CN104558575A - Production method of low-acetaldehyde titanium system polyester - Google Patents
Production method of low-acetaldehyde titanium system polyester Download PDFInfo
- Publication number
- CN104558575A CN104558575A CN201310514187.2A CN201310514187A CN104558575A CN 104558575 A CN104558575 A CN 104558575A CN 201310514187 A CN201310514187 A CN 201310514187A CN 104558575 A CN104558575 A CN 104558575A
- Authority
- CN
- China
- Prior art keywords
- polyester
- titanium
- compound
- acid
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention relates to a production method of low-acetaldehyde titanium system polyester, which is mainly used for solving the problem of relatively large amount of acetaldehyde residue in the polyester prepared by use of a titanium system catalyst before. The technical scheme adopts a catalyst obtained by the reactions of the following raw materials: (1) a titanium compound A:Ti(OR)4 with the general formula shown in the specification, wherein R is straight-chain or branched alkyl with 1-10 carbon atoms; (2) diol B with 2-10 carbon atoms; (3) a metal compound C selected from the periodic table of elements IA; (4) at least one aliphatic organic acid D selected from organic acids; (5) at least one phosphate compound E selected from phosphorus compounds; and (6) at least one metal compound F selected from IIA, IB, IIB, VIIB and VIII of the periodic table of elements. The technical scheme can be used for solving the problem relatively well and can be applied to industrial production of polyester with low acetaldehyde residue.
Description
Technical field
The present invention relates to a kind of production method of low acetaldehyde titanium polyester and reduce the method for acetaldehyde in titanium polyester.
Background technology
Polyethylene terephthalate is a kind of important industrial raw material, because it has excellent chemical property and physical properties, is widely used in the materials such as fiber, film, sheet, bottle.It has excellent physical strength, chemical stability, barrier properties for gases, fragrant retention, sanitation degree etc., and low price, lighter in weight, be particularly suitable for manufacturing the beverage container needing thermal sterilising filling.
The polyester catalyst catalyzer that mainly antimony, germanium and titanium three is serial that current industrial production is more with research, wherein use most often antimony-based catalyst (comprising antimonous oxide, antimony acetate and antimony glycol etc.) in polyester industrial device, the polyester of more than 90% is produced by antimony-based catalyst in the world at present, and the polyester device of China also mainly adopts antimony-based catalyst.Metallic antimony belongs to heavy metal element, when the resin of this Catalyst Production is applied in beverage container field, there will be a problem: antimony-based catalyst can out, cause the antimony of trace to enter in in-built beverage by wash-out under the high temperature conditions from container.Germanium series catalysts has satisfactory stability, and the side reaction caused in reaction process is less, and made PET hue is good, but due to resource few, expensive.Titanium series polyester catalyst has high reactivity, but there is poor heat stability and goods yellowing, muddy problem in the polyester that titanium series polyester catalyst obtains, easily decompose under the high temperature conditions and produce acetaldehyde, cause acetaldehyde to enter in-built beverage, thus never used on a large scale.
JP 2000-143789 discloses when one carries out polyreaction and adds titanium compound and be selected from magnesium compound, calorize
At least one compound of compound, barium compound etc., but the method for above-mentioned disclosure exists the polyester obtained has poor tone, and the problem that acetaldehyde after solid-phase polymerization is higher.
CN1328072 and CN1327985 discloses and generates a kind of diatomic alcohol compounds of granular titanium as polyester catalyst using titanic acid ester and glycol reaction, this granular polyester catalyst is likely with and is served application problem in the industrial production of polyester, and the acetaldehyde adopting this catalyzer to obtain polyester of not reporting for work in patent.
CN200880022488.0 discloses a kind of Hypophosporous Acid, 50 compound that adds to improve the solid phase polycondensation method of the polyester of organic titanate catalysis, wherein polyester demonstrates the generation of low acetaldehyde in melt-processed, but the relevant report of acetaldehyde after not relating to solid phase polycondensation in patent.
JP 2000-143789 discloses when one carries out polyreaction and adds titanium compound and be selected from magnesium compound, calorize
At least one compound of compound, barium compound etc., but the method for above-mentioned disclosure exists the polyester obtained has poor tone, and the problem that acetaldehyde after solid-phase polymerization is higher.
EP1013692 points out, in polycondensation and melt molding process, acetaldehyde is as the generation of by product, titanium and some metallic compounds can be used to suppress as polycondensation catalyst, and titanium atom and atoms metal such as the Specific amounts of magnesium should be specific ratio.
CN1457343 points out, can by adding the compound of titaniferous, magnesium, phosphorus, and order of addition is titanium after magnesium after first phosphorus, the method that titanium adds after esterification, prepare the polyester of low acetaldehyde content, according to the research of the present inventor, polyester prepared by this method truly has improvement in the generation of control acetaldehyde, but there is very large defect in polycondensation speed especially solid phase polycondensation speed.
CN1863839 points out, titanium, zinc, phosphorus and lactic acid can be used as polycondensation catalyst, prepares the polyester of high solid phase polycondensation speed, but in literary composition, the acetaldehyde of not mentioned obtained polyester controls.
Summary of the invention
Technical problem to be solved by this invention is the problem that acetaldehyde residual volume is high in the polyester prepared of Titanium series catalyst in the past, provides a kind of production method of low acetaldehyde titanium polyester newly.The method has the low advantage of acetaldehyde residual volume.
Two of technical problem to be solved by this invention is that the described production method corresponding with one of above-mentioned technical problem is reducing the application in titanium polyester in acetaldehyde residual volume.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of production method of low acetaldehyde titanium polyester, comprises the following steps:
A) with di-carboxylic acid and dibasic alcohol for raw material, adopt titanium series polyester catalyst in temperature of reaction be 230 ~ 280 DEG C, reaction pressure is carry out esterification under normal pressure ~ 0.5MPa condition, obtain prepolymer, then be 250 ~ 320 DEG C in temperature of reaction, reaction pressure is carry out melt polycondensation reaction under the vacuum condition being less than 150Pa to obtain polyester product; Catalyzer used comprises following raw material in 0 ~ 200 DEG C of reaction reaction product of 0.5 ~ 10 hour:
(1) there is the titanium compound A of following general formula:
Ti(OR)
4
R is the straight chain or the branched-alkyl that are selected from 1 ~ 10 carbon atom;
(2) the glycol B with 2 ~ 10 carbon atoms is selected from;
(3) a kind of metallic compound C in periodic table of elements IA is selected from;
(4) at least one aliphatic organic acid D in organic acid is selected from;
(5) at least one phosphate compound E in phosphorus compound is selected from;
(6) at least one metallic compound F in the periodic table of elements in IIA, IB, IIB, VIIB, VIII is selected from;
Wherein, the mol ratio of glycol B and titanium compound A is (1 ~ 8): 1; The mol ratio of metallic compound F and titanium compound A is (0.1 ~ 20): 1; The mol ratio of metallic compound C and titanium compound is (>0 and≤10): 1; The mol ratio of aliphatic organic acid D and titanium compound A is (1 ~ 20): 1; The mol ratio of phosphate compound E and titanium compound A is (>0 and≤10): 1;
B) polyester product obtained by melt phase polycondensation, after pre-crystallized process, is 200 ~ 250 DEG C in temperature of reaction, and reaction pressure is carry out solid state polymerization to obtain the polyester that limiting viscosity is greater than 0.8 deciliter/gram under the condition being less than 100Pa.
At least one of di-carboxylic acid described in technique scheme preferably in terephthalic acid, phthalic acid, m-phthalic acid, naphthalic acid, biphenyl dicarboxylic acid or cyclohexane cyclohexanedimethanodibasic; At least one of described dibasic alcohol preferably in ethylene glycol, 1,3-PD, BDO, 1,6-hexylene glycol and 1,4 cyclohexane dimethanol.
The A of titanium compound described in technique scheme has the general formula shown in formula (I):
（II）,
Wherein, R
1to R
4independently be selected from C
1~ C
8alkyl.As an example, described titanium compound A is selected from least one in metatitanic acid four methyl esters, tetraethyl titanate, the own ester of metatitanic acid tetraethyl-, metatitanic acid orthocarbonate, titanium isopropylate or tetrabutyl titanate, the different monooctyl ester of metatitanic acid four.
The excellent at least one be selected from 1,2-PD, 1,3-PD, BDO, ethylene glycol, 1,6-hexylene glycol, 1,4 cyclohexane dimethanol and Diethylene Glycol of the B of glycol described in technique scheme.
In technique scheme, at least one of IA race metal preferably in lithium, sodium or potassium in described metallic compound C.The preferred oxyhydroxide of described metallic compound C, carbonate, supercarbonate or C
2~ C
4the salt of carboxylic acid.Described metallic compound C more preferably scheme is selected from sodium hydroxide or potassium hydroxide; Most select sodium hydroxide.
In technique scheme, at least one of described aliphatic organic acid D preferably in lactic acid, citric acid, oxysuccinic acid, tartrate or oxalic acid.
In technique scheme, described phosphate compound E preferably has the general formula shown in formula (II):
（II），
Wherein R
5, R
6and R
7except independently can not be selected from H, C for except H simultaneously
2~ C
6alkyl.As an example, at least one in methyl-phosphoric acid, monoethyl-phosphate, trimethyl phosphite 99, triethyl phosphate, tricresyl phosphate propyl ester, tricresyl phosphate isopropyl ester, tributyl phosphate or triphenylphosphate can be such as selected from.
At least one of the F of metallic compound described in technique scheme preferably in zinc, manganese, magnesium, calcium or cobalt compound.At least one of described metallic compound F preferably in acetate, oxalate.
In technique scheme, obtain the weight of polyester product based on melt polycondensation reaction, the addition of catalyzer is preferably 1 ~ 20ppmw in titanium atom.
In technique scheme, the mol ratio of glycol B and titanium compound A is preferably (1 ~ 4): 1; The mol ratio of metallic compound C and titanium compound is preferably (1 ~ 10): 1; The mol ratio of aliphatic organic acid D and titanium compound A is preferably (1 ~ 15): 1; The mol ratio of phosphoric acid ester phosphorus compound E and titanium compound A is preferably (>0 and≤6): 1; The mol ratio of metallic compound F and titanium compound A is preferably (0.1 ~ 10): 1.
In technique scheme, the polyester product of the melt phase polycondensation for solid state polymerization obtained is solid-state.The temperature of reaction preferable range preparing polyester catalyst is 10 ~ 180 DEG C, and reaction times preferable range is 2 ~ 6 hours.
In order to solve the problems of the technologies described above two, technical scheme of the present invention is as follows: the method according to any one of the technical scheme of one of above-mentioned technical problem is reducing the application in titanium polyester in acetaldehyde residual volume.
The preparation method of titanium series polyester catalyst of the present invention is as follows:
Titanium compound added the dibasic alcohol of aequum, be selected from least one metallic compound of IA in the periodic table of elements, the periodic table of elements and be selected from least one metallic compound, organic acid and phosphatization in IIA, IB, IIB, VIIB or VIII and close and be obtained by reacting homogeneous phase liquid titanium polyester catalyzer.
The preparation method of polyester is as follows:
Can adopt known preparation process of polyester, the first step carries out esterification by di-carboxylic acid and dibasic alcohol, obtains prepolymer, and temperature of reaction is 230 ~ 280 DEG C, and reaction pressure is normal pressure ~ 0.5MPa.Second step carries out polycondensation under a high vacuum, and temperature of reaction 250 ~ 320 DEG C, reaction pressure is for being less than 150Pa.Titanium series polyester catalyst joins in reaction system before esterification starts.Pelletizing preservation is carried out after reaction terminates.
Solid state polymerization (SSP) method of polyester:
The polyester prepared by aforesaid method carries out solid state polymerization further and improves viscosity.Before carrying out solid state polymerization, first should carry out pre-crystallized process to polyester.By polyester granulate prepared by above-mentioned preparation process of polyester, be placed in 80 ~ 130 DEG C, preferably under the vacuum environment of 90 ~ 120 DEG C, heating carries out drying in 1 minute ~ 3 hours.After drying terminates, under atmosphere of inert gases or vacuum environment, by temperature increase to 100 ~ 180 DEG C, preferably 140 ~ 170 DEG C are carried out pre-crystallized, and crystallization time is 1 ~ 10 hour, preferably 3 ~ 7 hours.
After pre-crystallized end, particle is sent into heat-conducting oil heating reaction unit, under the state of nitrogen protection, solid-phase polymerization is carried out to particle.Temperature of reaction is 200 ~ 250 DEG C, preferably 210 ~ 230 DEG C, and nitrogen flow rate is 0 ~ 10L/min, preferably 1 ~ 5L/min.Equipment was warming up to set(ting)value in 1 hour.Reaction times is 1 ~ 10 hour, preferably 3 ~ 8 hours.
In the present invention, the limiting viscosity of polyester, form and aspect and acetaldehyde (AA) etc. are tested by the following method:
(1) limiting viscosity: phenol tetrachloroethane mixes liquid and makes solvent, uses determination of ubbelohde viscometer at the temperature of 25 DEG C.
(2) form and aspect: pellet sample measures its Hunter L value (brightness), a value (red-green form and aspect) and b value (yellow-blue form and aspect) with the color-view automatic colour difference meter of BYK Gardner company 135 DEG C of process after 1 hour.Wherein, L value is higher, and brightness is larger; B value height then polyester slice is partially yellow.For the present invention, it is desirable to pursue high L value, low b value.
(3) acetaldehyde (AA): accurate weighing 0.5g loads in ml headspace bottle after the polyester sample of solid phase polycondensation is pulverized, seals with air in nitrogen replacement bottle.Setting head-space sampler furnace temperature 150 DEG C, starting time 60 minutes.The acetaldehyde of sample uses gas chromatograph (GC7890, Agilent) to carry out quantitative analysis by headspace sampling.
The present invention prepares polyester by adopting Titanium series catalyst, and carries out solid-phase polymerization to obtained polyester.The discovery that the present inventor is surprised, the polyester adopting the method to obtain has lower acetaldehyde after solid state polymerization, and contrast after solid state polymerization with the titanium polyester not adding alkali metal carboxylate F metallizing thing F, after solid state polymerization, acetaldehyde obviously reduces.Acetaldehyde cut into slices after requiring solid phase polycondensation in the national standard of Bottle grade Polyester Chips lower than 1.0ppmw, and the polyester slice acetaldehyde prepared by the present invention is complied with the national standard requirements, and achieves good technique effect.
Below by embodiment, the present invention is further elaborated.
Embodiment
[embodiment 1]
The preparation of catalyst A
Ethylene glycol 12.4 grams (0.2 mole) is added in the reactor that agitator, condenser and thermometer are housed, slowly instillation titanium isopropylate 28.4 grams (0.1 mole) in reactor, separate out white depositions, react 2 hours at 70 DEG C, by product centrifugation, and with distilled water wash residue 3 times, by product vacuum-drying at 70 DEG C, obtain white powder material.
Dried white powder material is placed in the reactor with agitator, condenser and thermometer, add ethylene glycol 50 grams, the aqueous sodium hydroxide solution (0.3 mole) of 48 grams of 25wt%, magnesium acetate 64.2 grams (0.3 mole), lactic acid 18 grams (0.2 mole), trimethyl phosphite 99 25.2 grams (0.18 mole), reacts 2 hours under 150 DEG C of temperature of reaction, obtaining nearly colourless homogeneous liquid, is catalyst A.
The preparation of polyester
By 600 grams of terephthalic acids and 316 grams of ethylene glycol and catalyst A (based on the amount of the polyester generated, the weight of titanium atom is 5ppmw), mix and be made into slurry, join in polymeric kettle, carry out esterification, esterification temperature is 230 ~ 255 DEG C, and pressure is 0.25MPa, is discharged the water of reaction generation by rectifier unit.Be down to normal pressure after esterification terminates, vacuumize and be decompressed to system pressure lower than 100Pa, simultaneous reactions temperature rises to 280 DEG C gradually, and stopped reaction after system reaction reaches 150min, extrudes with bar shaped bottom polymeric kettle continuously by reaction product afterwards, cooling, pelletizing.
The solid state polymerization of polyester
The polyester granulate obtained by liquid polycondensation carries out drying under vacuum environment, the condition of 100 DEG C, after drying, temperature increase to 160 DEG C is carried out pre-crystallized process 6 hours.Being positioned in thermal oil reaction unit by particle after process and under nitrogen protection state, nitrogen flow rate 4L/min, the condition of 230 DEG C, carrying out the solid state polycondensation of polyester, the reaction times is 10 hours.Take out after cooling.
Test result is in table 1.
[embodiment 2]
Except nitrogen flow rate in solid state polymerization processes is changed into except 3L/min, adopt to use the same method with embodiment 1 and carry out the preparation of polyester and the solid-phase polymerization of polyester.
Test result is in table 1.
[embodiment 3]
Except nitrogen flow rate in solid state polymerization processes is changed into except 5L/min, adopt to use the same method with embodiment 1 and carry out the preparation of polyester and the solid-phase polymerization of polyester.
Test result is in table 1.
[embodiment 4]
The preparation of catalyst B
Ethylene glycol 12.4 grams (0.2 mole) is added in the reactor that agitator, condenser and thermometer are housed, slowly instillation titanium isopropylate 28.4 grams (0.1 mole) in reactor, separate out white depositions, react 2 hours at 70 DEG C, by product centrifugation, and with distilled water wash residue 3 times, by product vacuum-drying at 70 DEG C, obtain white powder material.
Dried white powder material is placed in the reactor with agitator, condenser and thermometer, add ethylene glycol 50 grams, the aqueous sodium hydroxide solution (0.2 mole) of 32 grams of 25wt%, trimethyl phosphite 99 28 grams (0.2 mole), magnesium acetate 42.6 grams (0.3 mole), Citric acid monohydrate Food grade 42 grams (0.2 mole), under 150 DEG C of temperature of reaction react 2 hours, obtaining nearly colourless homogeneous liquid, is catalyst B.
Adopt to use the same method with embodiment 1 and carry out the preparation of polyester and the solid-phase polymerization of polyester.
Test result is in table 1.
[embodiment 5]
Except in embodiment 1, interpolation aqueous sodium hydroxide solution is changed into 48 grams of 35wt% potassium hydroxide aqueous solutions outer (0.3 mole), adopt to use the same method with embodiment 1 and carry out the preparation of polyester and the solid-phase polymerization of polyester.
Test result is in table 1.
[embodiment 6]
The preparation of polyester
By 600 grams of terephthalic acids and 316 grams of ethylene glycol, mix and be made into slurry, join in polymeric kettle, carry out esterification, esterification temperature is 230 ~ 255 DEG C, and pressure is 0.25MPa, is discharged the water of reaction generation by rectifier unit.Normal pressure is down to after esterification terminates, add catalyst A (based on the amount of the polyester generated, the weight of titanium atom is 5ppmw), after stirring 5min, vacuumize and be decompressed to system pressure lower than 100Pa, simultaneous reactions temperature rises to 280 DEG C gradually, stopped reaction after system reaction reaches 150min, afterwards reaction product is extruded continuously with bar shaped bottom polymeric kettle, cooling, pelletizing.
By method similarly to Example 1 to polyester granulate solid state polymerization.
Test result is in table 1.
[comparative example 1]
Except in embodiment 1, change add aqueous sodium hydroxide solution as the calcium hydroxide aqueous dispersions outer (0.3 mole) of 48 grams of 46wt% into outward, adopt to use the same method with embodiment 1 and carry out the preparation of polyester and the solid-phase polymerization of polyester.
Test result is in table 1.
Table 1
Claims (10)
1. a production method for low acetaldehyde titanium polyester, comprises the following steps:
A) with di-carboxylic acid and dibasic alcohol for raw material, adopt titanium series polyester catalyst in temperature of reaction be 230 ~ 280 DEG C, reaction pressure is carry out esterification under normal pressure ~ 0.5MPa condition, obtain prepolymer, then be 250 ~ 320 DEG C in temperature of reaction, reaction pressure is carry out melt polycondensation reaction under the vacuum condition being less than 150Pa to obtain polyester product; Catalyzer used comprises following raw material in 0 ~ 200 DEG C of reaction reaction product of 0.5 ~ 10 hour:
(1) there is the titanium compound A of following general formula:
Ti(OR)
4
R is the straight chain or the branched-alkyl that are selected from 1 ~ 10 carbon atom;
(2) the glycol B with 2 ~ 10 carbon atoms is selected from;
(3) a kind of metallic compound C in periodic table of elements IA is selected from;
(4) at least one aliphatic organic acid D in organic acid is selected from;
(5) at least one phosphate compound E in phosphorus compound is selected from;
(6) at least one metallic compound F in the periodic table of elements in IIA, IB, IIB, VIIB, VIII is selected from;
Wherein, the mol ratio of glycol B and titanium compound A is (1 ~ 8): 1; The mol ratio of metallic compound F and titanium compound A is (0.1 ~ 20): 1; The mol ratio of metallic compound C and titanium compound is (>0 and≤10): 1; The mol ratio of aliphatic organic acid D and titanium compound A is (1 ~ 20): 1; The mol ratio of phosphate compound E and titanium compound A is (>0 and≤10): 1;
B) polyester product obtained by melt phase polycondensation, after pre-crystallized process, is 200 ~ 250 DEG C in temperature of reaction, and reaction pressure is carry out solid state polymerization to obtain the polyester that limiting viscosity is greater than 0.8 deciliter/gram under the condition being less than 100Pa.
2. the production method of low acetaldehyde titanium polyester according to claim 1, is characterized in that di-carboxylic acid is selected from least one in terephthalic acid, phthalic acid, m-phthalic acid, naphthalic acid, biphenyl dicarboxylic acid or cyclohexane cyclohexanedimethanodibasic; Dibasic alcohol is selected from least one in ethylene glycol, 1,3-PD, BDO, 1,6-hexylene glycol and 1,4 cyclohexane dimethanol.
3. the production method of low acetaldehyde titanium polyester according to claim 1, is characterized in that titanium compound A has the general formula shown in formula (I):
（II）,
Wherein, R
1to R
4independently be selected from C
1~ C
8alkyl.
4. the production method of low acetaldehyde titanium polyester according to claim 1, is characterized in that glycol B is selected from 1,2-PD, 1, ammediol, 1, at least one in 4-butyleneglycol, ethylene glycol, 1,6-hexylene glycol, 1,4 cyclohexane dimethanol and Diethylene Glycol.
5., according to claim 1 for the production of the titaniferous composition of degradable polyester, it is characterized in that in metallic compound C, IA race metal is selected from least one in lithium, sodium or potassium.
6. the production method of low acetaldehyde titanium polyester according to claim 1, is characterized in that aliphatic organic acid D is selected from least one in lactic acid, citric acid, oxysuccinic acid, tartrate or oxalic acid.
7. the production method of low acetaldehyde titanium polyester according to claim 1, is characterized in that phosphate compound E has the general formula shown in formula (II):
（II），
Wherein R
5, R
6and R
7except independently can not be selected from H, C for except H simultaneously
2~ C
6alkyl.
8. the production method of low acetaldehyde titanium polyester according to claim 1, is characterized in that metallic compound F is selected from least one in zinc, manganese, magnesium, calcium or cobalt compound.
9. the production method of low acetaldehyde titanium polyester according to claim 8, is characterized in that metallic compound F is selected from least one in acetate, oxalate.
10. production method according to any one of claim 1 to 9 is reducing the application in titanium polyester in acetaldehyde residual volume.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310514187.2A CN104558575A (en) | 2013-10-28 | 2013-10-28 | Production method of low-acetaldehyde titanium system polyester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310514187.2A CN104558575A (en) | 2013-10-28 | 2013-10-28 | Production method of low-acetaldehyde titanium system polyester |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104558575A true CN104558575A (en) | 2015-04-29 |
Family
ID=53075710
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310514187.2A Pending CN104558575A (en) | 2013-10-28 | 2013-10-28 | Production method of low-acetaldehyde titanium system polyester |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104558575A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106589340A (en) * | 2015-10-19 | 2017-04-26 | 中国石油化工股份有限公司 | Method for producing low-acetaldehyde polyester product |
| CN109666137A (en) * | 2017-10-17 | 2019-04-23 | 中国石油化工股份有限公司 | Polyester resin catalyst of low acetaldehyde and preparation method thereof |
| CN109666135A (en) * | 2017-10-17 | 2019-04-23 | 中国石油化工股份有限公司 | The preparation method of the polyester resin of low acetaldehyde |
| CN109666136A (en) * | 2017-10-17 | 2019-04-23 | 中国石油化工股份有限公司 | The preparation method of the polyester-injected parts of low acetaldehyde |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101012303A (en) * | 2007-02-01 | 2007-08-08 | 中国石化仪征化纤股份有限公司 | Method of preparing polyester with low content of acetaldehyde |
| CN101942076A (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 | Preparation method of polyester |
| CN103739834A (en) * | 2012-10-17 | 2014-04-23 | 中国石油化工股份有限公司 | Production method of solid-phase-polymerized titanium-containing polyester |
-
2013
- 2013-10-28 CN CN201310514187.2A patent/CN104558575A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101012303A (en) * | 2007-02-01 | 2007-08-08 | 中国石化仪征化纤股份有限公司 | Method of preparing polyester with low content of acetaldehyde |
| CN101942076A (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 | Preparation method of polyester |
| CN103739834A (en) * | 2012-10-17 | 2014-04-23 | 中国石油化工股份有限公司 | Production method of solid-phase-polymerized titanium-containing polyester |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106589340A (en) * | 2015-10-19 | 2017-04-26 | 中国石油化工股份有限公司 | Method for producing low-acetaldehyde polyester product |
| CN109666137A (en) * | 2017-10-17 | 2019-04-23 | 中国石油化工股份有限公司 | Polyester resin catalyst of low acetaldehyde and preparation method thereof |
| CN109666135A (en) * | 2017-10-17 | 2019-04-23 | 中国石油化工股份有限公司 | The preparation method of the polyester resin of low acetaldehyde |
| CN109666136A (en) * | 2017-10-17 | 2019-04-23 | 中国石油化工股份有限公司 | The preparation method of the polyester-injected parts of low acetaldehyde |
| CN109666137B (en) * | 2017-10-17 | 2021-07-30 | 中国石油化工股份有限公司 | Polyester resin catalyst with low acetaldehyde content and preparation method thereof |
| CN109666135B (en) * | 2017-10-17 | 2021-09-03 | 中国石油化工股份有限公司 | Preparation method of polyester resin with low acetaldehyde content |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103772684B (en) | The production method of the polyester of titanium catalysis | |
| TWI299047B (en) | Polyester resin, catalyst for the production of polyester, process for the production of polyester resin by using the catalyst, and hollow shaped container made from the polyester resin | |
| CN101942076B (en) | Preparation method of polyester | |
| CN101942078B (en) | Titanium polyester catalyst for preparing polyester | |
| CN104558574B (en) | Titanium series polyester catalyst | |
| KR101752927B1 (en) | Copolyesters having improved thermal stability, and methods for making them | |
| CN102219890B (en) | Method for producing titanium polyester | |
| CN102219894A (en) | Method for producing semi-dulling titanium series polyester | |
| TW201127871A (en) | Process for making polyethylene terephthalate | |
| CN104558575A (en) | Production method of low-acetaldehyde titanium system polyester | |
| TWI636073B (en) | Method for the production of a titanium containing catalyst, titanium containing catalyst, method for the production of polyester and polyester | |
| CN101121777B (en) | Titanium series polyester catalyst | |
| US8362189B2 (en) | Catalyst mixture and method for the production of polyesters with high viscosity | |
| CN104629033A (en) | Production method of low acetaldehyde titanium system polyester | |
| CN103539926B (en) | The production method of titanium polyester | |
| CN103772685A (en) | Production method of high-end carboxyl titanium polyester | |
| JP5455570B2 (en) | Titanium-containing mixture and its application to polyesterification reaction | |
| CN104558554B (en) | The preparation method of polyester resin | |
| CN106589340A (en) | Method for producing low-acetaldehyde polyester product | |
| CN103772672B (en) | The production method of full-dull titanium polyester | |
| CN101173038B (en) | Method for producing polyester | |
| CN101148499A (en) | Titanium series catalyst | |
| CN103739834B (en) | The production method of solid phase titanium polyester | |
| CN104558555B (en) | The polymerization of high-viscosity polyester resin | |
| CN109666137B (en) | Polyester resin catalyst with low acetaldehyde content and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20150429 |
|
| RJ01 | Rejection of invention patent application after publication |