CN1130643A - Catalyst composition for improving colour of polydiethyl terephthalate - Google Patents
Catalyst composition for improving colour of polydiethyl terephthalate Download PDFInfo
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- CN1130643A CN1130643A CN 95102382 CN95102382A CN1130643A CN 1130643 A CN1130643 A CN 1130643A CN 95102382 CN95102382 CN 95102382 CN 95102382 A CN95102382 A CN 95102382A CN 1130643 A CN1130643 A CN 1130643A
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Abstract
A catalyst composition to make poly-diethyl tere-phthalate) slightly blue not yellow caused by the by-reaction in its rapid polymerization reaction and optionally speed up polymerization reaction contains general polymerization catalyst of polydiethyl terephthalate, phosphates, phosphites, hypophosphites or polyphosphates. Said polymerization catalyst is the compounds of Sb and Mn or Mg or Zn or Co or Pb.
Description
The present invention relates to improve the catalyst composition of poly terephthalic acid diethyl ester color and luster.At poly terephthalic acid diethyl ester [PET; Poly (ethylene terephthalate)] rapid polymerization reaction in, side reaction makes the color and luster of synthetic poly terephthalic acid diethyl ester yellow partially easily when taking place, this catalyst composition mainly is the color and luster that improves the poly terephthalic acid diethyl ester, makes its color blue partially; Wherein some prescription except that can improve color and luster can speed the speed of polyreaction again.This catalyst composition mainly is to add institutes such as phosphoric acid salt, phosphorous acid salt, Hypophosporous Acid, 50 salt or polyphosphoric acid salt by the polymerisation catalysts of general poly terephthalic acid diethyl ester (antimony and manganese or magnesium or zinc or calcium or cobalt or plumbous based compound) to combine.
In the commercial methods of synthetic poly terephthalic acid diethyl ester, can be divided into dimethyl terephthalate (DMT) method (DMT process) and terephthalic acid process (TPAprocess) with the raw material differentiation.Early stage because of the purity of terephthaldehyde's acid starting material is not enough, and, in recent decades,, therefore generally all use terephthalic acid process instead because the purity of terephthalic acid is enough high based on the dimethyl terephthalate (DMT) method.Now dimethyl terephthalate (DMT) method and terephthalic acid process are described below respectively:
1. the dimethyl terephthalate (DMT) method is with dimethyl terephthalate (DMT) (DMT; Dimethyl terepthalate) and ethylene glycol (EG; Ethylene glycol) being raw material, is transesterification catalyst with acetic acid salts such as manganese, calcium, zinc, carries out transesterification reaction at 220～260 ℃, forms intermediate terephthalic acid diethyl alcohol ester [BHET; Bis (2-hydroxyethyltrerphalate)]; Be polymerisation catalysts in 250～290 ℃ and vacuum (below 1 torr) with antimonous oxide or antimony acetate then, carry out polycondensation reaction, sloughed glycol and synthetic poly terephthalic acid diethyl ester.
2. terephthalic acid process is to be raw material with terephthalic acid (TPA) and ethylene glycol, is catalyzer with the acidity of terephthalic acid oneself, carries out esterification under 220～265 ℃, dehydration and form intermediate terephthalic acid diethyl alcohol ester; At 250～290 ℃ and below 1 torr, be polymerisation catalysts with antimonous oxide or antimony acetate, carry out polycondensation reaction, slough ethylene glycol and synthetic poly terephthalic acid diethyl ester.
The terephthalic acid process of the synthetic poly terephthalic acid diethyl ester of commercialization at present can be divided into batch formula and continous way method two kind again.The so-called batch of formula method is meant that esterification and polycondensation reaction separately carry out, and after esterification should be finished, moves to the polycondensation reaction groove and carry out prepolymerization reaction and polycondensation reaction (entire reaction is to carry out) in two reactive tanks.What is called has the continous way method to have five reactive tanks, and wherein esterification is to carry out at two reactive tanks, and the prepolymerization reaction is to carry out at a reactive tank, and polyreaction is to carry out at two reactive tanks.
From general document or patent specification, can learn, nineteen sixty-eight English Patent Brit.1,135,233 announcements are catalyzer with manganese acetate, Cobaltous diacetate and antimonous oxide, add triphenyl (triphenyl phosphate) again and be stablizer, only can improve with antimonous oxide and Cobaltous diacetate or antimonous oxide and manganese acetate is that catalyzer and triphenyl are when being stablizer, by the synthetic yellowish green partially problem of poly terephthalic acid diethyl ester color and luster of terephthalic acid process.Japanese publication 79 in 1979,146, when 893 announcements are catalyzer with tetramethyl-titanium (tetramethyltitanate), Cobaltous diacetate and calcium acetate, more yellow during than Cobaltous diacetate useless and calcium acetate by the color of terephthalic acid process synthetic poly terephthalic acid diethyl ester.Japanese publication (Jp.79 in 1979,163,996) disclosing with antimonous oxide, dibutyl tin acetate (dibutyl tin diacetate), Cobaltous diacetate and magnesium acetate is catalyzer, of light color when ratio only is catalyzer with ANTIMONY TRIOXIDE SB 203 99.8 PCT when synthesizing the poly terephthalic acid diethyl ester by terephthalic acid process.It is catalyzer that Japanese publication 80,120,623 in 1980 discloses with antimonous oxide, Cobaltous diacetate and calcium acetate, and phosphoric acid is stablizer, and during with terephthalic acid process synthetic poly terephthalic acid diethyl ester, the spinning character of its synthesizing polyester is very good.United States Patent (USP) 5 in 1989,077,259 disclose when having at least a cobalt or zn cpds and (2) to have at least a zinc, magnesium, manganese and calcium or the like compound to be catalyzer with antimony compounds and (1), can speed the polymerization rate that is synthesized the poly terephthalic acid diethyl ester by terephthalic acid process than only with the antimony based compound time.U.S. patent application case US.Appl.No354 in 1989,947 disclose when having at least a cobalt or zn cpds and (2) to have at least a zinc, magnesium, manganese and calcium or the like compound to be catalyzer with antimony compounds and (1), can speed the polymerization rate that is synthesized the poly terephthalic acid diethyl ester by terephthalic acid process than only with the antimony based compound time.Nineteen ninety European patent Euro.Pat.Appl.0,399,742 disclose when having at least a cobalt or zn cpds and (2) to have at least compounds such as a zinc, magnesium, manganese and calcium to be catalyzer with antimony compounds and (1), can speed the polymerization rate that is synthesized the poly terephthalic acid diethyl ester by terephthalic acid process than only with the antimony based compound time.Nineteen ninety European patent Euro.Pat.Appl.399,799 announcements are catalyzer with compounds such as calcium halophosphate activated by antimony andmanganese and cobalts, phosphoric acid ester is (as the diethyl phosphoric acid ester; Diethylacidphosphate) be stablizer, can speed than only with the antimony based compound time by the polymerization rate and the minimizing polymer impurity of the synthetic poly terephthalic acid diethyl ester of terephthalic acid process and improve the color and luster of poly terephthalic acid diethyl ester.U.S. patent application case US.Appl.No.355 in 1989,543 disclose when having at least a cobalt or zn cpds and (2) to have at least a zinc, magnesium, manganese and calcium or the like compound to be catalyzer with antimony compounds and (1), can speed the polymerization rate that is synthesized the poly terephthalic acid diethyl ester by terephthalic acid process than only with the antimony based compound time.Nineteen ninety U.S. patent application case US.Appl.No.528,260 disclose when being catalyzer with compounds such as antimony, cobalt and manganese, can speed the polymerization rate that is synthesized the poly terephthalic acid diethyl ester by terephthalic acid process than only with the antimony based compound time.U.S. patent application case US.Appl.No.653 in 1991,389 disclose when having at least a cobalt or zn cpds and (2) to have at least a zinc, magnesium, manganese and calcium or the like compound to be catalyzer with antimony compounds and (1), can speed the polymerization rate that is synthesized the poly terephthalic acid diethyl ester by terephthalic acid process than only with the antimony based compound time.U.S. patent application case US.Appl.No.705 in 1991,871 disclose when having at least a cobalt or zn cpds and (2) to have at least a zinc, magnesium, manganese and calcium or the like compound to be catalyzer with antimony compounds and (1), can speed the polymerization rate that is synthesized the poly terephthalic acid diethyl ester by terephthalic acid process than only with the antimony based compound time.
In sum with the synthetic poly terephthalic acid diethyl ester of terephthalic acid process, in building-up process, if with antimony based compound and (1) have at least a cobalt or zn cpds and or (2) to have compounds such as a zinc, magnesium, manganese and calcium at least be catalyzer, polymerization rate when being catalyzer than general with antimonous oxide speeds a lot, therefore also there is side reaction to take place, makes the color and luster of synthetic poly terephthalic acid diethyl ester be difficult for blue partially.The present invention is in above-mentioned polymerisation catalysts, add basic metal family acetic acid salt (is that the effective alkali metallic element consumption of benchmark is 10 to 500PPM with poly terephthalic acid diethyl ester weight) again, its synthetic poly terephthalic acid diethyl ester color is blue partially, and some prescription removes and can improve color and luster and can speed polymerization rate again, and the polymerisation catalysts of indication is antimony based compound (effectively antimony element consumption be 10 to 1000PPM) and manganese or magnesium or zinc or calcium or cobalt or plumbous based compound (effective metal element consumption be 10 to 500PPM) here.
Now be described as follows for several embodiment, illustrated embodiment only is that method of the present invention is made the generality illustration, and the meaning of the unrestricted scope of the invention, at this point statement earlier.
Embodiment 1
An amount of terephthalic acid, ethylene glycol, terephthalic acid diethyl alcohol ester [BHET; Bis (2-hydroxyethyl tereohthalate)] and proper catalyst and additive (basic metal family acetic acid salt), with N
2Be forced into 3 to 5kg/cm
2, row pressure is to 0kg/cm then
2Remove residual air and oxygen, repetitiousness carries out for several times (needing more than 3 times at least).Temperature of reaction is set 290 ℃, stirs and sets 60 RPM (picking up counting simultaneously), to carry out esterification.The return line temperature is set 150 ℃, reactive tank must be with nitrogen pressure to 3kg, treat that liquid collecting to esterification degree is at 80% o'clock, slowly after the row pressure (about 3 minutes), the temperature of reaction setting is taken out rough vacuum with general vacuum pupm for 330 ℃ carry out the prepolymerization reaction, improve suction piecemeal gradually for eight sections according to vacuum meter index 10,20,30,40,50,60,70,74 minutes, every section 5 minutes pumpdown times kind, taking out the rough vacuum time altogether is 40 minutes, this section is the prepolymerization conversion zone, and now carries out pumping high vacuum section polyreaction.With high vacuum denys that pumping high vacuum carries out polyreaction, and keeps vacuum tightness at 0.4～0.5torr, and polyreaction stirs voltage and rises to discharge behind the number that fixes.Reactor product is measured its colourity and threshold concentration respectively.
The following page table one of the interpretation of embodiment 1.
L value in the table one is represented whiteness, refers to pure white when the L value equals 100; The L value equals to bear at 100 o'clock and refers to black; And the b value is represented Huang Du, wherein the b value heals little or negative value heals when big, representative products is more not yellow or product is more blue, and the I.V. value is meant the molecular weight size [method of measuring the I.V. threshold concentration is 30 ± 0.1 ℃ of measurements, and used solvent is phenol/tetrachloroethane (its weight ratio is 6/4)] of poly terephthalic acid diethyl ester.
Experimental result
Table one. after adding basic metal family acetic acid salt again, improve by catalyzer such as antimony, cobalt, manganese
The effect of polyester color and luster.Catalyst combination polyreaction I.V. L. b. (effective element content; Ppm) (annotate: ethylene glycol is 1.2 to the mol ratio of terephthalic acid (TPA) to time (dividing) antimony oxide/cobalt acetate 43 0.65 78.4 3.3/ manganese acetates (antimony/cobalt/manganese=300/30/88) antimony oxide/cobalt acetate/manganese acetate 48 0.64 75.0-1.2/ lithium acetates (antimony/cobalt/manganese/lithium=300/30/88/36) antimony oxide/cobalt acetate/manganese acetate 52 0.64 83.9 2.5/ sodium acetates (antimony/cobalt/manganese/sodium=300/30/88/36) antimony oxide/cobalt acetate/manganese acetate 43 0.64 77.5 1.9/ potassium acetates (antimony/cobalt/manganese/potassium=300/30/88/36), and reactive tank is numbered B. )
Can know when being catalyzer the effect of improving the polyester color is arranged after adding basic metal family acetic acid salt again with antimony/cobalt/manganese from the b value of last table.
Embodiment 2～11
An amount of terephthalic acid, ethylene glycol, terephthalic acid diethyl alcohol ester; React with the experimental procedure of embodiment 1 with proper catalyst and additive (basic metal family acetic acid salt), except catalyzer and additive types with consumption is different, all the other are all identical.
Its result is described in table two～11 respectively.
Table two. catalyzer such as calcium halophosphate activated by antimony andmanganese, zinc improve look after adding basic metal family acetate again
The effect in pool.Catalyst combination polyreaction I.V. L. b. (effective element content; Ppm) (annotate: ethylene glycol is 1.2 to the mol ratio of terephthalic acid to time (branch) antimonous oxide/manganese acetate 28 0.63 86.5 4.6/ zinc acetates (antimony/manganese/zinc=300/88/43) antimonous oxide/manganese acetate/zinc acetate 33 0.61 84.5 3.0/ Lithium Acetates (antimony/manganese/zinc/lithium=300/88/43/36), and reactive tank is numbered A.)
Can know when being catalyzer from the b value of last table with antimony/manganese/zinc, add basic metal family acetic acid salt again after, the effect of improving the polyester color is arranged.
Table three. after adding basic metal family acetate again, improve by catalyzer such as antimony, cobalt, calcium
Effect catalyst combination polyreaction I.V. L. b. (the effective element content of polyester color and luster; Ppm) (annotate: ethylene glycol is 1.2 to the mol ratio of terephthalic acid to time (branch) antimonous oxide/Cobaltous diacetate 43 0.65 80.5 3.8/ calcium acetates (antimony/cobalt/calcium=300/25/36) antimonous oxide/Cobaltous diacetate/calcium acetate 46 0.65 75.0-1.1/ Lithium Acetate (antimony/cobalt/calcium/lithium=300/25/36/36), and reactive tank is numbered B.)
Can know when being catalyzer the effect of improving the polyester color is arranged after adding basic metal family acetic acid salt again with antimony/cobalt/calcium from the b value of last table.
Table four. after adding basic metal family acetate again, improve by catalyzer such as antimony, cobalt, magnesium
Effect catalyst combination polyreaction I.V. L. b. (the effective element content of polyester color and luster; Ppm) (annotate: ethylene glycol is 1.2 to the mol ratio of terephthalic acid to time (branch) antimonous oxide/Cobaltous diacetate 35 0.65 84.9 4.5/ magnesium acetates (antimony/cobalt/magnesium=300/30/36) antimonous oxide/Cobaltous diacetate/magnesium acetate 46 0.64 79.6 3.8/ Lithium Acetates (antimony/cobalt/magnesium/lithium=300/30/36/36) antimonous oxide/Cobaltous diacetate/magnesium acetate 33 0.65 81.6 1.4/ Potassium ethanoates (antimony/cobalt/calcium/potassium=300/30/36/36), and reactive tank is numbered B.)
Can know when being catalyzer the effect of improving the polyester color is arranged after adding basic metal family acetic acid salt again with antimony/cobalt/magnesium from the b value of last table.
Table five. improvement was poly-after catalyzer such as antimony, magnesium, manganese added basic metal family acetate again
Effect catalyst combination polyreaction I.V. L. b. (the effective element content of ester color and luster; Ppm) time (branch) antimonous oxide/magnesium acetate 32 0.63 78.7 4.6/ manganese acetates (antimony/magnesium/manganese=300/36/88) antimonous oxide/magnesium acetate/(annotate: ethylene glycol is 1.2 to the mol ratio of terephthalic acid to manganese acetate 33 0.624 81.4 4.0/ esters acid lithium (antimony/magnesium/manganese/lithium=300/36/88/36), and reactive tank is numbered A.)
Can know when being catalyzer the effect of improving the polyester color is arranged after adding alkaline alkali metal family acetic acid salt again with antimony/magnesium/manganese from the b value of last table.
Table six. catalyzer such as calcium halophosphate activated by antimony andmanganese, calcium improve after adding basic metal family acetate again
Effect catalyst combination polyreaction I.V. L. b. (the effective element content of polyester color and luster; Ppm) (annotate: ethylene glycol is 1.2 to the mol ratio of terephthalic acid to time (branch) antimonous oxide/calcium acetate 37 0.62 75.6 4.9/ manganese acetates (antimony/manganese/calcium=300/36/88) antimonous oxide/calcium acetate/manganese acetate 28 0.62 83.6 2.9/ Lithium Acetates (antimony/manganese/calcium/lithium=300/36/88/36), and reactive tank is numbered A.)
Can know when being catalyzer the effect of improving the polyester color is arranged after adding basic metal family acetic acid salt again with antimony/manganese/calcium from the b value of last table.
Table seven. improvement was poly-after catalyzer such as antimony, calcium, zinc added alkali metal acetate again
Effect catalyst combination polyreaction I.V. L. b. (the effective element content of ester color and luster; Ppm) (annotate: ethylene glycol is 1.2 to the mol ratio of terephthalic acid to time (branch) antimonous oxide/calcium acetate 26 0.61 86.5 5.7/ zinc acetates (antimony/calcium/zinc=300/36/43) antimonous oxide/calcium acetate/zinc acetate 36 0.65 82.5 3.7/ Lithium Acetates (antimony/calcium/zinc/lithium=300/36/43/36), and reactive tank is numbered A.)
Can know when being catalyzer the effect of improving the polyester color is arranged after adding basic metal family acetic acid salt again with antimony/calcium/zinc from the b value of last table.
Table eight. improvement was poly-after catalyzer such as antimony, calcium, magnesium added alkali metal acetate again
Effect catalyst combination polyreaction I.V. L. b. (the effective element content of ester color and luster; Ppm) (annotate: ethylene glycol is 1.2 to the mol ratio of terephthalic acid to time (branch) antimonous oxide/calcium acetate 32 0.64 82.8 4.8/ magnesium acetates (antimony/calcium/magnesium=300/36/43) antimonous oxide/calcium acetate/magnesium acetate 30 0.66 81.2 2.8/ Lithium Acetates (antimony/calcium/magnesium/lithium=300/36/36/36), and reactive tank is numbered A.)
Can know when being catalyzer the effect of improving the polyester color is arranged after adding basic metal family acetic acid salt again with antimony/magnesium/calcium from the b value of last table.
Table nine. after adding basic metal family acetate again, improve by catalyzer such as antimony, cobalt, manganese
Effect catalyst combination polyreaction I.V. L. b. (the effective element content of polyester color and luster; Ppm) (annotate: ethylene glycol is 1.2 to the mol ratio of terephthalic acid to time (branch) antimony acetate/Cobaltous diacetate 25 0.60 79.8 4.5/ manganese acetates (antimony/cobalt/manganese=300/32/89) antimony acetate/Cobaltous diacetate/manganese acetate 32 0.59 73.9 1.2/ Lithium Acetates (antimony/cobalt/manganese/lithium=300/32/89/36) antimony acetate/Cobaltous diacetate/manganese acetate 31 0.61 79.9 1.7/ sodium-acetates (antimony/cobalt/manganese/sodium=300/32/89/36), and reactive tank is numbered B.)
Can know when being catalyzer the effect of improving the polyester color is arranged after adding basic metal family acetic acid salt again with antimony/cobalt/manganese from the b value of last table.
Table ten. improvement was poly-after catalyzer such as antimony, calcium added basic metal family acetic acid salt again
Effect catalyst combination polyreaction I.V. L. b. (the effective element content of ester color and luster; Ppm) (annotate: ethylene glycol is 1.2 to the mol ratio of terephthalic acid to time (branch) antimonous oxide/calcium acetate 48 0.66 85.8 6.7 (antimony/calcium=300/36) antimonous oxide/calcium acetate 50 0.65 84.1 4.8/ Lithium Acetates (antimony/calcium/lithium=300/36/36), and reactive tank is numbered B.)
Can know when being catalyzer the effect of improving the polyester color is arranged after adding basic metal family acetic acid salt again with antimony/calcium from the b value of last table.
Table ten one. catalyzer such as antimony, cobalt, manganese, lead add basic metal family acetate again
Class is improved effect catalyst polymerization mix reaction I.V. L. b. (the effective element content of polyester color and luster; Ppm) (annotate: ethylene glycol is 1.2 to the mol ratio of terephthalic acid to time (branch) antimonous oxide/Cobaltous diacetate/manganese acetate 40 0.65 83.3 1.3/ plumbic acetates (antimony/cobalt/manganese/lead=300/30/88/20) antimonous oxide/Cobaltous diacetates/manganese acetate 39 0.64 80.2 0.9/ plumbic acetates/Lithium Acetate (antimony/cobalt/manganese/lead/lithium=300/30/88/20/36), and reactive tank is numbered C.)
Can know when being catalyzer the effect of improving the polyester color is arranged after adding basic metal family acetate again with antimony/cobalt/manganese/lead from the b value of last table.
Claims (10)
1. one kind prepares the catalyst composition of poly terephthalic acid diethyl ester with terephthalic acid process, and said composition comprises:
(a): with poly terephthalic acid diethyl ester weight is that effective antimony element consumption of benchmark is
10 to 1000PPM antimony based compound;
(b): with poly terephthalic acid diethyl ester weight is that the effective metal element consumption of benchmark is
10 to 500PPM compound, this compound are to be selected from cobalt, magnesium, zinc, manganese, calcium
With one or more of plumbous based compound; And
(c): with poly terephthalic acid diethyl ester weight is the effective alkali metallic element consumption of benchmark
It is 10 to 500PPM basic metal family acetic acid salt.
2. as the catalyst composition in the claim 1, wherein said is to be reactant with terephthalic acid and ethylene glycol with the synthetic polyphenyl dicarboxylate of terephthalic acid process, via esterification and the synthetic poly terephthalic acid diethyl ester of polyreaction.
3. as the catalyst composition in the claim 1, wherein said antimony based compound is the oxide compound of antimony and the carbonate of antimony.
4. as the catalyst composition in the claim 1, wherein said antimony based compound is antimonous oxide and antimony acetate.
5. as the catalyst composition in the claim 1, the effective antimony element consumption in the wherein said antimony based compound is 30 to 600PPM.
6. as the catalyst composition in the claim 1, wherein said one or more compounds such as cobalt, magnesium, manganese, calcium, lead are cobalt, magnesium, zinc, manganese, calcium, plumbous carbonate.
7. as the catalyst composition in the claim 1, wherein said one or more compounds such as cobalt, magnesium, zinc, manganese, calcium, lead are cobalt, magnesium, zinc, manganese, calcium, plumbous acetic acid salt.
8. as the catalyst composition in the claim 1, wherein said one or more compound such as cobalt, zinc, manganese, calcium, lead, its effective metal element consumption are 20 to 300PPM.
9. as the catalyst composition in the claim 1, wherein said basic metal family acetic acid salt is the acetate of lithium, sodium and potassium.
10. as the catalyst composition in the claim 1, the effective alkali metallic element consumption of wherein said basic metal family acetic acid salt is 20 to 300PPM.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 95102382 CN1130643A (en) | 1995-03-07 | 1995-03-07 | Catalyst composition for improving colour of polydiethyl terephthalate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 95102382 CN1130643A (en) | 1995-03-07 | 1995-03-07 | Catalyst composition for improving colour of polydiethyl terephthalate |
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| CN1130643A true CN1130643A (en) | 1996-09-11 |
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| CN 95102382 Pending CN1130643A (en) | 1995-03-07 | 1995-03-07 | Catalyst composition for improving colour of polydiethyl terephthalate |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107075136A (en) * | 2014-08-05 | 2017-08-18 | 因温斯特技术公司 | Improved polyester ether resin blend |
| CN109608628A (en) * | 2018-11-30 | 2019-04-12 | 江阴赛胜新材料有限公司 | The preparation method of industrial yarn polyethylene terephthalate |
-
1995
- 1995-03-07 CN CN 95102382 patent/CN1130643A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107075136A (en) * | 2014-08-05 | 2017-08-18 | 因温斯特技术公司 | Improved polyester ether resin blend |
| CN107075136B (en) * | 2014-08-05 | 2019-11-05 | 英威达纺织（英国）有限公司 | Improved polyester-ether resin blend |
| CN109608628A (en) * | 2018-11-30 | 2019-04-12 | 江阴赛胜新材料有限公司 | The preparation method of industrial yarn polyethylene terephthalate |
| CN109608628B (en) * | 2018-11-30 | 2021-10-15 | 江阴赛胜新材料有限公司 | Preparation method of polyethylene terephthalate for industrial yarn |
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