CN103965583A - Shape memorizing liquid crystal epoxy resin-glass fiber-silicon dioxide composite and preparation method thereof - Google Patents
Shape memorizing liquid crystal epoxy resin-glass fiber-silicon dioxide composite and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to composites and the field of composite preparation, and discloses a shape memorizing liquid crystal epoxy resin-glass fiber-silicon dioxide composite and a preparation method thereof. The preparation method comprises the following steps: dissolving liquid crystal epoxy resin and a curing agent into acetone, then adding silicon dioxide subjected to surface treatment by a silane coupling agent so as to obtain a composite mixed liquid, and pouring the obtained composite mixed liquid into a mould laid with glass fiber subjected to surface treatment to be reacted and cured so as to obtain the liquid crystal epoxy resin-glass fiber-silicon dioxide composite with the shape memorizing performance. The obtained material has excellent mechanical performance and shape memorizing performance, and can be applied to the fields of science and technology such as biomedicine and 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, and it has disclosed the special essence of material inherence, for the innovation of material processing technique and the exploitation of product innovation provide brand-new approach.Since 1964 find Ni-Ti shape memory alloy, shape-memory material has caused that countries in the world pay close attention to and obtained huge progress widely.Since the eighties, the shape memory high molecule material of sudden emergence has become a kind of noticeable active material with its excellent over-all properties.Compared with shape memory alloy, the advantages such as lightweight, corrosion-resistant, easy shaping that shape memory high molecule material has processing, memory recovery temperature wide ranges, deformation quantity are large, insulation and good insulation preformance, low price.Therefore it has potential using value and application prospect widely in a lot of fields, be used widely and develop 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, its economic benefit and social effect are remarkable, are the most active fields of research and development in current shape-memory material.
In recent years, mesomorphic unit is incorporated in shape-memory material especially noticeable.The introducing of mesomorphic unit has improved the recovery stress of shape-memory polymer, has improved reply effect, is expected to obtain potential application in aerospace and bio-medical field.Pattrick T.Mather etc. has synthesized a kind of nearly crystal C type liquid crystal elastic body with shape memory effect first.Hiraoka etc. have reported 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 is that the Chinese invention patent application that 201110305569.5 Chinese invention patent and application number are 201010203910.1 discloses branched epoxy resin by using liquid crystal and biphenyl type epoxy resin by using liquid crystal and 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 to provide a kind of preparation method 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 being 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 processing: get the silicon-dioxide and the anhydrous propanone that were dried and mix, 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 and dry, obtain the silicon-dioxide after surface treatment; Get glass fibre washing by soaking 24h in acetone soln (acetone soln energy submergence glasscloth herein), take out room temperature and dry, obtain the glass fibre after surface treatment;
(2) matrix material mixed solution preparation: epoxy resin by using liquid crystal and solidifying agent are dissolved in to (it is dispersed that acetone can make its epoxy resin by using liquid crystal and solidifying agent dissolving and silicon-dioxide) in acetone herein, obtain mixed solution, add again the silicon-dioxide after surface treatment in step (1), ultrasonic vibration makes silicon-dioxide dispersed in mixed solution, obtains matrix material mixed solution;
(3) curing molding: the matrix material mixed solution that step (2) is obtained is poured in the mould that is covered with the glass fibre after surface treatment in big or small step (1) of mating with die size, under normal temperature, flood 30min, vacuum extracts solvent, die sinking after solidifying, 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, the nano silicon that purity is 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, the integer that n is 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), the amino sulfone of 4-aminophenyl (SAA), 4,4-diaminodiphenyl oxide (DDE), 4, at least one in 4-diamino-phenyl sulfoxide (DDS), methyl mphenylenediamine (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 described in step (2) after surface treatment is preferably 1%～3% of 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 the silicon-dioxide after epoxy resin by using liquid crystal, solidifying agent, surface treatment and spread into glass fibre total mass 20%～40%.
Described the solidifying of step (3) preferably solidified 12～16h more than epoxy resin by using liquid crystal fusing point under the condition of 5～10 DEG C, then at 150～170 DEG C, solidify 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 by above-mentioned preparation method is prepared.
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, can improve the interface cohesive force of glasscloth, silicon-dioxide and epoxy resin by using liquid crystal, make matrix material there is better thermomechanical property and shape-memory properties.
Have 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 in reducing costs;
(2) the present invention carries out surface treatment to silicon-dioxide, be beneficial to the dispersion of silicon-dioxide in matrix material mixed solution, 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 obtaining is good;
(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.
Brief description of the drawings
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 to this.
Comparative example 1
(1) fiberglass surfacing processing: 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) matrix material mixed solution preparation: take mol ratio and be epoxy resin by using liquid crystal 5.99g and the solidifying agent DDM1.01g shown in the formula 2 of 2:1, in 20ml acetone, dissolve, obtain matrix material mixed solution,
Formula 2
Wherein, n=6;
(3) curing molding: the matrix material mixed solution that step (2) is obtained is poured into and is covered with in the mould of 3g size for 10cm*10cm step (1) glasscloth after treatment, under normal temperature, flood 30min, vacuum extracts solvent, solidify 16h 75 DEG C (shown in formulas 2 more than epoxy resin by using liquid crystal fusing point 5 DEG C) successively, 160 DEG C of curing 6h, 200 DEG C of curing 1h, die sinking, obtains epoxy resin by using liquid crystal-glass fiber compound material.
Embodiment 2
(1) silicon-dioxide and fiberglass surfacing processing: getting the particle diameter being dried is 20nm, purity is that 99.9% nano silicon 10g, 100ml anhydrous propanone are in beaker, under ultrasonic state, drip gradually the acetone soln containing 1g silane coupling agent KH570, 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) matrix material mixed solution preparation: take mol ratio and be epoxy resin by using liquid crystal 5.81g and the solidifying agent DDM0.98g shown in the formula 2 of 2:1, in 20ml acetone, dissolve, obtain mixed solution, add again step (1) nano silicon 0.21g after treatment, ultrasonic vibration 30min, make silicon-dioxide dispersed in mixed solution, obtain matrix material mixed solution;
Formula 2
Wherein, n=6;
(3) curing molding: the matrix material mixed solution that step (2) is obtained is poured into and is covered with 3g, in the mould of 10cm*10cm step (1) glass fibre after treatment, under normal temperature, flood 30min, vacuum extracts solvent, solidify 16h, 160 DEG C of curing 6h, 200 DEG C of curing 1h 75 DEG C (shown in formulas 2 more than epoxy resin by using liquid crystal fusing point 5 DEG C) successively, die sinking, obtains epoxy resin by using liquid crystal-glass fibre-silicon dioxide composite material.
Embodiment 3
(1) silicon-dioxide and fiberglass surfacing processing: getting the particle diameter being dried is 20nm, purity is that 99.9% nano silicon 10g, 100ml anhydrous propanone are in beaker, under ultrasonic state, drip gradually the acetone soln containing 1g silane coupling agent KH570, 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) matrix material mixed solution preparation: take mol ratio and be epoxy resin by using liquid crystal 5.73g and the solidifying agent DDM1.06g shown in the formula 3 of 2:1, in 20ml acetone, dissolve, obtain mixed solution, add again step (1) nano silicon 0.21g after treatment, ultrasonic vibration 30min, make silicon-dioxide dispersed in mixed solution, obtain matrix material mixed solution;
Formula 3
Wherein, n=2;
(3) curing molding: the matrix material mixed solution that step (2) is obtained is poured into and is covered with 3g, in the mould of 10cm*10cm step (1) glass fibre after treatment, under normal temperature, flood 30min, vacuum extracts solvent, solidify 16h, 160 DEG C of curing 6h, 200 DEG C of curing 1h 115 DEG C (shown in formulas 3 more than epoxy resin by using liquid crystal fusing point 5 DEG C) successively, die sinking, obtains epoxy resin by using liquid crystal-glass fibre-silicon dioxide composite material.
Embodiment 4
(1) silicon-dioxide and fiberglass surfacing processing: getting the particle diameter being dried is 20nm, purity is that 99.9% nano silicon 10g, 100ml anhydrous propanone are in beaker, under ultrasonic state, drip gradually the acetone soln containing 1g silane coupling agent KH570, 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) matrix material mixed solution preparation: take mol ratio and be epoxy resin by using liquid crystal 5.89g and the solidifying agent DDM0.9g shown in the formula 4 of 2:1, in 20ml acetone, dissolve, obtain mixed solution, add again step (1) nano silicon 0.21g after treatment, ultrasonic vibration 30min, make silicon-dioxide dispersed in mixed solution, obtain matrix material mixed solution;
Formula 4
Wherein, n=10;
(3) curing molding: the matrix material mixed solution that step (2) is obtained is poured into and is covered with 3g, in the mould of 10cm*10cm step (1) glass fibre after treatment, under normal temperature, flood 30min, vacuum extracts solvent, solidify 16h, 160 DEG C of curing 6h, 200 DEG C of curing 1h 55 DEG C (shown in formulas 4 more than epoxy resin by using liquid crystal fusing point 5 DEG C) successively, die sinking, obtains epoxy resin by using liquid crystal-glass fibre-silicon dioxide composite material.
Embodiment 5
(1) silicon-dioxide and fiberglass surfacing processing: getting the particle diameter being dried is 20nm, purity is that 99.9% nano silicon 10g, 100ml anhydrous propanone are in beaker, under ultrasonic state, drip gradually the acetone soln containing 0.8g silane coupling agent KH560, 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) matrix material mixed solution preparation: take mol ratio and be epoxy resin by using liquid crystal 6.16g and the solidifying agent SAA0.70g shown in the formula 5 of 2:1, in 20ml acetone, dissolve, obtain mixed solution, add again step (1) nano silicon 0.14g after treatment, ultrasonic vibration 30min, make silicon-dioxide dispersed in mixed solution, obtain matrix material mixed solution;
Formula 5
Wherein, n=12;
(3) curing molding: the matrix material mixed solution that step (2) is obtained is poured into and is covered with 3g, in the mould of 10cm*10cm step (1) glass fibre after treatment, under normal temperature, flood 30min, vacuum extracts solvent, solidify 16h, 150 DEG C of curing 7h, 200 DEG C of curing 1h 45 DEG C (shown in formulas 5 more than epoxy resin by using liquid crystal fusing point 5 DEG C) successively, die sinking, obtains epoxy resin by using liquid crystal-glass fibre-silicon dioxide composite material.
Embodiment 6
(1) silicon-dioxide and fiberglass surfacing processing: getting the particle diameter being dried is 20nm, purity is that 99.9% nano silicon 10g, 100ml anhydrous propanone are in beaker, under ultrasonic state, drip gradually the acetone soln containing 0.5g Silane coupling agent KH550, 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) matrix material mixed solution preparation: take mol ratio and be epoxy resin by using liquid crystal 5.86g and the solidifying agent 4 shown in the formula 4 of 2:1,4-diaminodiphenyl oxide (DDE) 1.07g, in 20ml acetone, dissolve, obtain mixed solution, add again step (1) nano silicon 0.07g after treatment, ultrasonic vibration 30min, makes silicon-dioxide dispersed in mixed solution, obtains matrix material mixed solution;
Formula 4
Wherein, n=10;
(3) curing molding: the matrix material mixed solution that step (2) is obtained is poured into and is covered with 2g, in the mould of 10cm*10cm step (1) glass fibre after treatment, under normal temperature, flood 30min, vacuum extracts solvent, solidify 16h, 170 DEG C of curing 5h, 200 DEG C of curing 1h 55 DEG C (shown in formulas 4 more than epoxy resin by using liquid crystal fusing point 5 DEG C) successively, die sinking, obtains epoxy resin by using liquid crystal-glass fibre-silicon dioxide composite material.
Embodiment 7
(1) silicon-dioxide and fiberglass surfacing processing: getting the particle diameter being dried is 20nm, purity is that 99.9% nano silicon 10g, 100ml anhydrous propanone are in beaker, under ultrasonic state, drip gradually the acetone soln containing 1g Silane coupling agent KH550, 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) matrix material mixed solution preparation: take mol ratio and be epoxy resin by using liquid crystal 5.81g and the solidifying agent 4 shown in the formula 3 of 2:1,4-diamino-phenyl sulfoxide (DDS) 1.12g, in 20ml acetone, dissolve, obtain mixed solution, add again step (1) nano silicon 0.07g after treatment, ultrasonic vibration 30min, makes silicon-dioxide dispersed in mixed solution, obtains matrix material mixed solution;
Formula 4
Wherein, n=10;
(3) curing molding: the matrix material mixed solution that step (2) is obtained is poured into and is covered with 4g, in the mould of 10cm*10cm step (1) glass fibre after treatment, under normal temperature, flood 30min, vacuum extracts solvent, solidify 16h, 170 DEG C of curing 5h, 200 DEG C of curing 1h 60 DEG C (shown in formulas 4 more than epoxy resin by using liquid crystal fusing point 10 DEG C) successively, die sinking, obtains epoxy resin by using liquid crystal-glass fibre-silicon dioxide composite material.
Embodiment 8
(1) silicon-dioxide and fiberglass surfacing processing: getting the particle diameter being dried is 20nm, purity is that 99.9% nano silicon 10g, 100ml anhydrous propanone are in beaker, under ultrasonic state, drip gradually the acetone soln containing 1g silane coupling agent KH570, 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) matrix material mixed solution preparation: take mol ratio and be epoxy resin by using liquid crystal 6.33g and solidifying agent methyl mphenylenediamine (DAT) 0.6g shown in the formula 3 of 2:1, in 20ml acetone, dissolve, obtain mixed solution, add again step (1) nano silicon 0.07g after treatment, ultrasonic vibration 30min, make silicon-dioxide dispersed in mixed solution, obtain matrix material mixed solution;
Formula 4
Wherein, n=10;
(3) curing molding: the matrix material mixed solution that step (2) is obtained is poured into and is covered with 3g, in the mould of 10cm*10cm step (1) glass fibre after treatment, under normal temperature, flood 30min, vacuum extracts solvent, solidify 16h, 170 DEG C of curing 5h, 200 DEG C of curing 1h 58 DEG C (shown in formulas 4 more than epoxy resin by using liquid crystal fusing point 8 DEG C) successively, die sinking, obtains epoxy resin by using liquid crystal-glass fibre-silicon dioxide composite material.
Embodiment 9
(1) silicon-dioxide and fiberglass surfacing processing: getting the particle diameter being dried is 20nm, purity is that 99.9% nano silicon 10g, 100ml anhydrous propanone are in beaker, under ultrasonic state, drip gradually the acetone soln containing 1g silane coupling agent KH570, 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) matrix material mixed solution preparation: take mol ratio and be epoxy resin by using liquid crystal 6.61g and the curing agent ethylene diamine 0.32g shown in the formula 3 of 2:1, in 20ml acetone, dissolve, obtain mixed solution, add again step (1) nano silicon 0.07g after treatment, ultrasonic vibration 30min, make silicon-dioxide dispersed in mixed solution, obtain matrix material mixed solution;
Formula 4
Wherein, n=10;
(3) curing molding: the matrix material mixed solution that step (2) is obtained is poured into and is covered with 3g, in the mould of 10cm*10cm step (1) glass fibre after treatment, under normal temperature, flood 30min, vacuum extracts solvent, solidify 16h, 170 DEG C of curing 5h, 200 DEG C of curing 1h 55 DEG C (shown in formulas 4 more than epoxy resin by using liquid crystal fusing point 5 DEG C) successively, die sinking, obtains epoxy resin by using liquid crystal-glass fibre-silicon dioxide composite material.
The product of embodiment 2,3,4 is carried out to mechanical property, shape-memory properties analysis, and contrast with not adding glass fibre and silica modified common liquid crystals epoxy resin and the product of 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.
Product to embodiment 2,3,4 carries out cross-section morphology analysis, and contrasts with not adding glass fibre and silica modified common liquid crystals epoxy resin and the product of comparative example 1, and 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 been compared better bonding interface effect with comparative example.
Testing method
Mechanical Property Analysis: Dynamic thermo-mechanical property analysis (NETZSCH5) stretch mode, 5 DEG C/min of temperature rise rate, temperature range-120 DEG C～250 DEG C, frequency 2Hz, amplitude 30 μ m, dynamic force 5N, static force 0.5N.
Shape-memory properties is analyzed: by embodiment product and comparative sample respectively at the temperature higher than 20 DEG C of its second-order transition temperatures (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 SONY ILCE-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 Philips XL30 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 preferably embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and principle, substitutes, combination, simplify; all should be equivalent substitute mode, within being included in 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 processing: get the silicon-dioxide and the anhydrous propanone that were dried and mix, 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 and 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) matrix material mixed solution 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), ultrasonic vibration makes silicon-dioxide dispersed in mixed solution, obtains matrix material mixed solution again;
(3) curing molding: the matrix material mixed solution that step (2) is obtained is poured in the mould that is covered with the glass fibre after surface treatment in big or small step (1) of mating with die size, under normal temperature, flood 30min, vacuum extracts solvent, die sinking after solidifying, 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, the nano silicon that purity is 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: epoxy resin by using liquid crystal described in step (2) refers to have the branched epoxy resin by using liquid crystal shown in formula 1
Formula 1
Wherein, the integer that n is 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 4,4-diaminodiphenyl-methane, the amino sulfone, 4 of 4-aminophenyl, 4-diaminodiphenyl oxide, 4, at least one in 4-diamino-phenyl sulfoxide, methyl mphenylenediamine 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 described in step (2) after surface treatment is 1%～3% of 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 the 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: described in step (3), solidify and under the condition that refers to more than epoxy resin by using liquid crystal fusing point 5～10 DEG C, solidify 12～16h, 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, by prepared the obtaining of preparation method described in claim 1～9 any one.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN113563693A (en) * | 2021-06-25 | 2021-10-29 | 中科院广州化学有限公司 | Liquid crystal epoxy resin-mesoporous silica composite material, preparation method and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| 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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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| 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 |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN113563693A (en) * | 2021-06-25 | 2021-10-29 | 中科院广州化学有限公司 | Liquid crystal epoxy resin-mesoporous silica composite material, preparation method and application |
| 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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| CN103965583B (en) | 2016-04-13 |
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