CN104558554B - The preparation method of polyester resin - Google Patents
The preparation method of polyester resin Download PDFInfo
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- CN104558554B CN104558554B CN201310515667.0A CN201310515667A CN104558554B CN 104558554 B CN104558554 B CN 104558554B CN 201310515667 A CN201310515667 A CN 201310515667A CN 104558554 B CN104558554 B CN 104558554B
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Abstract
The present invention relates to the preparation method of polyester resin, mainly solve the problems, such as in existing production process titanium polyester section solid phase compared with it is slow, form and aspect are poor.The present invention is by using using dicarboxylic acids and dihydric alcohol as raw material, esterification is carried out in the presence of the catalyst of titaniferous, then polycondensation product is added into phosphate before discharging, and pass through before pelletizing in the solution containing metal salt, the scheme that solid state polycondensation obtains final product is carried out again and preferably solves the problem, available in the industrial production of polyester.
Description
Technical field
The preparation method of polyester resin under being catalyzed the present invention relates to Titanium series catalyst.
Background technology
Polyethylene terephthalate is a kind of important raw material of industry, because it has excellent chemical property and thing
Rationality matter, it is widely used in the materials such as fiber, film, piece, bottle.In industrial production research at present and application study, the whole world
More than 90% PET productions all use antimony-based catalyst (including antimony oxide, antimony acetate and antimony glycol etc.).The catalyst
The shortcomings that be：Antimony-based catalyst pollutes containing heavy metal to environment；Polymer belt grey.Mankind's life is increasingly paid close attention in the whole world
Under the background of dis environment, the overall development trend of polyester catalyst is developed to environmentally friendly, efficient, less toxic and nontoxic direction, green
The production and selling of product by be the development of following polyester trend, can the developed country using European Union as representative more and more
Reach green product standard as the condition into market, by the development of more than 10 years, European Union's eco-label (Eco-label) was
Through gradually being approved by European Union consumer, the pouplarity for sticking on ecological mark commodity also gradually steps up.
Titanium series polyester catalyst due to its activity is high, without heavy metal, in the absence of problem of environmental pollution, catalyst activity
Height, the reaction time can be shortened, improve unit production capacity, using under the polyester transparent degree increase of titanium series polyester catalyst production, gray scale
Drop, while the amount of metal remained in the polyester is only 1/the tens of antimony, can be used for producing high-grade film, spinning and packaging
Bottle.
When the polyester that Titanium series catalyst catalyzes and synthesizes is used for bottle production, its solid phase polycondensation speed is always to hinder more slowly
Its obstacle applied.Solid phase polycondensation speed can be speeded by improving Ti content merely, but form and aspect and heat endurance index can go out
Existing bad phenomenon, the dosage for increasing stabilizer also result in solid phase speed decrease.Therefore, it is steady to find a kind of addition of adaptation
The method determined agent and improve the auxiliary agent of solid phase speed is very necessary.If selection adds stabilizer before polycondensation terminates, that
The selection of the solvent of stabilizer is also very crucial, to select species that is not volatile, being not involved in reaction.The selection of auxiliary agent is also same
Sample.
CN1328072 and CN1327985 discloses generates the two of a kind of granular titanium with titanate esters and glycol reaction
As polyester catalyst, this granular polyester catalyst is possible to bring one in the industrial production of polyester first alcoholic compound
A little application problems, and the form and aspect using polyester made from this catalyst of not reported for work in patent.
CN1962722A and CN1962723A solves the problems, such as the photostability difference that titanium in conventional art be present；
CN101121778A is solved in conventional art to be dissolved in the presence of obtained titanium with dibastic alcohol compound catalyst in ethylene glycol
The problems such as property is poor, and obtained PET hue is partially yellow, but polyester solid phase polymerization made from this catalyst is not directed in patent
Relevant report.
CN1954012 and WO2008008836 discloses adds alkali metal salt and alkali salt in polymerization system, can
To improve the solid phase polycondensation speed of polyester, but to the addition sequence of alkali metal salt and alkali salt in production of polyester to solid phase
Relevant report is not made in the influence of polycondensation viscosity build.
CN101415749A discloses improves solid phase polycondensation speed by pellet after polycondensation terminates by the form of spraying, but
Relevant report is not made to the form and aspect of the processing of specific dosage and product.
The content of the invention
The technical problems to be solved by the invention are that conventional Titanium series catalyst prepares that polyester speed is relatively slow, PET hue
A kind of the problem of poor, there is provided preparation method of new polyester resin.This method is preferable with obtained PET hue, solid phase
Fireballing advantage.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is as follows：The preparation method of polyester resin, including
Following steps：
A) using dicarboxylic acids and dihydric alcohol as raw material, reaction temperature be 230~280 DEG C, reaction pressure be normal pressure~
Esterification is carried out under the conditions of 0.5MPa, obtains prepolymer, then reaction temperature be 250~320 DEG C, reaction pressure be less than
Melt polycondensation reaction is carried out under 150Pa vacuum condition and obtains polyester product；The catalyst used includes following raw material 0
The reaction product of~200 DEG C of reactions 0.5~10 hour：
(1) there is the titanium compound A of below general formula：
Ti(OR)4
R is straight chain or branched-alkyl selected from 1~10 carbon atom；
(2) it is selected from the glycol B with 2~10 carbon atoms；
(3) in the periodic table of elements IA at least one metallic compound C；
(4) selected from least one of organic acid aliphatic organic acid D；
(5) selected from least one of phosphorus compound phosphate E；
(6) at least one of IIA, IB, IIB, VIIB, VIII metallic compound F in the periodic table of elements；
Glycol B and titanium compound A mol ratio is (1~8): 1；Metallic compound C and titanium compound A mol ratio is
(0.1~10): 1；Metallic compound F and titanium compound A mol ratio is (0.1~20): 1；Aliphatic organic acid D closes with titanizing
Thing A mol ratio is (1~20): 1；Phosphate E and titanium compound A mol ratio for (>0 and≤10): 1；
B) phosphate J is dissolved in polyglycol solution, and after esterification and melt polycondensation terminate before add, phosphorus
The weight of polyester of the acid esters J addition based on generation is 1~20ppmw；
C) solution for being 1~50% after the polyester product for obtaining melt polycondensation discharges, by metal salt G mass concentration
In, temperature is 1~50 DEG C, and the time is 1~300min；Wherein metal salt G in IA, IIA, IIB in the periodic table of elements extremely
A kind of few acetate of metal, dosage is 1~300ppmw based on the weight that melt polycondensation reaction obtains polyester product；
D) pre-crystallized processing, it is then 200~250 DEG C in reaction temperature by polyester product pelletizing, reaction pressure is 10~
Solid phase is carried out under conditions of 500Pa to obtain the polyester that inherent viscosity dl/g is more than 0.8, preferably obtaining inherent viscosity is
The polyester of 0.8~1.1 deciliter/gram.
In above-mentioned technical proposal, the dicarboxylic acids preferably is selected from terephthalic acid (TPA), phthalic acid, M-phthalic acid, naphthalene
At least one of dioctyl phthalate, biphenyl dicarboxylic acid or cyclohexane dicarboxylic acid；Dihydric alcohol is selected from ethylene glycol, 1,3- propane diols, 1,4-
At least one of butanediol, 1,6-HD and 1,4 cyclohexane dimethanol.
In above-mentioned technical proposal, the titanium compound A preferably has the formula shown in formula (I)：
Wherein, R1To R4It is independently selected from C1~C8Alkyl.As an example, the titanium compound A be selected from tetramethoxy titanate ester,
In tetraethyl titanate, the own ester of metatitanic acid tetraethyl, metatitanic acid orthocarbonate, tetraisopropyl titanate or butyl titanate, four different monooctyl ester of metatitanic acid
At least one.
In above-mentioned technical proposal, the glycol B preferably is selected from 1,2-PD, 1,3-PD, BDO, second two
At least one of alcohol, diethylene glycol.
In above-mentioned technical proposal, the metallic compound C preferably is selected from the lithium of IA races, sodium or potassium compound in the periodic table of elements
At least one of.
In above-mentioned technical proposal, the aliphatic organic acid D preferably is selected from lactic acid, citric acid, malic acid, tartaric acid or oxalic acid
At least one of.
In above-mentioned technical proposal, the phosphate E and phosphate J are preferably independently derived from the change with formula shown in formula (II)
Compound：
Wherein R5、R6And R7H, C are independently selected from addition to it can not be simultaneously H2~C6Alkyl.As an example, the phosphoric acid
Ester E and phosphate J is independently selected from methyl-phosphoric acid, etherophosphoric acid, trimethyl phosphate, triethyl phosphate, tricresyl phosphate propyl ester, phosphorus
At least one of sour three isopropyl esters, tributyl phosphate or triphenyl phosphate.
In above-mentioned technical proposal, the number-average molecular weight of the polyethylene glycol is preferably 150~800.Such as optional autohemagglutination second
At least one of glycol 200, Liquid Macrogol, polyethylene glycol 400, Macrogol 600.
In above-mentioned technical proposal, the metallic compound F preferably is selected from least one in zinc, manganese, magnesium, calcium or cobalt compound
Kind；Such as at least one of magnesium acetate, zinc acetate, cobalt acetate.
In above-mentioned technical proposal, the metal salt G preferably be selected from lithium acetate, sodium acetate, potassium acetate, magnesium acetate, calcium acetate and
At least one of zinc acetate.
In above-mentioned technical proposal, the weight of polyester product, the addition of the catalyst are obtained based on melt polycondensation reaction
It is preferably 1~20ppmw in terms of titanium atom.
In above-mentioned technical proposal, glycol B and titanium compound A mol ratio preferred scope is (1~4): 1；Metallic compound C
Mol ratio preferred scope with titanium compound A is (0.1~6): 1；Aliphatic organic acid D and titanium compound A mol ratio are preferred
Scope is (1~15): 1；Phosphate E and titanium compound A mol ratio preferred scope for (>0 and≤6): 1；Metallic compound F with
Titanium compound A mol ratio preferred scope is (0.1~10): 1；Phosphate J is after esterification and before melt polycondensation terminates
It is preferred that addition is 1~10ppmw (weight of the polyester based on generation)；Metal salt G dosage is obtained based on melt polycondensation reaction
The weight preferred scope of polyester product is 1~300ppmw.
In above-mentioned technical proposal, the polyester product of the obtained melt polycondensation for solid phase is solid-state.Potassium acetate
Aqueous solution mass concentration is 1~50%, preferably 1~5%, and temperature is 1~50 DEG C, and preferably 1~20 DEG C, the time is 1~300min,
It is preferred that 1~20min.The reaction temperature preferred scope for preparing polyester catalyst is 10~180 DEG C, and reaction time preferred scope is 2
~6 hours.The weight of polyester product is obtained based on melt polycondensation reaction, the addition of catalyst is calculated as 1 with titanium atom~
20ppmw.Catalyst is homogeneous liquid catalyst, can be dissolved each other with ethylene glycol.
Step c) temperature is preferably 10~20 DEG C in above-mentioned technical proposal, and the time is preferably 1~20min.Step d) institutes
Preferably dried in advance before stating pre-crystallized processing, drying condition is preferably：Temperature is 80~130 DEG C, more preferably 90~120 DEG C；
Drying is preferably carried out under vacuum conditions, preferably 1 minute~3 hours drying time.Step d) is pre-crystallized preferably in inert gas
Under atmosphere or vacuum environment, temperature is promoted to 100~180 DEG C, preferably 140~170 DEG C progress are pre-crystallized, and the pre-crystallized time is excellent
Elect as 1 hour~10 hours, more preferably 3 hours~7 hours.
Solid phase in step d) is preferably carried out in the state of nitrogen protection；Preferably 210~230 DEG C of reaction temperature,
Nitrogen flow rate is preferably 0~10L/min, more preferably 1~5L/min.The solid-phase polymerization time is preferably 1~10 hour, more
It is preferred that 3~8 hours.
In the present invention, the inherent viscosity of polyester and form and aspect etc. are tested by the following method：
(1) inherent viscosity：Phenol tetrachloroethane mixed liquor makees solvent, and determination of ubbelohde viscometer is used at a temperature of 25 DEG C.
(2) form and aspect：Pellet sample uses the automatic aberration of color-view of BYK Gardner companies after being handled 1 hour at 135 DEG C
Meter determines its Hunter L value (brightness), a values (form and aspect of red-green) and b values (yellow-blue form and aspect).Wherein, L values are higher, brightness
It is bigger；The high then polyester slice of b values is partially yellow.For the present invention, it is desirable to pursue high L values, low b values.
The present invention prepares polyester by using Titanium series catalyst, and laggard by the solution equipped with auxiliary agent to obtained polyester
Row solid-phase polymerization.Present inventors have surprisingly found that using polyester made from this method after solid phase have it is higher
Viscosity, add phosphate before terminating with non-polycondensation and contrasted by the polyester after the solution equipped with auxiliary agent after solid phase, Gu
Phase-polymerization speed, form and aspect change is smaller, achieves preferable technique effect.
Below by embodiment, the present invention is further elaborated.
Embodiment
【Embodiment 1】
Catalyst A preparation
12.4 grams of ethylene glycol (0.2 mole) is added in the reactor equipped with agitator, condenser and thermometer, toward reaction
28.4 grams of tetraisopropyl titanate (0.1 mole) is slowly dropped into device, white depositions is separated out, reacts 2 hours, will produce at 70 DEG C
Thing centrifuges, and with distilled water wash residual thing 3 times, product is dried in vacuo at 70 DEG C, obtains white powder material.
Dried white powder material is placed in the reactor with agitator, condenser and thermometer, added
50 grams of ethylene glycol, 44.8 grams of 25wt% potassium hydroxide aqueous solution (0.2 mole), 73.2 grams of zinc acetate (0.4 mole), lactic acid 18
Gram (0.2 mole), 28 grams of trimethyl phosphate (0.2 mole), reacts 2 hours under 150 DEG C of reaction temperatures, obtains near colourless homogeneous
Liquid, it is catalyst A.
The preparation of polyester
By 600 grams of terephthalic acid (TPA)s and 316 grams of ethylene glycol and catalyst A (amount of the polyester based on generation, the weight of titanium atom
Measure as 3ppmw), mixing is made into slurry, is added in polymeric kettle, carries out esterification, and esterification temperature is 230~255 DEG C, pressure
For 0.25MPa, the water for reacting generation is discharged by rectifier unit.Esterification is down to normal pressure after terminating, and vacuumizes and is decompressed to system pressure
Power is less than 130Pa, and simultaneous reactions temperature is gradually increased to 280 DEG C, and after system reaction reaches 145min, addition is diluted in poly- second two
The tripotassium phosphate ester solution of alcohol 200, the wherein addition of trimethyl phosphate are 2ppmw (amount of the polyester based on generation).Work as body
It is to stop reaction after reaction reaches 150min, reaction product is continuously extruded from polymeric kettle bottom with bar shaped afterwards, passes through acetic acid
Potassium (amount of the polyester based on generation is 20ppmw) mass concentration is in 1% aqueous solution, is taken out after 2min, pelletizing.
The solid phase of polyester
It is dried under conditions of vacuum environment, 100 DEG C, temperature is promoted into 160 DEG C after drying carries out pre-crystallized place
Reason 6 hours.By the particle after processing be positioned in conduction oil reaction unit and nitrogen guard mode, nitrogen flow rate 4L/min,
The solid state polycondensation of polyester is carried out under conditions of 230 DEG C, the reaction time is 10 hours.Taken out after cooling.
Test result is shown in Table 1.
【Embodiment 2】
In addition to the residence time in the aqueous solution of potassium acetate is changed into 1min, same method is used with embodiment 1
Carry out the preparation of polyester and the solid-phase polymerization of polyester.
Test result is shown in Table 1.
【Embodiment 3】
In addition to the residence time in the aqueous solution of potassium acetate is changed into 3min, same method is used with embodiment 1
Carry out the preparation of polyester and the solid-phase polymerization of polyester.
Test result is shown in Table 1.
【Embodiment 4】
In addition to the addition of trimethyl phosphate to be changed to 1ppmw (amount of the polyester based on generation), used with embodiment 1
Same method carries out the preparation of polyester and the solid-phase polymerization of polyester.
Test result is shown in Table 1.
【Embodiment 5】
In addition to the addition of trimethyl phosphate to be changed to 3ppmw (amount of the polyester based on generation), used with embodiment 1
Same method carries out the preparation of polyester and the solid-phase polymerization of polyester.
Test result is shown in Table 1.
【Embodiment 6】
The preparation of polyester
By 600 grams of terephthalic acid (TPA)s and 316 grams of ethylene glycol and catalyst A (amount of the polyester based on generation, the weight of titanium atom
Measure as 3ppmw), mixing is made into slurry, is added in polymeric kettle, carries out esterification, and esterification temperature is 230~255 DEG C, pressure
For 0.25MPa, the water for reacting generation is discharged by rectifier unit.Esterification is down to normal pressure after terminating, and vacuumizes and is decompressed to system pressure
Power is less than 130Pa, and simultaneous reactions temperature is gradually increased to 280 DEG C.Stop reaction after system reaction reaches 150min, afterwards will be anti-
Product is answered continuously to be extruded with bar shaped from polymeric kettle bottom, it is dense by potassium acetate (amount of the polyester based on generation is 20ppmw) quality
Spend in the aqueous solution for 1%, taken out after 2min, pelletizing.
The preparation of polyester and the solid-phase polymerization of polyester are carried out using same method with embodiment 1.
Test result is shown in Table 1.
【Embodiment 7】
The preparation of polyester
By 600 grams of terephthalic acid (TPA)s and 316 grams of ethylene glycol and catalyst A (amount of the polyester based on generation, the weight of titanium atom
Measure as 3ppmw), mixing is made into slurry, is added in polymeric kettle, carries out esterification, and esterification temperature is 230~255 DEG C, pressure
For 0.25MPa, the water for reacting generation is discharged by rectifier unit.Esterification is down to normal pressure after terminating, and vacuumizes and is decompressed to system pressure
Power is less than 130Pa, and simultaneous reactions temperature is gradually increased to 280 DEG C, and after system reaction reaches 145min, addition is diluted in poly- second two
The tripotassium phosphate ester solution of alcohol 200, the wherein addition of trimethyl phosphate are 2ppmw (amount of the polyester based on generation).Work as body
It is to stop reaction after reaction reaches 150min, afterwards continuously extrudes reaction product with bar shaped from polymeric kettle bottom, pelletizing.
The preparation of polyester and the solid-phase polymerization of polyester are carried out using method similarly to Example 1.
Test result is shown in Table 1.
【Comparative example 1】
Except in embodiment 1, the aqueous solution of potassium acetate (the amount 20ppmw of the polyester based on generation) being replaced with into carbonic acid
Outside the aqueous solution of potassium (the amount 20ppmw of the polyester based on generation), the preparation of polyester is carried out using method similarly to Example 1
With the solid-phase polymerization of polyester.
Test result is shown in Table 1.
【Comparative example 2】
Except in embodiment 1, the aqueous solution of potassium acetate (the amount 20ppmw of the polyester based on generation) being replaced with into carbonic acid
Outside the aqueous solution of magnesium (the amount 20ppmw of the polyester based on generation), the preparation of polyester is carried out using method similarly to Example 1
With the solid-phase polymerization of polyester.
Test result is shown in Table 1.
【Comparative example 3】
Except in embodiment 1, the aqueous solution of potassium acetate (the amount 20ppmw of the polyester based on generation) being replaced with into carbonic acid
Outside the aqueous solution of calcium (the amount 20ppmw of the polyester based on generation), the preparation of polyester is carried out using same method with embodiment 1
With the solid-phase polymerization of polyester.
Test result is shown in Table 1.
【Comparative example 4】
The preparation of polyester
By 600 grams of terephthalic acid (TPA)s and 316 grams of ethylene glycol and catalyst A (amount of the polyester based on generation, the weight of titanium atom
Measure as 3ppmw), mixing is made into slurry, is added in polymeric kettle, carries out esterification, and esterification temperature is 230~255 DEG C, pressure
For 0.25MPa, the water for reacting generation is discharged by rectifier unit.Esterification is down to normal pressure after terminating, and vacuumizes and is decompressed to system pressure
Power is less than 130Pa, and simultaneous reactions temperature is gradually increased to 280 DEG C.Stop reaction after system reaction reaches 150min, afterwards will be anti-
Product is answered continuously to be extruded with bar shaped from polymeric kettle bottom, pelletizing.
The solid-phase polymerization of polyester is carried out using method similarly to Example 1.
Test result is shown in Table 1.
Table 1
Claims (10)
1. the preparation method of polyester resin, comprises the following steps：
A) it is 230~280 DEG C in reaction temperature, reaction pressure is normal pressure~0.5MPa using dicarboxylic acids and dihydric alcohol as raw material
Under the conditions of carry out esterification, obtain prepolymer, then reaction temperature be 250~320 DEG C, reaction pressure be less than 150Pa
Vacuum condition under carry out melt polycondensation reaction obtain polyester product；The catalyst used includes following raw material 0~200
DEG C reaction reaction product of 0.5~10 hour：
(1) there is the titanium compound A of below general formula：
Ti(OR)4
R is straight chain or branched-alkyl selected from 1~10 carbon atom；
(2) it is selected from the glycol B with 2~10 carbon atoms；
(3) in the periodic table of elements IA at least one metallic compound C；
(4) selected from least one of organic acid aliphatic organic acid D；
(5) selected from least one of phosphorus compound phosphate E；
(6) at least one of IIA, IB, IIB, VIIB, VIII metallic compound F in the periodic table of elements；
Glycol B and titanium compound A mol ratio is (1~8): 1；Metallic compound C and titanium compound A mol ratio for (0.1~
10)∶1；Metallic compound F and titanium compound A mol ratio is (0.1~20): 1；Aliphatic organic acid D and titanium compound A's
Mol ratio is (1~20): 1；Phosphate E and titanium compound A mol ratio for (>0 and≤10): 1；
B) phosphate J is dissolved in polyglycol solution, and after esterification and melt polycondensation terminate before add, phosphate
The weight of polyester of the J addition based on generation is 1~20ppmw；
C) it is in 1~50% solution after the polyester product discharging obtained melt polycondensation, by metal salt G mass concentration,
Temperature is 1~50 DEG C, and the time is 1~300min；Wherein metal salt G in IA, IIA, IIB in the periodic table of elements at least one
The acetate of kind metal, dosage is 1~300ppmw based on the weight that melt polycondensation reaction obtains polyester product；
D) pre-crystallized processing, it is then 200~250 DEG C in reaction temperature by polyester product pelletizing, reaction pressure is 10~
Solid phase is carried out under conditions of 500Pa to obtain the polyester that inherent viscosity dl/g is more than 0.8.
2. the preparation method of polyester resin according to claim 1, it is characterised in that dicarboxylic acids be selected from terephthalic acid (TPA),
At least one of phthalic acid, M-phthalic acid, naphthalenedicarboxylic acid, biphenyl dicarboxylic acid or cyclohexane dicarboxylic acid；Dihydric alcohol selects
From at least one of ethylene glycol, 1,3- propane diols, 1,4- butanediols, 1,6-HD and 1,4 cyclohexane dimethanol.
3. the preparation method of polyester resin according to claim 1, it is characterised in that titanium compound A has shown in formula (I)
Formula：
Wherein, R1To R4It is independently selected from C1~C8Alkyl.
4. the preparation method of polyester resin according to claim 1, it is characterised in that glycol B selected from 1,2-PD,
At least one of 1,3- propane diols, 1,4- butanediols, ethylene glycol, diethylene glycol
5. the preparation method of polyester resin according to claim 1, it is characterised in that metallic compound C is selected from period of element
At least one of lithium, sodium or potassium compound of Biao Zhong IA races.
6. the preparation method of polyester resin according to claim 1, it is characterised in that aliphatic organic acid D be selected from lactic acid,
At least one of citric acid, malic acid, tartaric acid or oxalic acid.
7. the preparation method of polyester resin according to claim 1, it is characterised in that phosphate E and phosphate J independently take
From the compound with formula shown in formula (II)：
Wherein R5、R6And R7H, C are independently selected from addition to it can not be simultaneously H2~C6Alkyl.
8. the preparation method of polyester resin according to claim 1, it is characterised in that the number-average molecular weight of polyethylene glycol is
150~800.
9. the preparation method of polyester resin according to claim 1, it is characterised in that metallic compound F be selected from zinc, manganese,
At least one of magnesium, calcium or cobalt compound.
10. the preparation method of polyester resin according to claim 1, it is characterised in that metal salt G is selected from lithium acetate, acetic acid
At least one of sodium, potassium acetate, magnesium acetate, calcium acetate and zinc acetate.
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| WO2021192962A1 (en) * | 2020-03-26 | 2021-09-30 | 東洋紡株式会社 | Polyester resin and method for producing blow molded body formed of polyester resin |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101525415A (en) * | 2008-03-04 | 2009-09-09 | 东丽纤维研究所（中国）有限公司 | Polyester for bottle and method for preparing same |
| CN101942078A (en) * | 2009-07-06 | 2011-01-12 | 中国石油化工股份有限公司上海石油化工研究院 | Titanium polyester catalyst for preparing polyester |
| CN102219890A (en) * | 2010-04-15 | 2011-10-19 | 中国石油化工股份有限公司 | Method for producing titanium polyester |
| CN102924698A (en) * | 2012-10-26 | 2013-02-13 | 中国石油化工股份有限公司 | Preparation method and use of titanium catalyst for synthesis of polybutylene terephthalate |
-
2013
- 2013-10-28 CN CN201310515667.0A patent/CN104558554B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101525415A (en) * | 2008-03-04 | 2009-09-09 | 东丽纤维研究所（中国）有限公司 | Polyester for bottle and method for preparing same |
| CN101942078A (en) * | 2009-07-06 | 2011-01-12 | 中国石油化工股份有限公司上海石油化工研究院 | Titanium polyester catalyst for preparing polyester |
| CN102219890A (en) * | 2010-04-15 | 2011-10-19 | 中国石油化工股份有限公司 | Method for producing titanium polyester |
| CN102924698A (en) * | 2012-10-26 | 2013-02-13 | 中国石油化工股份有限公司 | Preparation method and use of titanium catalyst for synthesis of polybutylene terephthalate |
Non-Patent Citations (1)
| Title |
|---|
| 合成聚对苯二甲酸丙二醇酯催化剂的研究进展;贾树勇;《石油化工》;20061231;第35卷(第6期);第599页 * |
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