CN101812219A - In situ growth preparing method of polyester/ silicon dioxide nano-hybrid material and product thereof - Google Patents
In situ growth preparing method of polyester/ silicon dioxide nano-hybrid material and product thereof Download PDFInfo
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Abstract
The invention belongs to the preparation field of organic and inorganic nano-hybrid material, and more particularly relates to an in situ growth preparing method of polyester/ silicon dioxide nano-hybrid material and a product thereof. The method is an improvement of the existing sol-gel method, and comprises the steps of: adding ortho-silicate ester sol solution into polyester solution; after organic solvent is volatilized, carrying out hydro-thermal treatment with mild condition; and leading the hydrolytic condensation reaction of the ortho-silicate ester to be carried out in polymer in situ. The in situ growth preparing method of the polyester/ silicon dioxide nano-hybrid material can be used for obtaining the polyester/ silicon dioxide nano-hybrid material which has the nano silicon dioxide granules with the grain diameter of 5-200nm, is evenly dispersed in a base body and has more uniform grain diameter. Compared with the prior art, the invention achieves the aim of even dispersion without surface treatment for the nano silicon dioxide, and has simple technique and mild reaction condition.
Description
Technical field
The invention belongs to the preparation field of organosilicon/inorganic nano-hybrid material, particularly a kind of growth in situ preparation method of polyester/silicon dioxide nano-hybrid material and the product that obtains by this method thereof.
Background technology
Along with science and technology development, the material of single character can not satisfy people's needs, the compound a kind of trend that changes into to the modern material development.Function by two or more materials is compound, performance complement and optimization, can obtain the matrix material of high comprehensive performance.Nano inoganic particle is because of its distinctive small-size effect, surface effects and quantum tunneling effect, add in the polymkeric substance, not only can improve intensity, toughness, the rigidity of polymkeric substance, it is functional also might to obtain excellent light transmission, barrier, thermotolerance, electroconductibility, fungus and mildew resistance, wave absorbtion, anti-ultraviolet radiation etc.
For general organic/inorganic composite material, be dispersed in inorganic component size in the polymeric matrix usually more than micron order, usually only as filler or weighting agent.People urgently wish to prepare a kind of inorganics and polymkeric substance carry out compound on the molecular level and inorganic component with the matrix material of nano level size dispersion in matrix, i.e. " organosilicon/inorganic nano-hybrid material ".
Organosilicon/inorganic nano-hybrid material combines characteristics separately such as toughness, workability of rigidity, thermostability and the polymer materials of inorganic materials.Its character not only depends on the character of single component, more depends on the interaction between biphase pattern and the two-phase.The character of nano-hybrid material be not only simply adding of two constitutive properties and, and show many other excellent properties usually.
A kind of important preparation method of organosilicon/inorganic nano-hybrid material is a sol-gel method.Sol-gel method prepares hybrid material can be divided into two types usually: a kind of is that presoma with inorganics joins the condensation reaction that is hydrolyzed in the polymeric matrix and obtains hybrid material, is referred to as the growth in situ method; Another kind is that the presoma with inorganics joins in the polymer monomer, and the hydrolysis-condensation reaction of monomer polymerization and presoma carries out simultaneously.At present, the report for preparing organosilicon/inorganic nano-hybrid material about sol-gel method is of common occurrence, for example polyimide silicon dioxide nano-hybrid material (CN 1831034A), Resins, epoxy silicon dioxide hybrid materials (CN 1887957A), polyacrylic acid (or polymethyl acrylic acid, Poly(Hydroxyethyl Methacrylate)) silicon dioxide nano-hybrid material (CN 1176951C) etc.Yet, be that the polymer inorganic nano-hybrid material of matrix does not appear in the newspapers as yet with the thermoplastic polyester about adopting sol-gel process.
Polyethylene terephthalate (be called for short PET) is widely used in fields such as synthon, film, wrapping material and engineering plastics as a kind of modal thermoplastic polyester with characteristics such as its excellent thermotolerance, chemical solvent resistance, dimensional stability, dielectric properties and mechanical property.Drawbacks limit such as but its crystallization velocity is slow, melt strength is low its large-scale application.In recent years, the investigator attempts introducing nano level inorganic component and improves its performance in the pet polymer matrix, and has obtained certain progress.
Nano silicon (chemical formula SiO
2) be applied in the polymkeric substance as a kind of inorganic nano-filler, can improve the over-all properties of polymkeric substance, but because the existence of its surface hydroxyl and unsaturated residual bond shows very strong wetting ability, poor with the polymeric matrix consistency, adopt general blend method to be difficult to reach homodisperse.Therefore must carry out surface treatment to nano silicon, make its surface show as hydrophobicity, yet this makes become complexity and cost of the preparation technology of matrix material improve again.Therefore how to realize that not needing to carry out surface treatment just can reach the homodisperse target of nano silicon in polyester matrix, just become the important topic of pendulum in face of material supplier author.The growth in situ legal system is equipped with polyester/silicon dioxide nano-hybrid material provides a kind of possibility for realizing this target.
Summary of the invention
The object of the present invention is to provide a kind of growth in situ preparation method of polyester/silicon dioxide nano-hybrid material.
Another object of the present invention is to provide polyester/silicon dioxide nano-hybrid material by the growth in situ preparation method acquisition of polyester/silicon dioxide nano-hybrid material, with the nano-grade size homodisperse, and can regulate and control by changing reaction conditions by the particle size of nano silicon in polyester matrix for silicon-dioxide.
The growth in situ preparation method of polyester/silicon dioxide nano-hybrid material of the present invention, it is the restricted clearance between nanoscale and micro-meter scale that utilizes the polymer molecule chain network to provide, make silica dioxide granule growth in situ in this restricted clearance, and the hydrogen bond action of ester group makes the silica dioxide granule stable existence in restricted clearance and be difficult for reuniting on the surface hydroxyl of silica dioxide granule and the polyester molecule chain, thereby obtains with the homodisperse organic-inorganic hybrid material of nano-grade size.
The growth in situ preparation method of polyester/silicon dioxide nano-hybrid material of the present invention may further comprise the steps:
1) under proper temperature and whipped state, the positive silicon ester of 1～10 weight part is slowly joined in the organic solvent, (being generally 0.5～3 hour) continued to stir in the reinforced back of finishing, and forms concentration and be the silicon ester sol solution just uniformly of 1～20wt%;
2) the positive silicon ester sol solution that step 1) is obtained joins in the polyester liquid that is mixed with the organic solvent dissolution polyester, under proper temperature, stir (being generally 0.5～3 hour) and form the transparent polyester of stable uniform/positive silicon ester sol system down, remove the organic solvent in the system then, form the hybrid material presoma;
Wherein, in polyester/positive silicon ester sol system, the concentration of polyester is 1～20wt%, and it is 0.1～40wt% that the concentration of positive silicon ester is calculated the content of positive silicon ester in polyester/positive silicon ester sol system with silicon-dioxide; It is 1～28wt% that the concentration of preferred positive silicon ester is calculated the content of positive silicon ester in polyester/positive silicon ester sol system with silicon-dioxide;
3) with step 2) to be presented to temperature be after carrying out hydrothermal treatment consists in 50～100 ℃ acidic aqueous solution or the alkaline aqueous solution for the hybrid material presoma that obtains, take out product, product at 50～100 ℃ of following constant pressure and dries or 50～100 ℃ of following vacuum-dryings, is promptly obtained polyester/silicon dioxide nano-hybrid material.
The polyester/silicon dioxide nano-hybrid material that obtains by aforesaid method, its nano silicon is uniformly dispersed in polyester matrix, and the content of nano silicon in hybrid material is 0.1～40wt%, and the particle diameter of nano silicon is 5～200nm, and size distribution is than homogeneous.
Step 1) and step 2) in the scope of preparation temperature all be-20～40 ℃, preferred stable range is 0～10 ℃.
The described positive silicon ester with 1～10 weight part of step 1) slowly joins in the organic solvent, is that the positive silicon ester with 1～10 weight part joins in the solvent of 50～100 weight parts, is as the criterion with the weight of positive silicon ester.
In order to make the organic solvent volatilization fully, step 2) described organic solvent removes, be earlier the organic solvent in polyester/positive silicon ester sol system to be vapored away, then at 50～100 ℃ of following constant pressure and dries or 50～100 ℃ of following vacuum-dryings, to remove organic solvent residual; Perhaps adopt earlier coprecipitation method to carry out co-precipitation: (described non-solvent is meant the organic solvent that mixes with above-mentioned organic solvent but at least can not dissolved polyester with non-solvent with polyester/positive silicon ester sol system earlier, as methyl alcohol, ethanol or their mixture etc.) carry out co-precipitation, make polyester and positive silicon ester colloidal sol precipitate simultaneously, then coprecipitation product is carried out constant pressure and dry under 50～100 ℃ or 50～100 ℃ of following vacuum-dryings.
The pH value scope of the described acidic aqueous solution of step 3) is 3～5; The pH value scope of described alkaline aqueous solution is 9～10.
The acid that is used to regulate pH value of water solution is mineral acid, organic acid or their mixture; Described mineral acid comprises hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid or any mixture between them; Described organic acid comprises acetate, formic acid, vinylformic acid, citric acid or any mixture between them.
The alkali that is used to regulate pH value of water solution is sodium hydroxide, potassium hydroxide, ammoniacal liquor or any mixture between them.
The described hydrothermal treatment consists time of step 3) is 2～24 hours; The described time at 50～100 ℃ of following constant pressure and dries is 2～24 hours; Described is 2～24 hours 50～100 ℃ of following vacuum drying times.
The used organic solvent of the positive silicon ester sol solution of preparation can be identical in the organic solvent of the dissolved polyester step 2) and the step 1), also can be different.
Described organic solvent comprises a kind of or any mixture between them in halohydrocarbon, aldehydes matter, halogenated carboxylic acid, hexafluoroisopropanol, phenylcarbinol, the oil of mirbane.
Described halogenated alkane is methylene dichloride, trichloromethane, tetrachloromethane, ethylene dichloride, chlorobenzene, company's dichlorobenzene etc. or any mixture between them.
Described aldehydes matter is phenol, methylphenol, chlorophenol etc. or any mixture between them.
Described halogenated carboxylic acid is Mono Chloro Acetic Acid, dichloro acetic acid, trichoroacetic acid(TCA), difluoroacetic acid, trifluoroacetic acid etc. or any mixture between them.
Described polyester is selected from polyethylene terephthalate (being called for short PET) or its multipolymer, polybutylene terephthalate (being called for short PBT) or its multipolymer, polytrimethylene terephthalate (be called for short PTT) or its multipolymer, a kind of in Polyethylene Naphthalate (being called for short PEN) or its multipolymer or greater than more than one mixture.
Described positive silicon ester is a kind of in methyl silicate (TMOS), tetraethoxy (TEOS), positive silicic acid propyl ester (TPOS), the butyl silicate (TBOS) or greater than more than one mixture.
Described stirring is selected from more than one in ultra-sonic oscillation, mechanical stirring and the magnetic agitation.
Method of the present invention is that existing sol-gel method is improved, in polyester liquid, add positive silicon ester sol solution, treat to carry out after organic solvent volatilizees the hydrothermal treatment consists of mild condition, make hydrolysis-condensation reaction original position in polymkeric substance of positive silicon ester carry out obtaining.Use the growth in situ preparation method of polyester/silicon dioxide nano-hybrid material provided by the invention, the nanometer silicon dioxide particle that can obtain particle diameter and be 5～200nm be dispersed in the matrix and size distribution than the polyester/silicon dioxide nano-hybrid material of homogeneous.Method of the present invention compared with prior art, method of the present invention not needing to have realized that nano silicon is carried out surface treatment just can reach aim of even dispersion, and technology is simple, the reaction conditions gentleness.
The polyester/silicon dioxide nano-hybrid material of the inventive method preparation has confirmed that through scanning electronic microscope (SEM) and transmission electron microscope (TEM) nano silicon is uniformly dispersed in polyester, and grain diameter is between 5～200nm.
Polyester/silicon dioxide nano-hybrid material of the present invention has higher thermostability, and silicon-dioxide can play effective heterogeneous nucleation effect, improves the crystallization rate of polyester.
Description of drawings
Fig. 1. nanometer silicon dioxide particle is dispersed in the transmission electron microscope photo in the alcohol solvent, and this nanometer silicon dioxide particle is the nanometer silicon dioxide particle after the PET/ silicon dioxide nano-hybrid material of preparation in the embodiment of the invention 4 is removed the PET matrix.
Fig. 2. the PET/ silicon dioxide nano-hybrid material adds pure PET through melt blending to be diluted to dioxide-containing silica is profile scanning Electronic Speculum (SEM) photo behind the 10wt% in the embodiment of the invention 4, and magnification is 20000 times.
Fig. 3. the PET/ silicon dioxide nano-hybrid material adds pure PET through melt blending to be diluted to dioxide-containing silica is profile scanning Electronic Speculum (SEM) photo behind the 10wt% in the embodiment of the invention 4, and magnification is 80000 times.
Fig. 4. the PET/ silicon dioxide nano-hybrid material adds pure PET through melt blending to be diluted to dioxide-containing silica is ultrathin section(ing) high-resolution-ration transmission electric-lens (HRTEM) macrograph behind the 1wt% in the embodiment of the invention 4.
Fig. 5. the PET/ silicon dioxide nano-hybrid material adds pure PET through melt blending to be diluted to dioxide-containing silica is ultrathin section(ing) high-resolution-ration transmission electric-lens (HRTEM) high power photo behind the 1wt% in the embodiment of the invention 4.
Embodiment
Below in conjunction with embodiment and accompanying drawing technical scheme of the present invention is further described, but these embodiment do not constitute the restriction to content of the present invention.
Embodiment 1
1.2g polyethylene terephthalate (PET) is joined the methylene dichloride and the trifluoroacetic acid that fill 6mL equal-volume ratio mix in the 10mL sample bottle of solvent, magnetic agitation is 1.5 hours in 8 ℃ ice-water bath, PET is fully dissolved obtain PET solution.0.044g tetraethoxy (TEOS) is joined the methylene dichloride and the trifluoroacetic acid that fill 1.5mL equal-volume ratio to be mixed in the 10mL sample bottle of solvent, magnetic agitation is 1.5 hours in 8 ℃ ice-water bath, and thorough mixing evenly obtains the tetraethoxy sol solution of transparent and stable homogeneous.
The tetraethoxy sol solution is joined in the PET solution, and magnetic agitation is 1.5 hours in 8 ℃ ice-water bath, mixes, pour in the weighing bottle of given volume, with solvent evaporates, the solvent that remains in the product is removed in 70 ℃ of following vacuum-drying 2 hours in stink cupboard.With the hybrid material presoma that obtains put into the pH value be 9～10 and temperature be that 70 ℃ ammonia soln carried out hydrothermal treatment consists 5 hours, take out product, at last with the product that takes out 70 ℃ of following vacuum-dryings 12 hours, promptly obtain PET/SiO
2Nano-hybrid material.Dioxide-containing silica in the hybrid material is 1wt%.Be uniformly dispersed in the PET matrix to nano silicon by transmission electron microscope observing, the median size of silicon dioxide granule is 67.4nm.
Embodiment 2
1.2g polybutylene terephthalate (PBT) is joined the methylene dichloride and the trifluoroacetic acid that fill 6mL equal-volume ratio mix in the 10mL sample bottle of solvent, magnetic agitation is 1.5 hours in 8 ℃ ice-water bath, PBT is fully dissolved obtain PBT solution.0.22g tetraethoxy (TEOS) is joined the methylene dichloride and the trifluoroacetic acid that fill 1.5mL equal-volume ratio to be mixed in the 10mL sample bottle of solvent, magnetic agitation is 1.5 hours in 8 ℃ ice-water bath, and thorough mixing evenly obtains the tetraethoxy sol solution of transparent and stable homogeneous.
The tetraethoxy sol solution is joined in the PBT solution, and magnetic agitation is 1.5 hours in 8 ℃ ice-water bath, mixes, and pours in the weighing bottle of given volume, and with solvent evaporates, the solvent that remains in the product is removed in 70 ℃ of following vacuum-drying 2 hours.With the hybrid material presoma that obtains put into the pH value be 9～10 and temperature be that 70 ℃ ammonia soln carried out hydrothermal treatment consists 5 hours, take out product, at last with the product that takes out 70 ℃ of following vacuum-dryings 12 hours, promptly obtain PBT/SiO
2Nano-hybrid material.Dioxide-containing silica in the hybrid material is 5wt%.Be uniformly dispersed in the PBT matrix to nano silicon by transmission electron microscope observing, the median size of silicon dioxide granule is 52.1nm.
Embodiment 3
1.2g PET is joined the methylene dichloride and the trifluoroacetic acid that fill 6mL equal-volume ratio mix in the 10mL sample bottle of solvent, magnetic agitation is 1.5 hours in 8 ℃ ice-water bath, PET is fully dissolved obtain PET solution.0.44g methyl silicate (TMOS) is joined the methylene dichloride and the trifluoroacetic acid that fill 1.5mL equal-volume ratio to be mixed in the 10mL sample bottle of solvent, magnetic agitation is 1.5 hours in 8 ℃ ice-water bath, and thorough mixing evenly obtains the TMOS sol solution of transparent and stable homogeneous.
The TMOS sol solution is joined in the PET solution, magnetic agitation is 1.5 hours in 8 ℃ ice-water bath, mix, use methyl alcohol as non-solvent then, adopt coprecipitation method that PET and TMOS colloidal sol are precipitated simultaneously, throw out 70 ℃ of following vacuum-dryings 2 hours, is removed the solvent that remains in the product.With the hybrid material presoma that obtains put into the pH value be 9～10 and temperature be that 70 ℃ sodium hydroxide solution carried out hydrothermal treatment consists 5 hours, take out product, at last with the product that takes out 70 ℃ of following vacuum-dryings 12 hours, promptly obtain PET/SiO
2Nano-hybrid material.Dioxide-containing silica in the hybrid material is 10wt%.Be uniformly dispersed in the PET matrix to nano silicon by transmission electron microscope observing, the median size of silicon dioxide granule is 25.3nm.
Embodiment 4
4.5g PET is joined the methylene dichloride and the trifluoroacetic acid that fill 20mL equal-volume ratio mix in the 50mL Erlenmeyer flask of solvent, magnetic agitation is 1.5 hours in 8 ℃ ice-water bath, PET is fully dissolved obtain PET solution.6.4g tetraethoxy (TEOS) is joined the methylene dichloride and the trifluoroacetic acid that fill 10mL equal-volume ratio to be mixed in the 50mL Erlenmeyer flask of solvent, mechanical stirring is 1.5 hours in 8 ℃ ice-water bath, and thorough mixing evenly obtains the TEOS sol solution of transparent and stable homogeneous.
The TEOS sol solution is joined in the PET solution, and mechanical stirring is 1.5 hours in 8 ℃ ice-water bath, mixes, and pours in the weighing bottle of given volume, and with solvent evaporates, the solvent that remains in the product is removed in 70 ℃ of following vacuum-drying 2 hours.With the hybrid material presoma that obtains put into the pH value be 9～10 and temperature be that 70 ℃ sodium hydroxide solution carried out hydrothermal treatment consists 5 hours, take out product, at last with the product that takes out 70 ℃ of following vacuum-dryings 12 hours, promptly obtain PET/SiO
2Nano-hybrid material.Dioxide-containing silica in the hybrid material is 40wt%.
The PET/ silicon dioxide nano-hybrid material that obtains is dissolved in the methylene dichloride and the mixed solvent of trifluoroacetic acid of equal-volume ratio, remove the PET matrix, centrifugation obtains nanometer silicon dioxide particle, this nanometer silicon dioxide particle is dispersed in the alcohol solvent, and the pattern by this nanometer silicon dioxide particle of transmission electron microscope observing as shown in Figure 1.The median size that is obtained silicon dioxide granule by figure is 18.2nm.
The PET/ silicon dioxide nano-hybrid material through melt blending add pure PET be diluted to dioxide-containing silica be behind the 10wt% profile scanning Electronic Speculum (SEM) macrograph as shown in Figure 2.
The PET/ silicon dioxide nano-hybrid material through melt blending add pure PET be diluted to dioxide-containing silica be behind the 10wt% profile scanning Electronic Speculum (SEM) high power photo as shown in Figure 3.
The PET/ silicon dioxide nano-hybrid material through melt blending add pure PET be diluted to dioxide-containing silica be behind the 1wt% ultrathin section(ing) high-resolution-ration transmission electric-lens (HRTEM) macrograph as shown in Figure 4.
The PET/ silicon dioxide nano-hybrid material through melt blending add pure PET be diluted to dioxide-containing silica be behind the 1wt% ultrathin section(ing) high-resolution-ration transmission electric-lens (HRTEM) high power photo as shown in Figure 5.
Embodiment 5
10g PET is joined the methylene dichloride and the trifluoroacetic acid that fill 50mL equal-volume ratio mix in the 200mL Erlenmeyer flask of solvent, magnetic agitation is 1.5 hours in 8 ℃ ice-water bath, PET is fully dissolved obtain PET solution.6.93gTEOS is joined the methylene dichloride and the trifluoroacetic acid that fill 12.5mL equal-volume ratio mix in the 50mL Erlenmeyer flask of solvent, magnetic agitation is 1.5 hours in 8 ℃ ice-water bath, and thorough mixing evenly obtains the TEOS sol solution of transparent and stable homogeneous.
The TEOS sol solution is joined in the PET solution, and magnetic agitation is 1.5 hours in 8 ℃ ice-water bath, mixes, and pours in the weighing bottle of given volume, and with solvent evaporates, the solvent that remains in the product is removed in 70 ℃ of following vacuum-drying 2 hours.With the hybrid material presoma that obtains put into the pH value be 9～10 and temperature be that 70 ℃ sodium hydroxide solution carried out hydrothermal treatment consists 5 hours, take out product, at last with the product that takes out 70 ℃ of following vacuum-dryings 12 hours, promptly obtain PET/SiO
2Nano-hybrid material.Dioxide-containing silica in the hybrid material is 20wt%.Be uniformly dispersed in the PET matrix to nano silicon by transmission electron microscope observing, the median size of silicon dioxide granule is 17.8nm.
Embodiment 6
Adopt preparation method and the processing condition of embodiment 1, just the hybrid material presoma that obtains among the embodiment 1 is not put into ammonia soln, carry out hydrothermal treatment consists but put into aqueous solution of hydrochloric acid, the pH value is 4～5, temperature is 70 ℃, treatment time is 5 hours, at last with product 70 ℃ of following vacuum-dryings 12 hours, can obtain PET/SiO equally
2Nano-hybrid material.Dioxide-containing silica in the hybrid material is 1wt%.Be uniformly dispersed in the PET matrix to nano silicon by transmission electron microscope observing, the median size of silicon dioxide granule is 67.4nm.
Claims (10)
1. the growth in situ preparation method of a polyester/silicon dioxide nano-hybrid material is characterized in that, this method may further comprise the steps:
1) under whipped state, the positive silicon ester of 1～10 weight part is slowly joined in the organic solvent, the reinforced back of finishing continues to stir, and forms concentration and be the silicon ester sol solution just uniformly of 1～20wt%;
2) the positive silicon ester sol solution that step 1) is obtained joins in the polyester liquid that is mixed with the organic solvent dissolution polyester, under agitation forms polyester/positive silicon ester sol system, removes the organic solvent in the system then, forms the hybrid material presoma;
Wherein, in polyester/positive silicon ester sol system, the concentration of polyester is 1～20wt%, and it is 0.1～40wt% that the concentration of positive silicon ester is calculated the content of positive silicon ester in polyester/positive silicon ester sol system with silicon-dioxide;
3) with step 2) to be presented to temperature be after carrying out hydrothermal treatment consists in 50～100 ℃ acidic aqueous solution or the alkaline aqueous solution for the hybrid material presoma that obtains, take out product, product at 50～100 ℃ of following constant pressure and dries or 50～100 ℃ of following vacuum-dryings, is promptly obtained polyester/silicon dioxide nano-hybrid material.
2. method according to claim 1 is characterized in that: step 1) and step 2) in the scope of preparation temperature be-20～40 ℃.
3. method according to claim 1, it is characterized in that: step 2) the removing of described organic solvent, be earlier the organic solvent in polyester/positive silicon ester sol system to be vapored away, then at 50～100 ℃ of following constant pressure and dries or 50～100 ℃ of following vacuum-dryings, to remove organic solvent residual; Perhaps adopt earlier coprecipitation method to carry out co-precipitation, then coprecipitation product is carried out constant pressure and dry under 50～100 ℃ or 50～100 ℃ of following vacuum-dryings.
4. method according to claim 1 is characterized in that: the pH value scope of the described acidic aqueous solution of step 3) is 3～5; The pH value scope of described alkaline aqueous solution is 9～10.
5. according to claim 1 or 4 described methods, it is characterized in that: the acid that is used to regulate pH value of water solution is hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetate, formic acid, vinylformic acid, citric acid or any mixture between them;
The alkali that is used to regulate pH value of water solution is sodium hydroxide, potassium hydroxide, ammoniacal liquor or any mixture between them.
6. method according to claim 1 is characterized in that: the described hydrothermal treatment consists time of step 3) is 2～24 hours.
7. according to claim 1 or 3 described methods, it is characterized in that: described organic solvent comprises a kind of or any mixture between them in halohydrocarbon, aldehydes matter, halogenated carboxylic acid, hexafluoroisopropanol, phenylcarbinol, the oil of mirbane.
8. method according to claim 7 is characterized in that: described halogenated alkane is methylene dichloride, trichloromethane, tetrachloromethane, ethylene dichloride, chlorobenzene, connects dichlorobenzene or any mixture between them;
Described aldehydes matter is phenol, methylphenol, chlorophenol or any mixture between them;
Described halogenated carboxylic acid is Mono Chloro Acetic Acid, dichloro acetic acid, trichoroacetic acid(TCA), difluoroacetic acid, trifluoroacetic acid or any mixture between them.
9. method according to claim 1, it is characterized in that: described polyester is selected from polyethylene terephthalate or its multipolymer, polybutylene terephthalate or its multipolymer, polytrimethylene terephthalate or its multipolymer, a kind of in Polyethylene Naphthalate or its multipolymer or greater than more than one mixture;
Described positive silicon ester is a kind of in methyl silicate, tetraethoxy, positive silicic acid propyl ester, the butyl silicate or greater than more than one mixture.
10. one kind by any polyester/silicon dioxide nano-hybrid material that method prepares of claim 1～9, it is characterized in that: nano silicon is uniformly dispersed in polyester matrix, and the content of nano silicon in hybrid material is 0.1～40wt%, and the particle diameter of nano silicon is 5～200nm.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103972445A (en) * | 2013-01-28 | 2014-08-06 | 海洋王照明科技股份有限公司 | Electrochemical power supply diaphragm and preparation method thereof, and electrochemical battery or capacitor |
| CN106585024A (en) * | 2016-12-28 | 2017-04-26 | 江苏东材新材料有限责任公司 | High-temperature low-precipitate optical polyester-based film and preparation method thereof |
| CN109321164A (en) * | 2016-12-25 | 2019-02-12 | 金福珍 | A kind of release film |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1085679C (en) * | 1998-05-09 | 2002-05-29 | 中国科学院长春应用化学研究所 | Synthesis of vinyl organic/inorganic nano-size hybridized material |
| CN1291911C (en) * | 2004-12-22 | 2006-12-27 | 华东师范大学 | Method for preparing carbon nanometer tube composites by sol and gel method |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103972445A (en) * | 2013-01-28 | 2014-08-06 | 海洋王照明科技股份有限公司 | Electrochemical power supply diaphragm and preparation method thereof, and electrochemical battery or capacitor |
| CN109321164A (en) * | 2016-12-25 | 2019-02-12 | 金福珍 | A kind of release film |
| CN106585024A (en) * | 2016-12-28 | 2017-04-26 | 江苏东材新材料有限责任公司 | High-temperature low-precipitate optical polyester-based film and preparation method thereof |
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