CN103290506B - Direct esterification-polycondensation process prepares the method for fine shrinkage controllable copolyester fiber - Google Patents
Direct esterification-polycondensation process prepares the method for fine shrinkage controllable copolyester fiber Download PDFInfo
- Publication number
- CN103290506B CN103290506B CN201210455179.0A CN201210455179A CN103290506B CN 103290506 B CN103290506 B CN 103290506B CN 201210455179 A CN201210455179 A CN 201210455179A CN 103290506 B CN103290506 B CN 103290506B
- Authority
- CN
- China
- Prior art keywords
- fiber
- temperature
- copolyesters
- esterification
- phthalic acid
- 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.)
- Expired - Fee Related
Links
- 239000000835 fiber Substances 0.000 title claims abstract description 41
- 229920001634 Copolyester Polymers 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 24
- 238000006068 polycondensation reaction Methods 0.000 title claims abstract description 13
- 230000008569 process Effects 0.000 title claims abstract description 11
- 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 61
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 48
- 230000032050 esterification Effects 0.000 claims abstract description 30
- 238000005886 esterification reaction Methods 0.000 claims abstract description 30
- 238000009987 spinning Methods 0.000 claims abstract description 25
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 17
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 15
- 238000005098 hot rolling Methods 0.000 claims abstract description 13
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 9
- 238000004804 winding Methods 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 238000005243 fluidization Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 229920000728 polyester Polymers 0.000 description 15
- 238000004519 manufacturing process Methods 0.000 description 13
- 230000008602 contraction Effects 0.000 description 7
- 238000009835 boiling Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 5
- 239000005020 polyethylene terephthalate Substances 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000035882 stress Effects 0.000 description 3
- 238000009941 weaving Methods 0.000 description 3
- 230000033228 biological regulation Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 230000032683 aging Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010036 direct spinning Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- -1 polyethylene terephthalate Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
Landscapes
- Artificial Filaments (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
Direct esterification-polycondensation process prepares the method for fine shrinkage controllable copolyester fiber, it is characterized in that terephthalic acid (TPA), M-phthalic acid to add in ethylene glycol to carry out esterification; Gained esterification products and polyethylene glycol carry out copolymerization, the copolyesters of obtained different shrinkage factor fiber; Copolyesters is carried out pre-crystallized and dry, and melt extruded by screw extruder, utilize three hot-rollings, 20 high-speed spinning equipment drawing-off windings.Product obtains the superfine fibre of total fiber number 20-30dtex or filament number 0.3-0.5dtex, and shrinkage factor is adjustable between 15-70%.
Description
Technical field
The invention belongs to field of textiles, relate to a kind of method that direct esterification-polycondensation process prepares fine shrinkage controllable copolyester fiber specifically.
Background technology
The clothes that polyester fiber is made are well-pressed, quick-drying washable, also there is shortcoming, therefore need to carry out modification to it.Method of modifying conventional on producing has modification by copolymerization and blending and modifying, modification by copolymerization can introduce useful chemical group in macromolecular chain, but the more important thing is the physical property and aggregated structure that change polyester, and it is blended also by being mixed into other polymer, change physical property and the aggregated structure of polyester, thus change the performance of polyester.More domestic enterprises and scientific research department add M-phthalic acid (IPA) and have the neopentyl glycol (DTG) of side-chain structure in PET polyester, have made shrinkage polyester slice and fiber.Along with IPA, DTG addition increases, the crystal property of copolyesters reduces, and the shrinkage factor of fiber then improves in regular, can arrive more than 50%, and have good ageing stability.Because the interpolation of IPA or DTG can destroy the regularity of macromolecular chain, destroy the crystallization of polyester, make its crystallization difficulty, after fiber drawn, the degree of orientation improves, but degree of crystallinity is not high.When fiber is again higher than when heat-treating under draft temperature, large molecule generation disorientation, makes fiber macroscopically present different contraction.When IPA mass fraction be 8%, DTG mass fraction is 1-4%, good shrinkage polyester slice can be produced.All can 50% be reached through its boiling water shrinkage of polyester fiber of modification and dry-hot shrinkage.But this Modified polyester chips fusing point is low, and spinning molten temperature is corresponding also low, thermal degradation is serious at relatively high temperatures, and production can not normally be carried out.But under too low spinning temperature, melt rheological property can decline, especially when weaving fine denier filament, lousiness obviously increases.The patent document 200810136551.5 applied for before applicant, be in polyester fiber, add second comonomer M-phthalic acid (IPA), PEG obtains different shrinkage copolyester, present patent application file is the improvement to technology before.
Summary of the invention
The present invention is the improvement to patent application document before, gained copolyesters is in the polymerization process of original polyethylene terephthalate, add M-phthalic acid and polyethylene glycol four component copolyesters obtained as copolymer components, its fusing point is higher, spinning molten temperature is also correspondingly higher, still can normally produce at relatively high temperatures; And under slightly low spinning temperature, its melt rheological property can better, when weaving fine denier filament, lousiness is less.This copolyesters is easy to spinning, and the fiber different shrinkage fiber different shrinkage obtained by it is excellent, and shrinkage factor can be set between 15-70% according to customer requirement, and shrinkage factor CV value is controlled.
Preparation method is as follows:
(1) add in ethylene glycol by terephthalic acid (TPA), M-phthalic acid under stirring, carry out esterification and obtain esterification products at 245-260 DEG C, a point fluidization tower capital control temperature is 100-110 DEG C; M-phthalic acid is the 3-15mol% of terephthaldehyde's acid content, and M-phthalic acid and terephthalic acid (TPA) amount sum and ethylene glycol mol ratio are 1:2;
(2) gained esterification products and polyethylene glycol carry out copolymerization, reaction 2-4 hour, and polycondensation final temperature is 285-295 DEG C, the copolyesters of obtained different shrinkage factor fiber.Polyethylene glycol consumption accounts for the 0.8-1.5wt% of esterification products;
(3) carried out by copolyesters pre-crystallized and dry, pre-crystallization temperature and baking temperature are respectively 150-180 DEG C and 150-160 DEG C, and melt extruded by screw extruder, the performance of shrinkage copolyester section determines spinning properties.Due to its Tg, Tm, comparatively PET is low, and intermolecular generation relative displacement is easy, and make polymer produce the required external energy of same flowing little, under identical spinning temperature, copolyesters fluidity of molten is better, and spinning is generally more easily carried out.Relatively conventional PET spinning temperature, the spinning temperature of contraction polyester controls must be lower, and generally at 280-293 DEG C, the existence due to PEG component will cause degraded to become large;
(4) utilize three hot-rollings, 20 high-speed spinning equipments, high speed high yield can be reached, simultaneously three hot-rolling (GR
1two hot-rollings, GR
2a hot-rolling) make stretching, sizing more abundant, stable, be conducive to the stability of Fiber Uniformity and shrinkage, and finally macroscopically show the impact on filament contraction performance.
The degree of orientation of winding speed on FDY has impact, and the height of the degree of orientation affects the draw ratio of fiber, after fiber drawn under the different spinning speed made, the inner macromolecular orientation degree of strand and degree of crystallinity there are differences, and then affect the shrinkage factor of superfine fibre to a certain extent.When other techniques are constant, spin speed higher, boiling water shrinkage is lower, but by other techniques of adjustment, shrinkage factor can reach requirement, thus from the angle reducing costs, improve output, uses high speed spinning as far as possible.Through overtesting, spin speed all better in 4200-5200m/min spinnability, can require to adjust accordingly according to shrinkage factor.The shrinkage factor of the fiber of copolyesters 1 under different spinning speed;
Draft temperature should be selected more than vitrification point, and for conventional polyester major effect dyeability, for copolyesters, degree of crystallinity changes greatly, and works as GR
1during increase in temperature, tensile stress declines, and the internal stress of fiber declines, and cause its noncrystalline domain degree of orientation to reduce, thus its shrinkage factor also decreases.In addition as temperature drift, strand shakes increase on hot-rolling, and yarn unevenness rises; And temperature lower time, undrafting wire may be produced, make tensile stress raise simultaneously, cause lousiness and broken end.According to the physicochemical characteristic of different shrinkage copolyester, the temperature that we select, between 80-85 DEG C, adds that what adopt aborning is three hot-rollings, 20 high-speed spinning equipments, make to add hot-stretch more fully, stable, be conducive to the stability of filament contraction performance.
The effect of sizing mainly allows the supramolecular structure produced during tensile fiber improve further and regulate shrinkage factor.In normal production, if setting temperature is on the low side may occur uneven dyeing, the unstable properties of fiber, in use shrinkage factor progressively reduces; And the higher meeting of setting temperature is breaked end because of the shake of silk.Therefore, consider the performance indications of contraction copolyester, produce each factor, by adjusting different setting temperatures, and coordinating suitably adjustment shaping time and stretching condition, being existing contraction in conjunction with copolyesters synthesis, spinning out the contractile filaments meeting requirements of weaving process.
The present invention has following positive effect: semi batch direct esterification method produce PET due to technique simple, easy to operate, small investment, produce the flexible and stability of product quality than features such as intermittently operated increase, be widely adopted in the differential polyester slice process producing multi items for many years.Its process characteristic is that terephthalic acid (TPA) (PTA) and ethylene glycol (EG) add reaction kettle of the esterification continuously by certain flow and carries out esterification, and product is not discharge continuously but carry out polycondensation reaction in batches, and polycondensation process adopts andnon-continuous operation manner.Owing to testing multiple formulations in production modified poly ester process, large-scale continuity method is not suitable with rolled product variety adjustment on the contrary, and therefore this project adopts semi batch direct esterification method to produce the controlled copolyesters of contraction.
Shrinking the controlled manufacturing technology of copolyesters direct spinning superfine fiber and the combination of super high-speed spinning technology is pursuit to the melt spinning limit, has the feature of low cost, low-carbon (LC), environmental protection.The raw materials used terephthalic acid (TPA) of this project system Preparation Method and ethylene glycol are base stock, and M-phthalic acid and polyethylene glycol are four component copolyesters of copolymer components, to change the Main Means of copolyesters component as regulation and control fibre shrinkage.A kind of novel rectifying device replacing annealer of the method design that combines according to model prediction and experimental data, use rectifier regulation and control fibre shrinkage CV value, the uniformity that stable fibers shrinks, utilize three hot-rollings, 20 high-speed spinning equipments, ensure that drawing and setting is more abundant, stable, product obtains the superfine fibre of total fiber number 20-30dtex or filament number 0.3-0.5dtex, and shrinkage factor is adjustable between 15-70%.
Accompanying drawing explanation
Fig. 1 is process chart of the present invention.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention is described in further detail.
Embodiment 1
(1) add in ethylene glycol by terephthalic acid (TPA), M-phthalic acid under stirring, carry out esterification and obtain esterification products at 245-260 DEG C, a point fluidization tower capital control temperature is 100 DEG C; M-phthalic acid is the 5mol% of terephthaldehyde's acid content, and M-phthalic acid and terephthalic acid (TPA) amount sum and ethylene glycol mol ratio are 1:2;
(2) gained esterification products and polyethylene glycol carry out copolymerization, reaction 2-4 hour, and polycondensation final temperature is 285-295 DEG C, the copolyesters of obtained different shrinkage factor.Polyethylene glycol consumption accounts for the 1wt% of esterification products;
(3) carried out by copolyesters pre-crystallized and dry, and melt extruded by screw extruder, relevant manufacturing condition is in table 1;
(4) utilize three hot-rollings, 20 high-speed spinning equipment drawing-off windings, relevant manufacturing condition is in table 1.Obtained fibre single thread fiber number is 0.3dtex, and boiling water shrinkage is 19.1%.
Embodiment 2
(1) add in ethylene glycol by terephthalic acid (TPA), M-phthalic acid under stirring, carry out esterification and obtain esterification products at 245-260 DEG C, a point fluidization tower capital control temperature is 100-110 DEG C; M-phthalic acid is the 13mol% of terephthaldehyde's acid content, and M-phthalic acid and terephthalic acid (TPA) amount sum and ethylene glycol mol ratio are 1:2;
(2) gained esterification products and polyethylene glycol carry out copolymerization, reaction 2-4 hour, and polycondensation final temperature is 285-295 DEG C, the copolyesters of obtained different shrinkage factor.Polyethylene glycol consumption accounts for the 1.3wt% of esterification products;
(1) carried out by copolyesters pre-crystallized and dry, and melt extruded by screw extruder, relevant manufacturing condition is in table 1;
(2) utilize three hot-rollings, 20 high-speed spinning equipment drawing-off windings, relevant manufacturing condition is in table 1.The filament number of obtained fiber is 0.4dtex, boiling water shrinkage is 64.1%.
Table 1 is about manufacturing condition
Embodiment 3
(1) add in ethylene glycol by terephthalic acid (TPA), M-phthalic acid under stirring, carry out esterification and obtain esterification products at 252 DEG C, a point fluidization tower capital control temperature is 100 DEG C; M-phthalic acid is the 3mol% of terephthaldehyde's acid content, and M-phthalic acid and terephthalic acid (TPA) amount sum and ethylene glycol mol ratio are 1:2;
(2) gained esterification products and polyethylene glycol carry out copolymerization, reaction 2-4 hour, and polycondensation final temperature is 285-295 DEG C, the copolyesters of obtained different shrinkage factor.Polyethylene glycol consumption accounts for the 0.8wt% of esterification products;
(3) carried out by copolyesters pre-crystallized and dry, and melt extruded by screw extruder, relevant manufacturing condition is in table 1;
(4) utilize three hot-rollings, 20 high-speed spinning equipment drawing-off windings, relevant manufacturing condition is in table 2.Obtained fibre single thread fiber number is 0.3dtex, and boiling water shrinkage is 19.1%.
Embodiment 4
(5) add in ethylene glycol by terephthalic acid (TPA), M-phthalic acid under stirring, carry out esterification and obtain esterification products at 252 DEG C, a point fluidization tower capital control temperature is 100 DEG C; M-phthalic acid is the 15mol% of terephthaldehyde's acid content, and M-phthalic acid and terephthalic acid (TPA) amount sum and ethylene glycol mol ratio are 1:2;
(6) gained esterification products and polyethylene glycol carry out copolymerization, reaction 2-4 hour, and polycondensation final temperature is 285-295 DEG C, the copolyesters of obtained different shrinkage factor.Polyethylene glycol consumption accounts for the 1.5wt% of esterification products;
(7) carried out by copolyesters pre-crystallized and dry, and melt extruded by screw extruder, relevant manufacturing condition is in table 2;
(8) utilize three hot-rollings, 20 high-speed spinning equipment drawing-off windings, relevant manufacturing condition is in table 1.Obtained fibre single thread fiber number is 0.3dtex, and boiling water shrinkage is 15%.
Table 2
Above-mentioned detailed description of the invention does not limit technical scheme of the present invention in any form, and the technical scheme that the mode that every employing is equal to replacement or equivalent transformation obtains all drops on protection scope of the present invention.
Claims (1)
1. direct esterification-polycondensation process prepares the method for fine shrinkage controllable copolyester fiber, it is characterized in that comprising the following steps:
Terephthalic acid (TPA), M-phthalic acid are added in ethylene glycol under stirring, at 245-260 DEG C, carry out esterification obtain esterification products, fluidization tower capital control temperature is divided to be 100-110 DEG C, M-phthalic acid is the 3-15mol% of terephthaldehyde's acid content, and M-phthalic acid and terephthalic acid (TPA) amount sum and ethylene glycol mol ratio are 1:2;
Gained esterification products and polyethylene glycol carry out copolymerization, reaction 2-4 hour, and polycondensation final temperature is 285-295 DEG C, the copolyesters of obtained different shrinkage factor fiber, and polyethylene glycol consumption accounts for the 0.8-1.5wt% of esterification products;
(3) carried out by copolyesters pre-crystallized and dry, pre-crystallization temperature and baking temperature are respectively 150-180 DEG C and 150-160 DEG C, and are melt extruded by screw extruder, and spinning temperature controls at 280-293 DEG C;
(4) three hot-rollings, 20 high-speed spinning equipment drawing-off windings are utilized; Spin speed at 4200-5200m/min; Draft temperature is between 80-110 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210455179.0A CN103290506B (en) | 2012-11-14 | 2012-11-14 | Direct esterification-polycondensation process prepares the method for fine shrinkage controllable copolyester fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210455179.0A CN103290506B (en) | 2012-11-14 | 2012-11-14 | Direct esterification-polycondensation process prepares the method for fine shrinkage controllable copolyester fiber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103290506A CN103290506A (en) | 2013-09-11 |
| CN103290506B true CN103290506B (en) | 2016-01-20 |
Family
ID=49092010
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210455179.0A Expired - Fee Related CN103290506B (en) | 2012-11-14 | 2012-11-14 | Direct esterification-polycondensation process prepares the method for fine shrinkage controllable copolyester fiber |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103290506B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104562425B (en) * | 2014-12-26 | 2017-08-04 | 深圳市骏鼎达新材料股份有限公司 | Thermal contraction structure, sleeve pipe, protection band and thermal contraction structure production method |
| CN111234188B (en) * | 2020-02-14 | 2021-06-04 | 东华大学 | High-shrinkage wool-like fiber and preparation method thereof |
| CN115182087A (en) * | 2021-04-07 | 2022-10-14 | 江苏福斯得纺织有限公司 | Processing technology of high-waterproofness textile fabric |
| CN113308762A (en) * | 2021-06-09 | 2021-08-27 | 江苏鑫博高分子材料有限公司 | PET/modified PET parallel composite elastic fiber and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101255618A (en) * | 2008-02-29 | 2008-09-03 | 龙岩成冠纺织有限公司 | Method for preparing easily-soluble polyester fiber |
| CN101407946A (en) * | 2008-10-17 | 2009-04-15 | 龙岩成冠化纤有限公司 | Method for preparing easy-to-hydrolyze polyester fiber |
| CN101434691A (en) * | 2008-12-11 | 2009-05-20 | 江苏新民纺织科技股份有限公司 | Different shrinkage copolyester and preparation thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007056420A (en) * | 2005-08-26 | 2007-03-08 | Toray Ind Inc | Cationic dyeability antistatic polyester fiber |
-
2012
- 2012-11-14 CN CN201210455179.0A patent/CN103290506B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101255618A (en) * | 2008-02-29 | 2008-09-03 | 龙岩成冠纺织有限公司 | Method for preparing easily-soluble polyester fiber |
| CN101407946A (en) * | 2008-10-17 | 2009-04-15 | 龙岩成冠化纤有限公司 | Method for preparing easy-to-hydrolyze polyester fiber |
| CN101434691A (en) * | 2008-12-11 | 2009-05-20 | 江苏新民纺织科技股份有限公司 | Different shrinkage copolyester and preparation thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103290506A (en) | 2013-09-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101671854B (en) | Method for producing polyester industrial yarn by one-step method | |
| CN100427651C (en) | Preparation technology of ultralow contraction terylene industry long filament | |
| CN103290506B (en) | Direct esterification-polycondensation process prepares the method for fine shrinkage controllable copolyester fiber | |
| US8962789B2 (en) | Method for preparing modified poly (1,3-propanediol terephthalate) | |
| CN101787584A (en) | Method for preparing continuous polymerization directly-spun high-shrinkage polyester staple fibers | |
| CN107574507B (en) | Three-dimensional crimped elastic fiber and preparation method thereof | |
| CN101089266B (en) | Manufacturing method of antithermal shrink polyster high strength yarn | |
| CN101434691A (en) | Different shrinkage copolyester and preparation thereof | |
| CN101575745A (en) | Heavy denier polyester fiber and production method thereof | |
| CN108998850A (en) | High-shrinkage fiber, preparation method and preparation system | |
| CN101824664B (en) | Method for preparing high-strength polyester industrial yarns | |
| CN102965761A (en) | One-step-process hydrophilic dacron/high-shrinkage dacron combined yarn and preparation method thereof | |
| CN101570596B (en) | Method for preparing cationic-dyeable copolyester | |
| CN111808274A (en) | Spinning filament type low-melting-point polyester chip and preparation method thereof | |
| CN101781811A (en) | Method for preparing continuous polymerization directly-spun cation-dyeable high-shrinkage polyester staple fibers | |
| CN103173889B (en) | Wool-like polyester staple fiber and preparation method thereof | |
| CN102345180A (en) | M-phthalic acid modified terylene low elastic network fiber | |
| CN102330174A (en) | Isophthalic acid modified polyester fully drawn yarn | |
| CN112778509A (en) | Anti-attenuation low-melting-point polyester chip prepared by one-step spinning method and preparation method thereof | |
| CN1896346A (en) | Preparation of multi-stage shrinkage polyester fibre by one-step method | |
| CN101781812A (en) | Method for preparing continuous polymerization directly-spun cation-dyeable high-shrinkage polyester filaments | |
| CN111100280A (en) | Method for adding catalyst in industrial production of optical film grade polyester chips | |
| CN108251909A (en) | A kind of blending-modification by copolymerization super fine denier polyester fiber and preparation method thereof | |
| CN104372436A (en) | Quaternary co-polyester fiber and preparation method thereof | |
| CN114230774A (en) | Polyester with excellent thermal stability 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 | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20160331 Address after: 215228 Shengze City, Suzhou Province, Wujiang District, the town of the ancient thinking of the bang bang, No. 1 Patentee after: SUZHOU XINMIN TEXTILE Co.,Ltd. Patentee after: SOOCHOW University Address before: Shengze town of Wulong road Suzhou City, Jiangsu province 215228 Wujiang City No. 22 Patentee before: Jiangsu Xinmin Textile Science & Technology Co.,Ltd. Patentee before: Soochow University |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160120 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |