CN101434691A - Different-shrinkage copolyester and preparation method thereof - Google Patents
Different-shrinkage copolyester and preparation method thereof Download PDFInfo
- Publication number
- CN101434691A CN101434691A CNA2008101365515A CN200810136551A CN101434691A CN 101434691 A CN101434691 A CN 101434691A CN A2008101365515 A CNA2008101365515 A CN A2008101365515A CN 200810136551 A CN200810136551 A CN 200810136551A CN 101434691 A CN101434691 A CN 101434691A
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- Prior art keywords
- different shrinkage
- temperature
- copolyester
- shrinkage copolyester
- ethylene glycol
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- 229920001634 Copolyester Polymers 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 68
- 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 24
- 238000005886 esterification reaction Methods 0.000 claims abstract description 23
- 230000032050 esterification Effects 0.000 claims abstract description 22
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 9
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 13
- -1 polyoxyethylene Polymers 0.000 claims description 12
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 11
- 238000007334 copolymerization reaction Methods 0.000 claims description 6
- 238000005243 fluidization Methods 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000009987 spinning Methods 0.000 abstract description 13
- 229920000728 polyester Polymers 0.000 abstract description 9
- 238000006116 polymerization reaction Methods 0.000 abstract description 4
- 238000002844 melting Methods 0.000 abstract 3
- 230000008018 melting Effects 0.000 abstract 3
- 239000002202 Polyethylene glycol Substances 0.000 abstract 2
- 229920001223 polyethylene glycol Polymers 0.000 abstract 2
- 239000000155 melt Substances 0.000 abstract 1
- 239000000835 fiber Substances 0.000 description 30
- 238000003756 stirring Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- 238000007385 chemical modification Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000008602 contraction Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229920004935 Trevira® Polymers 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
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- Polyesters Or Polycarbonates (AREA)
Abstract
The invention relates to a different shrinkage copolyester and a preparation method thereof, wherein the different shrinkage copolyester is obtained by esterifying terephthalic acid, isophthalic acid and ethylene glycol and then copolymerizing the esterified products with polyethylene glycol, wherein the melting point of the different shrinkage copolyester is 220-235 ℃, and the intrinsic viscosity of the different shrinkage copolyester is 0.69-0.72 dl/g. The preparation method of the polyester comprises the following steps: (1) esterifying terephthalic acid, isophthalic acid and ethylene glycol at 245-260 ℃ according to the proportion, and controlling the temperature of the top of a flow dividing column to be 100-110 ℃; (2) and after the esterification reaction is finished, copolymerizing the esterification product with polyethylene glycol, and performing polymerization reaction at the polycondensation final temperature of 285-295 ℃ to obtain the different-shrinkage copolyester. The polyester has higher melting point and correspondingly higher spinning melting temperature, and can still be normally produced at higher temperature; and at a slightly lower spinning temperature, the melt rheological property is better, and the broken filaments are less when the fine denier filaments are spun, so that the spinning is easy.
Description
Technical field
The present invention relates to different shrinkage copolyester of a kind of modification and preparation method thereof.
Background technology
Along with multifunctional composite fiber use increasingly extensive, the compound plying of chemical modification has obtained development at full speed with different shrinkage fiber.In a conjugated fibre, comprising two fibers that performance is different simultaneously, through weave and after arrangement, finally on lining, embody the novel style that the contraction difference effect owing to two fibers causes, be received by the market.The particularly industrialization of sea-island composite fiber manufacturing technology in recent years, make the plying of itself and different shrinkage fiber use the fashionable market of suede nap fabric lining of producing, the embodiment of the different shrinkage of modified fibre is a key of producing multifunctional composite fiber in twisted fiber.
The modification different shrinkage fiber refers to that boiling water shrinkage or dry-hot shrinkage are higher than the man-made fiber of 25% (6-10% that is different from conventional fibre), is a kind of differential fibre that makes by physics or chemical modification to trevira.Its feature be fiber when thermal treatment, shrinking percentage can reach 25%～70%.In the prior art, mainly produce different shrinkage fiber with chemical modification method, carry out esterification simultaneously with m-phthalic acid and terephthalic acid after copolymerization produce copolymer p EIT, after cutting into slices, carry out the FDY spinning technique again and get different contraction FDY fiber.
As textile raw material, common modification different shrinkage fiber has many advantages, but many weak points are arranged also: because the shrinking percentage of different shrinkage fiber is big, dyeing uniformity is than conventional fibre difference, spinning technique control difficulty height, this is just objectively limiting its possibility in the further broadened application of garment material.
At present, more domestic enterprises and scientific research department add m-phthalic acid (IPA) and have the neopentyl glycol (DTG) of side-chain structure in the PET polyester, made different retraction polyester chip and fiber.Along with IPA, DTG add-on increase, the crystal property of copolyesters reduces, and the shrinking percentage of fiber then is regular and improves, and can reach more than 50%, and have ageing stability preferably.Because the interpolation of IPA or DTG can destroy the regularity of macromolecular chain, destroyed the crystallization of polyester, make its crystallization difficulty, orientation degree improves behind the fiber drawn, but degree of crystallinity is not high.When fiber is being higher than when heat-treating under the draft temperature once more, macromole generation disorientation makes fiber present different contraction on macroscopic view.When the IPA massfraction is 8%, when the DTG massfraction is 1-4%, can produce different preferably retraction polyester chip.Its boiling water shrinkage of trevira and dry-hot shrinkage through modification all can reach 50%, far above pure PEIT fiber.But this modified poly ester section fusing point is low, and the spinning melt temperature is corresponding also low, under comparatively high temps thermal destruction serious, production can not normally be carried out.But under low excessively spinning temperature, melt rheological property can descend, and especially lousiness obviously increases in the spinning fine denier filament.
Summary of the invention
It is good and be easy to the different shrinkage copolyester of spinning that technical problem to be solved by this invention provides a kind of different shrinkage.
The present invention also will provide a kind of preparation method of above-mentioned different shrinkage copolyester.
For solving above technical problem, the present invention takes following technical scheme:
A kind of different shrinkage copolyester, it is obtained by following four kinds of monomer copolymerizations:
(1) terephthalic acid;
(2) m-phthalic acid;
(3) ethylene glycol;
(4) polyoxyethylene glycol,
Wherein, the ratio of the amount of substance of terephthalic acid, m-phthalic acid and ethylene glycol is 0.02～0.15:1:1.1～1.45, the adding quality of described polyoxyethylene glycol is 1～5% of a described ethylene glycol, the fusing point of described different shrinkage copolyester is 220～235 ℃, and limiting viscosity is 0.69～0.72d1/g.
The preferred molecular weight of described polyoxyethylene glycol is 600～2000.
The another kind of technical scheme that the present invention takes is:
A kind of preparation method of above-mentioned different shrinkage copolyester comprises the steps:
(1), terephthalic acid, m-phthalic acid are added under whipped state in the ethylene glycol by proportioning, carry out esterification and get esterification products under 245～260 ℃, branch fluidization tower capital controlled temperature is 100～110 ℃;
(2), described esterification products and polyoxyethylene glycol carry out copolymerization, reacted 2～4 hours, the whole temperature of polycondensation is to make different shrinkage copolyester under 285～295 ℃.
Because the enforcement of above technical scheme, the present invention compared with prior art has following advantage:
Copolyesters of the present invention is to add the four component copolyesters that m-phthalic acid and polyoxyethylene glycol make as the copolymerization component in the polymerization process kind of original polyethylene terephthalate, its fusing point is higher, the spinning melt temperature is also correspondingly higher, still can normally produce under comparatively high temps; And under low slightly spinning temperature, its melt rheological property can be better, and lousiness is less in the spinning fine denier filament.This polyester is easy to spinning, and good by its different shrinkage of fiber different shrinkage fiber that makes, shrinking percentage can be set between 15～70% according to customer requirement.
Embodiment
The present invention will be further described in detail below in conjunction with specific embodiment.
Embodiment 1
A kind of different shrinkage copolyester, 226 ℃ of fusing points, limiting viscosity 0.71dl/g prepares as follows:
(1) esterification: get 5000kg terephthalic acid (PTA), 650kg m-phthalic acid (IPA) and under whipped state, add in the 1900L ethylene glycol, its mixture progressively adds in first reaction kettle of the esterification, and adding 2825g catalyst glycol antimony, after stirring, under normal pressure, carry out esterification, esterification temperature is controlled at about 250 ℃, and dividing fluidization tower capital controlled temperature is 100～104 ℃, finishes to the esterification water outlet; In second reaction kettle of the esterification, add 200L ethylene glycol, add the 85kg molecular weight again and be 800 polyoxyethylene glycol, about temperature drop to 230 ℃, the oligopolymer after the esterification is imported in being stirred to, import polycondensation vessel after stirring half an hour;
(2) polycondensation: start and stir, vacuumize, heat up, the whole temperature of polycondensation is 290 ℃, and pressure is below 100Pa, and power of agitator is finished to the set(ting)value post polymerization, section.
Embodiment 2
A kind of different shrinkage copolyester, 235 ℃ of fusing points, limiting viscosity 0.69dl/g prepares as follows:
(1) esterification: get 5000kg terephthalic acid (PTA), 250kg m-phthalic acid (IPA) and under whipped state, add in the 1750L ethylene glycol, its mixture progressively adds in first reaction kettle of the esterification, and adding 2625g catalyst glycol antimony, after stirring, under normal pressure, carry out esterification, esterification temperature is controlled at about 250 ℃, and dividing fluidization tower capital controlled temperature is 100～104 ℃, finishes to the esterification water outlet; In second reaction kettle of the esterification, add 200L ethylene glycol, add the 60kg molecular weight again and be 800 polyoxyethylene glycol, about temperature drop to 230 ℃, the oligopolymer after the esterification is imported in being stirred to, import polycondensation vessel after stirring half an hour;
(2) polycondensation: start and stir, vacuumize, heat up, the whole temperature of polycondensation is 290 ℃, and pressure is below 100Pa, and power of agitator is finished to the set(ting)value post polymerization, section.
Carry drying machine to carry out drying the copolyester section of embodiment 1 and 2, dry back is pushed by screw extruder, and extrusion molding by reeling, is finally made different shrinkage polyester fibre then, surveys its physical index (seeing Table 1)..
Table 1 different shrinkage fiber physical index
| Index name | Embodiment 1 | Embodiment 2 |
| The linear density deviation ratio, % | 0.76 | 0.54 |
| Breaking tenacity, cN/dtex | 3.89 | 4.23 |
| Elongation at break, % | 25.6 | 23.4 |
| Boiling water shrinkage, % | 62.6 | 17.3 |
| Dyeing uniformity, level | 3.5 | 4.0 |
Claims (3)
1, a kind of different shrinkage copolyester is characterized in that: it is obtained by following four kinds of monomer copolymerizations:
(1) terephthalic acid;
(2) m-phthalic acid;
(3) ethylene glycol;
(4) polyoxyethylene glycol,
Wherein, the ratio of the amount of substance of terephthalic acid, m-phthalic acid and ethylene glycol is 0.02～0.15:1:1.1～1.45, the adding quality of described polyoxyethylene glycol is 1～5% of a described ethylene glycol, the fusing point of described different shrinkage copolyester is 220～235 ℃, and limiting viscosity is 0.69～0.72dl/g.
2, different shrinkage copolyester according to claim 1 is characterized in that: the molecular weight of described polyoxyethylene glycol is 600～2000.
3, the preparation method of the described different shrinkage copolyester of a kind of claim 1 is characterized in that: comprise the steps:
(1), terephthalic acid, m-phthalic acid are added under whipped state in the ethylene glycol by proportioning, carry out esterification and get esterification products under 245～260 ℃, branch fluidization tower column top temperature is 100～110 ℃;
(2), described esterification products and polyoxyethylene glycol carry out copolymerization, reacted 2～4 hours, the whole temperature of polycondensation is to make different shrinkage copolyester under 285～295 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008101365515A CN101434691A (en) | 2008-12-11 | 2008-12-11 | Different-shrinkage copolyester and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008101365515A CN101434691A (en) | 2008-12-11 | 2008-12-11 | Different-shrinkage copolyester and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101434691A true CN101434691A (en) | 2009-05-20 |
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| CNA2008101365515A Pending CN101434691A (en) | 2008-12-11 | 2008-12-11 | Different-shrinkage copolyester and preparation method thereof |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102534843A (en) * | 2010-12-31 | 2012-07-04 | 上海德福伦化纤有限公司 | Production method of modified polyester fiber capable of resisting pilling |
| CN102585185A (en) * | 2011-12-27 | 2012-07-18 | 厦门翔鹭化纤股份有限公司 | Manufacturing method of low-melting-point polyester granules |
| CN102965761A (en) * | 2012-12-12 | 2013-03-13 | 东华大学 | One-step-process hydrophilic dacron/high-shrinkage dacron combined yarn and preparation method thereof |
| CN103290506A (en) * | 2012-11-14 | 2013-09-11 | 江苏新民纺织科技股份有限公司 | Method for preparing ultrafine contractible controllable copolyester fiber by adopting direct esterification polycondensation method |
| CN103788350A (en) * | 2014-01-26 | 2014-05-14 | 东华大学 | Preparation method of polyhydric flexible polyester |
| CN103788349A (en) * | 2014-01-26 | 2014-05-14 | 东华大学 | Preparation method of functional polyester |
| CN103804665A (en) * | 2014-01-26 | 2014-05-21 | 东华大学 | Preparation method of polyhydroxyl polyester |
| CN104233500A (en) * | 2013-06-14 | 2014-12-24 | 中国石油化工股份有限公司 | Preparation method of polyester staple fiber used for vortex spinning |
| CN106400178A (en) * | 2016-08-31 | 2017-02-15 | 荣盛石化股份有限公司 | Manufacturing method of different shrinkage polyester draw texturing yarn |
| CN110952167A (en) * | 2019-12-07 | 2020-04-03 | 杭州东南纺织有限公司 | Method for manufacturing different-shrinkage polyester low-stretch yarns |
| CN114959927A (en) * | 2022-05-18 | 2022-08-30 | 浙江新乐纺织化纤有限公司 | Production process of composite linen-like effect polyester filament yarn |
-
2008
- 2008-12-11 CN CNA2008101365515A patent/CN101434691A/en active Pending
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102534843A (en) * | 2010-12-31 | 2012-07-04 | 上海德福伦化纤有限公司 | Production method of modified polyester fiber capable of resisting pilling |
| CN102585185B (en) * | 2011-12-27 | 2013-08-07 | 厦门翔鹭化纤股份有限公司 | Manufacturing method of low-melting-point polyester granules |
| CN102585185A (en) * | 2011-12-27 | 2012-07-18 | 厦门翔鹭化纤股份有限公司 | Manufacturing method of low-melting-point polyester granules |
| CN103290506B (en) * | 2012-11-14 | 2016-01-20 | 江苏新民纺织科技股份有限公司 | Direct esterification-polycondensation process prepares the method for fine shrinkage controllable copolyester fiber |
| CN103290506A (en) * | 2012-11-14 | 2013-09-11 | 江苏新民纺织科技股份有限公司 | Method for preparing ultrafine contractible controllable copolyester fiber by adopting direct esterification polycondensation method |
| CN102965761A (en) * | 2012-12-12 | 2013-03-13 | 东华大学 | One-step-process hydrophilic dacron/high-shrinkage dacron combined yarn and preparation method thereof |
| CN104233500A (en) * | 2013-06-14 | 2014-12-24 | 中国石油化工股份有限公司 | Preparation method of polyester staple fiber used for vortex spinning |
| CN104233500B (en) * | 2013-06-14 | 2016-08-10 | 中国石化仪征化纤有限责任公司 | The preparation method of vortex spinning polyester staple fiber |
| CN103788350A (en) * | 2014-01-26 | 2014-05-14 | 东华大学 | Preparation method of polyhydric flexible polyester |
| CN103788349A (en) * | 2014-01-26 | 2014-05-14 | 东华大学 | Preparation method of functional polyester |
| CN103804665A (en) * | 2014-01-26 | 2014-05-21 | 东华大学 | Preparation method of polyhydroxyl polyester |
| CN103804665B (en) * | 2014-01-26 | 2016-02-10 | 东华大学 | A kind of preparation method of polyol polyester |
| CN106400178A (en) * | 2016-08-31 | 2017-02-15 | 荣盛石化股份有限公司 | Manufacturing method of different shrinkage polyester draw texturing yarn |
| CN110952167A (en) * | 2019-12-07 | 2020-04-03 | 杭州东南纺织有限公司 | Method for manufacturing different-shrinkage polyester low-stretch yarns |
| CN114959927A (en) * | 2022-05-18 | 2022-08-30 | 浙江新乐纺织化纤有限公司 | Production process of composite linen-like effect polyester filament yarn |
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Open date: 20090520 |