CN101864067B - Preparation method of polyester with anti-ultraviolet function - Google Patents
Preparation method of polyester with anti-ultraviolet function Download PDFInfo
- Publication number
- CN101864067B CN101864067B CN 200910081977 CN200910081977A CN101864067B CN 101864067 B CN101864067 B CN 101864067B CN 200910081977 CN200910081977 CN 200910081977 CN 200910081977 A CN200910081977 A CN 200910081977A CN 101864067 B CN101864067 B CN 101864067B
- Authority
- CN
- China
- Prior art keywords
- agent
- polycondensation
- uvioresistant
- ethylene glycol
- anti ultraviolet
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
- 229920000728 polyester Polymers 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 28
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 15
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000005886 esterification reaction Methods 0.000 claims abstract description 11
- 239000000178 monomer Substances 0.000 claims abstract description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 4
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000012964 benzotriazole Substances 0.000 claims abstract description 3
- 239000002002 slurry Substances 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 14
- 230000032050 esterification Effects 0.000 claims description 10
- 238000012216 screening Methods 0.000 claims description 9
- 239000006096 absorbing agent Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 4
- FHUCUPVQDUPROK-UHFFFAOYSA-N acetic acid;antimony Chemical compound [Sb].CC(O)=O FHUCUPVQDUPROK-UHFFFAOYSA-N 0.000 claims description 3
- 239000006227 byproduct Substances 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 238000005453 pelletization Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 abstract description 4
- -1 dihydroxy ethyl terephthalate Chemical compound 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 239000004744 fabric Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- QPKOBORKPHRBPS-UHFFFAOYSA-N bis(2-hydroxyethyl) terephthalate Chemical compound OCCOC(=O)C1=CC=C(C(=O)OCCO)C=C1 QPKOBORKPHRBPS-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- UPLPHRJJTCUQAY-WIRWPRASSA-N 2,3-thioepoxy madol Chemical compound C([C@@H]1CC2)[C@@H]3S[C@@H]3C[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@](C)(O)[C@@]2(C)CC1 UPLPHRJJTCUQAY-WIRWPRASSA-N 0.000 description 1
- 229920004934 Dacron® Polymers 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 238000005008 domestic process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000004224 protection Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention relates to a preparation method of polyester with an anti-ultraviolet function; mixing 90-95 wt% of nano TiO2And Al2O3Or SiO2Mixing with organic substances of benzotriazole type; the weight ratio is 1: 1, the composite uvioresistant agent and the glycol are prepared into slurry, and the weight ratio is 1/4-5; carrying out esterification reaction on molten terephthalic acid and ethylene glycol at the temperature of 160 ℃ and the temperature of 220 ℃ and under the pressure of 0.3 Mpa; the obtained dihydroxy ethyl terephthalate monomer, 0.03 to 0.04 percent of catalyst and 1.5 to 2.0 percent of composite anti-ultraviolet agent are mixed; pre-polycondensation at the normal pressure of 215 ℃ and 255 ℃ and polycondensation at the absolute pressure of less than 150pa and the temperature of 285 +/-2 ℃; and slicing the uvioresistant polyester: the softening point is 245-.
Description
Technical field
The present invention relates to a kind of preparation method with polyester of anti-ultraviolet function.
Background technology
Because the pollution of environment causes the ozonosphere havoc, ultraviolet radiation increases severely, and the tetter that causes is just with annual 5% speed increment, and therefore exploitation has the ultraviolet fabric of obstruct and becomes extremely important.
The domestic method for preparing anti-ultraviolet fabric mainly contains rear arrangement cladding process and blending method.The shortcoming of rear arrangement cladding process fabric is that the weather resistance washing fastness of anti-ultraviolet property is poor etc.The shortcoming of blending method is anti ultraviolet agent maldistribution in fiber, causes the anti-ultraviolet property of fabric inhomogeneous.
Summary of the invention
The production method that the purpose of this invention is to provide a kind of anti-ultraviolet polyester section, this technique is the method that adds a kind of compound anti ultraviolet agent in the polycondensation stage of polyester production process, this compound anti ultraviolet agent is composited by organic uv absorbers and inorganic screening uv-ray agent, and is excellent with the dacron fabric anti-ultraviolet property of this explained hereafter.
Technique provided by the invention comprises following operation: compound anti ultraviolet agent manufacturing, esterification, polycondensation, section granulation etc.
(1) manufacturing of compound anti ultraviolet agent: this compound anti ultraviolet agent is comprised of inorganic uvioresistant screening agent and organic uv absorbers; The composition of inorganic uvioresistant screening agent is nano level TiO
2And Al
2O
3Or SiO
2Inorganic oxide, wherein TiO
2Account for the 90-95% of inorganic uvioresistant screening agent gross weight, organic uv absorbers is the benzotriazole category organic substance; The weight ratio of inorganic uvioresistant screening agent and organic uv absorbers is 1: 1, take by weighing this compound anti ultraviolet agent and ethylene glycol and be made into slurries, by weight, anti ultraviolet agent/ethylene glycol=1/4-5, then place ball mill to disperse 0.5-1 hour, namely can be used for polycondensation;
(2) esterification operation: the terephthalic acid of melting (PTA) and ethylene glycol (EG), continuous (or intermittently) supplies with esterifying kettle, and at temperature 160-220 ℃, pressure is to carry out esterification under the 0.3Mpa.Water byproduct to be steamed reach theoretical amount 90% the time, esterification stops.
(3) polycondensation operation: the esterification operation obtains terephthalic acid dihydroxyl ethyl ester (BHET) monomer after finishing, add compound anti ultraviolet agent, add simultaneously catalyst acetic acid antimony, send into polymerization process: in terephthalic acid weight 100%, the catalyzer add-on is 0.03-0.04%, and the add-on of compound anti ultraviolet agent is at 1.5-2.0%; Monomer first carries out precondensation under normal pressure 215-255 ℃ in polycondensation vessel, then at absolute pressure＜150pa, carry out polycondensation under 285 ± 2 ℃ of the temperature, impels reaction to reach certain polymerization degree, and the ethylene glycol of generation reclaims behind condenser.
(4) after polycondensation finished, material made the uvioresistant polyester section through Cast Strip, cooling, pelletizing, drying.
The effect of invention.Preparation method provided by the invention, its product P ET excellent property, softening temperature is 245-261 ℃, limiting viscosity is 0.66 ± 0.01 (g/dl), form and aspect (b value) 8-10, carboxyl (COOH) content≤35mol/t.
Preparation method provided by the invention, its fabric is tested according to the testing method that " assessment of ultraviolet protection fabric and classification " AS/N2 4,399 1996 provides, and grade is that protection effect is good.
Preparation method provided by the invention, the product spinning property is good, and the spinning drawability is good, produces smoothly, without broken end, the accidents such as sleave.
Embodiment
The present invention is illustrated by embodiment.
The PTA and the EG that get melting add in the esterifying kettle, react under certain condition, water byproduct to be steamed reach theoretical amount 90% the time, esterification finishes, and generates terephthalic acid dihydroxy acetic acid (BHET), BHET is transferred to the compound anti ultraviolet agent of adding in the polymeric kettle, add simultaneously catalyst acetic acid antimony, carry out prepolymerization under certain condition, carry out again polycondensation, make it to reach certain polymerization degree, proportioning, processing condition, the product performance of each experiment are listed in table 2.
Table 2 embodiment
Claims (1)
1. preparation method with polyester of anti-ultraviolet function is characterized in that:
(1) manufacturing of compound anti ultraviolet agent: this compound anti ultraviolet agent is comprised of inorganic uvioresistant screening agent and organic uv absorbers; The composition of inorganic uvioresistant screening agent is nano level TiO
2And Al
2O
3Or SiO
2A kind of in two kinds of inorganic oxides, wherein TiO
2Account for the 90-95% of inorganic uvioresistant screening agent gross weight, organic uv absorbers is the benzotriazole category organic substance; The weight ratio of inorganic uvioresistant screening agent and organic uv absorbers is 1: 1, take by weighing this compound anti ultraviolet agent and ethylene glycol and be made into slurries, by weight, anti ultraviolet agent/ethylene glycol=1/4-5, then place ball mill to disperse 0.5-1 hour, namely can be used for polycondensation;
(2) esterification operation: the terephthalic acid of melting and ethylene glycol, continuously or the intermittent entry esterifying kettle, at temperature 160-220 ℃, pressure is to carry out esterification under the 0.3Mpa, water byproduct to be steamed reach theoretical amount 90% the time, esterification stops;
(3) polycondensation operation: the esterification operation obtains terephthalic acid dihydroxyl ethyl ester monomer after finishing, add compound anti ultraviolet agent, add simultaneously catalyst acetic acid antimony, send into polymerization process: in the terephthalic acid % by weight, the catalyzer add-on is 0.03-0.04%, and the add-on of compound anti ultraviolet agent is at 1.5-2.0%; Monomer first carries out precondensation under normal pressure 215-255 ℃ in polycondensation vessel, then at absolute pressure＜150pa, carry out polycondensation under 285 ± 2 ℃ of the temperature, impels reaction to reach certain polymerization degree, and the ethylene glycol of generation reclaims behind condenser;
(4) after polycondensation finished, material made the uvioresistant polyester section through Cast Strip, cooling, pelletizing, drying.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910081977 CN101864067B (en) | 2009-04-15 | 2009-04-15 | Preparation method of polyester with anti-ultraviolet function |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910081977 CN101864067B (en) | 2009-04-15 | 2009-04-15 | Preparation method of polyester with anti-ultraviolet function |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101864067A CN101864067A (en) | 2010-10-20 |
| CN101864067B true CN101864067B (en) | 2013-02-13 |
Family
ID=42956015
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200910081977 Active CN101864067B (en) | 2009-04-15 | 2009-04-15 | Preparation method of polyester with anti-ultraviolet function |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101864067B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102505182B (en) * | 2011-09-28 | 2013-12-11 | 南京工业职业技术学院 | Method for preparing functional ultraviolet-resistant polyester staple fiber from waste renewable polyester bottle chips |
| CN102433606B (en) * | 2011-10-31 | 2013-01-09 | 福建百宏聚纤科技实业有限公司 | Ultra-strong reflecting low stretch yarn and preparation process thereof |
| CN103305959A (en) * | 2013-07-01 | 2013-09-18 | 江阴市江河化纤有限公司 | Nano TiO2 ceramic modified polyester staple fiber based on high-energy ball milling dispersion and preparation method of fiber |
| CN105732959A (en) * | 2014-12-11 | 2016-07-06 | 中国石油天然气股份有限公司 | Preparation method of ultraviolet-resistant and hydrolysis-resistant polyester material |
| CN105733202A (en) * | 2014-12-11 | 2016-07-06 | 中国石油天然气股份有限公司 | Ultraviolet-resistant and hydrolysis-resistant polyester material and photovoltaic cell backboard |
| CN111087594B (en) * | 2018-10-23 | 2022-04-05 | 中国石油化工股份有限公司 | Synthetic method of uvioresistant titanium polyester |
| TWI713998B (en) | 2019-02-22 | 2020-12-21 | 南亞塑膠工業股份有限公司 | Preparation of a titanium dioxide-containing slurry and its application to recycled polyester fiber |
| CN114481335B (en) * | 2021-12-17 | 2023-06-27 | 桐昆集团浙江恒通化纤有限公司 | High-strength sun-resistant anti-aging polyester pre-oriented yarn for curtain and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1153200A (en) * | 1995-12-29 | 1997-07-02 | 天津金山生物科技有限公司 | Ultraviolet ray-resistant material, its preparing method and use |
| CN1244545A (en) * | 1998-08-12 | 2000-02-16 | 天津石油化工公司研究所 | Preparation of violet ray resistant polyester |
| WO2002070253A1 (en) * | 2001-03-05 | 2002-09-12 | Mitsubishi Polyester Film Gmbh | Amorphous, subduedly colored functionalized film made of a bibenzol-modified thermoplastic material, method for the production and use thereof |
-
2009
- 2009-04-15 CN CN 200910081977 patent/CN101864067B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1153200A (en) * | 1995-12-29 | 1997-07-02 | 天津金山生物科技有限公司 | Ultraviolet ray-resistant material, its preparing method and use |
| CN1244545A (en) * | 1998-08-12 | 2000-02-16 | 天津石油化工公司研究所 | Preparation of violet ray resistant polyester |
| WO2002070253A1 (en) * | 2001-03-05 | 2002-09-12 | Mitsubishi Polyester Film Gmbh | Amorphous, subduedly colored functionalized film made of a bibenzol-modified thermoplastic material, method for the production and use thereof |
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| Publication number | Publication date |
|---|---|
| CN101864067A (en) | 2010-10-20 |
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