CN115785409B - Titanium catalyst and preparation method thereof - Google Patents
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- CN115785409B CN115785409B CN202211464328.XA CN202211464328A CN115785409B CN 115785409 B CN115785409 B CN 115785409B CN 202211464328 A CN202211464328 A CN 202211464328A CN 115785409 B CN115785409 B CN 115785409B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 57
- 239000010936 titanium Substances 0.000 title claims abstract description 48
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 150000001875 compounds Chemical class 0.000 claims abstract description 25
- 229940126062 Compound A Drugs 0.000 claims abstract description 23
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims abstract description 23
- MMCOUVMKNAHQOY-UHFFFAOYSA-N carbonoperoxoic acid Chemical compound OOC(O)=O MMCOUVMKNAHQOY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 12
- 150000003609 titanium compounds Chemical class 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 11
- -1 3, 5-di-tert-butyl-4-hydroxybenzyl diethyl phosphonate Chemical compound 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- RBNPOMFGQQGHHO-UHFFFAOYSA-N glyceric acid Chemical compound OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 6
- PDGXJDXVGMHUIR-UHFFFAOYSA-N 2,3-Dihydroxy-3-methylpentanoate Chemical compound CCC(C)(O)C(O)C(O)=O PDGXJDXVGMHUIR-UHFFFAOYSA-N 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- KJTLQQUUPVSXIM-UHFFFAOYSA-N mevalonic acid Chemical compound OCCC(O)(C)CC(O)=O KJTLQQUUPVSXIM-UHFFFAOYSA-N 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 abstract description 25
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000004090 dissolution Methods 0.000 abstract description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract 1
- 239000012265 solid product Substances 0.000 description 12
- 229910052787 antimony Inorganic materials 0.000 description 9
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 9
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 6
- 238000005886 esterification reaction Methods 0.000 description 4
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 4
- 230000032050 esterification Effects 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 2
- UOXJNGFFPMOZDM-UHFFFAOYSA-N 2-[di(propan-2-yl)amino]ethylsulfanyl-methylphosphinic acid Chemical compound CC(C)N(C(C)C)CCSP(C)(O)=O UOXJNGFFPMOZDM-UHFFFAOYSA-N 0.000 description 2
- SFHYNDMGZXWXBU-LIMNOBDPSA-N 6-amino-2-[[(e)-(3-formylphenyl)methylideneamino]carbamoylamino]-1,3-dioxobenzo[de]isoquinoline-5,8-disulfonic acid Chemical compound O=C1C(C2=3)=CC(S(O)(=O)=O)=CC=3C(N)=C(S(O)(=O)=O)C=C2C(=O)N1NC(=O)N\N=C\C1=CC=CC(C=O)=C1 SFHYNDMGZXWXBU-LIMNOBDPSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 description 1
- WSXIMVDZMNWNRF-UHFFFAOYSA-N antimony;ethane-1,2-diol Chemical compound [Sb].OCCO WSXIMVDZMNWNRF-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses a titanium catalyst and a preparation method thereof, wherein the titanium catalyst comprises a compound A which is of a four-membered ring or six-membered ring structure; when the compound A is in a four-membered ring structure, the structural formula is shown as a formula (1), and when the compound A is in a six-membered ring structure, the structural formula is shown as a formula (2). The compound B is also included, and the structural formula of the compound B is shown as a formula (3). The preparation method comprises the following steps: slowly adding the dihydroxycarboxylic acid solution into the titanium compound solution, filtering turbid liquid after the reaction is finished, and washing and drying to obtain a compound A; slowly adding the 3, 5-di-tert-butyl-4-hydroxybenzyl diethyl phosphonate solution into the titanium compound solution, filtering turbid liquid after the reaction is finished, and washing and drying to obtain a compound B; mixing the compound A with the compound B according to a certain proportion. The titanium catalyst has stable structure, simple preparation process, good dissolution in glycol, high catalytic activity and improved brightness of polyester products.
Description
Technical Field
The invention relates to a catalyst for polyester production and a preparation method thereof, in particular to a titanium catalyst and a preparation method thereof.
Background
At present, most of polyester production enterprises over 90% at home and abroad adopt antimony catalysts. Antimony is heavy metal, the activity is general, the environment-friendly requirement is not met, and the antimony is easy to separate out, so that the color of the product is grey. Since antimony is a heavy metal element, new requirements are put on the use of antimony in recent years, such as the European Union, the United states, japan, and the like.
Compared with the antimony catalyst, the titanium (Ti) catalyst is environment-friendly, has high catalytic activity and small addition amount, belongs to non-heavy metal elements, has no harm to human bodies, is considered by the scientific community to be the most likely environment-friendly catalyst for replacing the antimony catalyst and realizing application, and therefore, related researches are carried out from the 70 th century.
Disclosure of Invention
The invention aims to: the invention aims to provide a titanium catalyst with high catalytic activity for replacing an antimony catalyst;
the second object of the present invention is to provide a process for preparing the above titanium catalyst.
The technical scheme is as follows: the titanium catalyst comprises a compound A, wherein the compound A has a four-membered ring or six-membered ring structure; when the compound A is in a four-ring structure, the structural formula is shown as follows:
r in formula (1) 1 is-H or- (CH) 2 CH 3 )(CH 3 )；
When the compound A is a six-membered ring structure, the structural formula is shown as follows:
r in formula (2) 2 is-CH 3 or-CH 2 CH 3 。
The preparation method of the titanium catalyst comprises the following steps: and dissolving dihydroxycarboxylic acid in a solvent, slowly adding the solvent into a titanium compound solution, filtering turbid liquid after the reaction is finished, and washing and drying the obtained precipitate to obtain the compound A.
Wherein the dihydroxycarboxylic acid is a compound containing two hydroxyl groups and one carboxyl group in the structural formula. When the number of carbon atoms between two hydroxyl groups of the dihydroxycarboxylic acid is 2, the obtained compound A has a four-membered ring structure; when the number of carbon atoms between two hydroxyl groups of the dihydroxycarboxylic acid is 3, the obtained compound A has a six-membered ring structure.
Further, the dihydroxycarboxylic acid is at least one of 2, 3-dihydroxypropionic acid, 2-dimethylolpropionic acid, 2-dimethylolbutyric acid, 2, 3-dihydroxy-3-methylpentanoic acid, and 3, 5-dihydroxy-3-methylpentanoic acid.
As a further preferable embodiment, the titanium catalyst further comprises a compound B having the following structural formula:
wherein the molar ratio of the compound A to the compound B is as follows: 2 to 6; the compound a and the compound B are physically mixed.
The preparation method of the titanium catalyst comprises the following steps:
(1) Dissolving dihydroxycarboxylic acid in a solvent, slowly adding the solvent into a titanium compound solution, filtering turbid liquid after the reaction is finished, and washing and drying the obtained precipitate to obtain a compound A;
(2) Dissolving 3, 5-di-tert-butyl-4-hydroxybenzyl diethyl phosphonate in a solvent, slowly adding the solvent into a titanium compound solution, filtering turbid liquid after the reaction is finished, and washing and drying the obtained precipitate to obtain a compound B;
(3) And mixing the compound A with the compound B in proportion to obtain the titanium catalyst.
Wherein, the mole ratio M of the dihydroxycarboxylic acid and the titanium compound and the mole ratio M of the 3, 5-di-tert-butyl-4-hydroxybenzyl diethyl phosphonate and the titanium compound are: 2< M <3.
Wherein the solvent in the steps (1) and (2) is at least one of ethyl acetate, methanol, chloroform and N, N-dimethylformamide.
Wherein the reaction conditions in the steps (1) and (2) are as follows: the reaction temperature is 55-150 ℃; the reaction time is 60-120min. The mass concentrations of the dihydroxycarboxylic acid and the 3, 5-di-tert-butyl-4-hydroxybenzyl diethyl phosphonate are respectively 10-20%, and the slow addition time is respectively 30-60min;
wherein the dissolution temperature in the steps (1) and (2) is 25-150 ℃.
Wherein the titanium compound is one of tetrabutyl titanate and tetraethyl titanate.
Wherein, in the steps (1) and (2), the drying conditions are as follows: vacuum drying at 60-160deg.C for 1-3h.
The beneficial effects are that: compared with the prior art, the invention has the following remarkable effects: the titanium catalyst disclosed by the invention has the advantages of stable structure, high catalytic activity, improved brightness of products, good dissolution in ethylene glycol and capability of replacing antimony catalysts; 2. the titanium catalyst provided by the invention has a simple preparation process, and is convenient for large-scale application in the polyester industry.
Detailed Description
The present invention is described in further detail below.
Example 1
A method for preparing a titanium catalyst, comprising the steps of:
(1) Adding 2, 2-dimethylolpropionic acid into methanol solvent to obtain mass concentration of 20%, heating to 60 ℃, keeping stirring, slowly adding into tetrabutyl titanate solution after the mass concentration is completely dissolved, finishing the addition within 60min, wherein the molar ratio of the 2, 2-dimethylolpropionic acid to the tetrabutyl titanate is 2.5, and continuing stirring reaction within the temperature range of 60 ℃ for 120min after finishing the addition. Filtering and separating a solid product generated in the reaction process after the reaction is finished, washing the solid product for 3 times by using methanol heated to 60 ℃, and finally drying the thermally washed solid product in a vacuum oven at 80 ℃ for 2 hours to obtain the compound A1.
(2) Adding 3, 5-di-tert-butyl-4-hydroxybenzyl diethyl phosphonate into methanol solvent, heating to 50 ℃ to obtain the mass concentration of 20%, stirring, slowly adding the mixture into tetrabutyl titanate solution after the 3, 5-di-tert-butyl-4-hydroxybenzyl diethyl phosphonate is completely dissolved, and continuously stirring and reacting for 120min at the temperature range of 60 ℃ after the addition is completed, wherein the molar ratio of the 3, 5-di-tert-butyl-4-hydroxybenzyl diethyl phosphonate to the tetrabutyl titanate is 3. Filtering and separating a solid product generated in the reaction process after the reaction is finished, washing the solid product for 3 times by using methanol heated to 60 ℃, and finally drying the thermally washed solid product in a vacuum oven at 80 ℃ for 2 hours to obtain solid powder B.
(3) The molar ratio of the compound A1 to the compound B is A1: b=2: and 1, uniformly mixing to obtain the titanium catalyst C1.
Preparation of titanium polyester:
500g of terephthalic acid, 300g of ethylene glycol and a titanium catalyst C1 are added into a 2L polymerization kettle, the temperature is raised to carry out esterification reaction, wherein the adding amount of the titanium catalyst is 5ppm based on the weight of PET titanium atoms calculated by a compound A, the temperature range of the whole esterification process is 230-250 ℃, the pressure fluctuation range during esterification is 0.2-0.3Mpa, and water produced by the reaction is discharged through a fractionating column. Decompression to normal pressure after esterification, vacuum pumping and heating to perform pre-polycondensation, wherein the temperature is in the range of 250-280 ℃, the pressure is lower than 150pa, the time is 45min, the temperature of the prepolymer in the reaction kettle reaches 280 ℃ after the pre-polymerization is finished, the pressure reaches 150pa, then continuous decompression and heating to perform final polycondensation, the temperature is in the range of 280-285 ℃, the pressure is lower than 100pa, the reaction is stopped after the system reacts to the required viscosity, the reactant is extruded out from the bottom of the polymerization kettle by nitrogen, and the polyester chips are obtained after water cooling and granulating, wherein the test indexes are shown in table 1.
Example 2
A method for preparing a titanium catalyst, comprising the steps of:
(1) Adding 2, 3-dihydroxypropionic acid into N, N-dimethylformamide, heating to 150 ℃ to obtain a mass concentration of 15%, stirring, slowly adding into tetrabutyl titanate solution after the 2, 3-dihydroxypropionic acid is completely dissolved, and finishing the addition within 50 min; the molar ratio of the 2, 3-dihydroxypropionic acid to the tetrabutyl titanate is 2.5, and the stirring reaction is continued for 100min at the temperature of 150 ℃ after the addition is finished. Filtering and separating a solid product generated in the reaction process after the reaction is finished, washing the solid product for 3 times by using N, N-dimethylformamide which is heated to 150 ℃, and finally drying the solid product after the heat washing in a vacuum oven at 160 ℃ for 3 hours to obtain the compound A2.
(2) Compound A2 and compound B of example 1 were mixed in a molar ratio A2: b=3: and 1, uniformly mixing to obtain the titanium catalyst C2.
The method for preparing titanium polyester by using the titanium catalyst C2 comprises the following steps:
preparation procedure referring to example 1, except that the catalyst was titanium catalyst C2, the test index of the polyester chips is shown in table 1.
Example 3
A method for preparing a titanium catalyst, comprising the steps of:
(1) Adding 2, 3-dihydroxyl-3-methyl valeric acid into ethyl acetate solvent, heating to 55 ℃ with the mass concentration of 10%, keeping stirring, slowly adding the mixture into tetrabutyl titanate solution after the 3, 5-dihydroxyl-3-methyl valeric acid is completely dissolved, finishing the addition within 30min, and continuing to stir and react for 60min within the temperature range of 55 ℃ after the addition is finished, wherein the molar ratio of the 3, 5-dihydroxyl-3-methyl valeric acid to the tetraethyl titanate is 2.5. Filtering and separating a solid product generated in the reaction process after the reaction is finished, washing the solid product for 3 times by using ethyl acetate heated to 65 ℃, and finally drying the thermally washed solid product in a vacuum oven at 80 ℃ for 3 hours to obtain the compound A3.
(2) The molar ratio of compound A3 to compound B of example 1 is A3: b=4: 1 to obtain the titanium catalyst C3 of the invention, and the test indexes of the polyester chips are shown in Table 1.
The method for preparing titanium polyester by using the titanium catalyst C3 comprises the following steps:
the preparation process was as described in example 1, except that the catalyst was titanium catalyst C3.
Example 4
The preparation method of the compound A4 in the titanium catalyst is described with reference to example 1, except that the dihydroxycarboxylic acid compound is 2, 2-dimethylolbutyric acid.
The molar ratio of compound A4 to compound B of example 1 is A4: b=6: 1 to obtain the titanium catalyst C4.
Polyester production process referring to example 1, except that the catalyst was titanium catalyst C4, the test index of the polyester chips is shown in table 1.
Example 5
Polyester production procedure referring to example 1, except that the catalyst used was A1 and Ti content was 5ppm, the test index of the polyester chips is shown in Table 1.
Example 6
Polyester production procedure referring to example 2, except that the catalyst used was A2 and Ti content was 5ppm, the test index of the polyester chips is shown in Table 1.
Example 7
Polyester production procedure referring to example 3, except that the catalyst used was A3, ti content was 5ppm, and the test index of the polyester chips was shown in Table 1.
Example 8
Polyester production procedure referring to example 4, except that the catalyst used was A4, ti content was 5ppm, and the test index of the polyester chips was shown in Table 1.
Example 9
Polyester production procedure referring to example 1, except that the catalyst used was B, ti content was 5ppm, and the test index of the polyester chips was shown in Table 1.
Comparative example
Polyester production procedure referring to example 1, except that ethylene glycol antimony was used as the catalyst, the content was 200ppm, and the test index of the polyester chips was shown in Table 1.
TABLE 1 comparison of the Main conventional Properties of titanium-based polyesters
Claims (9)
1. A titanium catalyst, which is characterized by comprising a compound A, wherein the compound A has a four-membered ring or six-membered ring structure; when the compound A is in a four-ring structure, the structural formula is shown as follows:
r in formula (1) 1 is-H or- (CH) 2 CH 3 )(CH 3 )；
When the compound A is a six-membered ring structure, the structural formula is shown as follows:
r in formula (2) 2 is-CH 3 or-CH 2 CH 3 ；
Also comprises a compound B, which has the following structural formula:
2. the titanium catalyst according to claim 1, characterized in that the molar ratio of compound a to compound B is: 2-6.
3. A process for producing a titanium catalyst according to claim 1, wherein a dihydroxycarboxylic acid is dissolved in a solvent and slowly added to a titanium compound solution, and after the completion of the reaction, the turbid liquid is filtered, and the obtained precipitate is washed and dried to obtain the compound A.
4. The method for producing a titanium catalyst according to claim 3, wherein the dihydroxycarboxylic acid is a compound having two hydroxyl groups and one carboxyl group in the structural formula.
5. The method for producing a titanium catalyst according to claim 3, wherein the dihydroxycarboxylic acid is at least one of 2, 3-dihydroxypropionic acid, 2-dimethylolpropionic acid, 2-dimethylolbutyric acid, 2, 3-dihydroxy-3-methylpentanoic acid, and 3, 5-dihydroxy-3-methylpentanoic acid.
6. A method for preparing the titanium catalyst according to claim 1, comprising the steps of:
(1) Dissolving dihydroxycarboxylic acid in a solvent, slowly adding the solvent into a titanium compound solution for reaction, filtering turbid liquid after the reaction is finished, and washing and drying the obtained precipitate to obtain a compound A;
(2) Dissolving 3, 5-di-tert-butyl-4-hydroxybenzyl diethyl phosphonate in a solvent, slowly adding the solvent into a titanium compound solution for reaction, filtering turbid liquid after the reaction is finished, and washing and drying the obtained precipitate to obtain a compound B;
(3) The titanium catalyst is prepared by mixing the compound A with the compound B.
7. The method for preparing a titanium catalyst according to claim 6, wherein the molar ratio M of each of the dihydroxycarboxylic acid, 3, 5-di-tert-butyl-4-hydroxybenzyl diethyl phosphonate and the titanium compound is: 2< M <3.
8. The method for producing a titanium catalyst according to claim 6, wherein the solvent in the steps (1) and (2) is at least one of ethyl acetate, methanol, chloroform, and N, N-dimethylformamide.
9. The method of producing a titanium catalyst according to claim 6, wherein in the steps (1), (2): the reaction temperature is 55-150 ℃ and the reaction time is 60-120min.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1370632A (en) * | 1962-05-16 | 1964-08-28 | Du Pont | Preparation of linear polymeric polyesters, in particular terephthalic esters, in the presence of organic phosphorus compounds |
| US6376642B1 (en) * | 1998-07-07 | 2002-04-23 | Atofina Chemicals, Inc. | Polyester polycondensation with lithium titanyl oxalate catalyst |
| CN105061744A (en) * | 2015-08-17 | 2015-11-18 | 中国石油天然气集团公司 | Preparation method of PBS (poly butylenes succinate) |
| WO2017089099A1 (en) * | 2015-11-27 | 2017-06-01 | Sabic Global Technologies B.V. | Process for the production of polyether ester block copolymers |
| CN113881027A (en) * | 2020-07-01 | 2022-01-04 | 中国石油化工股份有限公司 | Titanium polyester catalyst and preparation method and application thereof |
| CN114874423A (en) * | 2021-02-05 | 2022-08-09 | 中国石油化工股份有限公司 | Titanium catalyst and preparation method thereof, and titanium catalyst composition and preparation method thereof |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1370632A (en) * | 1962-05-16 | 1964-08-28 | Du Pont | Preparation of linear polymeric polyesters, in particular terephthalic esters, in the presence of organic phosphorus compounds |
| US6376642B1 (en) * | 1998-07-07 | 2002-04-23 | Atofina Chemicals, Inc. | Polyester polycondensation with lithium titanyl oxalate catalyst |
| CN105061744A (en) * | 2015-08-17 | 2015-11-18 | 中国石油天然气集团公司 | Preparation method of PBS (poly butylenes succinate) |
| WO2017089099A1 (en) * | 2015-11-27 | 2017-06-01 | Sabic Global Technologies B.V. | Process for the production of polyether ester block copolymers |
| CN113881027A (en) * | 2020-07-01 | 2022-01-04 | 中国石油化工股份有限公司 | Titanium polyester catalyst and preparation method and application thereof |
| CN114874423A (en) * | 2021-02-05 | 2022-08-09 | 中国石油化工股份有限公司 | Titanium catalyst and preparation method thereof, and titanium catalyst composition and preparation method thereof |
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