CN1765951A - Antistatic terylene nanometer composite material and its preparation method - Google Patents
Antistatic terylene nanometer composite material and its preparation method Download PDFInfo
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- CN1765951A CN1765951A CN 200510110513 CN200510110513A CN1765951A CN 1765951 A CN1765951 A CN 1765951A CN 200510110513 CN200510110513 CN 200510110513 CN 200510110513 A CN200510110513 A CN 200510110513A CN 1765951 A CN1765951 A CN 1765951A
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Abstract
The invention discloses a nano composite material as antistatic terylene and its preparation method. Wherein, using TPA, ethandiol, nano particle, catalyst and stablizer s material, esteriying on condition as 1.5MPa at 220~260Deg, and condensing on 30~100Pa at 280Deg. In this invention, the irorganic particle combines with base surface well. This product has well physical and mechanical properties.
Description
Technical field
The present invention relates to a kind of anti-electrostatic polyester material and preparation method thereof, specifically, relate to a kind of terylene and ATO nano-component compound anti-static composite material.
Technical background
Terylene is one of five big synthon, and it has excellent properties such as high strength, high-modulus, high resilience, wear-resisting wiping, dimensional stabilizing, acidproof and pharmaceutical chemicals.The terylene molecule is with covalent bonds, but few polar group, macromolecular compound with regular structure is easy to crystallization, and the hydrophobicity of terylene is very strong, good insulating.Under general state, the ratio resistance of terylene is 10
14More than the Ω cm, friction voltage is greater than 1000 volts, and electrostatic half-life was several hours, even several days.Therefore, the electrostatic problem of terylene has directly had influence on the security of production, processing and the application of terylene textiles, even has restricted the development of terylene to the high-grade application field.
Therefore, providing a kind of antistatic terylene nanometer composite material and preparation method thereof, is the problem that the field of textiles utmost point need solve.
Summary of the invention
The technical issues that need to address of the present invention provide a kind of antistatic terylene nanometer composite material and preparation method thereof, to overcome the complaint defective that prior art exists, satisfy the needs of field of textiles development.
Technical conceive of the present invention is such:
Nano ATO is the adulterated tindioxide semi-conductor of a kind of antimony (ATO is the abbreviation of Antimony Doped TinOxide), and it is to utilize Sb
+ 3Or Sb
+ 5(antimony) doped and substituted Sn
+ 4Formed oxygen room or electronics conducted electricity as current carrier when (tin) formed the defective solid solution, therefore its electroconductibility is not subjected to the restriction of environment humidity, avoided organic antistatic agents to rely on the shortcoming of environment, therefore represented wide application prospect in fields such as electronics, plastics, coating.
The present invention's imagination is compound with the original position of nano ATO and PET, makes the nano ATO particle can really reach nano-scale and disperses, and its transmitance to visible light is increased, and transparency increases, thereby outward appearance, the color and luster of polyester do not exerted an influence; ATO particle nano-scale disperses, and its specific surface area is increased, and forms the conduction network chain, and its conductivity is increased; In addition, in-situ polymerization has solved the anti-static function persistent problem on the one hand.Avoid the antistatic finish process in later stage on the other hand, reduced cost of manufacture.
Antistatic terylene nanometer composite material of the present invention is to adopt the method for in-situ polymerization to obtain, and wherein, the parts by weight content of terylene is 40～100 times of the semi-conductive parts by weight of the adulterated tindioxide of antimony;
Said in-situ polymerization comprises the steps:
(1) be that the adulterated tindioxide semiconductor particle of antimony of 15～25nm is scattered in ethylene glycol with particle diameter;
(2) with terephthalic acid, be dispersed with the semi-conductive ethylene glycol solution of the adulterated tindioxide of antimony, catalyzer and stablizer and under nitrogen protection, react, generate ethylene glycol terephthalate, reaction pressure is 0.2～0.3Mpa, temperature of reaction is 220～265 ℃, the micromolecular water that the fractionation esterification generates during reaction is when there not being water to be the terminal point of esterification when fractionation is come out again;
Raw materials in part by weight is as follows:
100 parts of terephthalic acids
37.5～70 parts of ethylene glycol
0.7～15 part of the adulterated tindioxide semi-conductor of antimony
0.01～0.05 part of catalyzer
The adulterated tindioxide semi-conductor of said antimony is the particle through the silane coupling agent surface modification, and silane coupling agent comprises that aminopropyl triethoxysilane, glycidyl ether oxygen propyl trimethoxy silicane, methacryloxypropyl trimethoxy silicon are or/and 2-aminoethyl-aminopropyl trimethoxysilane;
Adopt silane coupling agent to carry out the method for surface modification to the adulterated tindioxide semi-conductor of antimony, in many documents, disclosed report has been arranged, as the preparation method of CN200510024671.2 nano stibium doped tin oxide dispersing method patent and CN01131908.9 inorganic antistatic water suspensoid in ethylene glycol.
The semi-conductive preparation method of the adulterated tindioxide of said antimony is at the journal 2001Vol of East China University of Science.27No.3 preparation technology is to the influence (author: Qin Changyong of ATO superfine powder conductivity; Luo Meifang; Gu Hongchen; figure south, side) the phase thermal treatment in 2004 the 5th of silicate circular is to influence (author: Hu Yong, Chen Guojian, the old snow plum of doped stannic oxide nanometer bar structure and conductivity; the fixed China of what; Chen Jianding) and 2000 13 phases of Shanghai chemical industry Multifunction ATO ultrafine electricity conductive powder material (author: Qin Changyong, Gu Hongchen, Fang Tunan)
Said catalyzer is a terylene polymerization catalyzer commonly used, in Science Press's terylene chemistry and novel process (1975), detailed report has been arranged, the an alkali metal salt of preferred phenol, alkaline earth salt, the ammonium salt of phosphofluoric acid, cerium salt and nickel salt, the an alkali metal salt of silicic acid, alkaline earth salt, manganese salt, cobalt salt or cadmium salt, the an alkali metal salt of hexafluorosilicic acid, alkaline earth salt, lead salt or manganese salt, alkali-metal hydride, the ammonium salt of second two ammoniums four acetic acid, alkaline earth salt, zinc salt, lead salt, a kind of in cobalt salt or the acetate, preferred manganese acetate of acetate or Cobaltous diacetate;
Said stablizer is a terylene polymerization stablizer commonly used, in Science Press's terylene chemistry and novel process (1975) document, detailed report is being arranged, the compound of compound, phosphoric acid ester, pyrocatechol phosphoric acid ester or the conjugated double bond of the compound of preferred manganese, the compound of antimony, germanium;
(3) product that step (2) is obtained obtains target product the vacuum tightness of 30～100Pa, 270～290 ℃ of following polycondensations 2～3.5 hours.
In the prepared matrix material of the present invention, the adulterated tindioxide semi-conductor nano particles of antimony combines well with the terylene basal body interface, and the fiber filament antistatic property that obtains after its master batch spinning is good, and mechanical property satisfies the post-treatment requirement.
Description of drawings
Fig. 1 is the infrared photograph of product section.
Fig. 2 is the electromicroscopic photograph that does not add the terylene chips of ATO nanoparticle.
Fig. 3 is the electromicroscopic photograph of product section.
Embodiment
The present invention is further elaborated below by embodiment, its objective is to be better understanding content of the present invention.Therefore, the cited case does not limit protection scope of the present invention:
415.7g ethylene glycol solution (the ATO nanoparticle 12.7g that particle diameter is the ATO nanoparticle of 25nm will be dispersed with, ethylene glycol 403g), terephthalic acid 830g, catalyzer (antimonous oxide 0.248g, Cobaltous diacetate 0.017g) and stablizer (trimethyl phosphite 99 14 μ L) add in the reactor feeding N
2, under 1.5MPa and 220 ℃, carrying out esterification, the micromolecular water that the fractionation esterification generates during reaction is when there not being water to be the terminal point of esterification when fractionation is come out again;
After esterification was finished, normal pressure stirred 10 minutes.Beginning vacuumizes the polycondensation of carrying out ethylene glycol terephthalate gradually, and polycondensation is carried out under 280 ℃, and vacuum tightness reached-0.1MPa in 1 hour, continues rapid vacuumizing, finally keeps vacuum tightness to reach 100Pa.Polycondensation 3.5 hours altogether.After reacting completely, stop stirring, pour N
2Pressurization is from discharge hole for discharge, through the water-cooled pelletizing.
The polyester master particle that makes placed after 48 hours, carry out spinning in 120 ℃ of dryings in the DZF-6050 type vacuum drying oven with small-sized spinning-drawing machine.After 24 hours, adopt the YG321 fiber type in 120 ℃ of dryings again after cutting off long filament after the spinning, the electrical property and the breaking tenacity of test fiber than resistance instrument and XL-1 yarn strength instrument (testing) in fiber material modification National Key Laboratory of Donghua University.Test performance is as shown in table 1.
Table 1 embodiment 1 The performance test results
| Volume resistivity ρ (Ω cm) | Average fracture strength (CN/dtex) |
| 4.4×10 9 | 2.22 |
The infrared photograph of product section is seen Fig. 1.
The electromicroscopic photograph of product section is seen Fig. 3.Fig. 2 is the electromicroscopic photograph that does not add the terylene chips of ATO nanoparticle.
Embodiment 2
466.5g ethylene glycol solution (the ATO nanoparticle 63.5g that particle diameter is the ATO nanoparticle of 15nm will be dispersed with, ethylene glycol 403g), terephthalic acid 830g, catalyzer (antimonous oxide 0.248g, Cobaltous diacetate 0.017g) and stablizer (trimethyl phosphite 99 14 μ L) add in the reactor feeding N
2, under 1.5MPa and 260 ℃, carrying out esterification, product is an ethylene glycol terephthalate.Entire reaction is under agitation carried out, and the micromolecular water that continuous fractionation esterification of reaction later stage generates is when there not being water to come to be when fractionation is come out again the terminal point of esterification;
After esterification was finished, normal pressure stirred 10 minutes.Beginning vacuumizes the polycondensation of carrying out ethylene glycol terephthalate gradually, and polycondensation is carried out under 280 ℃, and vacuum tightness reached-0.1MPa in 1 hour, continues rapid vacuumizing, finally keeps vacuum tightness to reach 300Pa.Polycondensation 3.5 hours altogether.After reacting completely, stop stirring, towards N
2Pressurization is from discharge hole for discharge, through the water-cooled pelletizing.
The polyester master particle that makes placed after 48 hours, carry out spinning in 120 ℃ of dryings in the DZF-6050 type vacuum drying oven with small-sized spinning-drawing machine.After 24 hours, adopt electrical property and the breaking tenacity of YG321 fiber type in 120 ℃ of dryings again after cutting off long filament after the spinning than resistance instrument and XL-1 yarn strength instrument (testing) test fiber in fiber material modification National Key Laboratory of Donghua University.Test performance is as shown in table 1.
Table 1 is implemented 2 The performance test results
| Volume resistivity ρ (Ω cm) | Average fracture strength (CN/dtex) |
| 1.8×10 9 | 2.29 |
Claims (5)
1. an antistatic terylene nanometer composite material is characterized in that, is to adopt the method for in-situ polymerization to obtain, and wherein, the parts by weight content of terylene is 40～100 times of the semi-conductive parts by weight of the adulterated tindioxide of antimony.
2. the preparation method of antistatic terylene nanometer composite material according to claim 1 is characterized in that, comprises the steps:
(1) be that the adulterated tindioxide semiconductor particle of antimony of 15～25nm is scattered in ethylene glycol with particle diameter;
(2) with terephthalic acid, be dispersed with the semi-conductive ethylene glycol solution of the adulterated tindioxide of antimony, catalyzer and stablizer and under nitrogen protection, react, generate ethylene glycol terephthalate, reaction pressure is 0.2～0.3Mpa, temperature of reaction is 220～265 ℃, the micromolecular water that the fractionation esterification generates during reaction is when there not being water to be the terminal point of esterification when fractionation is come out again;
Raw materials in part by weight is as follows:
100 parts of terephthalic acids
37.5～70 parts of ethylene glycol
0.7～15 part of the adulterated tindioxide semi-conductor of antimony
0.01～0.05 part of catalyzer
Stablizer 1 * 10
-5～8 * 10
-5Part;
(3) product that step (2) is obtained obtains target product the vacuum tightness of 30～100Pa, 270～290 ℃ of following polycondensations 2～3.5 hours.
3. method according to claim 2 is characterized in that, the adulterated tindioxide semi-conductor of said antimony is the nanoparticle that carries out surface modification through silane coupling agent.
4. method according to claim 3, it is characterized in that silane coupling agent is selected from aminopropyl triethoxysilane, glycidyl ether oxygen propyl trimethoxy silicane, methacryloxypropyl trimethoxy silicon or/and 2-aminoethyl-aminopropyl trimethoxysilane.
5. method according to claim 2, it is characterized in that, said catalyzer is selected from an alkali metal salt of phenol, alkaline earth salt, the ammonium salt of phosphofluoric acid, cerium salt and nickel salt, the an alkali metal salt of silicic acid, alkaline earth salt, manganese salt, cobalt salt or cadmium salt, the an alkali metal salt of hexafluorosilicic acid, alkaline earth salt, lead salt or manganese salt, alkali-metal hydride, the ammonium salt of second two ammoniums four acetic acid, alkaline earth salt, zinc salt, lead salt, a kind of in cobalt salt or the acetate, said stablizer is selected from the compound of manganese, the compound of antimony, the compound of germanium, phosphoric acid ester, the compound of pyrocatechol phosphoric acid ester or conjugated double bond.
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| CN 200510110513 CN1765951A (en) | 2005-11-18 | 2005-11-18 | Antistatic terylene nanometer composite material and its preparation method |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101215373B (en) * | 2008-01-10 | 2010-06-02 | 华东理工大学 | Static electricity resisting polyethylene terephthalate modified resin |
| CN101245217B (en) * | 2007-11-30 | 2011-04-06 | 东南大学 | Stibium doping nano-tin dioxide unsaturated polyester resin heat insulating coating film and manufacture method thereof |
| CN101775127B (en) * | 2009-12-30 | 2011-10-26 | 中国纺织科学研究院 | Hydrophobic modified polyester and preparation method thereof |
| CN101235132B (en) * | 2008-01-10 | 2012-03-21 | 华东理工大学 | Modified method for preparing polyester resin containing stibium doping tin dioxide nano particles |
| CN102391488A (en) * | 2011-09-26 | 2012-03-28 | 四川东方绝缘材料股份有限公司 | Preparation method for fluorine silicon phosphorus-containing anti-dropping flame-retardant polyethylene terephthalate |
| CN102719061A (en) * | 2012-06-07 | 2012-10-10 | 南通华盛高聚物科技发展有限公司 | Full-biodegradable polyester nano-composite and preparation process |
| CN104479117A (en) * | 2014-12-26 | 2015-04-01 | 佛山金智节能膜有限公司 | Method for preparing intelligent temperature-controlpolyester chip with in-situ polymerization method |
| CN104562278A (en) * | 2014-12-30 | 2015-04-29 | 佛山金智节能膜有限公司 | Vanadium dioxide uniformly-dispersed polyester fiber |
| CN105803567A (en) * | 2016-06-08 | 2016-07-27 | 上海洋帆实业有限公司 | Flame-retarded antistatic composite modified polyester fiber and preparation method thereof |
| CN107722247A (en) * | 2017-08-21 | 2018-02-23 | 宁波中金石化有限公司 | A kind of preparation method of antistatic inorganic material-modified paraxylene |
| CN108624010A (en) * | 2018-06-07 | 2018-10-09 | 广东轻工职业技术学院 | A kind of electrostatically dissipative high grade of transparency polyester and preparation method thereof |
| CN114456360A (en) * | 2022-01-20 | 2022-05-10 | 长江师范学院 | Method for preparing polyethylene terephthalate by catalysis |
| CN115094535A (en) * | 2022-06-25 | 2022-09-23 | 杭州明华纺织有限公司 | Antistatic low-stretch yarn fabric and preparation method thereof |
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2005
- 2005-11-18 CN CN 200510110513 patent/CN1765951A/en active Pending
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101245217B (en) * | 2007-11-30 | 2011-04-06 | 东南大学 | Stibium doping nano-tin dioxide unsaturated polyester resin heat insulating coating film and manufacture method thereof |
| CN101215373B (en) * | 2008-01-10 | 2010-06-02 | 华东理工大学 | Static electricity resisting polyethylene terephthalate modified resin |
| CN101235132B (en) * | 2008-01-10 | 2012-03-21 | 华东理工大学 | Modified method for preparing polyester resin containing stibium doping tin dioxide nano particles |
| CN101775127B (en) * | 2009-12-30 | 2011-10-26 | 中国纺织科学研究院 | Hydrophobic modified polyester and preparation method thereof |
| CN102391488B (en) * | 2011-09-26 | 2013-06-05 | 四川东方绝缘材料股份有限公司 | Preparation method for fluorine silicon phosphorus-containing anti-dropping flame-retardant polyethylene terephthalate |
| CN102391488A (en) * | 2011-09-26 | 2012-03-28 | 四川东方绝缘材料股份有限公司 | Preparation method for fluorine silicon phosphorus-containing anti-dropping flame-retardant polyethylene terephthalate |
| CN102719061A (en) * | 2012-06-07 | 2012-10-10 | 南通华盛高聚物科技发展有限公司 | Full-biodegradable polyester nano-composite and preparation process |
| CN104479117A (en) * | 2014-12-26 | 2015-04-01 | 佛山金智节能膜有限公司 | Method for preparing intelligent temperature-controlpolyester chip with in-situ polymerization method |
| CN104562278A (en) * | 2014-12-30 | 2015-04-29 | 佛山金智节能膜有限公司 | Vanadium dioxide uniformly-dispersed polyester fiber |
| CN105803567A (en) * | 2016-06-08 | 2016-07-27 | 上海洋帆实业有限公司 | Flame-retarded antistatic composite modified polyester fiber and preparation method thereof |
| CN107722247A (en) * | 2017-08-21 | 2018-02-23 | 宁波中金石化有限公司 | A kind of preparation method of antistatic inorganic material-modified paraxylene |
| CN108624010A (en) * | 2018-06-07 | 2018-10-09 | 广东轻工职业技术学院 | A kind of electrostatically dissipative high grade of transparency polyester and preparation method thereof |
| CN114456360A (en) * | 2022-01-20 | 2022-05-10 | 长江师范学院 | Method for preparing polyethylene terephthalate by catalysis |
| CN115094535A (en) * | 2022-06-25 | 2022-09-23 | 杭州明华纺织有限公司 | Antistatic low-stretch yarn fabric and preparation method thereof |
| CN115094535B (en) * | 2022-06-25 | 2024-01-26 | 杭州明华纺织有限公司 | Antistatic low stretch yarn fabric and preparation method thereof |
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