CN1167499C - Prepn and application of high-activity titanium catalyst - Google Patents
Prepn and application of high-activity titanium catalyst Download PDFInfo
- Publication number
- CN1167499C CN1167499C CNB021374384A CN02137438A CN1167499C CN 1167499 C CN1167499 C CN 1167499C CN B021374384 A CNB021374384 A CN B021374384A CN 02137438 A CN02137438 A CN 02137438A CN 1167499 C CN1167499 C CN 1167499C
- Authority
- CN
- China
- Prior art keywords
- titanium
- titanium dioxide
- organic
- catalyst
- polyester
- 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.)
- Expired - Fee Related
Links
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
The present invention relates to a method for preparing a titanium series catalyst with high activity, and an application thereof, and belongs to the field of polyester catalysts. The method comprises the following steps of dissolving titanium metal alkoxide in organic solvents, hydrating the titanium metal alkoxide to obtain titanium dioxide deposits, washing and filtering the titanium dioxide deposits, and putting the deposits into the solution of organic modified agents or directly adding the organic modified agents into organic solvents in a hydrating process to obtain organic modified titanium dioxide. The catalyst is used for preparing saturated polyester resin with relative molecular weight smaller than 10000 or thermoplastic polyester and copolyester with relative molecular weight larger than 10000. The present invention firstly puts forward the new way that titanium dioxide with high specific surface area is organically modified by the organic modified agents which improve the polyester quality, and the titanium dioxide modified by the organic modified agents has high activity and solves the problem of yellowing of PET polyester color phrases obtained in the catalytic polymerization process of titanium dioxide deposits.
Description
Technical field
What the present invention relates to is the preparation method and the application thereof of a kind of Preparation of catalysts method and application, particularly a kind of high-activity titanium catalyst, belongs to the polyester catalyst field.
Background technology
Polyester is widely used as the raw material of fabric, packing, industry silk and engineering plastics etc. at present.Since appearance and industrialization, the chemist never stopped the research of various catalyst, and still, industrial production application at present and research mainly are the compounds of Sb, Ge, three series of Ti than multi-catalyst.Use the compound of Ge, as germanium dioxide, the price height, general 1000 dollars/kg can significantly improve the manufacturing cost of polyester; Use the compound of Sb, catalytic activity is lower, makes the polyester belt grey easily, causes environmental pollution in spinning process.The Ti series catalysts is high to the polycondensation process catalytic activity, the toxicity minimum, however there is facile hydrolysis in the Ti series catalysts, active unstable, make the polyester thermal degradation generate problems such as end carboxyl and the jaundice of PET form and aspect easily, influence the quality of product, limited its application in production of polyester.In recent years, along with improving constantly of environmental requirement, the research of Ti series catalysts had become a big focus.The tradition Titanium series catalyst is that direct alcoholates with titanium uses as catalyst, the water that is generated in the course of reaction can make activity of such catalysts reduce greatly, for this reason, must strengthen catalyst consumption, the result increases side reaction, the polyester product quality descends (as becoming muddy, form and aspect jaundice, content of carboxyl end group increase etc.).U.S. Patent number is US3056817, and name is called " synthesizing of polyester ", and this patent has related to by TiCl
4The titanium dioxide precipitation of hydrolysis preparation or the hydrolysate of titanium dioxide are as esterification or polyester polycondensation catalyst, yet two shortcomings of this type of catalyst ubiquity: first, form and aspect with the resulting PET polyester of this type of catalyst are yellow partially, and the b value is higher, can't reach the requirement of control of product quality; The second, in the forming process of this type of catalyst, the residual a large amount of hydroxyl of catalyst surface, hydroxyl interacts, and the result causes in the catalyst stores process and reunites, and specific area descends, and catalytic activity descends rapidly.According to Chem.Fibers Int9 (international weaving Leader).1999.49 (1) .27-29 (Eng) report, German Acordis company develops a kind of with TiO in the world
2/ SiO
2Copolymerization mixed oxide compound high-activity polyester catalyst, wherein Ti/Si is 9: 1, catalytic activity is traditional Sb
2O
36-8 doubly, and be used for production of polyester, Co., Ltd checks and rates composite catalyst through Yizheng Fiber Optical plant, has confirmed its high activity, but is existed the problem of form and aspect jaundice equally by the polyester that it obtains.
Summary of the invention
The present invention is directed to the deficiencies in the prior art and defective, a kind of preparation method and application thereof of high-activity titanium catalyst are provided, make it in the synthetic PET polyester process of catalysis, improve esterification and polycondensation reaction speed, and the problem of environmental pollution of elimination antimony based compound existence, the PET hue of using this Preparation of Catalyst to obtain is good, and does not contain poisonous metal.Polycondensation catalyst of the present invention is the organically-modified titanium dioxide precipitation thing of a class, and this sediment is that the monobasic alcoholates hydrolysis by titanium obtains, and therefore has the characteristic of anti-hydrolysis.The present invention is achieved by the following technical solutions, true body method is as follows: the titanium alcoholates is dissolved in organic solvent, the titanium dioxide precipitation that obtains through hydrolysis, through washing and filtering, again precipitation is placed the solution of organic modifiers, perhaps organic modifiers directly joins in the organic solvent in hydrolytic process, obtains organically-modified titanium dioxide.The present invention prepares catalyst by organically-modified method, has improved the titanium dioxide catalytic performance, improves the every performance of final products simultaneously.
Below the invention will be further described:
(1) metal alcoholate is dissolved in organic solvent, the respective metal alcoholates that this metal alcoholate forms for the C1-6 monohydric alcohol;
(2) mixed solution with water and organic solvent joins alcoholates solution, obtains white precipitate, and organic solvent is ethanol or ethylene glycol;
(3) with the titanium dioxide precipitation washing, the filtration that obtain;
(4) through precipitation, drying has obtained the loose aggregate of titanium dioxide, and this aggregate has high-specific surface area＞400cm
2/ g;
(5) titanium dioxide is carried out modification in organic modifiers, organic modifiers is acrylic acid, acrylate, silane coupler, phosphoric acid ester, organic carboxyl acid, and the organic modifiers addition is the 1/20-1/2 of alcohol amount;
(6) being introduced in of organic modifiers generates in the precipitation process, or after generating precipitation.
The catalytic activity of the catalyst of the present invention's preparation is more than 10 times of original antimony-based catalyst, in the polyester building-up process, with organically-modified titanium dioxide as catalyst, for terephthalic acid (TPA), its preferred use amount is 10-150ppm, its most preferably use amount be 30-100ppm, can be used for preparing relative molecular weight less than 10,000 saturated polyester resin, or relative molecular weight is greater than 10,000 thermoplastic polyester and copolyesters.
Catalyst adds mode with the form of suspension of ethylene glycol, and the organically-modified titanium dioxide that the present invention relates to very easily disperses in ethylene glycol, therefore can be made into stable suspension and add in the reaction system, and more traditional antimony oxide has made things convenient for many.
The present invention has substantive distinguishing features and marked improvement, has at first proposed to use organic modifiers that high specific surface area titanic oxide is carried out organically-modified new approaches in the world, thereby has obtained the Titanium series catalyst of high catalytic activity.The introducing of organic modifiers is occupied some positions of titanium dioxide surface, and it is more even that active site is distributed, and active site quantity is descended, and part has reduced the catalytic activity of side reaction, improves the quality of polyester.Experimental result proves, not only has active highly through the titanium dioxide of organic modifiers modification, and overcome the problem of the PET PET hue jaundice that titanium dioxide precipitation thing catalyzed polymerization process obtains.
Embodiment 1
10.80g titanium tetraisopropylate (IV) (38 mM) is dissolved in the 10g GMA and the 40g absolute ethyl alcohol is made solution A.6.35g distilled water mixed with the 50g absolute ethyl alcohol obtain solution B.Earlier solution A is added in the reactor,, obtain white precipitate in the disposable adding solution B of room temperature.The white precipitate suction filtration except that desolvating, is washed secondary with distilled water then,, obtained the ester modified TiO of organic crylic acid 70 ℃ of bakings 1 hour
2Precipitation.
2200g terephthalic acid (TPA), 1100g ethylene glycol and this catalyst 0.11g are carried out polymerisation in the stainless steel cauldron of 5L.The esterification of this process is carried out under normal pressure, and polycondensation final stage still internal pressure should remain below 80Pa.Obtain PET hue L value 88.30, form and aspect b value 4.31, inherent viscosity are 0.664, and carboxyl-content is 19mol.t
-1, diethylene glycol (DEG) content is 1.1%.
Embodiment 2
10.80g titanium tetraisopropylate (IV) (38 mM) is dissolved in the 50g absolute ethyl alcohol makes solution A.6.35g distilled water and 50g absolute ethyl alcohol are mixed and made into solution B.Earlier solution A is added in the reactor,, obtain white precipitate in the disposable adding solution B of room temperature.The white precipitate suction filtration except that desolvating, is washed secondary with distilled water then, at 70 ℃ of bakings 1 hour, the TiO that obtains
2Precipitation.Precipitation is dissolved in the 50g GMA,, organic matter is fully adsorbed in precipitation surface, filter then, use the distilled water debris, dried by the fire about 1 hour the TiO that the organic crylic acid that obtains is ester modified at 70 ℃ down through ultrasonic processing 10 minutes
2Precipitation.
2200g terephthalic acid (TPA), 1100g ethylene glycol and this catalyst 0.22g are carried out polymerisation in the stainless steel cauldron of 5L.The esterification of this process is carried out under normal pressure, and polycondensation final stage still internal pressure should remain below 80Pa.Obtain PET hue L value 82.54, form and aspect b value 5.31, inherent viscosity are 0.676, and carboxyl-content is 21mol.t
-1, diethylene glycol (DEG) content is 1.3%.
Embodiment 3
10.80g titanium tetraisopropylate (IV) (38 mM) is dissolved in the 50g absolute ethyl alcohol makes solution A.6.35g distilled water and 50g absolute ethyl alcohol are mixed and made into solution B.Earlier solution A is added in the reactor,, obtain white precipitate in the disposable adding solution B of room temperature.The white precipitate suction filtration except that desolvating, is washed secondary with distilled water then, at 70 ℃ of bakings 1 hour, the TiO that obtains
2Precipitation.Precipitation is dissolved in the 50g10%KH560 ethanolic solution,, organic matter is fully adsorbed in precipitation surface, filter then, use the distilled water debris, dried by the fire about 1 hour the organosilane-modified TiO that obtains at 70 ℃ down through ultrasonic processing 10 minutes
2Precipitation.
2200g terephthalic acid (TPA), 1100g ethylene glycol and this catalyst 0.165g are carried out polymerisation in the stainless steel cauldron of 5L.The esterification of this process is carried out under normal pressure, and polycondensation final stage still internal pressure should remain below 80Pa.Obtain PET hue L value 89.96, form and aspect b value 4.18, inherent viscosity are 0.679, and carboxyl-content is 20mol.t
-1, diethylene glycol (DEG) content is 1.1%.
Embodiment 4
Obtain white TiO as example 3
2Post precipitation, precipitation is dissolved in 10g10% three (2-propyl group-2-dimethyl phosphate)-phosphite ester ethanolic solution, through ultrasonic processing 10 minutes, organic matter is fully adsorbed in precipitation surface, filter then, use the distilled water debris, dried by the fire about 1 hour the TiO of the organic phospholipid modification that obtains at 70 ℃ down
2Precipitation.
2200g terephthalic acid (TPA), 1100g ethylene glycol and this catalyst 0.22g are carried out polymerisation in the stainless steel cauldron of 5L.The esterification of this process is carried out under normal pressure, and polycondensation final stage still internal pressure should remain below 80Pa.Obtain PET hue L value 90.52, form and aspect b value 4.06, inherent viscosity are 0.668, and carboxyl-content is 15mol.t
-1, diethylene glycol (DEG) content is 0.9%.
Claims (3)
1, a kind of preparation method of high-activity titanium catalyst is characterized in that concrete grammar is as follows:
(1) metal alcoholate with titanium is dissolved in organic solvent, and the metal alcoholate of this titanium is the metal alcoholate of the corresponding titanium of C1-6 monohydric alcohol formation;
(2) mixed solution with water and organic solvent joins alcoholates solution, obtains white precipitate, and organic solvent is ethanol or ethylene glycol;
(3) with the white precipitate washing, the filtration that obtain;
(4) through precipitation, drying has obtained the loose aggregate of titanium dioxide, and this aggregate has high-specific surface area＞400cm
2/ g;
(5) the loose aggregate of titanium dioxide is carried out modification in organic modifiers, organic modifiers is acrylic acid, acrylate, silane coupler, phosphoric acid ester, organic carboxyl acid, and the organic modifiers addition is the 1/20-1/2 of alcohol amount;
(6) being introduced in of organic modifiers generates in the precipitation process, or after generating precipitation.
2, the application of high-activity titanium catalyst according to claim 1, it is characterized in that catalyst is used to prepare relative molecular weight less than 10,000 saturated polyester resin, or relative molecular weight is greater than 10,000 thermoplastic polyester and copolyesters, phthalic acid use amount are 10-150ppm.
3, the application of high-activity titanium catalyst according to claim 2 is characterized in that catalyst adds with the form of suspension of ethylene glycol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021374384A CN1167499C (en) | 2002-10-15 | 2002-10-15 | Prepn and application of high-activity titanium catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021374384A CN1167499C (en) | 2002-10-15 | 2002-10-15 | Prepn and application of high-activity titanium catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1403193A CN1403193A (en) | 2003-03-19 |
| CN1167499C true CN1167499C (en) | 2004-09-22 |
Family
ID=4749000
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021374384A Expired - Fee Related CN1167499C (en) | 2002-10-15 | 2002-10-15 | Prepn and application of high-activity titanium catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1167499C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1294176C (en) * | 2003-07-09 | 2007-01-10 | 中国石化上海石油化工股份有限公司 | Composite catalyst for preparing modified polyester |
| CN101381453B (en) * | 2008-10-24 | 2011-08-17 | 南亚塑胶工业股份有限公司 | PET resin without containing stibium heavy metal and PET polyester fibres made thereby |
| CN102172538B (en) * | 2011-03-16 | 2013-02-20 | 中国科学院长春应用化学研究所 | Titanium IV compound/nano silicon dioxide loaded catalyst and preparation method thereof |
| CN109312102A (en) * | 2016-06-30 | 2019-02-05 | 陶氏环球技术有限责任公司 | Phosphonate-modified metal oxide particle |
-
2002
- 2002-10-15 CN CNB021374384A patent/CN1167499C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1403193A (en) | 2003-03-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE19513056B4 (en) | Titanium-containing catalysts and process for the production of polyester | |
| EP0738292B1 (en) | Process for producing polyesters and copolyesters | |
| Cao et al. | Research and progress of chemical depolymerization of waste PET and high-value application of its depolymerization products | |
| CN101092506A (en) | Nano composite material of copolyester, and preparation method | |
| CN1167499C (en) | Prepn and application of high-activity titanium catalyst | |
| CN113388100B (en) | Catalyst system for synthesizing aliphatic-aromatic copolyester and application thereof | |
| CN114835886B (en) | Solid bimetallic titanium polyester catalyst and preparation method and application thereof | |
| CN102690410B (en) | Method for producing modified polyester and fiber thereof | |
| CN102391490B (en) | Preparation method and application of supported titanium-series polyester catalyst | |
| EP0716112B1 (en) | Process for the preparation of polyesters and copolyesters | |
| CN109503819B (en) | Method for synthesizing PBT polyester | |
| US7759270B2 (en) | Titanium oxide sol and process for producing polyalkylene terephthalate therewith | |
| CN111499661A (en) | Preparation method of tin oxide complex diisooctanoate | |
| CN1047187C (en) | Technology of producing paint of polyester enameled wire by normal pressure esterification of terephthalic acid | |
| CN1116928C (en) | Ti-series compound and/or carried catalyst and its preparing process | |
| CN1138060A (en) | Polyesters with low crystallization rate and catalytic system for their preparation | |
| CN1212304C (en) | Method for preparing long-chain dicarboxylic dialkyl ester | |
| CN102850534A (en) | Method for preparing high-quality polybutylene terephthalate (PBT) by TiO2/SiO2 composite nano-catalyst | |
| CN102649839A (en) | Emulsion type polyester catalyst, and preparation method and application thereof | |
| CN1958641A (en) | High active titanium catalyst, preparation method and application | |
| CN1931892A (en) | Prepn process of fiber-forming biodegradable fatty copolyester | |
| CN1223623C (en) | Method for preparing composite polyether polycondensation catalyst and using method thereof | |
| WO2013119004A1 (en) | Catalyst for synthesis of polyester resin and method for producing polyester resin using same | |
| CN108774312A (en) | Low adhesive aggregation ester and preparation method thereof | |
| CN111662441B (en) | Preparation method of polyester environment-friendly catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |