CN1329425C - Modified polyester and preparing method thereof - Google Patents
Modified polyester and preparing method thereof Download PDFInfo
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- CN1329425C CN1329425C CNB200410025181XA CN200410025181A CN1329425C CN 1329425 C CN1329425 C CN 1329425C CN B200410025181X A CNB200410025181X A CN B200410025181XA CN 200410025181 A CN200410025181 A CN 200410025181A CN 1329425 C CN1329425 C CN 1329425C
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- ethylene glycol
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- 229920000728 polyester Polymers 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims abstract description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 53
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 37
- -1 polyethylene terephthalate Polymers 0.000 claims abstract description 18
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 15
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 15
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 9
- 239000011734 sodium Substances 0.000 claims abstract description 9
- 229920000139 polyethylene terephthalate Polymers 0.000 claims abstract description 7
- 239000005020 polyethylene terephthalate Substances 0.000 claims abstract description 7
- 239000007790 solid phase Substances 0.000 claims abstract description 7
- 229920001634 Copolyester Polymers 0.000 claims abstract description 6
- 238000002425 crystallisation Methods 0.000 claims abstract description 5
- 230000008025 crystallization Effects 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 3
- 230000000694 effects Effects 0.000 claims abstract description 3
- 238000002360 preparation method Methods 0.000 claims abstract description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 13
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 8
- 239000005977 Ethylene Substances 0.000 claims description 8
- 230000032050 esterification Effects 0.000 claims description 8
- 238000005886 esterification reaction Methods 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 5
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 5
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000003112 inhibitor Substances 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 238000005453 pelletization Methods 0.000 claims description 3
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 2
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 claims 2
- 238000002156 mixing Methods 0.000 claims 1
- 239000000835 fiber Substances 0.000 abstract description 10
- 239000011347 resin Substances 0.000 abstract description 7
- 229920005989 resin Polymers 0.000 abstract description 7
- 239000002131 composite material Substances 0.000 abstract description 4
- 238000007334 copolymerization reaction Methods 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N perisophthalic acid Natural products OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 abstract description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 2
- 238000005904 alkaline hydrolysis reaction Methods 0.000 abstract 2
- 239000012071 phase Substances 0.000 abstract 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract 1
- 238000002844 melting Methods 0.000 abstract 1
- 230000008018 melting Effects 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 230000000707 stereoselective effect Effects 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 abstract 1
- 239000003518 caustics Substances 0.000 description 10
- 239000013078 crystal Substances 0.000 description 6
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 6
- 239000003513 alkali Substances 0.000 description 4
- 238000009987 spinning Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 229920004935 Trevira® Polymers 0.000 description 2
- QPKOBORKPHRBPS-UHFFFAOYSA-N bis(2-hydroxyethyl) terephthalate Chemical compound OCCOC(=O)C1=CC=C(C(=O)OCCO)C=C1 QPKOBORKPHRBPS-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 208000035126 Facies Diseases 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- FYIBGDKNYYMMAG-UHFFFAOYSA-N ethane-1,2-diol;terephthalic acid Chemical compound OCCO.OC(=O)C1=CC=C(C(O)=O)C=C1 FYIBGDKNYYMMAG-UHFFFAOYSA-N 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
- Artificial Filaments (AREA)
Abstract
The present invention relates to modified polyester. In the synthetic process of polyethylene terephthalate PET, terephthalic acid PTA and ethylene glycol EG are used as main materials, and 5-sodium sulfonate isophthalic acid ethyl diester SIPE and polyethylene glycol PEG are added for jointly carrying out a chemical reaction so as to generate new modified copolyester. The method for preparing the modified polyester is characterized in that a solid phase polycondensation method is used for achieving higher intrinsic viscosity, and specific substances of SIPE and PEG are added for copolymerization in the preparation process. Due to the introduction of sulfo-groups, the stereospecific blockade between giant molecules and the electron clouddensity of benzene rings are changed, which promotes the giant molecules to carry out an alkaline hydrolysis reaction. The introduction of ether bonds, which is not only helpful to the alkaline hydrolysis reaction, but also enables the crystallization performance of high polymers to be improved. The present invention has the advantages that 1, fiber division effects are good, when the post-treatment of sea island composite yarns is carried out, marine phases are quickly dissolved off, and thus, the separation of sea island phases is thorough; 2, the melting point of resin is high, molecular weight is high, and spinnability is good; 3, crystallization performance is superior, and adhesion can not occur at the time of slicing and drying.
Description
Technical field
The present invention relates to polyester art, mainly is a kind of modified poly ester and manufacture method thereof, is mainly used in the manufacturing of island composite superfine trevira.
Background technology
Trevira is widely used owing to its many good characteristic, use conventional melt spinning method at present and can only make the fiber that the single fiber linear density is higher than 0.3dtex, the island conjugate spinning is a main method of making the ultra-fine fibre of single fiber linear density below 0.3dtex." island " component in the composite filament of island is conventional polyester normally, " sea " component is mainly used alkali-soluble easy hydrolysis degradable polyester at present, utilize alkali soluble polyester good water-disintegrable sea component in the conjugated fibre of island is removed in sig water, keep the ultra-fine fibre of island component.In a commercially available class caustic solubility polyethylene terephthalate resin, on the one hand owing to adopted multiple organic acid compositions such as m-phthalic acid, SIPE and aliphatic diprotic acid, make the resin fusing point low excessively, the crystal property variation, the resin section is given in the crystallisation process in oven dry, be easy to produce adhesion, operational difficulty is very big; Because the adding of SIPE, the resin limiting viscosity is low excessively on the other hand, batch with batch between the limiting viscosity fluctuation bigger, lousiness, fracture of wire sharp increase in the spinning technique.
Summary of the invention
The present invention will solve deficiency recited above, and a kind of good caustic solubility that both kept is provided, and crystal property is good, and chip drying is difficult for adhesion, and limiting viscosity is easy to control, modified poly ester that cost is low again and manufacture method thereof.
The present invention adopts the method for the chemical modification of polyester to solve its technical problem.This modified poly ester, in polyethylene terephthalate PET building-up process, based on terephthalic acid PTA, ethylene glycol EG, add 5-sodium sulfonate ethylene m-phthalate SIPE, polyoxyethylene glycol PEG and carry out chemical reaction jointly, generate a kind of new modified copolyester; Its weight proportion is as follows:
The weight percent of terephthalic acid PTA, ethylene glycol EG is 1: 0.45-0.75.; 5-sodium sulfonate ethylene m-phthalate SIPE content is the 2.0-10% molar percentage of terephthalic acid PTA content, and polyoxyethylene glycol PEG content is the 2.5%-15% weight percent of terephthalic acid PTA content;
Its molecular formula of described new modified copolyester (caustic solubility modification polyethylene terephthalate polyester) is:
W, X, Y, Z represent the different components segmental polymerization degree in the formula; N represents number of ethylene glycol repeat units among the polyoxyethylene glycol PEG.
This modified poly ester obtains by the manufacturing of following method, carries out as follows:
Elder generation is with the catalyst S b of terephthalic acid, ethylene glycol and weight ratio 0.01-0.03%
2O
3Thermo-stabilizer, the oxidation inhibitor of weight ratio 0.5-1.5% is at 210-260 ℃, 0.2-0.4MPA under carry out esterification, generate ethylene glycol terephthalate, the 5-sodium sulfonate ethylene m-phthalate SIPE that adds terephthalic acid PTA content 2.0-10% (mol%) then, the 2.5-15% (wt%) of terephthalic acid PTA content, molecular weight is the polyoxyethylene glycol PEG of 600-6000, under normal pressure, carry out earlier polycondensation, after treating that the ethylene glycol quantity of distillate obviously reduces, vacuumize, pressure reacted 45 minutes under 50-5KPA, (pressure is below 50PA) carries out polycondensation under high vacuum then, treat that limiting viscosity rises to discharging behind the 0.40-0.50, the Cast Strip pelletizing, at last below 20PA, 190-220 ℃ following solid phase polycondensation 8-20 hour, after limiting viscosity reaches target value, the cooling, discharging.
The present invention both had been applicable to gap method esterification, polycondensation, also can be used for continuous esterification, gap polycondensation, and continuous esterification, continuous condensed technology, both available terephthalic acid PTA makes BHET for the raw material direct esterification, also available dimethyl terephthalate (DMT) (DMT) is a raw material, and ester-interchange method is made phthalic acid glycol ester BHET.
The limiting viscosity of modified poly ester of the present invention (I.V) is measured as follows: under 25 ℃, measure the I.V value of every 100ml solvent 0.5g superpolymer, solvent is that 60% (wt) phenol and 40% (wt) tetrachloroethane are formed.
The caustic solubility condition determination of modified poly ester of the present invention is: in the 1.5%NaOH solution, under 98 ℃, bath raio is 1: 100, handles after 60 minutes the percent value that weight reduces.
5-sodium sulfonate ethylene m-phthalate SIPE add-on of the present invention is at 2.5-10% (mol).The caustic solubility of modified poly ester increases with the SIPE add-on, and when SIPE add-on less than 2.5%, caustic solubility is poor, divides fibre not thorough in the conjugated fibre aftertreatment of island; After add-on surpassed 10%, melt viscosity increased severely, and the section spinning property is poor.
Polyoxyethylene glycol PEG add-on is in 2-15% (weight) among the present invention, and when PEG add-on less than 2%, the molecular weight of modified poly ester is low, and spinning property is poor, very easily adhesion during the section oven dry; After add-on surpassed 15%, the molten speed of alkali was obviously slack-off, the caustic solubility variation.
In the manufacturing processed of the present invention, the polycondensation end limiting viscosity should be controlled at 0.40-0.60dl/g, is preferably in 0.40-0.50dl/g, when limiting viscosity is lower than 0.40dl/g, and section granulation difficulty; Be higher than 0.60dl/g, terminal point is difficult to control, and limiting viscosity is too high, fluidity of molten variation, discharging difficulty.
The solid phase polycondensation condition: pressure is preferably in below the 20PA below 50PA; Temperature is preferably in 200-210 ℃ at 190-220 ℃.
The effect that the present invention is useful is: modified poly ester of the present invention adopts the solid phase polycondensation method to reach higher limiting viscosity, and has added specific material 5-sodium sulfonate ethylene m-phthalate SIPE and polyoxyethylene glycol PEG copolymerization in the preparation process.Because the introducing of sulfonic acid group, make the change of sterically hindered and phenyl ring cloud density between macromole, promoted the macromole macromolecule alkali for hydrolysis.The introducing of ehter bond had both helped the carrying out of macromolecule alkali for hydrolysis, and the superpolymer crystal performance is improved.Concrete advantage has: 1, divide fibre effective, and fast instant the going of marine facies during the composite filament aftertreatment of island, the island is separated thoroughly.2, resin fusing point height, molecular weight height, good spinnability.3, crystal property is good, can not stick together during the section oven dry.
Embodiment
Below in conjunction with embodiment the present invention is further described.
Embodiment:
Terephthalic acid, ethylene glycol are dropped in the esterifying kettle in 1: 0.7 ratio, add 0.01% catalyzer (Sb again
2O
3), oxidation inhibitor 1% (1010, DLTP), at 0.2MPA-0.4MPA, carry out esterification under 210-260 ℃, after esterification water quantity of distillate reaches target value, it is transferred to polycondensation vessel, earlier ratio drops into SIPE-EG solution on request, treat that temperature in the kettle is reduced to below 230 ℃ after, drop into a certain amount of PEG again, PEG is 5% (weight percent) of terephthalic acid PTA content, heating distillates EG, after 45 minutes in the time of intensification while stirring, temperature is risen to 260 ℃, open vacuum, below pressure 50Pa, 260 ℃-280 ℃, high vacuum polycondensation 1.5-2.0 hour, discharging after limiting viscosity reaches 0.40-0.50, Cast Strip, pelletizing.Then, will cut into slices under 80-120 ℃ of following normal pressure pre-crystallization treatment 2-4 hour, be warming up under 190-220 ℃, the following high vacuum of pressure 50Pa solid phase polycondensation 8-16 hour, treat that limiting viscosity reaches requirement after, be cooled to 120 ℃ with bottom discharge.
Table 1 is the embodiment of the invention and the resin performance synopsis that does not add the properties-correcting agent reference examples.As can be seen from the table:
1, caustic solubility increases with the SIPE add-on, and caustic solubility is from 9.5-97.1% within the scope of the present invention, transfer according to actual needs.
2, owing to the adding of PEG, crystal property improves.
Table 1
| Properties-correcting agent | Additive | Performance | Crystal property | Remarks | ||||
| SIPE addition % | PEG addition % | Section caustic solubility % | Fusing point ℃ | [η] | ||||
| Embodiment | 1 | 2 | 3.5 | 9.5 | 242 | 0.55 | Can | |
| 2 | 4 | 7.5 | 16.2 | 232 | 0.60 | Can | ||
| 3 | 6 | 10 | 72.6 | 220 | 0.45 | Can | ||
| 4 | 8 | 12 | 91.5 | 208 | 0.42 | Can | ||
| 5 | 10 | 15 | 97.1 | 201 | 0.40 | Can | ||
| Reference examples | 4 | 0 | 17.1 | 240 | 0.39 | Difficulty | ||
Claims (2)
1, a kind of modified poly ester, it is characterized in that: in the polyethylene terephthalate building-up process, based on terephthalic acid, ethylene glycol, interpolation 5-sodium sulfonate ethylene m-phthalate, polyoxyethylene glycol carry out chemical reaction jointly, generate a kind of new modified copolyester; Its weight proportion is as follows:
The weight percent of terephthalic acid, ethylene glycol is 1: 0.45-0.75; 5-sodium sulfonate ethylene m-phthalate content is the 2.0-10% molar percentage of terephthaldehyde's acid content, and polyethyleneglycol content is the 2.5%-15% weight percent of terephthaldehyde's acid content;
Described its molecular formula of new modified copolyester is:
W, X, Y, Z represent the different components segmental polymerization degree in the formula; N represents number of ethylene glycol repeat units in the polyoxyethylene glycol;
The modified copolyester limiting viscosity should be controlled at 0.40-0.60dl/g, and limiting viscosity is measured as follows: under 25 ℃, measure the inherent viscosity of every 100ml solvent 0.5g superpolymer, solvent is that 60wt% phenol and 40wt% tetrachloroethane are formed.
2, a kind of method of making modified poly ester as claimed in claim 1, carry out as follows:
1), the preparation of phthalic acid glycol ester;
Terephthalic acid, the ethylene glycol that will prepare by proportioning are at the catalyzer of weight ratio 0.01-0.03%: Sb
2O
3, weight ratio 0.5-1.5% oxidation inhibitor: 1010 and the effect of DLTP under carry out esterification, make phthalic acid glycol ester melt;
2), polycondensation;
5-sodium sulfonate ethylene m-phthalate-ethylene glycol solution is dropped in the phthalic acid glycol ester melt, after fully mixing, drop into polyoxyethylene glycol again and carry out polycondensation, make limiting viscosity at the 0.40-0.50 melt, the Cast Strip pelletizing;
3), solid-phase tack producing;
After above-mentioned section oven dry removed moisture, give crystallization treatment, then below 20PA, 190-220 ℃ following solid phase polycondensation 8-20 hour, after limiting viscosity reaches target value, cooling discharging.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200410025181XA CN1329425C (en) | 2004-06-16 | 2004-06-16 | Modified polyester and preparing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200410025181XA CN1329425C (en) | 2004-06-16 | 2004-06-16 | Modified polyester and preparing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1583822A CN1583822A (en) | 2005-02-23 |
| CN1329425C true CN1329425C (en) | 2007-08-01 |
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| CNB200410025181XA Expired - Fee Related CN1329425C (en) | 2004-06-16 | 2004-06-16 | Modified polyester and preparing method thereof |
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Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101144206B (en) * | 2007-10-23 | 2010-06-02 | 浙江理工大学 | Multi-micropore polyester fiber and preparation method thereof |
| CN101570596B (en) * | 2009-04-30 | 2013-07-17 | 江苏江南高纤股份有限公司 | Method for preparing cationic-dyeable copolyester |
| CN101701383B (en) * | 2009-11-02 | 2012-06-13 | 浙江天圣控股集团有限公司 | Method for producing copolymerized high-modifier content PET civilian filaments |
| CN102086261B (en) * | 2009-12-07 | 2012-10-17 | 上海联吉合纤有限公司 | Preparation method of polyol copolyester |
| CN101967225A (en) * | 2010-10-11 | 2011-02-09 | 苏州瀚海化学有限公司 | Method for preparing water-soluble sulfo-copolyester |
| CN102321934B (en) * | 2011-08-29 | 2013-05-15 | 苏州金辉纤维新材料有限公司 | Cotton imitation polyester filament with high hygroscopicity and preparation method thereof |
| CN102504224A (en) * | 2011-12-09 | 2012-06-20 | 东华大学 | Hydrophilic copolyester slices prepared by continuous method and preparation method thereof |
| CN106380585B (en) * | 2016-08-31 | 2019-01-22 | 浙江理工大学 | A kind of preparation method of antistatic copolyester |
| CN111823672A (en) * | 2020-07-15 | 2020-10-27 | 刁其松 | Towel with cooling and refreshing functions and preparation method thereof |
| CN112029149B (en) * | 2020-09-16 | 2022-02-18 | 贺州学院 | Polyester water-soluble polymer modifier for calcium carbonate surface modification and preparation method thereof |
| CN114656625B (en) * | 2022-03-19 | 2022-12-20 | 纤达峰(上海)新材料科技有限公司 | Antimony-catalyst-free polyester polymer easy to decompose and recover and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5363494A (en) * | 1976-11-19 | 1978-06-06 | Toray Ind Inc | Preparation of modified polyethylene terephthalate |
| US4785060A (en) * | 1986-08-28 | 1988-11-15 | Colgate-Palmolive Company | Soil release promoting pet-poet copolymer, method of producing same and use thereof in detergent composition having soil release promoting property |
| CN1464131A (en) * | 2002-06-13 | 2003-12-31 | 中国石化上海石油化工股份有限公司 | Process for manufacturing coloration additive for producing positive ionic dye dyeable polypropylene |
-
2004
- 2004-06-16 CN CNB200410025181XA patent/CN1329425C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5363494A (en) * | 1976-11-19 | 1978-06-06 | Toray Ind Inc | Preparation of modified polyethylene terephthalate |
| US4785060A (en) * | 1986-08-28 | 1988-11-15 | Colgate-Palmolive Company | Soil release promoting pet-poet copolymer, method of producing same and use thereof in detergent composition having soil release promoting property |
| CN1464131A (en) * | 2002-06-13 | 2003-12-31 | 中国石化上海石油化工股份有限公司 | Process for manufacturing coloration additive for producing positive ionic dye dyeable polypropylene |
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| CN1583822A (en) | 2005-02-23 |
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Assignee: Rongsheng Petrochemical Co., Ltd. Assignor: Zhejiang Sci-Tech University Contract fulfillment period: 2007.10.10 to 2013.10.9 contract change Contract record no.: 2008330001152 Denomination of invention: Modified polyester and preparing method thereof Granted publication date: 20070801 License type: Exclusive license Record date: 20081017 |
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