CN101050274A - Method for preparing hydrolytic resisting polyester - Google Patents
Method for preparing hydrolytic resisting polyester Download PDFInfo
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- CN101050274A CN101050274A CN 200610039519 CN200610039519A CN101050274A CN 101050274 A CN101050274 A CN 101050274A CN 200610039519 CN200610039519 CN 200610039519 CN 200610039519 A CN200610039519 A CN 200610039519A CN 101050274 A CN101050274 A CN 101050274A
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- phosphorous
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Abstract
This invention discloses a method for preparing hydrolysis-resistant polyester. The method comprises: pre-polycondensing aromatic dicarboxylic acid or aromatic dicarboxylate with aliphatic diol to obtain an oligomer, adding inorganic phosphate buffer, and polycondensing the oligomer to obtain polyester. The obtained polyester has high hydrolysis resistance, which is proven by the fact that the intrinsic viscosity is hardly decreased after the polyester slices are treated with high-temperature steam.
Description
Technical field
The present invention relates to a kind of manufacture method of polyester.
Background technology
Polyester is widely used in fiber, film, resin and bottle because of its excellent characteristic in various fields.Wherein, polyethylene terephthalate is well suited for using because of its excellent mechanical intensity, chemical property and dimensional stability etc.Yet the hydrolytic resistance of most polyester under the environment of high temperature humidity is not good.Under this kind condition, polyester very easily is subjected to the catalysis of its remaining terminal acidic group and hydrolysis, causes the deterioration of physicals.
Because this characteristic to moisture-sensitive of polyester terminal group has limited the application of polyester on industry significantly, therefore,, be necessary the polyester of seeking on performance, to be improved at the problems referred to above in fact in order to expand its Application Areas.
Under xeothermic situation, the hydrolytic resistance of polyester is splendid, and it stablizes 5000 times than the oxidative degradation under the same temperature, stablizes 1000 times than the thermal destruction under the same temperature, but at the damp and hot hydrolytic cleavage that very easily takes place down.More than 100 ℃, relative humidity is that the hydrolysis rate of polyester is than the thermal destruction under the uniform temp fast 10 under 100% the condition
4Doubly, than aerial oxidative degradation fast 500 times, this is because polyester backbone contains ester bond, end group is carboxyl and hydroxyl, the resistant polyester hydrolysis property is relatively poor, and particularly because polyester is hydrolyzed to self-accelerating reaction, acid content increases can quicken hydrolysis, then hold the content of carboxyl high more, the hydrolytic resistance of polyester is poor more.The mechanics of the polyester material that hydrolysis makes and the rapid severe exacerbation of other performances, this has just greatly limited it in a lot of Application for Field.
The stability to hydrolysis of polyester has been done many research abroad, as far back as nineteen fifty-nine, Daniels just proposes to improve by the method that reduces the polyester content of carboxyl end group stability to hydrolysis of polyester, and afterwards, the someone proposes with crosslinked, the method for top coat.But more still is to reach by the method for adding auxiliary agent.
Technology is come the remaining terminal group of end capped polyesters with low molecule-type end-capping reagent now, to improve its hydrolytic resistance, but because the poor heat resistance of low molecule end-capping reagent, easily decomposition and volatile, so end-blocking weak effect, usually by adding excessive end-capping reagent to remedy the volatilization loss of high temperature end-capping reagent when reacting, for example, it is as PET terminal group end-capping reagent with mono-oxyzanone that Japanese patent gazette spy opens clear 57-49620, special public clear 61-39973,61-48531,61-48532 etc. are end-capping reagent with single azoles quinoline, and the spy opens clear 53-112796 and special to disclose clear 63-10731 be as end-capping reagent with mono-epoxy.
The resistance to hydrolysis that can add epoxy material improvement polyester.Yet when introducing under the high level that need to be required by present resistance to hydrolysis, epoxy material has the shortcoming that influences material property unfriendly usually.Depend on the epoxy material of use, melt viscosity can and reach higher melt viscosity from required viscosity variation, and given epoxy material also can influence important physicals unfriendly, as the low temperature impact strength of product.
Known also can be by adding carbodiimide or poly-carbodiimide additive improved resistance to hydrolysis.U.S. patent 3193522 discloses the stable of the polyester that adopts poly-carbodiimide, the stable of the conjugated polyether ester elastomer that adopts poly-carbodiimide disclosed with the embodiment 4 of this patent, although the adding of poly-carbodiimide has improved stability to hydrolysis, it also has some important shortcomings, it is undesirable for use that this shortcoming makes it, it increases the melt viscosity of resin usually, this viscosity increase makes it more be difficult to filling component in Shooting Technique, and can produce irritating smell, think this smell part by being used under the processing temperature of casting resin, the formation of volatile isocyanate causes.
Summary of the invention:
The preparation method who the objective of the invention is to solve the facile hydrolysis problem of polyester existence and a kind of hydrolysis-resistant polyester is provided.
Technical solution of the present invention is:
A kind of preparation method of hydrolysis-resistant polyester, carry out prepolymerization reaction by aromatic acid or aromatic dicarboxylic acid esters and aliphatic dihydroxy alcohol and generate oligopolymer, carry out polycondensation by oligopolymer again and obtain polyester, it is characterized in that: in polycondensation, add the inorganic phosphate salt buffer agent.
The consumption of inorganic phosphate salt buffer agent is: with respect to weight polyester, the content of phosphoric is 1～100ppm in the inorganic phosphate.
The inorganic phosphate salt buffer agent is phosphorous an alkali metal salt and/or phosphorous alkaline earth salt.
Phosphorous an alkali metal salt, phosphorous alkaline earth salt are phosphate cpd, phosphorons acid compound or ortho phosphorous acid compound.
The inorganic phosphate salt buffer agent is Na
2HPO
4, NaH
2PO
4, K
2HPO
4, KH
2PO
4, Na
2HPO
3, K
2HPO
3, NaH
2PO
2, KH
2PO
2, Ca3 (PO
4)
2, Ca (H
2PO
2)
2, CaHPO
4, CaHPO
3In one or more combination.
The polyester that above-mentioned reaction obtains, its content of carboxyl end group is no more than 20eq/t.
In order to realize goal of the invention, the present invention selects the buffer reagent of high temperature resistant and not volatile inorganic phosphate as polyreaction for use, in polymerization process by adding buffer reagent to reach the hydrolytic resistance that improves polyester.
The present invention relates to a kind of preparation method of hydrolysis-resistant polyester, its comprise the following steps: (A) aromatic acid and dibasic alcohol under certain condition precondensation obtain oligomer; (B) oligomer carries out the polyester that polycondensation obtains the low terminal carboxy content of target call under the effect of catalyzer and buffer reagent.
The prepared hydrolysis-resistant polyester of the present invention comprises the various thermoplastic polyesters that are used as monofilament, fiber, film, moulded product, for example: aromatic acid and diol reaction and the polyester that forms, the example of aromatic acid comprises: terephthalic acid, m-phthalic acid, naphthalene are polyester synthesis materials such as diprotic acid or its mixture.Dibasic alcohol can be the alkyl diol of 2-10 carbon atom, and the example comprises: ethylene glycol, butyleneglycol, 1, polyester synthesis materials such as 3-glycerol.
Being suitable for the polyester that the present invention adds buffer reagent for example has: the multipolymer of polyethylene terephthalate (PET), polybutylene terephthalate (PBT), poly-naphthoic acid glycol ester (PEN), PET, the copolymerization of PBT are poly-, the multipolymer of PEN etc.Be good with PET again wherein.
Above-mentioned hydrolysis-resistant polyester can be made according to traditional pet reaction, just adds a certain amount of inorganic phosphate as buffer reagent in polycondensation process.Usually polyester can be got by diprotic acid and dibasic alcohol direct esterification and polycondensation, or is carried out transesterification reaction and polycondensation and got by its esters monomer.For example, PET can be by ethylene glycol and terephthalic acid direct esterification and polycondensation and is got, and perhaps, also can carry out transesterification reaction and polycondensation by ethylene glycol and terephthaldehyde's ester dimethyl ester and gets.Gained polyester of the present invention before hydrolysis treatment content of carboxyl end group (COOH) in 0～20eq/t.
Used basic metal of the present invention or alkali earth metal phosphate buffer reagent have high temperature resistant not volatile characteristic, and basic metal wherein generally refers to potassium, sodium; Alkaline-earth metal wherein generally refers to calcium, magnesium.
The selected alkali metal phosphorous compound of the present invention.Phosphate cpd preferably, elite is dihydrogen phosphate.
The used phosphoric acid salt of the present invention is alkali metal phosphate, preferably sodium, potassium, and elite is SODIUM PHOSPHATE, MONOBASIC.
The phosphate buffer that the present invention is used is 1～100ppm with respect to the addition of phosphoric in the phosphorus compound of weight polyester.20～80ppm more preferably.
The polyester prepared via the present invention has preferable hydrolytic resistance compared with known technology, and by the decline degree of polyester slice slicing characteristics viscosity (IV) after high-temperature vapor is handled seldom, %BB is very for a short time to be confirmed this advantage.
To process for producing polyester of the present invention, be that example is illustrated below with ethylene glycol terephthalate.
Used ethylene glycol terephthalates such as fiber, film, resin or bottle are used following any method manufacturing usually.Promptly, (1) be raw material with terephthalic acid and ethylene glycol, the temperature in about 240～270 ℃, normal pressure or add is depressed, react with direct esterification, obtain low-molecular-weight ethylene glycol terephthalate or oligomer, then, be warming up near 290 ℃, simultaneously, system is decompressed to below the 133Pa, carries out polycondensation, obtain the method for high-molecular weight polymer.(2) dimethyl terephthalate (DMT) (DMT) and ethylene glycol are made raw material, and reaction system is warming up near 240 ℃ from 150 ℃ under normal pressure, use transesterification reaction, obtain the method for high-molecular weight polymer.Even also can carry out esterification without catalyzer here, but, in transesterification reaction, the general compound as catalyst such as manganese, calcium, magnesium, zinc, lithium that use carry out, separately, after in fact transesterification reaction is finished, lose activity, carry out to wherein adding phosphorus compound for making catalyzer used in this reaction.
Manufacture method of the present invention is to add the catalyzer that inorganic phosphorus salt buffer agent of the present invention and polycondensation are used in the oligopolymer that obtains toward the initial stage of (1) and (2) series reaction or first half, carry out rear section polycondensation thereafter, obtain the high-molecular weight polyethylene terephthalate.In addition, modes such as the available intermittent type of above-mentioned reaction, semibatch or continous way are implemented.
The following describes characteristic measurement method of the present invention and evaluation method.
(1) limiting viscosity (IV) (dL/g)
With 0.5 gram polyester/milliliter phenol and sym.-tetrachloroethane etc. in the solution of weight mixture, in 25 ℃ of mensuration its limiting viscosities (IV) down
(2) hydrolysis stability
Get the hydrolysis system for handling that a certain amount of polyester granules places sealing, under 155 ℃, the water vapor conditions of 0.46MPa, handled 4～8 hours, measure its limiting viscosity after getting the sample drying after the processing then, the polyester slice viscosity change is reflected at the variation of the %BB of polyester slice before and after the comparison process.
％BB
＝0.27×{[IV
1]
-4/3-[IV
0]
-4/3}
In the equation, IV
0Represent the limiting viscosity of the preceding polyester of hydrolysis treatment, IV
1Represent the limiting viscosity of polyester after the hydrolysis treatment.
(3) carboxyl-content (COOH):
Adopt the optics titration measuring.Polyester is dissolved in the mixed solution (weight ratio 70: 30) of neighbour-cresols and chloroform, adds bromthymol blue indicator, carry out titration in the ethanolic soln with the potassium hydroxide of 0.05N then
(4) tone b value
Measure by GB GB/T 14190-1993
For further specifying above-mentioned and other purposes, feature and advantage of the present invention.Compare and be illustrated especially exemplified by going out preferred embodiment and comparative example below.
Embodiment:
The present invention is further described by following embodiment
Embodiment 1
Make according to a conventional method from high purity terephthalic acid and ethylene glycol, that is, and the oligopolymer of making in advance, under the normal pressure, stir fusion, the slowly past slurries that wherein add high purity terephthalic acid and ethylene glycol in 250 ℃, carry out esterification (ES), finally do not contained the oligopolymer of catalyzer.
The polyester catalyst of previous preparation: the ethylene glycol solution of phosphoric acid, antimonous oxide, magnesium acetate and potassium hydroxide and inorganic phosphorated metal-salt buffer reagent NaH
2PO
4Ethylene glycol solution in 255 ℃ of fused solutions that add down these oligopolymer, the metal phosphorus content that makes phosphoric acid in the polyester that finally obtains is 16ppm, antimony atoms content is 95ppm, MAGNESIUM METAL content is 40ppm, the content of potassium metal is at 6ppm, buffer reagent NaH
2PO
4The content of phosphorus be 70ppm.Then, on one side stir oligopolymer with 48rmp, on one side reaction system slowly is warming up to 290 ℃ from 255 ℃, system pressure is reduced to below the 300Pa, react after 3 hours, when reaching predetermined stirring torque,, make it return to normal pressure to the logical nitrogen of reaction system, stop polycondensation, be released into monofilament in water, cutting obtains the hydrolysis-resistant polyester particle immediately.
The intrinsic viscosity of the polymkeric substance that obtains is 0.66, and polymerization reaction time is: 2 hours 55 minutes.Polyester end acidic group content was 11eq/t before hydrolysis was handled, the tone of polymkeric substance is L=68.5 a=-1.3b=4.8, handling the %BB that measures and calculate polyester slice in the back by hydrolysis is 0.45, compare with the %BB:0.95 of the identical polyester slice that does not add buffer reagent, the hydrolytic resistance of polyester slice obviously improves, and other performance is also very good.
Embodiment 2
Make raw material with dimethyl terephthalate (DMT) (DMT) and ethylene glycol, reaction system is warming up near 240 ℃ from 140 ℃ under normal pressure,, obtain low-molecular weight polymer with ester-interchange method (EI) reaction.
The polyester catalyst of previous preparation: the ethylene glycol solution of phosphoric acid, antimonous oxide, magnesium acetate and potassium hydroxide and inorganic phosphorated metal-salt buffer reagent NaH
2PO
4Ethylene glycol solution in 255 ℃ of fused solutions that add down these oligopolymer, the metal phosphorus content that makes phosphoric acid in the polyester that finally obtains is 16ppm, antimony atoms content is 95ppm, MAGNESIUM METAL content is 40ppm, the content of potassium metal is at 6ppm, buffer reagent NaH
2PO
4The content of phosphorus be 70ppm.Then, on one side stir oligopolymer with 48rmp, on one side reaction system slowly is warming up to 290 ℃ from 255 ℃, system pressure is reduced to below the 300Pa, react after 3 hours, when reaching predetermined stirring torque,, make it return to normal pressure to the logical nitrogen of reaction system, stop polycondensation, be released into monofilament in water, cutting obtains the hydrolysis-resistant polyester particle immediately.
The intrinsic viscosity of the polymkeric substance that obtains is 0.67, and polymerization reaction time is: 2 hours 50 minutes.Polyester end acidic group content was 6eq/t before hydrolysis was handled, the tone of polymkeric substance is L=67.2 a=-1.5b=5.8, handling the %BB that measures and calculate polyester slice in the back by hydrolysis is 0.35, carry out the polyester slice that polymerization obtains again with oligopolymer that ES reaction obtains and compare, hydrolytic resistance is more excellent.
Embodiment 3
According to embodiment 1 described polymerization process, in the polycondensation stage, other conditions are constant, with buffer reagent NaH
2PO
4Amount change into: with respect to weight polyester, the content of phosphoric is 46ppm in the inorganic phosphate, and polyreaction obtains polyester slice.
The intrinsic viscosity of the polymkeric substance that obtains is 0.64, and polymerization reaction time is: 2 hours 45 minutes.Polyester end acidic group content was 14eq/t before hydrolysis was handled, and the tone of polymkeric substance is L=66.95 a=-1.0b=6.8, and handling the %BB that measures and calculate polyester slice in the back by hydrolysis is 0.48
Embodiment 4
According to embodiment 1 described polymerization process, in the polycondensation stage, other conditions are constant, with buffer reagent NaH
2PO
4Amount change into: with respect to weight polyester, the content of phosphoric is 23ppm in the inorganic phosphate, and polyreaction obtains polyester slice.
The intrinsic viscosity of the polymkeric substance that obtains is 0.65, and polymerization reaction time is: 2 hours 40 minutes.Polyester end acidic group content was 16eq/t before hydrolysis was handled, and the tone of polymkeric substance is L=64.4 a=-0.6b=6.2, and handling the %BB that measures and calculate polyester slice in the back by hydrolysis is 0.52.
Embodiment 5
According to embodiment 1 described polymerization process, in the polycondensation stage, other conditions are constant, with buffer reagent NaH
2PO
4Amount change into: with respect to weight polyester, the content of phosphoric is 70ppm in the inorganic phosphate, and polyreaction obtains polyester slice.
The intrinsic viscosity of the polymkeric substance that obtains is 0.68, and polymerization reaction time is: 3 hours 05 minute.Polyester end acidic group content was 14eq/t before hydrolysis was handled, and the tone of polymkeric substance is L=65.5 a=-2.1b=6.5, and handling the %BB that measures and calculate polyester slice in the back by hydrolysis is 0.50.
Embodiment 6
According to embodiment 1 described polymerization process, in the polycondensation stage, other conditions are constant, use Na
2HPO
4And NaH
2PO
4Combination buffer (by a certain percentage) and the consumption of buffer reagent be: with respect to weight polyester, the content of phosphoric is 70ppm in the inorganic phosphate, and polyreaction obtains polyester slice.
The intrinsic viscosity of the polymkeric substance that obtains is 0.67, and polymerization reaction time is: 2 hours 55 minutes.Polyester end acidic group content was 12eq/t before hydrolysis was handled, and the tone of polymkeric substance is L=66.7 a=-0.9b=5.9, and handling the %BB that measures and calculate polyester slice in the back by hydrolysis is 0.44.
Comparison example 1: according to embodiment 1 described polymerization process, in the polycondensation stage, other conditions are constant, do not add any phosphorous an alkali metal salt as buffer reagent, and the ordinary method polymerization obtains polyester slice.
The intrinsic viscosity of the polymkeric substance that obtains is 0.66, and polymerization reaction time is: 2 hours 55 minutes.Polyester end acidic group content was 29eq/t before hydrolysis was handled, and the tone of polymkeric substance is L=63.5 a=-1.3b=7.6, and handling the %BB that measures and calculate polyester slice in the back by hydrolysis is 0.95.
Comparison example 2
According to embodiment 1 described polymerization process, in the polycondensation stage, other conditions are constant, the consumption of buffer reagent Na2HPO4 be the content of phosphorus at 120ppm, polyreaction obtains polyester slice.The intrinsic viscosity of the polymkeric substance that obtains is 0.67, and polymerization reaction time is: 4 hours 30 minutes.Polyester end acidic group content was 12eq/t before hydrolysis was handled, and the tone of polymkeric substance is L=67.5 a=-1.3 b=6.5, and handling the %BB that measures and calculate polyester slice in the back by hydrolysis is 0.46.
Data by above embodiment and comparative example more as can be seen, add the inorganic base metal phosphorus compound can obviously improve polyester as buffer reagent hydrolytic resistance in the polymerization process, the limiting viscosity that is reflected in polyester slice polyester slice after pyrohydrolysis is handled changes very little, can also find by contrasting us, the consumption of buffer reagent is not The more the better, when consumption is too big, because buffer reagent is the phosphorous compound that contains, influence the time of polyreaction (from comparative example 2 we as can be seen) thereby excessive phosphorus can suppress other activity of such catalysts, this is both uneconomical also irrational in actual production.Therefore, the consumption of buffer reagent is will consider, promptly will reach the purpose that improves the resistant polyester hydrolysis, can not influence other characteristic of polymeric reaction times and polyester simultaneously.
| Metallic compound | Polycondensation reaction time | Polymer property | |||||||
| Polymerizing catalyst | Phosphorous metal addition (ppm) in the buffer reagent | Intrinsic viscosity | Content of carboxyl end group (eq/t) before the hydrolysis | The L value | The a value | Value | The B value | ||
| Embodiment 1 | Phosphoric acid, ANTIMONY TRIOXIDE SB 203 99.8 PCT, magnesium acetate, potassium hydroxide | NaH2PO4 metal phosphorus content 70ppm | 2:55 | 0.66 | 11 | 68.5 | -1.3 | 4.8 | 0.45 |
| Embodiment 2 | Phosphoric acid, ANTIMONY TRIOXIDE SB 203 99.8 PCT, magnesium acetate, potassium hydroxide | NaH2PO4 metal phosphorus content 70ppm | 2:50 | 0.67 | 6 | 67.2 | -1.5 | 5.8 | 0.35 |
| Embodiment 3 | Phosphoric acid, ANTIMONY TRIOXIDE SB 203 99.8 PCT, magnesium acetate, oxychlorination potassium | NaH2PO4 metal phosphorus content 46ppm | 2:45 | 0.64 | 14 | 66.95 | -1.0 | 6.8 | 0.48 |
| Embodiment 4 | Phosphoric acid, ANTIMONY TRIOXIDE SB 203 99.8 PCT, magnesium acetate, potassium hydroxide | NaH2PO4 metal phosphorus content 23ppm | 2:40 | 0.65 | 16 | 64.4 | -0.6 | 6.2 | 0.52 |
| Embodiment 5 | Phosphoric acid, ANTIMONY TRIOXIDE SB 203 99.8 PCT, magnesium acetate, potassium hydroxide | Na2HPO4 metal phosphorus content 70ppm | 3:05 | 0.68 | 14 | 65.5 | -2.1 | 6.5 | 0.50 |
| Embodiment 6 | Phosphoric acid, ANTIMONY TRIOXIDE SB 203 99.8 PCT, magnesium acetate, potassium hydroxide | Na2HPO4 and NaH2PO4 combination metal phosphorus content 70ppm | 2:55 | 0.67 | 12 | 66.7 | -0.9 | 5.9 | 0.44 |
| The comparative example 1 | Phosphoric acid, ANTIMONY TRIOXIDE SB 203 99.8 PCT, magnesium acetate, potassium hydroxide | - | 2:55 | 0.66 | 29 | 63.5 | -1.3 | 7.6 | 0.95 |
| The comparative example 2 | Phosphoric acid, ANTIMONY TRIOXIDE SB 203 99.8 PCT, magnesium acetate, potassium hydroxide | NaH2PO4 metal phosphorus content 120ppm | 4:30 | 0.67 | 12 | 67.5 | -1.3 | 6.5 | 0.46 |
Claims (5)
1, a kind of preparation method of hydrolysis-resistant polyester, carry out prepolymerization reaction by aromatic acid or aromatic dicarboxylic acid esters and aliphatic dihydroxy alcohol and generate oligopolymer, carry out polycondensation by oligopolymer again and obtain polyester, it is characterized in that: in polycondensation, add the inorganic phosphate salt buffer agent.
2, the preparation method of hydrolysis-resistant polyester according to claim 1 is characterized in that: the consumption of inorganic phosphate salt buffer agent is: with respect to weight polyester, the content of phosphoric is 1～100ppm in the inorganic phosphate.
3, the preparation method of hydrolysis-resistant polyester according to claim 1 and 2 is characterized in that: the inorganic phosphate salt buffer agent is phosphorous an alkali metal salt and/or phosphorous alkaline earth salt.
4, the preparation method of hydrolysis-resistant polyester according to claim 3 is characterized in that: phosphorous an alkali metal salt, phosphorous alkaline earth salt are phosphate cpd, phosphorons acid compound or ortho phosphorous acid compound.
5, the preparation method of hydrolysis-resistant polyester according to claim 4 is characterized in that: the inorganic phosphate salt buffer agent is Na
2HPO
4, NaH
2PO
4, K
2HPO
4, KH
2PO
4, Na
2HPO
3, K
2HPO
3, NaH
2PO
2, KH
2PO
2, Ca
3(PO
4)
2, Ca (H
2PO
2)
2, CaHPO
4, CaHPO
3In one or more combination.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200610039519 CN101050274A (en) | 2006-04-04 | 2006-04-04 | Method for preparing hydrolytic resisting polyester |
| JP2007097222A JP2007277548A (en) | 2006-04-04 | 2007-04-03 | Method for producing hydrolysis resistant polyester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200610039519 CN101050274A (en) | 2006-04-04 | 2006-04-04 | Method for preparing hydrolytic resisting polyester |
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| Publication Number | Publication Date |
|---|---|
| CN101050274A true CN101050274A (en) | 2007-10-10 |
Family
ID=38679316
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|---|---|---|---|
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|---|---|
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| CN (1) | CN101050274A (en) |
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| CN101469108B (en) * | 2007-12-24 | 2011-11-23 | 东丽纤维研究所（中国）有限公司 | Production method of hydrolysis resistant polyester composition |
| CN102282211A (en) * | 2009-03-09 | 2011-12-14 | 东丽株式会社 | Polyester resin composition, process for production of same, and film |
| CN101525413B (en) * | 2008-03-04 | 2012-01-18 | 东丽纤维研究所（中国）有限公司 | Method for producing hydrolysis-resistant polyester composition |
| CN102575090A (en) * | 2009-10-27 | 2012-07-11 | 东丽株式会社 | Polyethylene terephthalate composition, manufacturing method therefor, and polyethylene terephthalate film |
| CN103189415A (en) * | 2010-09-08 | 2013-07-03 | 东丽株式会社 | Method for producing polyester compositions |
| CN108715633A (en) * | 2018-06-01 | 2018-10-30 | 江苏尚科聚合新材料有限公司 | A kind of hydrolysis-resistant polyester and preparation method thereof |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101469108B (en) * | 2007-12-24 | 2011-11-23 | 东丽纤维研究所（中国）有限公司 | Production method of hydrolysis resistant polyester composition |
| CN101525413B (en) * | 2008-03-04 | 2012-01-18 | 东丽纤维研究所（中国）有限公司 | Method for producing hydrolysis-resistant polyester composition |
| CN102282211A (en) * | 2009-03-09 | 2011-12-14 | 东丽株式会社 | Polyester resin composition, process for production of same, and film |
| CN102282211B (en) * | 2009-03-09 | 2014-07-23 | 东丽株式会社 | Polyester resin composition, process for production of same, and film |
| TWI476245B (en) * | 2009-03-09 | 2015-03-11 | Toray Industries | Polyester resin composition, producing method thereof and thin film |
| CN102575090A (en) * | 2009-10-27 | 2012-07-11 | 东丽株式会社 | Polyethylene terephthalate composition, manufacturing method therefor, and polyethylene terephthalate film |
| CN102575090B (en) * | 2009-10-27 | 2013-12-11 | 东丽株式会社 | Polyethylene terephthalate composition, manufacturing method therefor, and polyethylene terephthalate film |
| CN103189415A (en) * | 2010-09-08 | 2013-07-03 | 东丽株式会社 | Method for producing polyester compositions |
| CN103189415B (en) * | 2010-09-08 | 2015-04-15 | 东丽株式会社 | Method for producing polyester compositions |
| CN110055604A (en) * | 2018-01-18 | 2019-07-26 | 上海湘伊实业有限公司 | A kind of production system and master batch production technology of plant extraction scribbled |
| CN108715633A (en) * | 2018-06-01 | 2018-10-30 | 江苏尚科聚合新材料有限公司 | A kind of hydrolysis-resistant polyester and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| JP2007277548A (en) | 2007-10-25 |
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