CN107365413A - A kind of preparation method and application of titanium complex catalyst - Google Patents
A kind of preparation method and application of titanium complex catalyst Download PDFInfo
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- CN107365413A CN107365413A CN201710615703.9A CN201710615703A CN107365413A CN 107365413 A CN107365413 A CN 107365413A CN 201710615703 A CN201710615703 A CN 201710615703A CN 107365413 A CN107365413 A CN 107365413A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/87—Non-metals or inter-compounds thereof
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- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The present invention relates to a kind of preparation method of titanium complex catalyst：Deionized water, absolute ethyl alcohol, zirconium oxychloride and organic phospho acid are added in reaction vessel, 8~12h of heating stirring, filtration washing, chlorion is removed, obtains zirconium phosphonate colloidal compound；Titanium compound, ethylene glycol, obtained zirconium phosphonate colloidal compound and alkyl benzene sulfonate compound are reacted into 0.5~2h for 50~150 DEG C in isopropanol, complexing agent is added after removing the small molecule in reaction system, 0.5~4h is reacted again, reaction temperature is 80~180 DEG C, and obtained settled solution is liquid titanium complex catalyst.The liquid titanium complex catalyst catalytic activity prepared using this method is moderate, solve the problems, such as presently disclosed titanium catalyst exist in the production application of bottle grade PET form and aspect jaundice, solid-phase tack producing not up, the technical bottleneck such as acetaldehyde height, and obtained polyester slice it is green, without heavy metal.
Description
Technical field
The present invention relates to a kind of preparation method of titanium complex catalyst, is related to and prepares environmental protection using titanium complex catalyst
Method of the type without antimony bottle-grade polyester chip.
Background technology
Various titanium catalysts are come out one after another in recent years, are the focuses of current polyester industrial development.Increasingly focus in the whole world
Under the background of ecological, environmental protective, the overall development trend of polyester catalyst is that environmentally friendly, efficient, less toxic and nontoxic direction is developed, green
The production and selling of product is the trend of polyester industry development from now on.PET industry makes great efforts research and development new catalyst to improve enterprise
Survival ability, at present, disclosed polyester titanium catalyst has both at home and abroad：Butyl titanate, metatitanic acid tetraethyl ester, C-94, second two
The ethylene glycol solution of alcohol titanium, titanium potassium oxalate, titanium and phosphorus the titanium such as complex compound compound or complex compound.But in commercial Application
Present in problem, have impact on the industrialization progress of titanium catalyst, especially apply in the production process of bottle grade PET.Bottle level
Polyester is mainly that food Package is used, and green polyester product of the production without heavy metal has become the development of domestic and international PET industry
Trend and inevitable requirement.Polyester for bottle product is produced using titanium catalyst, is the development trend of current PET industry.
Patent CN104479123 discloses a kind of titanium using titanium as catalytic activity medium supplemented by main catalytic activity medium, lithium
Series catalysts, its step are to add titanium tetrachloride, lithium chloride without water glycol in nitrogen atmosphere, are passed through ammonia, finally mistake
Elimination removes ammonium chloride, obtains the complex solution of titanium ethylene glycolate-lithium, and this catalyst is used in polyester lab scale polymerisation, obtained
Polymerization product color and luster it is partially not yellow, but be used on industrial installation, obtained polymerization product form and aspect are partially yellow, and characteristic is glued
Degree is not high, and later stage thickening does not get on.
Patent CN102382287, which is disclosed, a kind of is used for polyester and the liquid condition titanium series catalyst of copolyesters and its preparation side
Method, step add phosphorus compound in the reaction product for titanium compound, tetraethyl orthosilicate, hydroxycarboxylic acid are reacted in a solvent
A period of time is reacted with metal promoters, removes small molecule, liquid condition titanium series catalyst is made.This Titanium series catalyst can be with second
Glycol dissolves each other, high to the catalytic activity of polyester polycondensation reaction, and addition is few, and gained fiber-grade polyester product form and aspect are good, but will
This catalyst is applied to bottle grade PET production technology, it will during subsequent technique, the yellowing of product form and aspect occurs, does not viscosify
The technical problem such as go, influence end product quality.
It using nano silicon is carrier, titanium ethylene glycolate for catalytic active center that patent CN103709383A, which is disclosed a kind of,
Supported titanium-series polyester catalyst, its advantage be using alcohol exchange method realize catalyst load, avoid traditional system
Acidic by-products simplify preparation technology to titanium ethylene glycolate purification and the influence of yield in Preparation Method.Using the catalyst compared with
The preferable polyester product of colour can be prepared under low catalyst concn and condensation temperature.Solves current titanium series polyester catalyst
Synthesizing polyester product yellow problem, still, cut into slices for the solid phase polycondensation speed and thickening being related to during production bottle grade PET
Acetaldehyde problem do not relate to.
The problem of titanium catalyst developed in recent years exists in actual applications based on more than, invention it is a kind of with
Titanium, zirconium, the liquid phase titanium complex catalyst of alkyl benzene sulfonate compound complexing.Titanium can effectively be suppressed by adding zirconium compounds
Atom catalytic activity in the reaction, solve the problems, such as to apply hue of chip caused by titanium catalyst to turn to be yellow in polyester synthesis, add
Solid phase polycondensation speed can be improved by entering alkyl benzene sulfonate compound, save the energy, reduce cost, improve the daily output.This is urged
Agent catalytic activity is moderate, the production for the bottle grade PET that is particularly suitable for use in, and for obtained polyester slice without antimony, environmental protection, hue of chip is good,
Solid phase polycondensation speed is fast, and acetaldehyde is low.
The content of the invention
It is an object of the invention to provide a kind of preparation method and application titanium system composite catalyzing of liquid titanium complex catalyst
Agent produces environment-friendly type without antimony bottle-grade polyester chip.The technical problem of solution is：Overcome following defect present in prior art：Titanium
Catalyst is used in the production technology of bottle grade PET, partially yellow synthesizing polyester hue of chip, acetaldehyde height, solid-phase tack producing speed be present
The technical bottlenecks such as rate is slow.
A kind of liquid titanium complex catalyst for polyester synthesis, mainly by titanium compound, zirconium compounds and alkylbenzene
Sulfonates compound reacts a kind of complex compound of formation under certain conditions.
Preferably, the mol ratio of titanium and zirconium is 20 in described catalyst:1~5:1；Titanium and alkyl benzene sulfonate
The mol ratio of compound is 1:1~1:10.
Present disclosure scheme is as follows：
A kind of titanium complex catalyst preparation method；Comprise the following steps：
(1) deionized water, absolute ethyl alcohol, zirconium oxychloride and organic phospho acid, 80~90 DEG C of heating are added in reaction vessel
8~12h is stirred, filtration washing, chlorion is removed, obtains zirconium phosphonate colloidal compound；
(2) by zirconium phosphonate colloidal compound and alkyl benzene sulphonate made from titanium compound, ethylene glycol and step (1)
Salt compounds 50~150 DEG C of 0.5~2h of reaction in isopropanol, complexing agent is added after removing the small molecule in reaction system,
0.5~4h is reacted again, and reaction temperature is 80~180 DEG C, and obtained settled solution is liquid titanium complex catalyst.
It is preferred that deionized water, absolute ethyl alcohol, zirconium oxychloride, organic phospho acid, mol ratio 400:40:20:1~25:75:2:
1。
The titanium compound is preferably derived from one kind in tetraethyl titanate, tetraisopropyl titanate or butyl titanate.
The alkyl benzene sulfonate compound is preferably derived from one in paratoluenesulfonic acid sodium salt, neopelex
Kind.
Described complexing agent is preferably citric acid, tartaric acid or salicylic acid.
Described organic phospho acid is preferably 1-hydroxy ethylidene-1,1-diphosphonic acid (HEDP) or ATMP (ATMP).
Described titanium compound and the mol ratio of ethylene glycol are preferably 1:10~1:40；Mole of titanium compound and isopropanol
Than being preferably 1:20~1:50；The mol ratio of titanium compound and complexing agent is preferably 1:2~1:10.
Catalyst prepared by the present invention is used for the synthesis of bottle grade PET, and the addition of catalyst is calculated as benzene diformazan with titanium atom
5~15ppm of sour weight.
The present invention prepares the liquid titanium complex catalyst for polyester synthesis, the catalyst be mainly by titanium compound,
Zirconium compounds and alkyl benzene sulfonate compound react a kind of complex compound of formation under certain conditions, add zirconium chemical combination
Thing can solve the problems, such as to add alkyl benzene sulfonate compound using the hue of chip jaundice of Titanium series catalyst generation at present
The speed of later process solid-phase tack producing can also be improved in the application of bottle-grade polyester chip, the energy is saved, reduces cost.
Embodiment
Embodiment 1
Catalyst A preparation
(1) 36g (2mol) deionized waters and 9.2g (0.2mol) absolute ethyl alcohol are added in reaction vessel, adds 1.03g
(0.005mol) 1-hydroxy ethylidene-1,1-diphosphonic acid (HEDP), 3.22g (0.01mol) zirconium oxychloride is added after heating for dissolving, and temperature is kept
80 DEG C, 8h is stirred, filtering, is washed with ethanol and removes chlorion, obtain organic phospho acid colloidal zirconia.
(2) organic phospho acid colloidal zirconia made from step (1) is added and leaked with having heaters, agitator, condenser and liquid separation
In the four-hole boiling flask of bucket, 56.8g (0.2mol) tetraisopropyl titanate, 120g isopropanols, 400g ethylene glycol and 38.8g are added
(0.2mol) paratoluenesulfonic acid sodium salt, 50 DEG C of heating 1h, is well mixed, then toward adding 84.4g (0.4mol) citric acid in reactor
With the mixed solution of 120g isopropanols, 80 DEG C of heating stirring 0.5h, small molecule is removed, clarified to solution, obtain catalyst A.Through
Calculate, it is 1.84% that titanium atom content in catalyst, which is made,.
Preparation without antimony bottle grade PET
In 2L pet reaction kettles, 485g terephthalic acid (TPA)s, 15g M-phthalic acids, 260g ethylene glycol and 0.435g are added
Catalyst A (weight of the amount titanium atom based on phthalic acid is 8ppm), adds organic blue toner 5g and (is based on benzene diformazan
The amount of acid is 5ppm), organic red toner 3g (amount based on phthalic acid is 3ppm), stabilizer 1.2g (is based on benzene diformazan
The amount of acid is 2.2ppm), mixing is made into slurry, and at 230 DEG C~245 DEG C, esterification is carried out under the conditions of 0.20~0.30Mpa,
It is esterified and terminates when distillating water and reaching more than the 95% of theoretical value, be down to normal pressure, vacuumizes and be decompressed to system pressure and be less than
150Pa, simultaneous reactions temperature gradually rise up to carry out polymerisation at 275~285 DEG C, treat that polycondensation product reaches required characteristic and glued
Stop reaction after degree, afterwards continuously extrude reaction product with bar shaped from bottom of polymerizing pot, cooling, pelletizing, obtain no antimony bottle level and gather
Ester ground sections.The performance test results are shown in Table 1.Vacuum drum is put into after obtained ground sections are dried and carries out solid-phase tack producing, is delayed
Slow heating, temperature control keep 24h at 210-220 DEG C.Obtain no antimony bottle grade PET solid-phase tack producing section, i.e. SSP sections.Performance
Test result is shown in Table 1.
Embodiment 2
Catalyst B preparation
(1) 27g (1.5mol) deionized waters and 23g (0.5mol) ethanol are added in reaction vessel, adds 2.99g
(0.01mol) ATMP (ATMP), 9.66g (0.03mol) zirconium oxychloride is added after heating for dissolving, and temperature keeps 90
DEG C, 10h is stirred, filtering, is washed with ethanol and removes chlorion, obtain organic phospho acid colloidal zirconia.
(2) organic phospho acid colloidal zirconia made from step (1) is added and leaked with having heaters, agitator, condenser and liquid separation
In the four-hole boiling flask of bucket, 45.6g (0.2mol) tetraethyl titanate, 150g isopropanols, 300g ethylene glycol and 13.9g are added
(0.04mol) neopelex, 120 DEG C of heating 0.5h, is well mixed, then toward adding 120g (0.8mol) in reactor
The mixed solution of tartaric acid acid and 150g isopropanols, 120 DEG C of heating stirring 1h, removes small molecule, clarifies, is catalyzed to solution
Agent B.It is computed, titanium atom content is 1.77% in obtained catalyst.
Preparation without antimony bottle grade PET
Method similarly to Example 1 is prepared without antimony bottle grade PET, using 0.734g catalyst B as polycondensation catalyst
(amount based on phthalic acid, the weight of titanium atom is 13ppm), organic blue toner, (amount based on phthalic acid is 8g
8ppm), organic red toner 5g (amount based on phthalic acid is 5ppm), (amount based on phthalic acid is stabilizer 1.2g
2.2ppm), through esterification, polycondensation is obtained to be shown in Table 1 without antimony bottle grade PET ground sections the performance test results.By obtained ground sections
Vacuum drum is put into after drying and carries out solid-phase tack producing, slowly heating, temperature control keeps 24h at 210-220 DEG C.Obtain no antimony bottle
The solid-phase tack producing section of level polyester, i.e. SSP sections.The performance test results are shown in Table 1.
Embodiment 3
Catalyst C preparation
(1) 18g (1mol) deionized waters and 46g (1mol) ethanol are added in reaction vessel, adds 3.09g
(0.015mol) 1-hydroxy ethylidene-1,1-diphosphonic acid (HEDP), 4.83g (0.015mol) zirconium oxychloride is added after heating for dissolving, and temperature is kept
85 DEG C, 12h is stirred, filtering, is washed with ethanol and removes chlorion, obtain organic phospho acid colloidal zirconia.
(2) organic phospho acid colloidal zirconia made from step (1) is added and leaked with having heaters, agitator, condenser and liquid separation
In the four-hole boiling flask of bucket, 56.8g (0.2mol) tetraisopropyl titanate, 200g isopropanols, 496g ethylene glycol and 6.9g are added
(0.02mol) neopelex, 150 DEG C of heating 1h, is well mixed, then toward adding 221g (1.6mol) water in reactor
The mixed solution of poplar acid and 200g isopropanols, 180 DEG C of heating stirring 3h, removes small molecule, is clarified to solution, obtains catalyst C,
It is computed, titanium atom content is 1.63% in obtained catalyst.
Preparation without antimony bottle grade PET
Method similarly to Example 1 is prepared without antimony bottle grade PET, using 0.920g catalyst C as polycondensation catalyst
(amount based on phthalic acid, the weight of titanium atom is 15ppm), (amount based on phthalic acid is by organic blue toner 8g
8ppm), organic red toner 5g (amount based on phthalic acid is 5ppm), (amount based on phthalic acid is stabilizer 1.8g
3.3ppm), through esterification, polycondensation is obtained to be shown in Table 1 without antimony bottle grade PET ground sections the performance test results.By obtained ground sections
Vacuum drum is put into after drying and carries out solid-phase tack producing, slowly heating, temperature control keeps 24h at 210-220 DEG C.Obtain no antimony bottle
The solid-phase tack producing section of level polyester, i.e. SSP sections.The performance test results are shown in Table 1.
Embodiment 4
Catalyst D preparation
(1) 9g (0.5mol) deionized waters and 69g (1.5mol) ethanol are added in reaction vessel, adds 4.12g
(0.02mol) 1-hydroxy ethylidene-1,1-diphosphonic acid (HEDP), 12.88g (0.04mol) zirconium oxychloride is added after heating for dissolving, and temperature is kept
80 DEG C, 10h is stirred, filtering, is washed with ethanol and removes chlorion, obtain organic phospho acid colloidal zirconia.
(2) organic phospho acid colloidal zirconia made from step (1) is added and leaked with having heaters, agitator, condenser and liquid separation
In the four-hole boiling flask of bucket, 68.1g (0.2mol) butyl titanate, 300g isopropanols, 124g ethylene glycol and 19.4g are added
(0.1mol) paratoluenesulfonic acid sodium salt, 100 DEG C of heating 2h, is well mixed, then toward adding 274.24g (2.0mol) lemon in reactor
The mixed solution of acid and 300g isopropanols, 150 DEG C of heating stirring 4h, small molecule is removed, clarified to solution, obtain catalyst D, passed through
Calculate, titanium atom content is 1.50% in obtained catalyst.
Preparation without antimony bottle grade PET
Method similarly to Example 1 is prepared without antimony bottle grade PET, using 0.333g catalyst D as polycondensation catalyst
(amount based on phthalic acid, the weight of titanium atom is 5ppm), (amount based on phthalic acid is by organic blue toner 5g
5ppm), organic red toner 3g (amount based on phthalic acid is 3ppm), (amount based on phthalic acid is stabilizer 1.2g
2.2ppm), through esterification, polycondensation is obtained to be shown in Table 1 without antimony bottle grade PET ground sections the performance test results.By obtained ground sections
Vacuum drum is put into after drying and carries out solid-phase tack producing, slowly heating, temperature control keeps 24h at 210-220 DEG C.Obtain no antimony bottle
The solid-phase tack producing section of level polyester, i.e. SSP sections.The performance test results are shown in Table 1.
Comparative example 1
Catalyst：Antimony glycol, it is commercially available.
The preparation of antimony system bottle grade PET
In 2L pet reaction kettles, 485g terephthalic acid (TPA)s, 15g M-phthalic acids, 260g ethylene glycol and 0.225g are added
Antimony glycol (amount based on phthalic acid is 245ppm), adding organic blue toner 3g, (amount based on phthalic acid is
3ppm), organic red toner 1g (amount based on phthalic acid is 1ppm), (amount based on phthalic acid is stabilizer 5g
9.2ppm), mixing is made into slurry, and at 230 DEG C~245 DEG C, esterification is carried out under the conditions of 0.20~0.30Mpa, when distillating water
Amount when reaching more than the 95% of theoretical value esterification terminate, be down to normal pressure, vacuumize and be decompressed to system pressure and be less than 150Pa, simultaneously
Reaction temperature gradually rises up to carry out polymerisation at 275~285 DEG C, stops after inherent viscosity needed for polycondensation product reaches anti-
Should, reaction product is continuously extruded from bottom of polymerizing pot with bar shaped afterwards, cooling, pelletizing, obtains antimony system bottle grade PET ground sections.
The performance test results are shown in Table 1.Vacuum drum is put into after obtained ground sections are dried and carries out solid-phase tack producing, slowly heating, temperature
Control keeps 24h at 210-220 DEG C.Obtain the bottle grade PET solid-phase tack producing section of antimony system, i.e. SSP sections.The performance test results are shown in
Table 1.
The bottle-grade polyester chip Testing index of table 1
Compared with antimony system polyester slice, the invention has the advantages that：The liquid titanium complex catalyst prepared using this method
Catalytic activity is moderate, there is catalytic action, the colour of the polyester slice of production, end carboxyl, spy to esterification and polymerisation
Property the technical indicator such as viscosity, acetaldehyde, diethylene glycol (DEG) it is qualified, and obtained polyester slice is without antimony metal, green.
In follow-up solid phase polycondensation process, polycondensation speed is fast, and obtained polyester bottle slice form and aspect are good, and acetaldehyde is low.The present invention solves mesh
Preceding disclosed titanium catalyst exist in the production application of bottle grade PET form and aspect jaundice, solid-phase tack producing not up, acetaldehyde it is high
Etc. technical bottleneck problem, and obtained polyester slice it is green, without heavy metal.
Claims (8)
1. a kind of titanium complex catalyst preparation method, it is characterised in that comprise the following steps：
(1) deionized water, absolute ethyl alcohol, zirconium oxychloride and organic phospho acid, 80~90 DEG C of heating stirrings 8 are added in reaction vessel
~12h, filtration washing, chlorion is removed, obtains zirconium phosphonate colloidal compound；
(2) by zirconium phosphonate colloidal compound and alkyl benzene sulfonate made from titanium compound, ethylene glycol and step (1)
Compound 50~150 DEG C of 0.5~2h of reaction in isopropanol, complexing agent is added after removing the small molecule in reaction system, then instead
0.5~4h is answered, reaction temperature is 80~180 DEG C, and obtained settled solution is liquid titanium complex catalyst.
2. the method as described in claim 1, it is characterized in that deionized water, absolute ethyl alcohol, zirconium oxychloride, organic phospho acid, mole
Than for 400:40:20:1~25:75:2:1.
3. the method as described in claim 1, it is characterized in that the titanium compound be derived from tetraethyl titanate, tetraisopropyl titanate or
One kind in butyl titanate.
4. the method as described in claim 1, it is characterized in that the alkyl benzene sulfonate compound be derived from paratoluenesulfonic acid sodium salt,
One kind in neopelex.
5. the method as described in claim 1, it is characterized in that described complexing agent is citric acid, tartaric acid or salicylic acid.
6. the method as described in claim 1, it is characterized in that described organic phospho acid is 1-hydroxy ethylidene-1,1-diphosphonic acid or amino front three
Pitch phosphonic acids.
7. the method as described in claim 1, it is characterized in that described titanium compound and the mol ratio of ethylene glycol are 1:10~40；
The mol ratio of titanium compound and isopropanol is 1:20~50；The mol ratio of titanium compound and complexing agent is 1:2~10.
8. the catalyst prepared described in claim 1 is used for the synthesis of bottle grade PET, the addition of catalyst is calculated as with titanium atom
5~15ppm of phthalic acid weight.
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| CN108034046A (en) * | 2017-11-23 | 2018-05-15 | 中国科学院理化技术研究所 | Efficient polyester composite catalyst and preparation method and application thereof |
| CN110643026A (en) * | 2019-10-22 | 2020-01-03 | 华润化学材料科技有限公司 | Novel titanium catalyst for polyester and preparation method thereof |
| CN114057919A (en) * | 2020-07-31 | 2022-02-18 | 中国石油化工股份有限公司 | Catalyst for preparing polyethylene resin by gas phase polymerization |
| CN114989405A (en) * | 2022-07-11 | 2022-09-02 | 青岛大学 | Titanium catalyst for synthesizing polyester by DMT method, preparation method and application thereof |
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| CN110643026A (en) * | 2019-10-22 | 2020-01-03 | 华润化学材料科技有限公司 | Novel titanium catalyst for polyester and preparation method thereof |
| CN110643026B (en) * | 2019-10-22 | 2022-02-18 | 华润化学材料科技股份有限公司 | Titanium catalyst for polyester and preparation method thereof |
| CN114057919A (en) * | 2020-07-31 | 2022-02-18 | 中国石油化工股份有限公司 | Catalyst for preparing polyethylene resin by gas phase polymerization |
| CN114057919B (en) * | 2020-07-31 | 2023-04-21 | 中国石油化工股份有限公司 | Catalyst for preparing polyethylene resin by gas phase polymerization |
| CN114989405A (en) * | 2022-07-11 | 2022-09-02 | 青岛大学 | Titanium catalyst for synthesizing polyester by DMT method, preparation method and application thereof |
| CN114989405B (en) * | 2022-07-11 | 2024-02-20 | 青岛大学 | Titanium catalyst for synthesizing polyester by DMT method and preparation method and application thereof |
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