be beneficial to the dispersion of silicon-dioxide in composite material mixture, surface-treated silicon-dioxide is incorporated in the matrix material of epoxy resin by using liquid crystal-glass fibre, improve the interface cohesive force of epoxy resin by using liquid crystal and glasscloth, make matrices of composite material have very strong interface cohesive force, the composite property obtained is excellent;
(3) composite material of shape memory that prepared by the present invention has high shape fixed rate and deformation-recovery rate, can be applied to the science and technology field such as bio-medical, aerospace.
Accompanying drawing explanation
In Fig. 1, LCE6 is the cross-section morphology figure of common liquid crystals epoxy resin; LEC6 GF be the cross-section morphology figure of comparative example 1 epoxy resin by using liquid crystal-glass fiber compound material; LEC6 GF SiO
2for the cross-section morphology figure of embodiment 2 epoxy resin by using liquid crystal-glass fibre-silicon dioxide composite material; LEC2 GF SiO
2for the cross-section morphology figure of embodiment 3 epoxy resin by using liquid crystal-glass fibre-silicon dioxide composite material; LEC10 GF SiO
2for the cross-section morphology figure of embodiment 4 epoxy resin by using liquid crystal-glass fibre-silicon dioxide composite material.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Comparative example 1
(1) fiberglass surfacing process: getting thickness is 0.1mm, and grammes per square metre is 300g/m
2alkali-free glass fiber cloth washing by soaking 24h in acetone soln, take out room temperature dry, obtain the glasscloth after surface treatment;
(2) composite material mixture preparation: the epoxy resin by using liquid crystal 5.99g shown in formula 2 that to take mol ratio be 2:1 and solidifying agent DDM1.01g, dissolves, obtains composite material mixture in 20ml acetone,
Formula 2
Wherein, n=6;
(3) curing molding: the composite material mixture that step (2) obtains is poured into be covered with 3g size be 10cm*10cm step (1) process after glasscloth mould in, 30min is flooded under normal temperature, vacuum extracts solvent, successively at 75 DEG C (more than epoxy resin by using liquid crystal fusing point shown in formula 25 DEG C) solidification 16h, 160 DEG C of solidification 6h, 200 DEG C of solidification 1h, die sinking, obtains epoxy resin by using liquid crystal-glass fiber compound material.
Embodiment 2
(1) silicon-dioxide and fiberglass surfacing process: getting dried particle diameter is 20nm, purity is that nano silicon 10g, 100ml anhydrous propanone of 99.9% is in beaker, under ultrasonic state, drip the acetone soln containing 1g silane coupling agent KH570 gradually, after ultrasonic 30min, suction filtration, is placed in vacuum drying oven and dries, and obtains the silicon-dioxide after surface treatment; Getting thickness is 0.1mm, and grammes per square metre is 300g/m
2alkali-free glass fiber cloth washing by soaking 24h in acetone soln, take out room temperature dry, obtain the glass fibre after surface treatment;
(2) composite material mixture preparation: the epoxy resin by using liquid crystal 5.81g shown in formula 2 that to take mol ratio be 2:1 and solidifying agent DDM0.98g, dissolve in 20ml acetone, obtain mixed solution, add the nano silicon 0.21g after step (1) process again, ultrasonic vibration 30min, make silicon-dioxide dispersed in mixed solution, obtain composite material mixture;
Formula 2
Wherein, n=6;
(3) curing molding: the composite material mixture that step (2) obtains is poured into and is covered with 3g, in the mould of the glass fibre after 10cm*10cm step (1) process, 30min is flooded under normal temperature, vacuum extracts solvent, successively at 75 DEG C (more than epoxy resin by using liquid crystal fusing point shown in formula 25 DEG C) solidification 16h, 160 DEG C of solidification 6h, 200 DEG C of solidification 1h, die sinking, obtains epoxy resin by using liquid crystal-glass fibre-silicon dioxide composite material.
Embodiment 3
(1) silicon-dioxide and fiberglass surfacing process: getting dried particle diameter is 20nm, purity is that nano silicon 10g, 100ml anhydrous propanone of 99.9% is in beaker, under ultrasonic state, drip the acetone soln containing 1g silane coupling agent KH570 gradually, after ultrasonic 30min, suction filtration, is placed in vacuum drying oven and dries, and obtains the silicon-dioxide after surface treatment; Getting thickness is 0.1mm, and grammes per square metre is 300g/m
2alkali-free glass fiber cloth washing by soaking 24h in acetone soln, take out room temperature dry, obtain the glass fibre after surface treatment;
(2) composite material mixture preparation: the epoxy resin by using liquid crystal 5.73g shown in formula 3 that to take mol ratio be 2:1 and solidifying agent DDM1.06g, dissolve in 20ml acetone, obtain mixed solution, add the nano silicon 0.21g after step (1) process again, ultrasonic vibration 30min, make silicon-dioxide dispersed in mixed solution, obtain composite material mixture;
Formula 3
Wherein, n=2;
(3) curing molding: the composite material mixture that step (2) obtains is poured into and is covered with 3g, in the mould of the glass fibre after 10cm*10cm step (1) process, 30min is flooded under normal temperature, vacuum extracts solvent, successively at 115 DEG C (more than epoxy resin by using liquid crystal fusing point shown in formula 35 DEG C) solidification 16h, 160 DEG C of solidification 6h, 200 DEG C of solidification 1h, die sinking, obtains epoxy resin by using liquid crystal-glass fibre-silicon dioxide composite material.
Embodiment 4
(1) silicon-dioxide and fiberglass surfacing process: getting dried particle diameter is 20nm, purity is that nano silicon 10g, 100ml anhydrous propanone of 99.9% is in beaker, under ultrasonic state, drip the acetone soln containing 1g silane coupling agent KH570 gradually, after ultrasonic 30min, suction filtration, is placed in vacuum drying oven and dries, and obtains the silicon-dioxide after surface treatment; Getting thickness is 0.1mm, and grammes per square metre is 300g/m
2alkali-free glass fiber cloth washing by soaking 24h in acetone soln, take out room temperature dry, obtain the glass fibre after surface treatment;
(2) composite material mixture preparation: the epoxy resin by using liquid crystal 5.89g shown in formula 4 that to take mol ratio be 2:1 and solidifying agent DDM0.9g, dissolve in 20ml acetone, obtain mixed solution, add the nano silicon 0.21g after step (1) process again, ultrasonic vibration 30min, make silicon-dioxide dispersed in mixed solution, obtain composite material mixture;
Formula 4
Wherein, n=10;
(3) curing molding: the composite material mixture that step (2) obtains is poured into and is covered with 3g, in the mould of the glass fibre after 10cm*10cm step (1) process, 30min is flooded under normal temperature, vacuum extracts solvent, successively at 55 DEG C (more than epoxy resin by using liquid crystal fusing point shown in formula 45 DEG C) solidification 16h, 160 DEG C of solidification 6h, 200 DEG C of solidification 1h, die sinking, obtains epoxy resin by using liquid crystal-glass fibre-silicon dioxide composite material.
Embodiment 5
(1) silicon-dioxide and fiberglass surfacing process: getting dried particle diameter is 20nm, purity is that nano silicon 10g, 100ml anhydrous propanone of 99.9% is in beaker, under ultrasonic state, drip the acetone soln containing 0.8g silane coupling agent KH560 gradually, after ultrasonic 30min, suction filtration, is placed in vacuum drying oven and dries, and obtains the silicon-dioxide after surface treatment; Getting thickness is 0.1mm, and grammes per square metre is 300g/m
2alkali-free glass fiber cloth washing by soaking 24h in acetone soln, take out room temperature dry, obtain the glass fibre after surface treatment;
(2) composite material mixture preparation: the epoxy resin by using liquid crystal 6.16g shown in formula 5 that to take mol ratio be 2:1 and solidifying agent SAA0.70g, dissolve in 20ml acetone, obtain mixed solution, add the nano silicon 0.14g after step (1) process again, ultrasonic vibration 30min, make silicon-dioxide dispersed in mixed solution, obtain composite material mixture;
Formula 5
Wherein, n=12;
(3) curing molding: the composite material mixture that step (2) obtains is poured into and is covered with 3g, in the mould of the glass fibre after 10cm*10cm step (1) process, 30min is flooded under normal temperature, vacuum extracts solvent, successively at 45 DEG C (more than epoxy resin by using liquid crystal fusing point shown in formula 55 DEG C) solidification 16h, 150 DEG C of solidification 7h, 200 DEG C of solidification 1h, die sinking, obtains epoxy resin by using liquid crystal-glass fibre-silicon dioxide composite material.
Embodiment 6
(1) silicon-dioxide and fiberglass surfacing process: getting dried particle diameter is 20nm, purity is that nano silicon 10g, 100ml anhydrous propanone of 99.9% is in beaker, under ultrasonic state, drip the acetone soln containing 0.5g Silane coupling agent KH550 gradually, after ultrasonic 30min, suction filtration, is placed in vacuum drying oven and dries, and obtains the silicon-dioxide after surface treatment; Getting thickness is 0.1mm, and grammes per square metre is 300g/m
2alkali-free glass fiber cloth washing by soaking 24h in acetone soln, take out room temperature dry, obtain the glass fibre after surface treatment;
(2) composite material mixture preparation: the epoxy resin by using liquid crystal 5.86g shown in formula 4 that to take mol ratio be 2:1 and solidifying agent 4,4-diaminodiphenyl oxide (DDE) 1.07g, dissolve in 20ml acetone, obtain mixed solution, add the nano silicon 0.07g after step (1) process again, ultrasonic vibration 30min, makes silicon-dioxide dispersed in mixed solution, obtains composite material mixture;
Formula 4
Wherein, n=10;
(3) curing molding: the composite material mixture that step (2) obtains is poured into and is covered with 2g, in the mould of the glass fibre after 10cm*10cm step (1) process, 30min is flooded under normal temperature, vacuum extracts solvent, successively at 55 DEG C (more than epoxy resin by using liquid crystal fusing point shown in formula 45 DEG C) solidification 16h, 170 DEG C of solidification 5h, 200 DEG C of solidification 1h, die sinking, obtains epoxy resin by using liquid crystal-glass fibre-silicon dioxide composite material.
Embodiment 7
(1) silicon-dioxide and fiberglass surfacing process: getting dried particle diameter is 20nm, purity is that nano silicon 10g, 100ml anhydrous propanone of 99.9% is in beaker, under ultrasonic state, drip the acetone soln containing 1g Silane coupling agent KH550 gradually, after ultrasonic 30min, suction filtration, is placed in vacuum drying oven and dries, and obtains the silicon-dioxide after surface treatment; Getting thickness is 0.1mm, and grammes per square metre is 300g/m
2alkali-free glass fiber cloth washing by soaking 24h in acetone soln, take out room temperature dry, obtain the glass fibre after surface treatment;
(2) composite material mixture preparation: the epoxy resin by using liquid crystal 5.81g shown in formula 3 that to take mol ratio be 2:1 and solidifying agent 4,4-diamino-phenyl sulfoxide (DDS) 1.12g, dissolve in 20ml acetone, obtain mixed solution, add the nano silicon 0.07g after step (1) process again, ultrasonic vibration 30min, makes silicon-dioxide dispersed in mixed solution, obtains composite material mixture;
Formula 4
Wherein, n=10;
(3) curing molding: the composite material mixture that step (2) obtains is poured into and is covered with 4g, in the mould of the glass fibre after 10cm*10cm step (1) process, 30min is flooded under normal temperature, vacuum extracts solvent, successively at 60 DEG C (more than epoxy resin by using liquid crystal fusing point shown in formula 4 10 DEG C) solidification 16h, 170 DEG C of solidification 5h, 200 DEG C of solidification 1h, die sinking, obtains epoxy resin by using liquid crystal-glass fibre-silicon dioxide composite material.
Embodiment 8
(1) silicon-dioxide and fiberglass surfacing process: getting dried particle diameter is 20nm, purity is that nano silicon 10g, 100ml anhydrous propanone of 99.9% is in beaker, under ultrasonic state, drip the acetone soln containing 1g silane coupling agent KH570 gradually, after ultrasonic 30min, suction filtration, is placed in vacuum drying oven and dries, and obtains the silicon-dioxide after surface treatment; Getting thickness is 0.1mm, and grammes per square metre is 300g/m
2alkali-free glass fiber cloth washing by soaking 24h in acetone soln, take out room temperature dry, obtain the glass fibre after surface treatment;
(2) composite material mixture preparation: the epoxy resin by using liquid crystal 6.33g shown in formula 3 that to take mol ratio be 2:1 and solidifying agent methylresorcinol diamines (DAT) 0.6g, dissolve in 20ml acetone, obtain mixed solution, add the nano silicon 0.07g after step (1) process again, ultrasonic vibration 30min, make silicon-dioxide dispersed in mixed solution, obtain composite material mixture;
Formula 4
Wherein, n=10;
(3) curing molding: the composite material mixture that step (2) obtains is poured into and is covered with 3g, in the mould of the glass fibre after 10cm*10cm step (1) process, 30min is flooded under normal temperature, vacuum extracts solvent, successively at 58 DEG C (more than epoxy resin by using liquid crystal fusing point shown in formula 48 DEG C) solidification 16h, 170 DEG C of solidification 5h, 200 DEG C of solidification 1h, die sinking, obtains epoxy resin by using liquid crystal-glass fibre-silicon dioxide composite material.
Embodiment 9
(1) silicon-dioxide and fiberglass surfacing process: getting dried particle diameter is 20nm, purity is that nano silicon 10g, 100ml anhydrous propanone of 99.9% is in beaker, under ultrasonic state, drip the acetone soln containing 1g silane coupling agent KH570 gradually, after ultrasonic 30min, suction filtration, is placed in vacuum drying oven and dries, and obtains the silicon-dioxide after surface treatment; Getting thickness is 0.1mm, and grammes per square metre is 300g/m
2alkali-free glass fiber cloth washing by soaking 24h in acetone soln, take out room temperature dry, obtain the glass fibre after surface treatment;
(2) composite material mixture preparation: the epoxy resin by using liquid crystal 6.61g shown in formula 3 that to take mol ratio be 2:1 and curing agent ethylene diamine 0.32g, dissolve in 20ml acetone, obtain mixed solution, add the nano silicon 0.07g after step (1) process again, ultrasonic vibration 30min, make silicon-dioxide dispersed in mixed solution, obtain composite material mixture;
Formula 4
Wherein, n=10;
(3) curing molding: the composite material mixture that step (2) obtains is poured into and is covered with 3g, in the mould of the glass fibre after 10cm*10cm step (1) process, 30min is flooded under normal temperature, vacuum extracts solvent, successively at 55 DEG C (more than epoxy resin by using liquid crystal fusing point shown in formula 45 DEG C) solidification 16h, 170 DEG C of solidification 5h, 200 DEG C of solidification 1h, die sinking, obtains epoxy resin by using liquid crystal-glass fibre-silicon dioxide composite material.
Carry out mechanical property, shape-memory properties analysis to the product of embodiment 2,3,4, and contrast with the product not adding glass fibre and silica modified common liquid crystals epoxy resin and comparative example 1, contrast test result is respectively as shown in table 1, table 2.Can be learnt by result in table, product epoxy resin by using liquid crystal-glass fibre-silicon dioxide composite material of the present invention has obvious lifting than common epoxy resin by using liquid crystal in mechanical property, and shape-memory properties does not reduce.
Carry out cross-section morphology analysis to the product of embodiment 2,3,4, and contrast with the product not adding glass fibre and silica modified common liquid crystals epoxy resin and comparative example 1, contrast test result as shown in Figure 1.Can be found out by result in figure, product epoxy resin by using liquid crystal-glass fibre-silicon dioxide composite material of the present invention has compared better bonding interface effect with comparative example.
Testing method
Mechanical Property Analysis: Dynamic thermo-mechanical property analysis (NETZSCH5) stretch mode, temperature rise rate 5 DEG C/min, temperature range-120 DEG C ~ 250 DEG C, frequency 2Hz, amplitude 30 μm, dynamic force 5N, static force 0.5N.
Shape-memory properties is analyzed: by embodiment product and comparative sample respectively at the temperature higher than its second-order transition temperature 20 DEG C (Tg+20 DEG C) be deformed into annular, quenching is to room temperature, then in silicone oil, allow the batten of distortion reply, adopt the relation of SONYILCE-5000L digital camera real time record distortion-time, adopt two-dimensional measurement computed in software curvature and the relation of time.
Cross-section morphology is analyzed: adopt PhilipsXL30 type scanning electron microscope (SEM), it is high that the batten after tension fracture is cut into 2mm, then adheres on the conductive resin in sample table, and plasma sputtering metal spraying is to increase conductive capability.
Test result
Table 1
Table 2
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. a preparation method for shape memory epoxy resin by using liquid crystal-glass fibre-silicon dioxide composite material, is characterized in that: concrete operation step is as follows:
(1) silicon-dioxide and fiberglass surfacing process: get dried silicon-dioxide and anhydrous propanone mixing, under ultrasonic state, dropwise add the acetone soln of silane coupling agent, suction filtration after the ultrasonic 30min of solution, be placed in vacuum drying oven to dry, obtain the silicon-dioxide after surface treatment; Get glass fibre washing by soaking 24h in acetone soln, take out room temperature and dry, obtain the glass fibre after surface treatment;
(2) composite material mixture preparation: epoxy resin by using liquid crystal and solidifying agent are dissolved in acetone, obtain mixed solution, add the silicon-dioxide after surface treatment in step (1) again, ultrasonic vibration makes silicon-dioxide dispersed in mixed solution, obtains composite material mixture;
(3) curing molding: the composite material mixture that step (2) obtains is poured in the mould of the glass fibre in the step (1) being covered with size and mating with die size after surface treatment, 30min is flooded under normal temperature, vacuum extracts solvent, die sinking after solidification, obtains shape memory epoxy resin by using liquid crystal-glass fibre-silicon dioxide composite material.
2. the preparation method of a kind of shape memory epoxy resin by using liquid crystal-glass fibre-silicon dioxide composite material according to claim 1, it is characterized in that: silicon-dioxide described in step (1) refers to that particle diameter is 20nm, and purity is the nano silicon of 99.9%; Described silane coupling agent is at least one in γ-aminopropyl triethoxysilane, γ-(2,3-glycidoxy) propyl trimethoxy silicane or γ-(methacryloxypropyl) propyl trimethoxy silicane; Described glass fibre refers to that thickness is 0.1mm, and grammes per square metre is 300g/m
2alkali-free glass fiber cloth.
3. the preparation method of a kind of shape memory epoxy resin by using liquid crystal-glass fibre-silicon dioxide composite material according to claim 1, is characterized in that: described in step (1), the add-on of silane coupling agent is 0.5% ~ 1% of silicon-dioxide quality.
4. the preparation method of a kind of shape memory epoxy resin by using liquid crystal-glass fibre-silicon dioxide composite material according to claim 1, it is characterized in that: described in step (2), epoxy resin by using liquid crystal refers to the branched epoxy resin by using liquid crystal had shown in formula 1
Wherein, n is the integer of 1 ~ 12; Described solidifying agent is amine curing agent.
5. the preparation method of a kind of shape memory epoxy resin by using liquid crystal-glass fibre-silicon dioxide composite material according to claim 4, it is characterized in that: described amine curing agent is 4, at least one in 4'-diaminodiphenyl-methane, 4,4'-diaminodiphenyl oxides, methylresorcinol diamines or quadrol.
6. the preparation method of a kind of shape memory epoxy resin by using liquid crystal-glass fibre-silicon dioxide composite material according to claim 1, is characterized in that: described in step (2), the mol ratio of epoxy resin by using liquid crystal and solidifying agent add-on is 2:1.
7. the preparation method of a kind of shape memory epoxy resin by using liquid crystal-glass fibre-silicon dioxide composite material according to claim 1, is characterized in that: the add-on of the silicon-dioxide after surface treatment described in step (2) is 1% ~ 3% of the silicon-dioxide total mass after epoxy resin by using liquid crystal, solidifying agent and surface treatment.
8. the preparation method of a kind of shape memory epoxy resin by using liquid crystal-glass fibre-silicon dioxide composite material according to claim 1, is characterized in that: the paving of glass fibre described in step (3) enter amount be silicon-dioxide after epoxy resin by using liquid crystal, solidifying agent, surface treatment and spread into glass fibre total mass 20% ~ 40%.
9. the preparation method of a kind of shape memory epoxy resin by using liquid crystal-glass fibre-silicon dioxide composite material according to claim 1, it is characterized in that: solidification described in step (3) solidifies 12 ~ 16h under referring to the condition of 5 ~ 10 DEG C more than epoxy resin by using liquid crystal fusing point, then at 150 ~ 170 DEG C, solidify 5 ~ 7h, finally at 200 DEG C, solidify 1h.
10. shape memory epoxy resin by using liquid crystal-glass fibre-silicon dioxide composite material, obtains prepared by the preparation method described in any one of claim 1 ~ 9.
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| CN105885090A (en) * | 2016-04-26 | 2016-08-24 | 哈尔滨工程大学 | Method for enhancing interfacial properties of SMA (styrene maleic anhydride) reinforced resin intelligent composite materials |
| CN110938284A (en) * | 2018-09-21 | 2020-03-31 | 广西大学 | Preparation method of bagasse fiber epoxy resin composite material coated with nanoparticles |
| CN113172793A (en) * | 2020-06-22 | 2021-07-27 | 中国石化集团胜利石油管理局有限公司电力分公司 | Carbon-glass hybrid composite material curing process |
| CN113563693B (en) * | 2021-06-25 | 2024-03-29 | 中科院广州化学有限公司 | Liquid crystal epoxy resin-mesoporous silica composite material, preparation method and application |
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| CN101195701A (en) * | 2007-11-09 | 2008-06-11 | 中国科学院广州化学研究所 | Epoxy resin shape memory polymer material and method for producing the same |
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| CN103602042A (en) * | 2013-10-31 | 2014-02-26 | 中科院广州化学有限公司 | Liquid crystal epoxy resin - carbon fiber composite material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101195701A (en) * | 2007-11-09 | 2008-06-11 | 中国科学院广州化学研究所 | Epoxy resin shape memory polymer material and method for producing the same |
| CN102504202A (en) * | 2011-10-10 | 2012-06-20 | 中科院广州化学有限公司 | Liquid crystal epoxy resin with shape memory effect and preparation method and application thereof |
| CN103602042A (en) * | 2013-10-31 | 2014-02-26 | 中科院广州化学有限公司 | Liquid crystal epoxy resin - carbon fiber composite material and preparation method thereof |
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