CN101928445A - Uvioresistant polyester and application thereof - Google Patents
Uvioresistant polyester and application thereof Download PDFInfo
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- CN101928445A CN101928445A CN2009101523975A CN200910152397A CN101928445A CN 101928445 A CN101928445 A CN 101928445A CN 2009101523975 A CN2009101523975 A CN 2009101523975A CN 200910152397 A CN200910152397 A CN 200910152397A CN 101928445 A CN101928445 A CN 101928445A
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- polyester
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- uvioresistant
- titanium
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Abstract
The invention discloses an uvioresistant polyester, which is characterized in that (1) at least one titanium compound is added, wherein the content of the titanium element is more than 3ppm and less then 30ppm relative to the weight of polyester; and (2) at least one uvioresistant particle is added, wherein the particle diameter of the uvioresistant particle is 60-300nm, and the content of the uvioresistant particle is 0.5-30% by weight relative to the weight of polyester. The uvioresistant polyester of the invention has simple preparation method, easy operation, no environment pollution, uniform uvioresistant particle dispersion and stable variety, can be applied to uvioresistant fibre and textile and can also be applied to the fields such as thin film, resin and the like.
Description
Technical field:
The present invention relates to a kind of anti-ultraviolet polyester.
Background technology:
In recent years, because forest vegetation is destroyed aggravation, Sunspot Activities is frequent and factors such as a large amount of uses freon refrigerant make the mankind be faced with enhanced ultraviolet radiation day by day, ultraviolet ray be divided into UVC (200～280nn), UVB (280～320nm), UVA (320～400nm) three districts.Under solar radiation, should avoid directly contact skin generation detrimentally affect of ultraviolet ray; efficient manner then can have the clothing of the high UV protection coefficient (UPF) that fiber was made into of ultraviolet radiation absorption and obstruct, reaches to prevent the effect of ultraviolet ray to the human injury.
Synthetic polyester fibers, be subject to the characteristic of its comonomer itself, only can absorb partly particular range of wavelengths to ultraviolet ray, and the program that absorbs is limited, as polyester such as PET, PTT, PBT, though have aromatic ring shape structure, owing to be all the polymerization single polymerization monomer long-chain that only contains single aromatic nucleus, all below 320nm, UVA partly then can't be absorbed to ultraviolet absorption.After trevira forms fabric to ultraviolet barriering effect, then be subjected to fabric knitting tightness, thickness, dyeing, and the painted degree of depth influence, generally to weave close, thick and heavy and dark more more its ultraviolet barriering effect the best of clothing.Yet ultraviolet ray belongs to summer in the strongest season, and it is unactual to reach anti-ultraviolet function in this way; Therefore press for exploitation anti-ultraviolet polyester fiber.
At present, the polyester with anti-ultraviolet function mainly adopts with polymkeric substance and uvioresistant particle blended melting method or with the uvioresistant particle and directly is coated in the surface of fabric or adopts the method for in-situ polymerization to prepare.
In addition, adopt chemical process processing textiles and chemical fiber plus material to obtain the method less stable of anti-ultraviolet function, and use the secondary printing and dyeing to handle more, on lining is selected, certain limitation is arranged also.
CN200310122743.8 " utilizes the method for nano titanium oxide in-situ preparing anti-ultraviolet radiation poly ester ", its preparation method is as follows: at first adopting nano titanium oxide is ultraviolet screening agent, then it is carried out inorganic/organic complex surface modification, making one of its monomer that can be dispersed in polyester is in the dibasic alcohol, by metering the nano titanium oxide/dibasic alcohol slurry for preparing is arrived the median size of nano-titanium oxide less than 50 nanometers by high speed dispersion and circulation sanded then, last and other monomers of polyester carry out polymerization or copolymerization, and original position obtains having good mechanics in polymerization process, uvioresistant nano titanium oxide/the polyester composite of thermal property.
CN98116588.5 " a kind of preparation method of anti-ultraviolet polyester " makes anti-ultraviolet polyester by transesterification reaction and reaction, also adds screening uv-ray agent in the polyester and reaches anti-ultraviolet effect.Added polyester catalyzer antimony catalyst series antimonous oxide commonly used in this preparation process, this catalyzer is to use the most general polyester catalyst in the production process of polyester.And the catalyzer of antimony series comprises Sb2O3, SbAc3 and antimony glycol etc., and 90% polyester is produced by the antimony catalyst series in the world at present.The shortcoming of antimony catalyst series is: low activity; Heavy metal catalyst pollutes environment; The polymer belt grey.Therefore necessary use not the catalyzer of antimony containing compounds come synthesizing polyester.
Fabric with anti-ultraviolet function has uvioresistant, covers and the reflective thermal radiation line, makes fabric have refrigerant sense, comfort, and is at field works such as clothes, sportswear, agricultural, fishery clothes, rather well received.Thereby enlarged uvioresistant application corresponding scope, i.e. fields such as fiber, film and engineering plastics.
Summary of the invention:
Purpose of the present invention is to provide and uses non-antimony catalyst (titanium catalyst) and uvioresistant particle to prepare a kind of anti-ultraviolet polyester, and prepared polyester has excellent anti-ultraviolet property and environmental friendliness performance.
Technical solution of the present invention is:
A kind of anti-ultraviolet polyester, (1) contains a kind of titanium compound at least, is 3ppm＜Ti＜30ppm with respect to the titanium elements content of weight polyester; (2) contain a kind of uvioresistant particle at least, its particle diameter is 60～300nm, and its content with respect to weight polyester is 0.5～30wt%.
Anti-ultraviolet polyester of the present invention also adds a kind of dispersion agent and a kind of auxiliary agent, and the addition of dispersion agent is with respect to 0.1～5.0wt% of weight polyester, and the addition of auxiliary agent is with respect to 0.1～2.0wt% of weight polyester.
Titanium compound is the compound of structure such as chemical general formula (1):
Chemical general formula (1)
R wherein
1～R
4Be the compound of following general formula:
R in the formula
7～R
9Be that hydrogen atom or carbon are 1～30 alkyl, ether, hydroxyl, carboxyl, carbonyl, ester group or amido.
Titanium compound can also be the metallic compound that titanium and part form the chelating type structure, and its part is 1～30 ketone group, aldehyde radical, carboxyl or ester group.The example part can be Succinic Acid, hexanodioic acid, adjacent benzene dicarboxylic acid, terephthalic acid, vinyl-acetic ester, methyl-formiate, dimethyl malonate, pentyl acetate, methyl phenyl ketone, 2-phenylpropionaldehyde, salicylaldhyde, crotonic aldehyde, 3-phenylacrolein etc.
The uvioresistant particle is one or more co-oxidation thing or the mixture in ferric oxide, titanium oxide, zinc oxide, the cerium oxide.
Dispersion agent is 1,1, one or more in 1-trimethylolethane (TME), polyoxyethylene glycol, polyvinylpyrrolidone, polyvinyl alcohol, polyacrylic acid, the polyacrylamide.
Auxiliary agent is oxidation inhibitor or coupling agent.Wherein coupling agent is silane coupling agent, titanate coupling agent or aluminium titanium compound coupling agent.
The consumption of oxidation inhibitor is 0.01～0.5% of a polyester gross weight, for example oxidation inhibitor IR1010, antioxidant 1076, oxidation inhibitor TNP, 168 etc.
Polyester among the present invention can be polyethylene terephthalate, Poly(Trimethylene Terephthalate), polybutylene terephthalate, terephthalic acid/isophthalic acid copolymerization glycol ester, terephthalic acid/isophthalic acid copolymerization propylene glycol ester or terephthalic acid/isophthalic acid copolymerization butanediol ester.Preferred polyester wherein of the present invention is a polyethylene terephthalate.
The method of anti-ultraviolet polyester preparation comprises the following steps: the uvioresistant particle is dispersed in after the dispersion agent surface disperses pre-treatment in the monomer dibasic alcohol of polyester and obtains slurry among the present invention, when disperseing pre-treatment, also adds auxiliary agent; Another monomer aromatic binary carboxylic acid with polyester carries out polyreaction then, uses titanium compound as catalyzer in polymerization process, obtains having the polyester of anti-ultraviolet function.
The inventive method is simple, and is easy to operate, and the uvioresistant particle disperses homogeneous, and anti-ultraviolet function is stable, and the anti-ultraviolet polyester of production can be applied in fields such as fiber, film and engineering materials.Adding anti-ultraviolet polyester of the present invention carries out spinning and can obtain uvioresistant fiber, after weaving, all or part of use uvioresistant fiber makes anti-ultraviolet fabric, the cover factor of fabric (Cover Factor) is not less than 1500, the anti-ultraviolet fabric that obtain this moment, its ultraviolet ray transmissivity≤1.0%, fabric UPF value 〉=30.
The following describes the measuring method and the evaluation method of the every index of the present invention.
(1) the ultraviolet ray transmissivity measuring method is, adopts ultraviolet spectrophotometer to measure the transmittance of fabric in the 200-400nm scope.
Fabric sample UPF value of the present invention is the transmittance values after analyzing through ultraviolet transmittance, and the international standard regulation is blocked coefficient UPF value 15～24 better, and 25～39 is fine, and 40～50 is splendid.Can convert with reference to the relation of the UPF value of Australia actual human body test and transmissivity in addition the UPF value.And according to Australia regulation, UPF just calculates the fabric of tool ultraviolet isolating at least more than 15.
In order to further specify the advantage more than the present invention, will be described in detail from listed examples and comparative example below.Yet the present invention has more than and is limited to following embodiment.
Raw material that some relate among the present invention and medicament explanation:
Terephthalic acid (PTA): Mitsui Chemicals, polymerization-grade
Ethylene glycol (EG): BASF AG
Titanium compound (AC420): Johnson Matthey Company (England)
Titanium compound (Tyzor PC50): Dupont
The specific embodiment mode:
Embodiment 1:
The anti-ultraviolet function powder titanium dioxide is carried out the surface with TME (NCM) disperse pre-treatment, be scattered in after the drying in the monomer ethylene glycol of polyester and obtain slurry, when disperseing pre-treatment, also add antioxidant IR1010; Then resulting slurry is mixed with high speed dispersor, use ultrasonic wave that slurry is disperseed to reach 60nm until the uvioresistant particle diameter; Then another monomers terephthalic acid of resulting slurry and polyester is carried out esterification, its esterification condition is for to carry out esterification under 220-250 ℃, the preferred 240-250 of end reaction temperature ℃.When the water that generates reaches 95% when above of theoretical amount, esterification end.
After above-mentioned esterification finishes, carry out polycondensation, and adding polycondensation catalyst titanium compound, the content 5ppm (with respect to weight polyester) of titanium elements, precondensation 45～60min under rough vacuum carries out polycondensation under the high vacuum more then, and vacuum tightness is below the 200Pa, temperature of reaction is 220 ℃～320 ℃, preferred 250 ℃～300 ℃.When polymer viscosity reached 0.55～0.75, polycondensation finished, and obtained the uvioresistant polyethylene terephtalate section of 1.0wt% content, adopted common spinning-drawing machine to carry out conventional spinning and draft process is made uvioresistant fiber.Fiber is made into certain fabric through weaving process.
Gained fabric ultraviolet ray transmissivity is 0.85%, and the UPF value is 32.
Embodiment 2～embodiment 9:
Each raw material and consumption see Table 1, and all the other are with embodiment 1.
Comparative Examples 1:
Directly adopt common spinning-drawing machine to carry out conventional spinning polyester slice and draft process is made fiber, fiber is made into certain fabric through weaving process.Carry out coating then and handle, the content of its uvioresistant particle is 6%.The ultraviolet ray transmissivity of fabric is 1.3%, and the UPF value is 19.
Claims (7)
1. anti-ultraviolet polyester is characterized in that:
(1) containing a kind of titanium compound at least, is 3ppm＜Ti＜30ppm with respect to the titanium elements content of weight polyester;
(2) contain a kind of uvioresistant particle at least, its particle diameter is 60～300nm, and its content with respect to weight polyester is 0.5～30wt%.
2. a kind of anti-ultraviolet polyester according to claim 1 is characterized in that:
(1) at least also add a kind of dispersion agent, its addition is 0.1～5.0wt% with respect to weight polyester;
(2) at least also add a kind of auxiliary agent, its addition is 0.1～2.0wt% with respect to weight polyester.
3. a kind of anti-ultraviolet polyester according to claim 1 and 2, it is characterized in that: described titanium compound is the compound of structure such as chemical general formula (1), the chelating type structural metal compound that perhaps contains titanium and part, its part are 1～30 ketone group, aldehyde radical, carboxyl or ester group:
Chemical general formula (1)
R wherein
1～R
4Be the compound of following general formula:
R in the formula
7～R
9Be that hydrogen atom or carbon are 1～30 alkyl, ether, hydroxyl, carboxyl, carbonyl, ester group or amido.
4. a kind of anti-ultraviolet polyester according to claim 1 and 2 is characterized in that: the uvioresistant particle is one or more co-oxidation thing or the mixture in ferric oxide, titanium oxide, zinc oxide, the cerium oxide.
5. a kind of anti-ultraviolet polyester according to claim 2 is characterized in that: dispersion agent is 1,1, one or more in 1-trimethylolethane, polyoxyethylene glycol, polyvinylpyrrolidone, polyvinyl alcohol, polyacrylic acid, the polyacrylamide.
6. a kind of anti-ultraviolet polyester according to claim 2 is characterized in that: auxiliary agent is oxidation inhibitor or coupling agent, and wherein oxidation inhibitor is IR1010, antioxidant 1076, oxidation inhibitor TNP, 168; Coupling agent is silane coupling agent, titanate coupling agent or aluminium titanium compound coupling agent.
7. the described a kind of anti-ultraviolet polyester of claim 1, the application in preparation uvioresistant fiber and fabric.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101523975A CN101928445A (en) | 2009-06-23 | 2009-06-23 | Uvioresistant polyester and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN2009101523975A CN101928445A (en) | 2009-06-23 | 2009-06-23 | Uvioresistant polyester and application thereof |
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| CN101928445A true CN101928445A (en) | 2010-12-29 |
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| CN2009101523975A Pending CN101928445A (en) | 2009-06-23 | 2009-06-23 | Uvioresistant polyester and application thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102704111A (en) * | 2012-06-19 | 2012-10-03 | 苏州龙杰特种纤维股份有限公司 | Preparation method for stranded PTT (Polytrimethylene Terephthalate) fiber filament with cooling function |
| CN105778070A (en) * | 2016-03-24 | 2016-07-20 | 江苏裕兴薄膜科技股份有限公司 | Preparation method of anti-fog anti-ultraviolet polyester film |
| CN105778442A (en) * | 2016-05-05 | 2016-07-20 | 无锡市长安曙光手套厂 | High-temperature-resistant antistatic PBT (polybutylene terephthalate) material and preparation method thereof |
| CN113265720A (en) * | 2021-05-17 | 2021-08-17 | 福建师范大学泉港石化研究院 | Polyester fiber with uvioresistant performance and preparation method thereof |
| CN114644752A (en) * | 2022-03-31 | 2022-06-21 | 福建赛隆科技有限公司 | anti-UV (ultraviolet) regenerated polyester chip and preparation method and application thereof |
| CN114685956A (en) * | 2022-05-07 | 2022-07-01 | 河源市可顺绝缘材料有限公司 | Plastic material and plastic-coated wiper blade using same |
-
2009
- 2009-06-23 CN CN2009101523975A patent/CN101928445A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102704111A (en) * | 2012-06-19 | 2012-10-03 | 苏州龙杰特种纤维股份有限公司 | Preparation method for stranded PTT (Polytrimethylene Terephthalate) fiber filament with cooling function |
| CN105778070A (en) * | 2016-03-24 | 2016-07-20 | 江苏裕兴薄膜科技股份有限公司 | Preparation method of anti-fog anti-ultraviolet polyester film |
| CN105778070B (en) * | 2016-03-24 | 2017-06-16 | 江苏裕兴薄膜科技股份有限公司 | The preparation method of antifog uvioresistant poly ester film |
| CN105778442A (en) * | 2016-05-05 | 2016-07-20 | 无锡市长安曙光手套厂 | High-temperature-resistant antistatic PBT (polybutylene terephthalate) material and preparation method thereof |
| CN113265720A (en) * | 2021-05-17 | 2021-08-17 | 福建师范大学泉港石化研究院 | Polyester fiber with uvioresistant performance and preparation method thereof |
| WO2022242168A1 (en) * | 2021-05-17 | 2022-11-24 | 福建师范大学泉港石化研究院 | Ultraviolet-resistant polyester fiber and preparation method therefor |
| CN114644752A (en) * | 2022-03-31 | 2022-06-21 | 福建赛隆科技有限公司 | anti-UV (ultraviolet) regenerated polyester chip and preparation method and application thereof |
| CN114685956A (en) * | 2022-05-07 | 2022-07-01 | 河源市可顺绝缘材料有限公司 | Plastic material and plastic-coated wiper blade using same |
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Application publication date: 20101229 |