CN100494273C - Method for preparing polyester/SiO2 nano composite material - Google Patents
Method for preparing polyester/SiO2 nano composite material Download PDFInfo
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- CN100494273C CN100494273C CNB2007101306705A CN200710130670A CN100494273C CN 100494273 C CN100494273 C CN 100494273C CN B2007101306705 A CNB2007101306705 A CN B2007101306705A CN 200710130670 A CN200710130670 A CN 200710130670A CN 100494273 C CN100494273 C CN 100494273C
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Abstract
The present invention provides sol-gel process for producing nanometer composite polyester/SiO2 material, and features that inorganic component precursor ethyl silicate is added into the esterification reaction system of aromatic binary carboxylic acid or its ester and glycol before the polycondensation reaction to prepare the nanometer composite polyester/SiO2 material.
Description
Technical field
The present invention relates to the polymer based nanocomposites field, more particularly relate to polyester/SiO
2The preparation method of nano composite material.
Background technology
Polyester is a kind of polymkeric substance of high comprehensive performance, is widely used in textile fibres, wrapping material and engineering plastics.Yet it also has easy firing, and thermal denaturation temperature is low, and crystallization rate is also low, and shortcoming such as easy balling-up has limited it and used more widely when using as fiber.Inorganic materials has excellent heat resistance and flame retardant resistance, high strength, high rigidity, and inorganic nano-particle has nanoscale effect, big specific surface area, volume effect, with the strong interfacial interaction of polymeric matrix etc.If polymkeric substance and inorganic nano material are reached the compound of nanoscale, just can be in conjunction with the advantage of two kinds of materials.
Disclose the method for utilizing in-situ method synthesizing polyester/nanometer silicon dioxide composite material in Chinese patent application 200410066594.2, wherein nano silicon can obviously improve the Tc and the polymerization degree of polyester as crystallization nucleating agent.But the shortcoming of this method is to adopt before preparation one or more special coupling agents to nanometer SiO
2Surface modification and dispersion, thus complex manufacturing made, limited the application of this method.
The applicant has carried out a large amount of deep researchs to the production method of polyester/nano silicon dioxide composite material, found that with the tetraethoxy to be precursor, adopt sol-gel method to produce the short-cut method of polyester/nano silicon dioxide composite material, thereby finished the present invention.
Summary of the invention
The object of the present invention is to provide a kind of novel polyester/SiO
2The preparation method of nano composite material.
Specifically, the invention provides and utilize sol-gel method to produce polyester/SiO
2The method of nano composite material is characterized in that the precursor tetraethoxy of inorganic component is joined in the esterification system of aromatic binary carboxylic acid or its ester and ethylene glycol, prepares polyester/SiO by polycondensation then
2Nano composite material.
More particularly, polyester/SiO of the present invention
2Nano composite material is prepared as follows: make aromatic binary carboxylic acid or its ester and ethylene glycol carry out esterification according to mol ratio 1:1.2～2.0, in esterification reaction process, tetraethoxy is dropwise added, utilize the water that generates in the esterification process, and under the hot environment of system, make tetraethoxy generation sol gel reaction generate SiO
2, esterification is undertaken promptly getting polyester/SiO after the polycondensation by the polyester polycondensation reaction condition after finishing
2Nano composite material.
Perhaps,
More particularly, polyester/SiO of the present invention
2Nano composite material is prepared as follows: make aromatic binary carboxylic acid or its ester and ethylene glycol carry out esterification according to 1:2.5～3.5, after esterification finished, system was cooled to 120～130 ℃, with tetraethoxy and H
2O 1:4～8 in molar ratio adds, and the tetraethoxy consumption accounts for 0.1～20% of polyester total amount in the amount of silicon-dioxide; Keep system temperature to stir 0.5～1.5hr fast at 120～130 ℃, ethanol and the redundant moisture of deviating to produce gradually, and intensification then undertaken promptly getting polyester/SiO after the polycondensation by the polyester polycondensation reaction condition
2Nano composite material.
Further specifically, polyester/SiO of the present invention
2Nano composite material is prepared as follows: in polymerization reaction kettle, add terephthalic acid and ethylene glycol and antimonous oxide, wherein the mol ratio of terephthalic acid and ethylene glycol is 1:1.2～2.0, esterification 3～6hr under 220～240 ℃ and 4～5atm is added dropwise to tetraethoxy gradually in this process; Be warming up to 240～280 ℃, and be evacuated to gradually below the 80Pa, carry out polycondensation 1.0～3hr, promptly get PET/SiO
2Nano composite material.
Perhaps
More specifically progressive, polyester/SiO of the present invention
2Nano composite material is prepared as follows: in polymerization reaction kettle, add terephthalic acid and ethylene glycol and antimonous oxide, the mol ratio of terephthalic acid and ethylene glycol is 1:2.5～3.5, under 220～240 ℃ and 4～5atm, obtain containing the BHET of ethylene glycol behind esterification 3～6hr, be cooled to 130～155 ℃, it is zero exitting to air pressure, adds tetraethoxy and deionized water, wherein tetraethoxy and H
2The mol ratio of O is 1:4～8, and reaction 0.5～1.5hr distills out the ethanol of reaction generation and unnecessary water gradually; Be warming up to 240～280 ℃, and be evacuated to gradually below the 80Pa, carry out polycondensation 1.0～3hr, promptly obtain PET/SiO
2Nano composite material.
Maximum characteristics of the present invention are in sol-gel method, and the hydrolytic process of tetraethoxy is without any need for catalyzer, but utilize the system high-temperature environment, sol gel reaction just can take place within a short period of time generate SiO
2The water hydrolysis that first method in the sol-gel method, tetraethoxy can directly utilize esterification to generate.And sol gel reaction after tetraethoxy then can be realized the uniform mixing of molecular level level with esterification products, takes place and generates SiO in second method in the sol-gel method again
2So, can realize nanometer SiO
2Particle or cubic network reach nano level dispersion in polyester, do not reunite, and make nanometer SiO
2Be dispersed in uniformly in the polyester matrix, so both saved in-situ method before preparation to SiO
2Dispersing technology, can not introduce other impurity again.Simplify reaction process, saved preparation time.
Description of drawings
Fig. 1,2 all is to SiO in the embodiment of the invention 1 and 2 with day island proper Tianjin JEM-1200EX type transmission electron microscope
2Content is 1% matrix material freezing microtome section, the photo of shooting, wherein SiO
2Particle diameter in several nanometers between tens nanometers.
Embodiment
Embodiment 1:
Sol-gel technology: in polymerization reaction kettle, add 393 gram terephthalic acids and 263 gram ethylene glycol, 0.14 gram antimonous oxide, at 220～240 ℃, esterification 3～6hr under 4～5atm is added dropwise to 16 gram tetraethoxys gradually in this process; Be warming up to 240～280 ℃, and be evacuated to gradually below the 80Pa, carry out polycondensation 1.0～3hr, promptly obtain SiO shown in Figure 1
2Content is 1% PET/SiO
2Nano composite material.
Embodiment 2:
Sol-gel technology: in polymerization reaction kettle, add 393 gram terephthalic acids and 440 gram ethylene glycol, 0.14 the gram antimonous oxide at 220～240 ℃, obtains containing the BHET of ethylene glycol behind esterification 3～6hr under 4～5atm, be cooled to 130～155 ℃, it is zero exitting to air pressure, adds tetraethoxy 16 grams, deionized water 6.5 grams, reaction 0.5～1.5hr distills out the ethanol of reaction generation and unnecessary water gradually; Be warming up to 240～280 ℃, and be evacuated to gradually below the 80Pa, carry out polycondensation 1.0～3hr, promptly obtain SiO as shown in Figure 2
2Content is 1% PET/SiO
2Nano composite material.
Claims (2)
1. utilize sol-gel method to produce polyester/SiO
2The method of nano composite material, it is characterized in that may further comprise the steps: make aromatic binary carboxylic acid or its ester and ethylene glycol carry out esterification according to mol ratio 1:1.2～2.0, in esterification reaction process, tetraethoxy is dropwise added, utilize the water that generates in the esterification process, and under the hot environment of system, make tetraethoxy generation sol gel reaction generate SiO
2, esterification is undertaken promptly getting polyester/SiO after the polycondensation by the polyester polycondensation reaction condition after finishing
2Nano composite material.
2. produce polyester/SiO according to the described sol-gel method of utilizing of claim 1
2The method of nano composite material, it is characterized in that may further comprise the steps: in polymerization reaction kettle, add terephthalic acid and ethylene glycol and antimonous oxide, wherein the mol ratio of terephthalic acid and ethylene glycol is 1:1.2～2.0, esterification 3～6hr under 220～240 ℃ and 4～5atm dropwise adds tetraethoxy in this process; Be warming up to 240～280 ℃, and be evacuated to gradually below the 80Pa, carry out polycondensation 1.0～3hr, promptly get polyethylene terephthalate/SiO
2Nano composite material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007101306705A CN100494273C (en) | 2007-07-13 | 2007-07-13 | Method for preparing polyester/SiO2 nano composite material |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007101306705A CN100494273C (en) | 2007-07-13 | 2007-07-13 | Method for preparing polyester/SiO2 nano composite material |
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|---|---|
| CN101077924A CN101077924A (en) | 2007-11-28 |
| CN100494273C true CN100494273C (en) | 2009-06-03 |
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| CNB2007101306705A Expired - Fee Related CN100494273C (en) | 2007-07-13 | 2007-07-13 | Method for preparing polyester/SiO2 nano composite material |
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Families Citing this family (12)
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| CN101293115B (en) * | 2008-06-25 | 2011-05-04 | 山东大学 | Method for preparing stephanoporate bracket with biological activity by introducing SiO2 into polymer |
| CN101775124B (en) * | 2010-02-11 | 2012-07-25 | 东华大学 | Method for preparing abrasion-resistant scratch-resistant stable transparent polyester paint substrate |
| CN101838447B (en) * | 2010-05-25 | 2012-05-30 | 南通华盛新材料股份有限公司 | Fully-degradable polyester/inorganic nanoparticle composite material and method for preparing same |
| CN105111692B (en) * | 2015-10-12 | 2018-02-06 | 天津凯华绝缘材料股份有限公司 | One kind contains Nano-meter SiO_22High-flexibility composition epoxy resin of material and preparation method thereof |
| CN105400162A (en) * | 2016-01-04 | 2016-03-16 | 无限极（中国）有限公司 | Plastic material, preparation method thereof and finished plastic product |
| CN106084196B (en) * | 2016-08-12 | 2018-02-06 | 青岛大学 | A kind of two block low polymer engrafted nanometer silicon dioxide granules, preparation method and polyester |
| CN109321164B (en) * | 2016-12-25 | 2021-04-13 | 清远市汇合彩新材料有限公司 | Release film |
| CN109092246A (en) * | 2018-08-29 | 2018-12-28 | 佛山市禅城区诺高环保科技有限公司 | A kind of preparation method of porous carbon adsorbing material |
| CN109265973A (en) * | 2018-09-26 | 2019-01-25 | 德清舒华泡沫座椅有限公司 | A kind of preparation method of anti-electromagnetic radiation polyurethane foam |
| CN109280363A (en) * | 2018-09-26 | 2019-01-29 | 德清舒华泡沫座椅有限公司 | A kind of anti-electromagnetic radiation polyurethane foam |
| CN111019304B (en) * | 2019-12-23 | 2021-05-18 | 浙江大学 | Biodegradable nano composite material |
| CN113956448A (en) * | 2021-10-26 | 2022-01-21 | 四川东材科技集团股份有限公司 | Polyester master batch for optical film and preparation method thereof |
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