CN104327493A - Preparation method of nanometer SiO2 modified PVA-EP-PU interpenetrating polymer network composite material - Google Patents

Preparation method of nanometer SiO2 modified PVA-EP-PU interpenetrating polymer network composite material Download PDF

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CN104327493A
CN104327493A CN201410625127.2A CN201410625127A CN104327493A CN 104327493 A CN104327493 A CN 104327493A CN 201410625127 A CN201410625127 A CN 201410625127A CN 104327493 A CN104327493 A CN 104327493A
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polyvinyl alcohol
silicon dioxide
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nano
epoxy resin
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CN104327493B (en
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杜正银
武俊成
车富寿
雷自强
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Suzhou Teng Teng Intellectual Property Advisory Co ltd
Zhejiang Geyang New Materials Co ltd
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Northwest Normal University
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Abstract

The invention relates to a preparation method of a nanometer SiO2 modified PVA-EP-PU interpenetrating polymer network composite material. The method comprises the following steps: (1) preparing silicon dioxide suspension liquid; (2) preparing a polyvinyl alcohol solution; (3) adding the silicon dioxide suspension liquid into the polyvinyl alcohol solution, forming a film through ultrasonic radiation and curtain coating, and drying to obtain a dried polyvinyl alcohol-silicon dioxide film; (4) cutting the dried polyvinyl alcohol-silicon dioxide film into pieces and then dissolving in dried dimethylsulfoxide, adding epoxy resin and performing ultrasonic radiation to obtain a polyvinyl alcohol-silicon dioxide-epoxy resin solution; (5) adding castor oil into N,N-dimethylformamide, dropwise adding methylbenzene-2,4-diisocyanate in the presence of nitrogen, reacting and then performing vacuum degassing and drying to obtain a dried polyurethane prepolymer; and (6) mixing the polyvinyl alcohol-silicon dioxide-epoxy resin solution with the polyurethane prepolymer, afterwards adding DMP-30, stirring until the mixture is cured, and then performing vacuum degassing and drying to obtain the nanometer SiO2 modified PVA-EP-PU interpenetrating polymer network composite material. The nanometer composite material prepared by the method disclosed by the invention is excellent in performance.

Description

Nano-meter SiO_2 2the preparation method of modified PVA-EP-PU interpenetrating polymer networks matrix material
Technical field
The present invention relates to interpenetrating polymer networks material in polymeric material field, particularly relate to Nano-meter SiO_2 2modified PVA-EP-PU(polyvinyl alcohol-epoxy resin-polyurethane) preparation method of interpenetrating polymer networks matrix material.
Background technology
Polyvinyl alcohol (PVA) is a kind of important water-soluble polymers, and its transparency is good, good mechanical performance, oil resistant, solvent resistant, not static electrification, and printing and excellent in barrier property have vast potential for future development in film packaging industry.Epoxy resin (EP) has good electrical property, chemical stability, cementability and processibility, and at machinery, electrically, there is important application in the field such as electronics, space flight and aviation.The maximum weakness of epoxy resin is that after solidification, matter is crisp, shock-resistance is poor and easily ftractures.Urethane (PU) is the macromolecular compound of a class containing Polar Amides manthanoate repeating segment, there is the excellent properties such as wear-resisting, high temperature resistant, corrosion-resistant, sealing, sound insulation, good processability, degradable, be widely used as the aspects such as sizing agent, coating, water-proof material and biological medicine material.Mix with epoxy resin using urethane as a kind of component, have in epoxy resin can with the hydroxyl of isocyanic ester radical reaction, make urethane and polymerization of epoxy resins also crosslinked, interpenetrating polymer networks (IPNs) material of forming property excellence, this interpenetrating polymer networks structure not only can improve the adhesiveproperties of urethane, improve its rigidity, obviously can improve the toughness of epoxy resin simultaneously.But have not yet to see the report of polyvinyl alcohol-epoxy resin-polyurethane ternary IPN.
Nanoparticle is widely applied in polymer modification field owing to having the features such as quantum size effect, macro quanta tunnel effect, surface and interface effect.All the time, researchist achieves certain achievement to inorganic nano particle modified organic polymer aspect.Silicon-dioxide (SiO 2) also known as white carbon black, in Rubber processing industry, be widely used as filling toughener.Nano silicon is owing to having many premium propertiess, and as small-size effect, interfacial effect, photoelectric characteristic, has high-strength, high tenacity under high temperature, good stability, and preparation is simple, and raw material is easy to get, and is thus recently widely applied.Research shows form tangled structure between nano silicon and polymer molecular chain, thus produces obviously impact to the performance of polymkeric substance.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of Nano-meter SiO_2 of easy to implement, products obtained therefrom excellent property 2the preparation method of modified PVA-EP-PU interpenetrating polymer networks matrix material.
For solving the problem, Nano-meter SiO_2 of the present invention 2the preparation method of modified PVA-EP-PU interpenetrating polymer networks matrix material, comprises the following steps:
(1), under the speed stirring of 1300 ~ 1500 revs/min, 0.01 ~ 0.05kg nano silicon is joined in 100 ~ 300mL distilled water, stir 1 ~ 2h, be mixed with silica suspension;
(2), under the speed stirring of 1300 ~ 1500 revs/min, 0.15 ~ 0.25kg polyvinyl alcohol is joined in 200 ~ 500mL distilled water, is warming up to 80 ~ 90 DEG C and makes it dissolve, make polyvinyl alcohol solution;
(3) be under the condition of 80 ~ 100 DEG C in temperature, described silica suspension is all joined in described polyvinyl alcohol solution, stir with the speed of 1400 ~ 1600 revs/min, after 1.5 ~ 2.5 hours, be cooled to room temperature, then ultrasonic radiation 20 ~ 40 minutes, obtains mixed solution; Described mixed solution curtain coating on the sheet glass of level cleaning becomes thickness to be the polyvinyl alcohol-silica membrane of 0.3 ~ 0.5mm, and drying at room temperature took off film after 20 ~ 28 hours, in the baking oven of 70 ~ 90 DEG C dry 3 ~ 5 hours, obtains dry polyethylene alcohol-silicon dioxide film;
(4) be dissolved in dry methyl-sulphoxide after described dry polyethylene alcohol-silicon dioxide film being shredded, add epoxy resin again, stir, ultrasonic radiation 0.5 ~ 1.5 hour at 70 ~ 90 DEG C, then mechanical stirring 8 ~ 12 hours, obtains polyvinyl alcohol-silica-epoxy solution; Described dry polyethylene alcohol-silicon dioxide film and described methyl-sulphoxide ratio be 0.15 ~ 0.25kg:100 ~ 500mL; The ratio of described epoxy resin and described methyl-sulphoxide is 0.15 ~ 0.25kg:100 ~ 500mL;
(5) Viscotrol C is joined in DMF, and be heated to 100 ~ 140 DEG C, after vacuumizing 20 ~ 40 minutes under mechanical stirring, drying dewaters, and is then cooled to 40 ~ 60 DEG C, drips Toluene-2,4-diisocyanate under nitrogen protection, 4-vulcabond, react 1 ~ 2 hour at 50 ~ 70 DEG C, obtain base polyurethane prepolymer for use as, wash away unreacted Toluene-2,4-diisocyanate with sherwood oil, 4-vulcabond, thereafter under vacuo degassed three times, at 50 ~ 70 DEG C of temperature, be dried to constant weight, obtain dry base polyurethane prepolymer for use as; The ratio of described Viscotrol C and described DMF is 0.2 ~ 0.3kg:300 ~ 700mL; Described Viscotrol C and described Toluene-2,4-diisocyanate, the ratio of 4-vulcabond is 0.2 ~ 0.3kg:0.3 ~ 0.42kg;
(6) after described polyvinyl alcohol-silica-epoxy solution being mixed with described base polyurethane prepolymer for use as, mechanical stirring 1 ~ 2 h at 50 ~ 70 DEG C, then linking agent DMP-30 is added rapidly, continue to be stirred to mixture solidification, solid vacuum outgas at 70 ~ 90 DEG C, drying 10 ~ 14 hours, namely obtain Nano-meter SiO_2 2modified PVA-EP-PU interpenetrating polymer networks matrix material; Described DMP-30 add-on is 1 ~ 2% of epoxy resin quality.
Described step (1) in the median size of nano silicon be 20 ~ 50 nanometers.
Described step (2) in the equal relative molecular mass of number of polyvinyl alcohol be 140000 ~ 210000.
The present invention compared with prior art has the following advantages:
1, compared with existing EP-PU interpenetrating polymer networks, EP-PU multipolymer, PVA-EP blend, the present invention adopts Nano-meter SiO_2 2as blending and modifying agent, the abundant hydroxyl in its surface with the hydroxyl generating portion condensation of polyvinyl alcohol and epoxy resin and can form hydrogen bond, and produces and act synergistically, and silicon-dioxide is dispersed in the middle of polymkeric substance, thus makes PVA-SiO 2the thermostability of-EP-PU interpenetrating polymer networks nano composite material and mechanical property obtain and effectively promote, and meanwhile, also have very strong water tolerance and uvioresistant, ageing resistance.
2, the matrix material of gained of the present invention is carried out performance test (see table 1), can find out, this matrix material is amorphousness, its surface is dense, nano silicon is uniformly dispersed wherein, may be used on day and night temperature comparatively large, in the improvement of the region Desertification that uv-radiation content is higher.
table 1 nano composite material performance test of the present invention
The matrix material of gained of the present invention is carried out Fourier transform infrared spectroscopy (FT-IR) test to show (see Fig. 1), Nano-meter SiO_2 2at 1065 cm after adding -1, 1250 cm -1there is the asymmetrical stretching vibration absorption peak of Si-O-C, at 870-919 cm -1there is the symmetrical stretching vibration absorption peak of Si-O-C in place, demonstrates SiO 2on hydroxyl and hydroxylic moiety on PVA or EP there occurs dehydration condensation, define Si-O-C key.
The matrix material of gained of the present invention being carried out X-ray diffraction spectrum (XRD) at 2 θ is 20 onear there is a wider peak, illustrate that this material is amorphousness (see Fig. 2).Obviously, nano silicon serves the effect of activeness and quietness polymkeric substance.
The matrix material of gained of the present invention is carried out thermogravimetric analysis (TGA) and can find out that the decomposition temperature (decompose 10% time temperature) of this material is 280.7 DEG C (see Fig. 3, table 1).
The matrix material of gained of the present invention is carried out scanning electron microscope (SEM) photo can find out (see Fig. 4 ~ 6), the surface of this matrix material is dense, and nano silicon is uniformly dispersed wherein.
3, the present invention prepares nano-silicon dioxide modified ternary PVA-EP-PU interpenetrating polymer networks MATERIALS METHODS simply, workable, has good reference to the material of other similar polynary interpenetrating polymer networks structures of preparation.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in further detail.
Fig. 1 is Fourier transform infrared spectroscopy (FT-IR) figure of the present invention and pure PVA.
Fig. 2 is X-ray diffraction spectrum (XRD) figure of the present invention.
Fig. 3 is thermogravimetric analysis of the present invention (TGA) figure.
Fig. 4 is scanning electron microscope of the present invention (SEM) photo.Wherein SiO 2content is 1 wt%.
Fig. 5 is profile scanning Electronic Speculum (SEM) photo of the present invention.Wherein SiO 2content is 3 wt%.
Fig. 6 is scanning electron microscope of the present invention (SEM) photo.Wherein SiO 2content is 4 wt%.
Embodiment
embodiment 1nano-meter SiO_2 2the preparation method of modified PVA-EP-PU interpenetrating polymer networks matrix material, comprises the following steps:
(1), under the speed stirring of 1300 revs/min, be that the nano silicon of 20 nanometers joins in 100mL distilled water by 0.01kg median size, stir 1h, be mixed with silica suspension.
(2), under the speed stirring of 1300 revs/min, the polyvinyl alcohol being 140000 by equal for 0.15kg number relative molecular mass joins in 200mL distilled water, is warming up to 80 DEG C and makes it dissolve, make polyvinyl alcohol solution.
(3) be under the condition of 80 DEG C in temperature, all joined in polyvinyl alcohol solution by silica suspension, stir with the speed of 1400 revs/min, be cooled to room temperature after 1.5 hours, then ultrasonic radiation 20 minutes, obtains mixed solution; Mixed solution curtain coating on the sheet glass of level cleaning becomes thickness to be the polyvinyl alcohol-silica membrane of 0.3mm, and drying at room temperature took off film after 20 hours, in the baking oven of 70 DEG C dry 3 hours, obtains dry polyethylene alcohol-silicon dioxide film.
(4) be dissolved in after being shredded by dry polyethylene alcohol-silicon dioxide film in dry methyl-sulphoxide, then add epoxy resin, stir, ultrasonic radiation 0.5 hour at 70 DEG C, then mechanical stirring 8 hours, obtain polyvinyl alcohol-silica-epoxy solution.
Wherein:
Dry polyethylene alcohol-silicon dioxide film and methyl-sulphoxide ratio be 0.15kg:100mL.
The ratio of epoxy resin and methyl-sulphoxide is 0.15kg:100mL.
(5) Viscotrol C is joined in DMF, and be heated to 100 DEG C; after vacuumizing 20 minutes under mechanical stirring, drying dewaters, and is then cooled to 40 DEG C, and dripping massfraction is under nitrogen protection the Toluene-2,4-diisocyanate of 30%; 4-vulcabond; react 1 hour at 50 DEG C, obtain base polyurethane prepolymer for use as, wash away unreacted Toluene-2,4-diisocyanate with sherwood oil; 4-vulcabond; thereafter under vacuo degassed three times, at 50 DEG C of temperature, be dried to constant weight, obtain dry base polyurethane prepolymer for use as.
Wherein:
The ratio of Viscotrol C and DMF is 0.2kg:300mL.
Viscotrol C and Toluene-2,4-diisocyanate, the ratio of 4-vulcabond is 0.2kg:0.3kg.
(6) after polyvinyl alcohol-silica-epoxy solution being mixed with base polyurethane prepolymer for use as, at 50 DEG C, mechanical stirring 1 h, then adds rapidly linking agent DMP-30, continues to be stirred to mixture solidification, solid vacuum outgas at 70 DEG C, drying 10 hours, namely obtain Nano-meter SiO_2 2modified PVA-EP-PU interpenetrating polymer networks matrix material.
Wherein: DMP-30 add-on is 1% of epoxy resin quality.
embodiment 2nano-meter SiO_2 2the preparation method of modified PVA-EP-PU interpenetrating polymer networks matrix material, comprises the following steps:
(1), under the speed stirring of 1500 revs/min, be that the nano silicon of 30 nanometers joins in 200mL distilled water by 0.02kg median size, stir 2h, be mixed with silica suspension.
(2), under the speed stirring of 1500 revs/min, the polyvinyl alcohol being 170000 by equal for 0.2kg number relative molecular mass joins in 300mL distilled water, is warming up to 90 DEG C and makes it dissolve, make polyvinyl alcohol solution.
(3) be under the condition of 100 DEG C in temperature, all joined in polyvinyl alcohol solution by silica suspension, stir with the speed of 1600 revs/min, be cooled to room temperature after 2.5 hours, then ultrasonic radiation 400 minutes, obtains mixed solution; Mixed solution curtain coating on the sheet glass of level cleaning becomes thickness to be the polyvinyl alcohol-silica membrane of 0.5mm, and drying at room temperature took off film after 28 hours, in the baking oven of 90 DEG C dry 5 hours, obtains dry polyethylene alcohol-silicon dioxide film.
(4) be dissolved in after being shredded by dry polyethylene alcohol-silicon dioxide film in dry methyl-sulphoxide, then add epoxy resin, stir, ultrasonic radiation 1.5 hours at 90 DEG C, then mechanical stirring 12 hours, obtain polyvinyl alcohol-silica-epoxy solution.
Wherein:
Dry polyethylene alcohol-silicon dioxide film and methyl-sulphoxide ratio be 0.2kg:200mL.
The ratio of epoxy resin and methyl-sulphoxide is 0.2kg:200mL.
(5) Viscotrol C is joined in DMF, and be heated to 140 DEG C; after vacuumizing 40 minutes under mechanical stirring, drying dewaters, and is then cooled to 60 DEG C, and dripping massfraction is under nitrogen protection the Toluene-2,4-diisocyanate of 40%; 4-vulcabond; react 2 hours at 70 DEG C, obtain base polyurethane prepolymer for use as, wash away unreacted Toluene-2,4-diisocyanate with sherwood oil; 4-vulcabond; thereafter under vacuo degassed three times, at 70 DEG C of temperature, be dried to constant weight, obtain dry base polyurethane prepolymer for use as.
Wherein:
The ratio of Viscotrol C and DMF is 0.24kg:400mL.
Viscotrol C and Toluene-2,4-diisocyanate, the ratio of 4-vulcabond is 0.24kg:0.36kg.
(6) after polyvinyl alcohol-silica-epoxy solution being mixed with base polyurethane prepolymer for use as, at 70 DEG C, mechanical stirring 2 h, then adds rapidly linking agent DMP-30, continues to be stirred to mixture solidification, solid vacuum outgas at 90 DEG C, drying 14 hours, namely obtain Nano-meter SiO_2 2modified PVA-EP-PU interpenetrating polymer networks matrix material.
Wherein: DMP-30 add-on is 2% of epoxy resin quality.
embodiment 3nano-meter SiO_2 2the preparation method of modified PVA-EP-PU interpenetrating polymer networks matrix material, comprises the following steps:
(1), under the speed stirring of 1400 revs/min, be that the nano silicon of 40 nanometers joins in 300mL distilled water by 0.03kg median size, stir 1.5h, be mixed with silica suspension.
(2), under the speed stirring of 1400 revs/min, the polyvinyl alcohol being 160000 by equal for 0.25kg number relative molecular mass joins in 400mL distilled water, is warming up to 85 DEG C and makes it dissolve, make polyvinyl alcohol solution.
(3) be under the condition of 90 DEG C in temperature, all joined in polyvinyl alcohol solution by silica suspension, stir with the speed of 1500 revs/min, be cooled to room temperature after 2 hours, then ultrasonic radiation 30 minutes, obtains mixed solution; Mixed solution curtain coating on the sheet glass of level cleaning becomes thickness to be the polyvinyl alcohol-silica membrane of 0.4mm, and drying at room temperature took off film after 24 hours, in the baking oven of 80 DEG C dry 4 hours, obtains dry polyethylene alcohol-silicon dioxide film.
(4) be dissolved in after being shredded by dry polyethylene alcohol-silicon dioxide film in dry methyl-sulphoxide, then add epoxy resin, stir, ultrasonic radiation 1 hour at 80 DEG C, then mechanical stirring 10 hours, obtain polyvinyl alcohol-silica-epoxy solution.
Wherein:
Dry polyethylene alcohol-silicon dioxide film and methyl-sulphoxide ratio be 0.25kg:500mL.
The ratio of epoxy resin and methyl-sulphoxide is 0.25kg:500mL.
(5) Viscotrol C is joined in DMF, and be heated to 120 DEG C; after vacuumizing 30 minutes under mechanical stirring, drying dewaters, and is then cooled to 50 DEG C, and dripping massfraction is under nitrogen protection the Toluene-2,4-diisocyanate of 35%; 4-vulcabond; react 1.5 hours at 60 DEG C, obtain base polyurethane prepolymer for use as, wash away unreacted Toluene-2,4-diisocyanate with sherwood oil; 4-vulcabond; thereafter under vacuo degassed three times, at 60 DEG C of temperature, be dried to constant weight, obtain dry base polyurethane prepolymer for use as.
Wherein:
The ratio of Viscotrol C and DMF is 0.3kg:700mL.
Viscotrol C and Toluene-2,4-diisocyanate, the ratio of 4-vulcabond is 0.3kg:0.42kg.
(6) after polyvinyl alcohol-silica-epoxy solution being mixed with base polyurethane prepolymer for use as, at 60 DEG C, mechanical stirring 1.5 h, then adds rapidly linking agent DMP-30, continues to be stirred to mixture solidification, solid vacuum outgas at 80 DEG C, drying 12 hours, namely obtain Nano-meter SiO_2 2modified PVA-EP-PU interpenetrating polymer networks matrix material.
Wherein: DMP-30 add-on is 1.5% of epoxy resin quality.
embodiment 4nano-meter SiO_2 2the preparation method of modified PVA-EP-PU interpenetrating polymer networks matrix material, comprises the following steps:
(1), under the speed stirring of 1350 revs/min, be that the nano silicon of 50 nanometers joins in 200mL distilled water by 0.04kg median size, stir 1h, be mixed with silica suspension.
(2), under the speed stirring of 1350 revs/min, the polyvinyl alcohol being 210000 by equal for 0.18kg number relative molecular mass joins in 500mL distilled water, is warming up to 80 DEG C and makes it dissolve, make polyvinyl alcohol solution.
(3) be under the condition of 85 DEG C in temperature, all joined in polyvinyl alcohol solution by silica suspension, stir with the speed of 1450 revs/min, be cooled to room temperature after 1.5 hours, then ultrasonic radiation 25 minutes, obtains mixed solution; Mixed solution curtain coating on the sheet glass of level cleaning becomes thickness to be the polyvinyl alcohol-silica membrane of 0.3mm, and drying at room temperature took off film after 22 hours, in the baking oven of 75 DEG C dry 3.5 hours, obtains dry polyethylene alcohol-silicon dioxide film.
(4) be dissolved in after being shredded by dry polyethylene alcohol-silicon dioxide film in dry methyl-sulphoxide, then add epoxy resin, stir, ultrasonic radiation 0.5 hour at 75 DEG C, then mechanical stirring 9 hours, obtain polyvinyl alcohol-silica-epoxy solution.
Wherein:
Dry polyethylene alcohol-silicon dioxide film and methyl-sulphoxide ratio be 0.22kg:400mL.
The ratio of epoxy resin and methyl-sulphoxide is 0.22kg:400mL.
(5) Viscotrol C is joined in DMF, and be heated to 110 DEG C; after vacuumizing 25 minutes under mechanical stirring, drying dewaters, and is then cooled to 45 DEG C, and dripping massfraction is under nitrogen protection the Toluene-2,4-diisocyanate of 30%; 4-vulcabond; react 1 hour at 55 DEG C, obtain base polyurethane prepolymer for use as, wash away unreacted Toluene-2,4-diisocyanate with sherwood oil; 4-vulcabond; thereafter under vacuo degassed three times, at 55 DEG C of temperature, be dried to constant weight, obtain dry base polyurethane prepolymer for use as.
Wherein:
The ratio of Viscotrol C and DMF is 0.22kg:400mL.
Viscotrol C and Toluene-2,4-diisocyanate, the ratio of 4-vulcabond is 0.22kg:0.33kg.
(6) after polyvinyl alcohol-silica-epoxy solution being mixed with base polyurethane prepolymer for use as, mechanical stirring 1h at 55 DEG C, then adds rapidly linking agent DMP-30, continues to be stirred to mixture solidification, solid vacuum outgas at 75 DEG C, drying 11 hours, namely obtain Nano-meter SiO_2 2modified PVA-EP-PU interpenetrating polymer networks matrix material.
Wherein: DMP-30 add-on is 1% of epoxy resin quality.
embodiment 5nano-meter SiO_2 2the preparation method of modified PVA-EP-PU interpenetrating polymer networks matrix material, comprises the following steps:
(1), under the speed stirring of 1450 revs/min, be that the nano silicon of 20 nanometers joins in 250mL distilled water by 0.05kg median size, stir 2h, be mixed with silica suspension.
(2), under the speed stirring of 1450 revs/min, the polyvinyl alcohol being 180000 by equal for 0.23kg number relative molecular mass joins in 300mL distilled water, is warming up to 90 DEG C and makes it dissolve, make polyvinyl alcohol solution.
(3) be under the condition of 95 DEG C in temperature, all joined in polyvinyl alcohol solution by silica suspension, stir with the speed of 1450 revs/min, be cooled to room temperature after 2.5 hours, then ultrasonic radiation 35 minutes, obtains mixed solution; Mixed solution curtain coating on the sheet glass of level cleaning becomes thickness to be the polyvinyl alcohol-silica membrane of 0.5mm, and drying at room temperature took off film after 26 hours, in the baking oven of 85 DEG C dry 5 hours, obtains dry polyethylene alcohol-silicon dioxide film.
(4) be dissolved in after being shredded by dry polyethylene alcohol-silicon dioxide film in dry methyl-sulphoxide, then add epoxy resin, stir, ultrasonic radiation 1.5 hours at 85 DEG C, then mechanical stirring 11 hours, obtain polyvinyl alcohol-silica-epoxy solution.
Wherein:
Dry polyethylene alcohol-silicon dioxide film and methyl-sulphoxide ratio be 0.18kg:350mL.
The ratio of epoxy resin and methyl-sulphoxide is 0.2kg:350mL.
(5) Viscotrol C is joined in DMF, and be heated to 130 DEG C; after vacuumizing 35 minutes under mechanical stirring, drying dewaters, and is then cooled to 55 DEG C, and dripping massfraction is under nitrogen protection the Toluene-2,4-diisocyanate of 40%; 4-vulcabond; react 2 hours at 65 DEG C, obtain base polyurethane prepolymer for use as, wash away unreacted Toluene-2,4-diisocyanate with sherwood oil; 4-vulcabond; thereafter under vacuo degassed three times, at 65 DEG C of temperature, be dried to constant weight, obtain dry base polyurethane prepolymer for use as.
Wherein:
The ratio of Viscotrol C and DMF is 0.28kg:650mL.
Viscotrol C and Toluene-2,4-diisocyanate, the ratio of 4-vulcabond is 0.28kg:0.40kg.
(6) after polyvinyl alcohol-silica-epoxy solution being mixed with base polyurethane prepolymer for use as, at 65 DEG C, mechanical stirring 2 h, then adds rapidly linking agent DMP-30, continues to be stirred to mixture solidification, solid vacuum outgas at 85 DEG C, drying 13 hours, namely obtain Nano-meter SiO_2 2modified PVA-EP-PU interpenetrating polymer networks matrix material.
Wherein: DMP-30 add-on is 2% of epoxy resin quality.
embodiment 6nano-meter SiO_2 2the preparation method of modified PVA-EP-PU interpenetrating polymer networks matrix material, comprises the following steps:
(1), under the speed stirring of 1300 revs/min, be that the nano silicon of 20 nanometers joins in 200mL distilled water by 0.03kg median size, stir 1h, be mixed with silica suspension.
(2), under the speed stirring of 1300 revs/min, the polyvinyl alcohol being 210000 by equal for 0.21kg number relative molecular mass joins in 450mL distilled water, is warming up to 80 DEG C and makes it dissolve, make polyvinyl alcohol solution.
(3) be under the condition of 80 DEG C in temperature, all joined in polyvinyl alcohol solution by silica suspension, stir with the speed of 1400 revs/min, be cooled to room temperature after 1.5 hours, then ultrasonic radiation 20 minutes, obtains mixed solution; Mixed solution curtain coating on the sheet glass of level cleaning becomes thickness to be the polyvinyl alcohol-silica membrane of 0.3mm, and drying at room temperature took off film after 20 hours, in the baking oven of 70 DEG C dry 3 hours, obtains dry polyethylene alcohol-silicon dioxide film.
(4) be dissolved in after being shredded by dry polyethylene alcohol-silicon dioxide film in dry methyl-sulphoxide, then add epoxy resin, stir, ultrasonic radiation 0.5 hour at 70 DEG C, then mechanical stirring 8 hours, obtain polyvinyl alcohol-silica-epoxy solution.
Wherein:
The ratio of dry polyethylene alcohol-silicon dioxide film and methyl-sulphoxide is 0.23kg:300mL.
The ratio of epoxy resin and methyl-sulphoxide is 0.23kg:300mL.
(5) Viscotrol C is joined in DMF, and be heated to 100 DEG C; after vacuumizing 20 minutes under mechanical stirring, drying dewaters, and is then cooled to 40 DEG C, and dripping massfraction is under nitrogen protection the Toluene-2,4-diisocyanate of 30%; 4-vulcabond; react 1 hour at 50 DEG C, obtain base polyurethane prepolymer for use as, wash away unreacted Toluene-2,4-diisocyanate with sherwood oil; 4-vulcabond; thereafter under vacuo degassed three times, at 50 DEG C of temperature, be dried to constant weight, obtain dry base polyurethane prepolymer for use as.
Wherein:
The ratio of Viscotrol C and DMF is 0.25kg:500mL.
Viscotrol C and Toluene-2,4-diisocyanate, the ratio of 4-vulcabond is 0.25kg:0.37kg.
(6) after polyvinyl alcohol-silica-epoxy solution being mixed with base polyurethane prepolymer for use as, at 50 DEG C, mechanical stirring 1 h, then adds rapidly linking agent DMP-30, continues to be stirred to mixture solidification, solid vacuum outgas at 70 DEG C, drying 10 hours, namely obtain Nano-meter SiO_2 2modified PVA-EP-PU interpenetrating polymer networks matrix material.
Wherein: DMP-30 add-on is 1% of epoxy resin quality.
embodiment 7nano-meter SiO_2 2the preparation method of modified PVA-EP-PU interpenetrating polymer networks matrix material, comprises the following steps:
(1), under the speed stirring of 1500 revs/min, be that the nano silicon of 30 nanometers joins in 300mL distilled water by 0.04kg median size, stir 2h, be mixed with silica suspension.
(2), under the speed stirring of 1500 revs/min, the polyvinyl alcohol being 160000 by equal for 0.15kg number relative molecular mass joins in 200mL distilled water, is warming up to 90 DEG C and makes it dissolve, make polyvinyl alcohol solution.
(3) be under the condition of 100 DEG C in temperature, all joined in polyvinyl alcohol solution by silica suspension, stir with the speed of 1600 revs/min, be cooled to room temperature after 2.5 hours, then ultrasonic radiation 40 minutes, obtains mixed solution; Mixed solution curtain coating on the sheet glass of level cleaning becomes thickness to be the polyvinyl alcohol-silica membrane of 0.5mm, and drying at room temperature took off film after 28 hours, in the baking oven of 90 DEG C dry 5 hours, obtains dry polyethylene alcohol-silicon dioxide film.
(4) be dissolved in after being shredded by dry polyethylene alcohol-silicon dioxide film in dry methyl-sulphoxide, then add epoxy resin, stir, ultrasonic radiation 1.5 hours at 90 DEG C, then mechanical stirring 12 hours, obtain polyvinyl alcohol-silica-epoxy solution.
Wherein:
The ratio of dry polyethylene alcohol-silicon dioxide film and methyl-sulphoxide is 0.24kg:200mL.
The ratio of epoxy resin and methyl-sulphoxide is 0.15kg:200mL.
(5) Viscotrol C is joined in DMF, and be heated to 140 DEG C; after vacuumizing 40 minutes under mechanical stirring, drying dewaters, and is then cooled to 60 DEG C, and dripping massfraction is under nitrogen protection the Toluene-2,4-diisocyanate of 40%; 4-vulcabond; react 2 hours at 70 DEG C, obtain base polyurethane prepolymer for use as, wash away unreacted Toluene-2,4-diisocyanate with sherwood oil; 4-vulcabond; thereafter under vacuo degassed three times, at 70 DEG C of temperature, be dried to constant weight, obtain dry base polyurethane prepolymer for use as.
Wherein:
The ratio of Viscotrol C and DMF is 0.2kg:400mL.
Viscotrol C and Toluene-2,4-diisocyanate, the ratio of 4-vulcabond is 0.2kg:0.3kg.
(6) after polyvinyl alcohol-silica-epoxy solution being mixed with base polyurethane prepolymer for use as, at 70 DEG C, mechanical stirring 2 h, then adds rapidly linking agent DMP-30, continues to be stirred to mixture solidification, solid vacuum outgas at 90 DEG C, drying 14 hours, namely obtain Nano-meter SiO_2 2modified PVA-EP-PU interpenetrating polymer networks matrix material.
Wherein: DMP-30 add-on is 2% of epoxy resin quality.
embodiment 8nano-meter SiO_2 2the preparation method of modified PVA-EP-PU interpenetrating polymer networks matrix material, comprises the following steps:
(1), under the speed stirring of 1400 revs/min, be that the nano silicon of 40 nanometers joins in 100mL distilled water by 0.03kg median size, stir 1.5h, be mixed with silica suspension.
(2), under the speed stirring of 1400 revs/min, the polyvinyl alcohol being 140000 by equal for 0.25kg number relative molecular mass joins in 300mL distilled water, is warming up to 85 DEG C and makes it dissolve, make polyvinyl alcohol solution.
(3) be under the condition of 90 DEG C in temperature, all joined in polyvinyl alcohol solution by silica suspension, stir with the speed of 1500 revs/min, be cooled to room temperature after 2 hours, then ultrasonic radiation 30 minutes, obtains mixed solution; Mixed solution curtain coating on the sheet glass of level cleaning becomes thickness to be the polyvinyl alcohol-silica membrane of 0.4mm, and drying at room temperature took off film after 24 hours, in the baking oven of 80 DEG C dry 4 hours, obtains dry polyethylene alcohol-silicon dioxide film.
(4) be dissolved in after being shredded by dry polyethylene alcohol-silicon dioxide film in dry methyl-sulphoxide, then add epoxy resin, stir, ultrasonic radiation 1 hour at 80 DEG C, then mechanical stirring 10 hours, obtain polyvinyl alcohol-silica-epoxy solution.
Wherein:
The ratio of dry polyethylene alcohol-silicon dioxide film and methyl-sulphoxide is 0.25kg:400mL.
The ratio of epoxy resin and methyl-sulphoxide is 0.25kg:400mL.
(5) Viscotrol C is joined in DMF, and be heated to 120 DEG C; after vacuumizing 30 minutes under mechanical stirring, drying dewaters, and is then cooled to 50 DEG C, and dripping massfraction is under nitrogen protection the Toluene-2,4-diisocyanate of 35%; 4-vulcabond; react 1.5 hours at 60 DEG C, obtain base polyurethane prepolymer for use as, wash away unreacted Toluene-2,4-diisocyanate with sherwood oil; 4-vulcabond; thereafter under vacuo degassed three times, at 60 DEG C of temperature, be dried to constant weight, obtain dry base polyurethane prepolymer for use as.
Wherein:
The ratio of Viscotrol C and DMF is 0.26kg:600mL.
Viscotrol C and Toluene-2,4-diisocyanate, the ratio of 4-vulcabond is 0.26kg:0.39kg.
(6) after polyvinyl alcohol-silica-epoxy solution being mixed with base polyurethane prepolymer for use as, at 60 DEG C, mechanical stirring 1.5 h, then adds rapidly linking agent DMP-30, continues to be stirred to mixture solidification, solid vacuum outgas at 80 DEG C, drying 12 hours, namely obtain Nano-meter SiO_2 2modified PVA-EP-PU interpenetrating polymer networks matrix material.
Wherein: DMP-30 add-on is 1.5% of epoxy resin quality.
embodiment 9nano-meter SiO_2 2the preparation method of modified PVA-EP-PU interpenetrating polymer networks matrix material, comprises the following steps:
(1), under the speed stirring of 1300 revs/min, be that the nano silicon of 30 nanometers joins in 200mL distilled water by 0.04kg median size, stir 1h, be mixed with silica suspension.
(2), under the speed stirring of 1300 revs/min, the polyvinyl alcohol being 190000 by equal for 0.2kg number relative molecular mass joins in 200mL distilled water, is warming up to 80 DEG C and makes it dissolve, make polyvinyl alcohol solution.
(3) be under the condition of 80 DEG C in temperature, all joined in polyvinyl alcohol solution by silica suspension, stir with the speed of 1400 revs/min, be cooled to room temperature after 1.5 hours, then ultrasonic radiation 20 minutes, obtains mixed solution; Mixed solution curtain coating on the sheet glass of level cleaning becomes thickness to be the polyvinyl alcohol-silica membrane of 0.3mm, and drying at room temperature took off film after 20 hours, in the baking oven of 70 DEG C dry 3 hours, obtains dry polyethylene alcohol-silicon dioxide film.
(4) be dissolved in after being shredded by dry polyethylene alcohol-silicon dioxide film in dry methyl-sulphoxide, then add epoxy resin, stir, ultrasonic radiation 0.5 hour at 70 DEG C, then mechanical stirring 8 hours, obtain polyvinyl alcohol-silica-epoxy solution.
Wherein:
The ratio of dry polyethylene alcohol-silicon dioxide film and methyl-sulphoxide is 0.23kg:300mL.
The ratio of epoxy resin and methyl-sulphoxide is 0.23kg:300mL.
(5) Viscotrol C is joined in DMF, and be heated to 100 DEG C; after vacuumizing 20 minutes under mechanical stirring, drying dewaters, and is then cooled to 40 DEG C, and dripping massfraction is under nitrogen protection the Toluene-2,4-diisocyanate of 30%; 4-vulcabond; react 1 hour at 50 DEG C, obtain base polyurethane prepolymer for use as, wash away unreacted Toluene-2,4-diisocyanate with sherwood oil; 4-vulcabond; thereafter under vacuo degassed three times, at 50 DEG C of temperature, be dried to constant weight, obtain dry base polyurethane prepolymer for use as.
Wherein:
The ratio of Viscotrol C and DMF is 0.22kg:500mL.
Viscotrol C and Toluene-2,4-diisocyanate, the ratio of 4-vulcabond is 0.22kg:0.33kg.
(6) after polyvinyl alcohol-silica-epoxy solution being mixed with base polyurethane prepolymer for use as, mechanical stirring 1h at 50 DEG C, then adds rapidly linking agent DMP-30, continues to be stirred to mixture solidification, solid vacuum outgas at 70 DEG C, drying 10 hours, namely obtain Nano-meter SiO_2 2modified PVA-EP-PU interpenetrating polymer networks matrix material.
Wherein: DMP-30 add-on is 1% of epoxy resin quality.

Claims (3)

1. Nano-meter SiO_2 2the preparation method of modified PVA-EP-PU interpenetrating polymer networks matrix material, comprises the following steps:
(1), under the speed stirring of 1300 ~ 1500 revs/min, 0.01 ~ 0.05kg nano silicon is joined in 100 ~ 300mL distilled water, stir 1 ~ 2h, be mixed with silica suspension;
(2), under the speed stirring of 1300 ~ 1500 revs/min, 0.15 ~ 0.25kg polyvinyl alcohol is joined in 200 ~ 500mL distilled water, is warming up to 80 ~ 90 DEG C and makes it dissolve, make polyvinyl alcohol solution;
(3) be under the condition of 80 ~ 100 DEG C in temperature, described silica suspension is all joined in described polyvinyl alcohol solution, stir with the speed of 1400 ~ 1600 revs/min, after 1.5 ~ 2.5 hours, be cooled to room temperature, then ultrasonic radiation 20 ~ 40 minutes, obtains mixed solution; Described mixed solution curtain coating on the sheet glass of level cleaning becomes thickness to be the polyvinyl alcohol-silica membrane of 0.3 ~ 0.5mm, and drying at room temperature took off film after 20 ~ 28 hours, in the baking oven of 70 ~ 90 DEG C dry 3 ~ 5 hours, obtains dry polyethylene alcohol-silicon dioxide film;
(4) be dissolved in dry methyl-sulphoxide after described dry polyethylene alcohol-silicon dioxide film being shredded, add epoxy resin again, stir, ultrasonic radiation 0.5 ~ 1.5 hour at 70 ~ 90 DEG C, then mechanical stirring 8 ~ 12 hours, obtains polyvinyl alcohol-silica-epoxy solution; Described dry polyethylene alcohol-silicon dioxide film and described methyl-sulphoxide ratio be 0.15 ~ 0.25kg:100 ~ 500mL; The ratio of described epoxy resin and described methyl-sulphoxide is 0.15 ~ 0.25kg:100 ~ 500mL;
(5) Viscotrol C is joined in DMF, and be heated to 100 ~ 140 DEG C, after vacuumizing 20 ~ 40 minutes under mechanical stirring, drying dewaters, and is then cooled to 40 ~ 60 DEG C, drips Toluene-2,4-diisocyanate under nitrogen protection, 4-vulcabond, react 1 ~ 2 hour at 50 ~ 70 DEG C, obtain base polyurethane prepolymer for use as, wash away unreacted Toluene-2,4-diisocyanate with sherwood oil, 4-vulcabond, thereafter under vacuo degassed three times, at 50 ~ 70 DEG C of temperature, be dried to constant weight, obtain dry base polyurethane prepolymer for use as; The ratio of described Viscotrol C and described DMF is 0.2 ~ 0.3kg:300 ~ 700mL; Described Viscotrol C and described Toluene-2,4-diisocyanate, the ratio of 4-vulcabond is 0.2 ~ 0.3kg:0.3 ~ 0.42kg;
(6) after described polyvinyl alcohol-silica-epoxy solution being mixed with described base polyurethane prepolymer for use as, mechanical stirring 1 ~ 2 h at 50 ~ 70 DEG C, then linking agent DMP-30 is added rapidly, continue to be stirred to mixture solidification, solid vacuum outgas at 70 ~ 90 DEG C, drying 10 ~ 14 hours, namely obtain Nano-meter SiO_2 2modified PVA-EP-PU interpenetrating polymer networks matrix material; Described DMP-30 add-on is 1 ~ 2% of epoxy resin quality.
2. nano Si O as claimed in claim 1 2the preparation method of modified PVA-EP-PU interpenetrating polymer networks matrix material, is characterized in that: described step (1) in the median size of nano silicon be 20 ~ 50 nanometers.
3. nano Si O as claimed in claim 1 2the preparation method of modified PVA-EP-PU interpenetrating polymer networks matrix material, is characterized in that: described step (2) in the equal relative molecular mass of number of polyvinyl alcohol be 140000 ~ 210000.
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CN105774182A (en) * 2016-03-24 2016-07-20 中国科学技术大学 Composite material having shell nacre-imitated layered structure as well as preparation method and application of composite material
CN108144130A (en) * 2016-12-02 2018-06-12 先健科技(深圳)有限公司 Anti- high pressure sacculus and its preparation method on surface layer
CN108751209A (en) * 2018-06-08 2018-11-06 安徽大学 Preparation method and application of chain-shaped nano silicon dioxide
CN114632500A (en) * 2022-03-31 2022-06-17 杭州干将实业有限公司 Drying agent for precise optical instrument and preparation method thereof
CN115724435A (en) * 2022-12-15 2023-03-03 深圳先进电子材料国际创新研究院 Silicon dioxide powder and preparation method and application thereof

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CN103935092A (en) * 2014-04-11 2014-07-23 四川东材科技集团股份有限公司 Polyester-phenol-polyvinyl butyral-epoxy composite material and preparation method thereof

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CN102372815A (en) * 2010-08-23 2012-03-14 中国石油化工股份有限公司 Preparation method for organic/inorganic nano composite resin
CN103935092A (en) * 2014-04-11 2014-07-23 四川东材科技集团股份有限公司 Polyester-phenol-polyvinyl butyral-epoxy composite material and preparation method thereof

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105774182A (en) * 2016-03-24 2016-07-20 中国科学技术大学 Composite material having shell nacre-imitated layered structure as well as preparation method and application of composite material
CN108144130A (en) * 2016-12-02 2018-06-12 先健科技(深圳)有限公司 Anti- high pressure sacculus and its preparation method on surface layer
CN108751209A (en) * 2018-06-08 2018-11-06 安徽大学 Preparation method and application of chain-shaped nano silicon dioxide
CN108751209B (en) * 2018-06-08 2022-01-18 安徽大学 Preparation method and application of chain-shaped nano silicon dioxide
CN114632500A (en) * 2022-03-31 2022-06-17 杭州干将实业有限公司 Drying agent for precise optical instrument and preparation method thereof
CN115724435A (en) * 2022-12-15 2023-03-03 深圳先进电子材料国际创新研究院 Silicon dioxide powder and preparation method and application thereof

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