CN102492121A - Preparation method and use of rare earth coated titanium polyesterification catalyst - Google Patents
Preparation method and use of rare earth coated titanium polyesterification catalyst Download PDFInfo
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Abstract
The invention provides a preparation method and use of a rare earth coated titanium polyesterification catalyst. The preparation method comprises: heating a solvent to a certain temperature; dissolving a titanate, a phosphate, a silicate ester and other metal compounds in the organic solvent, stirring, keeping the temperature, dripping a small amount of water to promote hydrolysis and obtaining a red precipitate; and repeatedly washing the obtained red precipitate with acetone, removing residual ethanediol, drying the precipitate at 70 DEG C under vacuum and obtaining red powdered catalyst. The polyester prepared by using the catalyst has good hue, other properties of the titanium catalyst are also improved, the catalyst does not contain toxic stibium compounds, and therefore the toxicity of the stibium compounds to the environment and human body is eliminated. The preparation method is mainly to solve the technical problem of the conventional polyesterification process and the yellowing problem of polyethylene glycol terephthalate (PET) and improve the quality of the polyester.
Description
Technical field
What the present invention relates to is a kind of Preparation of catalysts method and application thereof; What be particularly related to is a kind of preparation method and application thereof that utilizes positive tetraethyl orthosilicate and trimethyl phosphate to carry out the rare earth coated titanium series polyester catalyst of modification, belongs to the polyester catalyst field.
Background technology
Polyethylene terephthalate (being called for short polyester, i.e. PET) is widely used owing to having multiple premium properties, and especially trevira is the maximum kind of synthon, is dominating man-made fiber market always.Polyester industrial is the emphasis of China's chemical fibre industry development always, and annual growth remains on more than 10%, and expectation to China's polyester production capacity in 2005 will be above 1,500 ten thousand tons/year.Several years ago because in great demand, each macrocyclic polyester factory enhances production capacities one after another, causes whole world PET over capacity, and product price drops, Market competition.
The research autopolyester of polyester catalyst had never stopped since coming out; Industrial production mainly is the compound of germanium, titanium, three kinds of elements of antimony with the more polyester catalyst of research at present; Wherein use antimony-based catalyst the most generally, present 90% polyester is produced by antimony-based catalyst.Antimony-based catalyst is compared with other catalyzer, and it is moderate to have activity, and price is low; To advantage such as the promoter action of side reaction is less; Therefore be used widely, but antimony-based catalyst is faced with new challenges in recent years first; In order to adapt to the keen competition of polyester market, must seek active higher catalyzer; The second, antimony-based catalyst has infringement to human body, in polycondensation, is reduced into antimony, makes the polyester grey, simultaneously contaminate environment in subsequent handling.The germanium series catalysts has satisfactory stability property, and the side reaction that in reaction process, causes is less, and the synthetic PET hue is good, but owing to scarcity of resources, costs an arm and a leg.Traditional Titanium series catalyst exists the jaundice of poor stability and goods, muddy problem, thereby is never used on a large scale.Titanium series catalyst is the research focus of polyester catalyst in recent years.Early stage what use is the inorganic salt (like potassium fluotitanate, titanium potassium oxalate(T.P.O.) etc.) or the organosilane ester (like tetrabutyl titanate, isopropyl titanate etc.) of titanium, but the PET form and aspect yellowing that makes, end carboxyl raise, and this has just limited its application in PET is synthetic.People's expectation is carried out modification on traditional titanate catalyst basis, develop environmental protection, the highly active Novel Titanium series catalysts that can overcome traditional titanium series polyester catalyst shortcoming again.At present existing how tame Overseas Company announces to have developed the titanium series polyester catalyst of excellent property like companies such as Teijin, Mitsubishi chemical, Synetix, Acordis, Zimmer, Dupont, and has commercially produced product to come out.But product jaundice problem is also failed perfect the solution.
The form and aspect L value of polyester is relevant with the brightness of polyester, and numerical value is higher for well, and the form and aspect L value of general polyester is about 60; The form and aspect b value of polyester and polyester are anti-yellow relevant, and numerical value is low more, shows that this polyester is not easy anti-Huang more, when form and aspect b value greater than 3.0, explain the polyester produced all the more Huang seriously influence the effect of polyester.
Summary of the invention
Learn by foregoing: Titanium series catalyst catalyzed reaction excessive velocities, cause side reaction to increase, produce many by products, polyester color jaundice then, hue difference.
In order to solve some shortcomings and the defective that exists in the above-mentioned technology; The present invention is directed to the problems referred to above a kind of preparation method and application thereof of rare earth coated titanium series polyester catalyst are provided; This rare earth coated titanium series polyester catalyst specifically is a kind of coated titanium series polyester catalyst that promptly adopts titanic acid ester and the two hydrolysis of other metallic compounds to be prepared from through other metals of complexing and organically-modified method; Make it in the process of the synthetic PET polyester of catalysis, can reduce titanium atom and extraneous contact area effectively, reduce speed of response then; The PET hue of preparation is good; Can also improve other performances of Titanium series catalyst, not contain deleterious antimony based compound simultaneously, eliminate of the murder by poisoning of antimony based compound environment and human body.
Polyester catalyst of the present invention is a kind of catalyzer of organically-modified coated, because tetrabutyl titanate hydrolysis generates white titanium oxide in the water of trace, poorly water-soluble does not react with water, and character is very stable, so this catalyzer has resistance to hydrolysis.
The present invention realizes through following technical scheme:
Concrete grammar is following: earlier solvent is heated to a certain temperature, then titanic acid ester, SULPHOSUCCINIC ACID ESTER, silicon ester and other metallic compounds is dissolved in the organic solvent, stir; Constant temperature drips a spot of water simultaneously and promotes that hydrolysis makes red precipitate then, and the red precipitate that makes is used the acetone repetitive scrubbing; Remove residual terepthaloyl moietie; To be deposited at last under 70 ℃, vacuum-drying promptly gets the red powder catalyzer.
Below the present invention is done further description:
1, titanic acid ester is a tetrabutyl titanate, and SULPHOSUCCINIC ACID ESTER is a trimethyl phosphate, and silicon ester is positive tetraethyl orthosilicate, and other metallic compound is Cerium II Chloride, Lanthanum trichloride.
2, the water of pH value for 8-8.5 slowly is added drop-wise in the organic solvent, makes red precipitate, organic solvent is a terepthaloyl moietie; The consumption of terepthaloyl moietie is 2500-2600ml/molTi, and the reaction steady temperature is 190 ℃, and the speed of stirring is 2000-3000r/min; The consumption of water is 250-260ml/molTi, and the pH value of water is at 8-8.5, and the time of dropping is in 25-30min;
3, with acetone repetitive scrubbing red precipitate, to filter, last vacuum-drying makes the red powder catalyzer;
4, organic modifiers is trimethyl phosphate and positive tetraethyl orthosilicate, and the amount that trimethyl phosphate adds and the consumption (quality) of titanic acid ester are than being 9:1; The consumption mol ratio of positive tetraethyl orthosilicate and titanic acid ester is 1:2; The consumption mol ratio of Cerium II Chloride, Lanthanum trichloride and titanic acid ester is 1:1:10, the preparation red precipitate;
5, organic modifiers adds in the preparation precipitation process, more helps the modification of catalyzer.
Tetrabutyl titanate, Cerium II Chloride and Lanthanum trichloride hydrolysis produce red precipitate.Pass through coordination then; Formation is the center with the Ti atom; Trimethylammonium phosphoric acid is the complex compound of ligating atom, simultaneously ester carbonyl group in a plurality of hydroxyl ethoxycarbonyies of complex compound and hydroxyl oxygen can with metallic cerium, lanthanum coordination, therefore; The Ti atom just is wrapped in wherein, promptly makes the hydrolysate of coated titanic acid ester.
This coated catalytic agent utilizes steric effect, can reduce Ti atom and extraneous contact area effectively, and the catalytic activity of may command Ti atom can overcome effectively and cause polyester jaundice problem because of speed of response is too fast.
This activity of such catalysts is more than 20 times of original antimony-based catalyst, and in the polyester building-up process, its consumption is 20-30 μ g/g, and catalyst consumption is reference with the consumption of terephthalic acid.The adding form of catalyzer does not influence activity of such catalysts, because activity of such catalysts is by the decision of the content of Ti.Catalyzer joins reaction system with form of powder.
The present invention uses center coordination principle and introduces the principle of organic modifiers trimethyl phosphate with positive tetraethyl orthosilicate; Catalyzer is carried out modification and design, increase the steric hindrance of titanium atom, reduce the contact area of itself and reaction system; And then the reduction speed of reaction, reduce side reaction.This catalyzer has substantial characteristics and progress really through verification experimental verification, can overcome the problem of polyester jaundice effectively.
Embodiment below in conjunction with concrete further specifies the present invention.
Embodiment
Case study on implementation 1
The preparation of rare earth coated titanium series polyester catalyst; Earlier solvent is heated to a certain temperature; Then tetrabutyl titanate, trimethyl phosphate, positive tetraethyl orthosilicate and Cerium II Chloride, Lanthanum trichloride are dissolved in the terepthaloyl moietie; Wherein: the amount that trimethyl phosphate adds and the mass ratio of titanic acid ester are 9:1, and the consumption mol ratio of positive tetraethyl orthosilicate and titanic acid ester is 1:2, and the consumption mol ratio of Cerium II Chloride, Lanthanum trichloride and titanic acid ester is 1:1:10; The consumption of terepthaloyl moietie is 2500ml/molTi, and the reaction steady temperature is 190 ℃, and the speed of stirring is 2000r/min; Drip a spot of water simultaneously and promote hydrolysis, the consumption of water is 250ml/molTi, and the pH value of water is 8; The time that drips is stirred constant temperature in 25min; The red precipitate that makes is used the acetone repetitive scrubbing, removes residual terepthaloyl moietie, will be deposited at last under 70 ℃; Vacuum-drying promptly gets the red powder catalyzer;
2000g terephthalic acid, 1000g terepthaloyl moietie and this catalyzer 0.04g are carried out pet reaction in the stainless steel cauldron of 5L.This process is in vacuum, carries out under 270 ℃.The PET hue L value that makes is 88.48, and form and aspect b value 1.8, limiting viscosity are 0.702, and carboxyl-content is 13mol/t.
Case study on implementation 2
The preparation of rare earth coated titanium series polyester catalyst; Earlier solvent is heated to a certain temperature; Then tetrabutyl titanate, trimethyl phosphate, positive tetraethyl orthosilicate and Cerium II Chloride, Lanthanum trichloride are dissolved in the terepthaloyl moietie; Wherein: the amount that trimethyl phosphate adds and the mass ratio of titanic acid ester are 9:1, and the consumption mol ratio of positive tetraethyl orthosilicate and titanic acid ester is 1:2, and the consumption mol ratio of Cerium II Chloride, Lanthanum trichloride and titanic acid ester is 1:1:10; The consumption of terepthaloyl moietie is 2600ml/molTi, and the reaction steady temperature is 190 ℃, and the speed of stirring is 3000r/min; Drip a spot of water simultaneously and promote hydrolysis, the consumption of water is 260ml/molTi, and the pH value of water is 8.5; The time that drips is stirred constant temperature in 30min; The red precipitate that makes is used the acetone repetitive scrubbing, removes residual terepthaloyl moietie, will be deposited at last under 70 ℃; Vacuum-drying promptly gets the red powder catalyzer;
2000g terephthalic acid, 1000g terepthaloyl moietie and this catalyzer 0.05g are carried out pet reaction in the stainless steel cauldron of 5L.This process is in vacuum, carries out under 270 ℃.The PET hue L value that makes is 89.68, and form and aspect b value 1.5, limiting viscosity are 0.712, and carboxyl-content is 12mol/t.
Case study on implementation 3
The preparation of rare earth coated titanium series polyester catalyst; Earlier solvent is heated to a certain temperature; Then tetrabutyl titanate, trimethyl phosphate, positive tetraethyl orthosilicate and Cerium II Chloride, Lanthanum trichloride are dissolved in the terepthaloyl moietie; Wherein: the amount that trimethyl phosphate adds and the mass ratio of titanic acid ester are 9:1, and the consumption mol ratio of positive tetraethyl orthosilicate and titanic acid ester is 1:2, and the consumption mol ratio of Cerium II Chloride, Lanthanum trichloride and titanic acid ester is 1:1:10; The consumption of terepthaloyl moietie is 2500ml/molTi, and the reaction steady temperature is 190 ℃, and the speed of stirring is 3000r/min; Drip a spot of water simultaneously and promote hydrolysis, the consumption of water is 260ml/molTi, and the pH value of water is 8; The time that drips is stirred constant temperature in 25-30min; The red precipitate that makes is used the acetone repetitive scrubbing, removes residual terepthaloyl moietie, will be deposited at last under 70 ℃; Vacuum-drying promptly gets the red powder catalyzer;
2000g terephthalic acid, 1000g terepthaloyl moietie and this catalyzer 0.06g are carried out pet reaction in the stainless steel cauldron of 5L.This process is in vacuum, carries out under 270 ℃.The PET hue L value that makes is 87.28, and form and aspect b value 1.6, limiting viscosity are 0.722, and carboxyl-content is 16mol/t.
Case study on implementation 4
The preparation of rare earth coated titanium series polyester catalyst; Earlier solvent is heated to a certain temperature; Then tetrabutyl titanate, trimethyl phosphate, positive tetraethyl orthosilicate and Cerium II Chloride, Lanthanum trichloride are dissolved in the terepthaloyl moietie; Wherein: the amount that trimethyl phosphate adds and the mass ratio of titanic acid ester are 8:1, and the consumption mol ratio of positive tetraethyl orthosilicate and titanic acid ester is 1:3, and the consumption mol ratio of Cerium II Chloride, Lanthanum trichloride and titanic acid ester is 1.5:1.5:10; The consumption of terepthaloyl moietie is 2600ml/molTi, and the reaction steady temperature is 190 ℃, and the speed of stirring is 3000r/min; Drip a spot of water simultaneously and promote hydrolysis, the consumption of water is 260ml/molTi, and the pH value of water is 8.5; The time that drips is stirred constant temperature in 25min; The red precipitate that makes is used the acetone repetitive scrubbing, removes residual terepthaloyl moietie, will be deposited at last under 70 ℃; Vacuum-drying promptly gets the red powder catalyzer;
2000g terephthalic acid, 1000g terepthaloyl moietie and this catalyzer 0.06g are carried out pet reaction in the stainless steel cauldron of 5L.This process is in vacuum, carries out under 270 ℃.The PET hue L value that makes is 87.28, and form and aspect b value 3.5, limiting viscosity are 0.722, and carboxyl-content is 16mol/t.
Case study on implementation 5
The preparation of rare earth coated titanium series polyester catalyst; Earlier solvent is heated to a certain temperature; Then tetrabutyl titanate, trimethyl phosphate, positive tetraethyl orthosilicate and Cerium II Chloride, Lanthanum trichloride are dissolved in the terepthaloyl moietie; Wherein: the amount that trimethyl phosphate adds and the mass ratio of titanic acid ester are 9:1.5, and the consumption mol ratio of positive tetraethyl orthosilicate and titanic acid ester is 1.5:2, and the consumption mol ratio of Cerium II Chloride, Lanthanum trichloride and titanic acid ester is 1:1.5:9; The consumption of terepthaloyl moietie is 2500ml/molTi, and the reaction steady temperature is 190 ℃, and the speed of stirring is 2000r/min; Drip a spot of water simultaneously and promote hydrolysis, the consumption of water is 260ml/molTi, and the pH value of water is 8; The time that drips is stirred constant temperature in 25min; The red precipitate that makes is used the acetone repetitive scrubbing, removes residual terepthaloyl moietie, will be deposited at last under 70 ℃; Vacuum-drying promptly gets the red powder catalyzer;
2000g terephthalic acid, 1000g terepthaloyl moietie and this catalyzer 0.05g are carried out pet reaction in the stainless steel cauldron of 5L.This process is in vacuum, carries out under 270 ℃.The PET hue L value that makes is 87.28, and form and aspect b value 3.5, limiting viscosity are 0.722, and carboxyl-content is 16mol/t.
Case study on implementation 6
The preparation of rare earth coated titanium series polyester catalyst; Earlier solvent is heated to a certain temperature; Then tetrabutyl titanate, trimethyl phosphate, positive tetraethyl orthosilicate and Cerium II Chloride, Lanthanum trichloride are dissolved in the terepthaloyl moietie; Wherein: the amount that trimethyl phosphate adds and the mass ratio of titanic acid ester are 8:1.5, and the consumption mol ratio of positive tetraethyl orthosilicate and titanic acid ester is 1:2.5, and the consumption mol ratio of Cerium II Chloride, Lanthanum trichloride and titanic acid ester is 1.5:1:8; The consumption of terepthaloyl moietie is 2600ml/molTi, and the reaction steady temperature is 190 ℃, and the speed of stirring is 3000r/min; Drip a spot of water simultaneously and promote hydrolysis, the consumption of water is 250ml/molTi, and the pH value of water is 8.5; The time that drips is stirred constant temperature in 25min; The red precipitate that makes is used the acetone repetitive scrubbing, removes residual terepthaloyl moietie, will be deposited at last under 70 ℃; Vacuum-drying promptly gets the red powder catalyzer;
2000g terephthalic acid, 1000g terepthaloyl moietie and this catalyzer 0.04g are carried out pet reaction in the stainless steel cauldron of 5L.This process is in vacuum, carries out under 270 ℃.The PET hue L value that makes is 87.28, and form and aspect b value 3.6, limiting viscosity are 0.722, and carboxyl-content is 16mol/t.
Conclusion: the embodiment data through above can show that the PET hue L value that embodiment 2 makes is 89.68, form and aspect b value 1.5, and the higher while b of its L value value is also lower, is preferred plan of the present invention; The major influence factors that influences PET hue L value and form and aspect b value is trimethyl phosphate adds in the preparation process of low specific surface area titanium series polyester catalyst a amount and the mass ratio of titanic acid ester, the consumption mol ratio of consumption mol ratio, Cerium II Chloride, Lanthanum trichloride and the titanic acid ester of tetraethyl orthosilicate and titanic acid ester just; Other factors do not influence activity of such catalysts, thereby influence PET hue L value and form and aspect b value.
Claims (4)
1. the preparation method of a rare earth coated titanium series polyester catalyst: earlier solvent is heated to a certain temperature, then titanic acid ester, SULPHOSUCCINIC ACID ESTER, silicon ester and other metallic compounds is dissolved in the organic solvent, stir; Constant temperature drips a spot of water simultaneously and promotes that hydrolysis makes red precipitate then, and the red precipitate that makes is used the acetone repetitive scrubbing; Remove residual terepthaloyl moietie, will be deposited under 70 ℃ vacuum-drying at last; Promptly get the red powder catalyzer, it is characterized in that:
(1) titanic acid ester is a tetrabutyl titanate, and SULPHOSUCCINIC ACID ESTER is a trimethyl phosphate, and silicon ester is positive tetraethyl orthosilicate, and other metallic compound is Cerium II Chloride, Lanthanum trichloride;
(2) water of pH value for 8-8.5 slowly is added drop-wise in the organic solvent, makes red precipitate, organic solvent is a terepthaloyl moietie; The consumption of terepthaloyl moietie is 2500-2600ml/molTi, and the reaction steady temperature is 190 ℃, and the speed of stirring is 2000-3000r/min; The consumption of water is 250-260ml/molTi, and the pH value of water is at 8-8.5, and the time of dropping is in 25-30min;
(3), with acetone repetitive scrubbing red precipitate, filter, last vacuum-drying makes the red powder catalyzer;
(4), organic modifiers is trimethyl phosphate and positive tetraethyl orthosilicate; The amount that trimethyl phosphate adds and the mass ratio of titanic acid ester are 9:1; The consumption mol ratio of positive tetraethyl orthosilicate and titanic acid ester is 1:2; The consumption mol ratio of Cerium II Chloride, Lanthanum trichloride and titanic acid ester is 1:1:10, the preparation red precipitate;
(5), organic modifiers adds in the precipitation process in preparation, more helps the modification of catalyzer.
2. the preparation method of a kind of rare earth coated titanium series polyester catalyst as claimed in claim 1 is characterized in that: this activity of such catalysts is more than 20 times of original antimony-based catalyst.
3. the application of a kind of rare earth coated titanium series polyester catalyst according to claim 1; It is characterized in that: the synthetic form and aspect b value of catalysis is lower than 2 PET polyester; In the polyester building-up process, its consumption is 20-30 μ g/g, and catalyst consumption is reference with the consumption of terephthalic acid.
4. the application of a kind of low specific surface area titanium series polyester catalyst according to claim 3; It is characterized in that: the adding form of catalyzer does not influence activity of such catalysts; Because activity of such catalysts is that catalyzer joins reaction system with form of powder by the decision of the content of Ti.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106608967A (en) * | 2016-11-07 | 2017-05-03 | 北京服装学院 | Composite catalyst for synthesis of polyethylene glycol terephthalate |
| CN106832817A (en) * | 2017-02-08 | 2017-06-13 | 新疆蓝山屯河化工股份有限公司 | Excellent polyester thermoplastic elastomer of S. E. A. and preparation method thereof |
| CN106832241A (en) * | 2016-11-07 | 2017-06-13 | 北京服装学院 | A kind of method that utilization composite catalyst prepares polyethylene terephthalate |
| CN110982052A (en) * | 2019-12-31 | 2020-04-10 | 上海慧翌新材料科技有限公司 | Titanium-based polyester for Persian and preparation method thereof |
| CN113336926A (en) * | 2021-06-02 | 2021-09-03 | 安庆和兴化工有限责任公司 | Polyester polycondensation preparation method for producing PPAT \ PBS by rare earth catalyst |
| CN113372542A (en) * | 2021-05-17 | 2021-09-10 | 俏东方生物燃料集团有限公司 | Preparation method of bio-based polyethylene glycol oxalate resin |
| WO2023123699A1 (en) * | 2021-12-31 | 2023-07-06 | 江苏新视界先进功能纤维创新中心有限公司 | Titanium-based composite catalyst for polyester synthesis as well as preparation and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1138339A (en) * | 1994-01-07 | 1996-12-18 | 阿克佐诺贝尔公司 | Process for producing polyesters and copolyesters |
| CN1259969A (en) * | 1997-06-10 | 2000-07-12 | 阿克佐诺贝尔公司 | Method for producing polyesters and copolyestors |
| US6166170A (en) * | 1999-12-02 | 2000-12-26 | E. I. Du Pont De Nemours And Company | Esterification catalysts and processes therefor and therewith |
| CN1644601A (en) * | 2004-12-29 | 2005-07-27 | 中国石化集团天津石油化工公司 | Preparation of liquid titanium polyester polycondensation catalyst |
-
2011
- 2011-12-13 CN CN 201110414196 patent/CN102492121B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1138339A (en) * | 1994-01-07 | 1996-12-18 | 阿克佐诺贝尔公司 | Process for producing polyesters and copolyesters |
| CN1259969A (en) * | 1997-06-10 | 2000-07-12 | 阿克佐诺贝尔公司 | Method for producing polyesters and copolyestors |
| US6166170A (en) * | 1999-12-02 | 2000-12-26 | E. I. Du Pont De Nemours And Company | Esterification catalysts and processes therefor and therewith |
| CN1644601A (en) * | 2004-12-29 | 2005-07-27 | 中国石化集团天津石油化工公司 | Preparation of liquid titanium polyester polycondensation catalyst |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106608967A (en) * | 2016-11-07 | 2017-05-03 | 北京服装学院 | Composite catalyst for synthesis of polyethylene glycol terephthalate |
| CN106832241A (en) * | 2016-11-07 | 2017-06-13 | 北京服装学院 | A kind of method that utilization composite catalyst prepares polyethylene terephthalate |
| CN106608967B (en) * | 2016-11-07 | 2018-10-16 | 北京服装学院 | A kind of composite catalyst for synthesizing polyethylene terephthalate |
| CN106832241B (en) * | 2016-11-07 | 2019-03-12 | 北京服装学院 | A method of polyethylene terephthalate is prepared using composite catalyst |
| CN106832817A (en) * | 2017-02-08 | 2017-06-13 | 新疆蓝山屯河化工股份有限公司 | Excellent polyester thermoplastic elastomer of S. E. A. and preparation method thereof |
| CN110982052A (en) * | 2019-12-31 | 2020-04-10 | 上海慧翌新材料科技有限公司 | Titanium-based polyester for Persian and preparation method thereof |
| CN113372542A (en) * | 2021-05-17 | 2021-09-10 | 俏东方生物燃料集团有限公司 | Preparation method of bio-based polyethylene glycol oxalate resin |
| CN113336926A (en) * | 2021-06-02 | 2021-09-03 | 安庆和兴化工有限责任公司 | Polyester polycondensation preparation method for producing PPAT \ PBS by rare earth catalyst |
| WO2023123699A1 (en) * | 2021-12-31 | 2023-07-06 | 江苏新视界先进功能纤维创新中心有限公司 | Titanium-based composite catalyst for polyester synthesis as well as preparation and application thereof |
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|---|---|
| CN102492121B (en) | 2013-06-12 |
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