CN107365413B - 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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- CN107365413B CN107365413B CN201710615703.9A CN201710615703A CN107365413B CN 107365413 B CN107365413 B CN 107365413B CN 201710615703 A CN201710615703 A CN 201710615703A CN 107365413 B CN107365413 B CN 107365413B
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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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Abstract
The present invention relates to a kind of preparation methods of titanium complex catalyst: deionized water, dehydrated alcohol, zirconium oxychloride and organic phospho acid, 8~12h of heating stirring being added in the reaction vessel, filtration washing removes chloride ion, obtains zirconium phosphonate colloidal compound；By titanium compound, ethylene glycol, zirconium phosphonate colloidal compound obtained and alkyl benzene sulfonate compound in isopropanol 50~150 DEG C of 0.5~2h of reaction, 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 clear 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 in the production application of bottle grade PET there are form and aspect jaundice, solid-phase tack producing not up, the technical bottlenecks such as acetaldehyde height, and polyester slice obtained is environmentally protective, is free of heavy metal.
Description
Technical field
The present invention relates to a kind of preparation method of titanium complex catalyst, it is related to using titanium complex catalyst preparation environmental protection
Method of the type without antimony bottle-grade polyester chip.
Background technique
Various titanium catalysts are come out one after another in recent years, are the hot spots 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 environmental protection, efficient, low toxicity and nontoxic direction are 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, currently, 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 titaniums such as complex compound compound or complex compound.But in industrial application
The problem of, the industrialization progress of titanium catalyst is affected, is especially applied in the production process of bottle grade PET.Bottle grade
Polyester is mainly that food Package is used, and production has become the development of domestic and international PET industry without the green polyester product of heavy metal
Trend and inevitable requirement.Polyester for bottle product is produced using titanium catalyst, is the development trend of current PET industry.
Patent CN104479123 disclose it is a kind of with titanium be main catalytic activity medium, supplemented by lithium catalytic activity medium titanium
Series catalysts, step are that titanium tetrachloride, lithium chloride are added without water glycol in nitrogen atmosphere, are passed through ammonia, finally mistake
It filters off and removes ammonium chloride, obtain titanium ethylene glycolate-lithium complex solution, this catalyst is used in polyester lab scale polymerization reaction, is obtained
Polymerization product color it is partially not yellow, but be used on industrial production equipment, obtained polymerization product form and aspect are partially yellow, and characteristic is viscous
Degree is not high, and later period thickening does not get on.
Patent CN102382287 discloses a kind of liquid condition titanium series catalyst and its preparation side for polyester and copolyesters
Method, step are to react titanium compound, ethyl orthosilicate, hydroxycarboxylic acid in a solvent, and phosphorus compound is added in the reaction product
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 additive amount 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
It the technical problems such as goes, influences end product quality.
It is carrier, titanium ethylene glycolate for catalytic active center that patent CN103709383A, which discloses one kind using nano silica,
Supported titanium-series polyester catalyst, its advantage is that using alcohol exchange method realize catalyst load, avoid traditional system
Influence of the acidic by-products to titanium ethylene glycolate purification and yield, simplifies preparation process in Preparation Method.Using the catalyst compared with
The preferable polyester product of color value can be prepared under low catalyst concn and condensation temperature.Solves current titanium series polyester catalyst
Polyester product yellow problem is synthesized, still, solid phase polycondensation rate involved in production bottle grade PET process and thickening are sliced
Acetaldehyde problem do not relate to.
The problem of being existed in practical applications based on the titanium catalyst developed in recent years above, invention it is a kind of with
The liquid phase titanium complex catalyst that titanium, zirconium, alkyl benzene sulfonate compound are complexed.Zirconium compounds, which is added, can effectively inhibit titanium
Atom catalytic activity in the reaction solves the problems, such as the hue of chip generated in polyester synthesis using titanium catalyst jaundice, adds
Entering alkyl benzene sulfonate compound can be improved solid phase polycondensation rate, save the energy, reduce cost, improve the daily output.This is urged
Agent catalytic activity is moderate, is particularly suitable for the production of bottle grade PET, and for polyester slice obtained without antimony, environmental protection, hue of chip is good,
Solid phase polycondensation rate is fast, and acetaldehyde is low.
Summary of the invention
The object of the present invention is to provide a kind of preparation method and application titanium system composite catalyzings of liquid titanium complex catalyst
Agent produces environment-friendly type without antimony bottle-grade polyester chip.The technical issues of solution, is: overcoming following defect existing in the prior art: titanium
Synthesis hue of PET chip is partially yellow, acetaldehyde is high, solid-phase tack producing speed for existing in the production technology of bottle grade PET for catalyst
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 molar ratio of titanium and zirconium is 20:1~5:1 in the catalyst；Titanium and alkyl benzene sulfonate
The molar ratio for closing object is 1:1~1:10.
Contents of the present invention scheme is as follows:
A kind of titanium complex catalyst preparation method；The following steps are included:
(1) deionized water, dehydrated alcohol, zirconium oxychloride and organic phospho acid, 80~90 DEG C of heating are added in the reaction vessel
8~12h is stirred, filtration washing removes chloride ion, obtains zirconium phosphonate colloidal compound；
(2) by zirconium phosphonate colloidal compound and alkyl benzene sulphonate made from titanium compound, ethylene glycol and step (1)
Complexing agent is added after removing the small molecule in reaction system in salt compounds 50~150 DEG C of 0.5~2h of reaction in isopropanol,
0.5~4h is reacted again, and reaction temperature is 80~180 DEG C, and obtained clear solution is liquid titanium complex catalyst.
It is preferred that deionized water, dehydrated alcohol, zirconium oxychloride, organic phospho acid, molar ratio is 400:40:20:1~25:75:2:
1。
The titanium compound is preferably derived from one of tetraethyl titanate, tetraisopropyl titanate or butyl titanate.
The alkyl benzene sulfonate compound is preferably derived from paratoluenesulfonic acid sodium salt, one in neopelex
Kind.
The complexing agent is preferably citric acid, tartaric acid or salicylic acid.
The organic phospho acid is preferably 1-hydroxy ethylidene-1,1-diphosphonic acid (HEDP) or aminotrimethylenephosphonic acid (ATMP).
The molar ratio of the titanium compound and ethylene glycol is preferably 1:10~1:40；Mole of titanium compound and isopropanol
Than being preferably 1:20~1:50；The molar 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 additive amount of catalyst is calculated as benzene diformazan with titanium atom
5~15ppm of sour weight.
The present invention preparation be used for polyester synthesis liquid titanium complex catalyst, 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, and zirconium chemical combination is added
Object can solve the problem of hue of chip jaundice generated at present using Titanium series catalyst, and alkyl benzene sulfonate compound is added
The rate of later process solid-phase tack producing can also be improved in the application of bottle-grade polyester chip, it is energy saving, reduce cost.
Specific embodiment
Embodiment 1
The preparation of catalyst A
(1) 36g (2mol) deionized water and 9.2g (0.2mol) dehydrated 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 removes chloride ion with ethanol washing, obtains organic phospho acid colloidal zirconia.
(2) organic phospho acid colloidal zirconia made from step (1) is added and is leaked with having heaters, blender, condenser and liquid separation
In the four-hole boiling flask of bucket, 56.8g (0.2mol) tetraisopropyl titanate, 120g isopropanol, 400g ethylene glycol and 38.8g are added
(0.2mol) paratoluenesulfonic acid sodium salt, 50 DEG C of heating 1h are uniformly mixed, then 84.4g (0.4mol) citric acid is added into reactor
With the mixed solution of 120g isopropanol, 80 DEG C of heating stirring 0.5h remove small molecule, until solution is clarified, obtain catalyst A.Through
It calculates, it is 1.84% that titanium atom content in catalyst, which is made,.
Preparation without antimony bottle grade PET
In 2L pet reaction kettle, 485g terephthalic acid (TPA), 15g M-phthalic acid, 260g ethylene glycol and 0.435g is added
Catalyst A (weight of the amount titanium atom based on phthalic acid is 8ppm), adds organic blue toner 5g (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, at 230 DEG C~245 DEG C, esterification is carried out under the conditions of 0.20~0.30Mpa,
Being esterified when distillating water and reaching 95% or more of theoretical value terminates, and is down to normal pressure, vacuumizes and is decompressed to system pressure and is lower than
150Pa, simultaneous reactions temperature gradually rise up to carry out polymerization reaction at 275~285 DEG C, and it is viscous to reach required characteristic to polycondensation product
Stop reaction after degree, later continuously squeeze out reaction product with bar shaped from bottom of polymerizing pot, it is poly- to obtain no antimony bottle grade for cooling, pelletizing
Ester ground sections.The performance test results are shown in Table 1.Solid-phase tack producing is carried out by vacuum drum is put into after the drying of obtained ground sections, is delayed
Slow heating, temperature control are kept for 24 hours at 210-220 DEG C.Obtain no antimony bottle grade PET solid-phase tack producing slice, i.e. SSP slice.Performance
Test result is shown in Table 1.
Embodiment 2
The preparation of catalyst B
(1) 27g (1.5mol) deionized water and 23g (0.5mol) ethyl alcohol are added in reaction vessel, adds 2.99g
(0.01mol) aminotrimethylenephosphonic acid (ATMP), 9.66g (0.03mol) zirconium oxychloride is added after heating for dissolving, and temperature keeps 90
DEG C, 10h is stirred, filtering removes chloride ion with ethanol washing, obtains organic phospho acid colloidal zirconia.
(2) organic phospho acid colloidal zirconia made from step (1) is added and is leaked with having heaters, blender, condenser and liquid separation
In the four-hole boiling flask of bucket, 45.6g (0.2mol) tetraethyl titanate, 150g isopropanol, 300g ethylene glycol and 13.9g are added
(0.04mol) neopelex, 120 DEG C of heating 0.5h are uniformly mixed, then 120g (0.8mol) is added into reactor
The mixed solution of tartaric acid acid and 150g isopropanol, 120 DEG C of heating stirring 1h remove small molecule, until solution is clarified, are catalyzed
Agent B.It is computed, titanium atom content is 1.77% in catalyst obtained.
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 are 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 being esterified, polycondensation is obtained to be shown in Table 1 without antimony bottle grade PET ground sections the performance test results.By obtained ground sections
It is put into vacuum drum after drying and carries out solid-phase tack producing, slowly heats up, temperature control is kept for 24 hours at 210-220 DEG C.Obtain no antimony bottle
Grade polyester solid-phase tack producing slice, i.e. SSP slice.The performance test results are shown in Table 1.
Embodiment 3
The preparation of catalyst C
(1) 18g (1mol) deionized water and 46g (1mol) ethyl alcohol 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 removes chloride ion with ethanol washing, obtains organic phospho acid colloidal zirconia.
(2) organic phospho acid colloidal zirconia made from step (1) is added and is leaked with having heaters, blender, condenser and liquid separation
In the four-hole boiling flask of bucket, 56.8g (0.2mol) tetraisopropyl titanate, 200g isopropanol, 496g ethylene glycol and 6.9g are added
(0.02mol) neopelex, 150 DEG C of heating 1h are uniformly mixed, then 221g (1.6mol) water is added into reactor
The mixed solution of poplar acid and 200g isopropanol, 180 DEG C of heating stirring 3h remove small molecule, until solution is clarified, obtain catalyst C,
It is computed, titanium atom content is 1.63% in catalyst obtained.
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 are 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 being esterified, polycondensation is obtained to be shown in Table 1 without antimony bottle grade PET ground sections the performance test results.By obtained ground sections
It is put into vacuum drum after drying and carries out solid-phase tack producing, slowly heats up, temperature control is kept for 24 hours at 210-220 DEG C.Obtain no antimony bottle
Grade polyester solid-phase tack producing slice, i.e. SSP slice.The performance test results are shown in Table 1.
Embodiment 4
The preparation of catalyst D
(1) 9g (0.5mol) deionized water and 69g (1.5mol) ethyl alcohol 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 removes chloride ion with ethanol washing, obtains organic phospho acid colloidal zirconia.
(2) organic phospho acid colloidal zirconia made from step (1) is added and is leaked with having heaters, blender, condenser and liquid separation
In the four-hole boiling flask of bucket, 68.1g (0.2mol) butyl titanate, 300g isopropanol, 124g ethylene glycol and 19.4g are added
(0.1mol) paratoluenesulfonic acid sodium salt, 100 DEG C of heating 2h are uniformly mixed, then 274.24g (2.0mol) lemon is added into reactor
The mixed solution of acid and 300g isopropanol, 150 DEG C of heating stirring 4h remove small molecule, until solution is clarified, obtain catalyst D, pass through
It calculates, titanium atom content is 1.50% in catalyst obtained.
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 are 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 being esterified, polycondensation is obtained to be shown in Table 1 without antimony bottle grade PET ground sections the performance test results.By obtained ground sections
It is put into vacuum drum after drying and carries out solid-phase tack producing, slowly heats up, temperature control is kept for 24 hours at 210-220 DEG C.Obtain no antimony bottle
Grade polyester solid-phase tack producing slice, i.e. SSP slice.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 kettle, 485g terephthalic acid (TPA), 15g M-phthalic acid, 260g ethylene glycol and 0.225g is added
Antimony glycol (amount based on phthalic acid be 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
Esterification terminates when amount reaches 95% of theoretical value or more, is down to normal pressure, vacuumizes and is decompressed to system pressure lower than 150Pa, simultaneously
Reaction temperature gradually rises up to carry out polymerization reaction at 275~285 DEG C, stops after polycondensation product reaches required inherent viscosity anti-
It answers, later continuously squeezes out reaction product with bar shaped from bottom of polymerizing pot, cooling, pelletizing obtains antimony system bottle grade PET ground sections.
The performance test results are shown in Table 1.It will be put into vacuum drum after the drying of obtained ground sections and carry out solid-phase tack producing, slowly heat up, temperature
Control is kept for 24 hours at 210-220 DEG C.Obtain antimony system bottle grade PET solid-phase tack producing slice, i.e. SSP slice.The performance test results are shown in
Table 1.
1 bottle-grade polyester chip Testing index of table
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, has catalytic action, the color value of the polyester slice of production, carboxyl end group, spy to esterification and polymerization reaction
Property the technical indicators such as viscosity, acetaldehyde, diethylene glycol (DEG) it is qualified, and polyester slice obtained is without antimony metal, environmentally protective.?
In subsequent solid phase polycondensation process, polycondensation rate 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 in the production application of bottle grade PET there are form and aspect jaundice, solid-phase tack producing not up, acetaldehyde it is high
Etc. technical bottlenecks problem, and polyester slice obtained it is environmentally protective, be free of heavy metal.
Claims (8)
1. a kind of titanium complex catalyst preparation method, it is characterised in that the following steps are included:
(1) deionized water, dehydrated alcohol, zirconium oxychloride and organic phospho acid, 80~90 DEG C of heating stirrings 8 are added in the reaction vessel
~12h, filtration washing remove chloride ion, obtain zirconium phosphonate colloidal compound；
(2) by zirconium phosphonate colloidal compound and alkyl benzene sulfonate made from titanium compound, ethylene glycol and step (1)
Complexing agent is added after removing the small molecule in reaction system in compound 50~150 DEG C of 0.5~2h of reaction in isopropanol, then instead
0.5~4h is answered, reaction temperature is 80~180 DEG C, and obtained clear solution is liquid titanium complex catalyst.
2. the method as described in claim 1, it is characterized in that deionized water, dehydrated 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 of 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 of neopelex.
5. the method as described in claim 1, it is characterized in that the complexing agent is citric acid, tartaric acid or salicylic acid.
6. the method as described in claim 1, it is characterized in that the 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 the molar ratio of the titanium compound and ethylene glycol is 1:10~40；
The molar ratio of titanium compound and isopropanol is 1:20~50；The molar ratio of titanium compound and complexing agent is 1:2~10.
8. the catalyst of claim 1 the method preparation is used for the synthesis of bottle grade PET, the additive amount of catalyst is with titanium atom
It is calculated as 5~15ppm of phthalic acid weight.
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| 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 |
| 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 |
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| CN102219894B (en) * | 2010-04-15 | 2013-03-06 | 中国石油化工股份有限公司 | Method for producing semi-dulling titanium series polyester |
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