CN103255500B - Preparation method of polyurethane elastic fiber suitable for low-temperature setting - Google Patents
Preparation method of polyurethane elastic fiber suitable for low-temperature setting Download PDFInfo
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- CN103255500B CN103255500B CN201310211952.3A CN201310211952A CN103255500B CN 103255500 B CN103255500 B CN 103255500B CN 201310211952 A CN201310211952 A CN 201310211952A CN 103255500 B CN103255500 B CN 103255500B
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Abstract
The invention relates to a preparation method of polyurethane elastic fiber suitable for low-temperature setting. The preparation method uses one or more of N-methylethylenediamine, N-ethylethylenediamine, and N-isopropyl-1,3-propanediamine, the content of which is 20-80 mole% of a chain extender, wherein the chain expander further comprises one or more of ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, hexamethylenediamine or 2-methylpentanediamine. The polyurethane elastic fiber prepared by the preparation method provided by the invention has excellent heat setting efficiency below the setting temperature of 170 DEG C; and compared with the prior art, when the polyurethane elastic fiber prepared by the preparation method provided by the invention is woven with heat sensitive fiber, the obtained product can be heat-set at a temperature lower than 170 DEG C, and has excellent heat-setting efficiency, so that the field of spandex application is broadened.
Description
Technical field
The present invention relates to a kind of preparation method of polyurethane elastomeric fiber of applicable low temperature setting, a kind of preparation method setting temperature less than 170 DEG C with the polyurethane elastomeric fiber of higher heat-set efficiency is particularly provided, belongs to the technical field that a kind of macromolecular material manufactures.
Background technology
Polyurethane elastomeric fiber has that resilience is high, fracture strength is large, elongation at break high, and is widely used in multiple fields.Along with the continuous expansion of its purposes, the requirement of client to elastomer is also more and more higher.
Under normal circumstances, polyurethane elastomeric fiber at high temperature (about 190 DEG C) can carry out heat setting in last handling process, and high temperature can cause heat sensitive fibers generation thermal degradation, as nylon, wool, polypropylene, artificial silk, cotton yarn etc.When wool, cotton yarn, nylon blended cloths need to carry out heat setting at a lower temperature, and fabric can not reach suitably and heat setting effectively.In order to the generation and fabric that prevent high temperature degradation effectively do not formalize and make the comfort level of fabric be deteriorated, how a lot of research institution all carries out heat setting to polyurethane elastomeric fiber at a lower temperature in research at present.
At present existing more relevant report, United States Patent (USP) 5539037 is disclosed in low concentration alkali metal carboxylate and rhodanate to increase its heat-set efficiency, but this salt easily decomposes and reduces its effect in following process.United States Patent (USP) 6403682B1 openly uses a kind of additive comprising quaternary amine to improve heat setting, but the setting temperature of the method is higher, cannot meet the setting temperature of the elastomer containing wool.United States Patent (USP) 5000899 and 5948875 openly uses 2-methyl isophthalic acid, and 5-pentanediamine increases the heat-set efficiency of polyurethane elastomeric fiber as chain extender.Patent CN1273510C announces and uses ortho position to replace vulcabond and the chain extender compared with macromolecular diamine, improves heat-set efficiency.Patent 00816584.X openly uses in copolymerization alkylene ether containing adding part tetramethylene ether or 1,2-propylidene ether improves heat-set efficiency.Japan Patent JP08-020625, JP08-176268 and United States Patent (USP) 3631138,5879799 all disclose and use 2,4 '-MDI of different amount, improve heat-set efficiency.
But the good temperature of the set efficiency of these patents is all at about 170 DEG C or more, the requirement of the heat sensitive fibers of some needs lower temperatures setting cannot be met, and openly do not use chain extender N-methyl ethylenediamine, NEED, N-isopropyl-1,3-propane diamine.
Summary of the invention
Technical problem: the preparation method that the object of this invention is to provide a kind of polyurethane elastomeric fiber of applicable low temperature setting.
Technical scheme: the preparation method of the polyurethane elastomeric fiber of a kind of applicable low temperature setting of the present invention comprises the following steps:
A). polytetramethylene ether diol PTMG and 4,4-diphenyl methane MDI reacts in solvent DMA DMAC, preparation prepolymer solution;
B). after prepolymer solution is cooled to 8 ~ 15 DEG C, the DMAC solution adding chain extender and reaction controlling agent in prepolymer solution carries out chain extending reaction, obtains the polymer solution of high molecular;
C). in the heavy polymer solution obtained, add anti-flavescence agent, antioxidant, ultra-violet absorber, lubrication discongest agent, fully mix, prepare polyurethane spinning solution;
D). prepared polyurethane spinning solution is obtained polyurethane elastomeric fiber by dry spinning.
The mol ratio of described MDI and PTMG is 1.8:1 ~ 2.2:1.
Described chain extender comprises two parts, Part I comprise N-methyl ethylenediamine, NEED, N-isopropyl-1,3-propane diamine one or more, this content is 20% ~ 80% of chain extender total mole number; The Part II of described chain extender comprise in ethylenediamine, 1,2-propane diamine, 1,3-propane diamine, hexamethylene diamine or 2 methyl pentamethylenediamine one or more.
Described reaction controlling agent comprises one or both mixture of diethylamine and monoethanolamine, and its addition is the 0.2wt% ~ 0.8wt% of polytetramethylene ether diol PTMG.
Beneficial effect: compared with prior art, polyurethane elastomeric fiber prepared by the present invention and heat sensitive fibers interweave, and can carry out heat setting at the temperature lower than 170 DEG C, and have excellent heat-set efficiency, widen spandex Application Areas.
Detailed description of the invention
The present invention adopts at least containing N-methyl ethylenediamine, NEED, the N-isopropyl-1 of 20 % by mole ~ 80 % by mole, one or more chain extender of 3-propane diamine is prepared and is adapted at setting temperature less than 170 DEG C, and has the polyurethane elastomeric fiber of higher set efficiency.
Method provided by the invention is as follows:
1 polytetramethylene ether diol (PTMG) reacts in solvent DMF (DMAC) with 4,4-diphenyl methanes (MDI), preparation prepolymer solution;
Described reaction temperature 38 ~ 50 DEG C;
Described reaction time 60 ~ 180min;
The mol ratio of described MDI and PTMG is 1.8:1 ~ 2.2:1.
2 after prepolymer solution is cooled to 8 ~ 15 DEG C, and the DMAC solution adding chain extender and reaction controlling agent carries out chain extending reaction, obtains the polymer solution of high molecular;
Described chain extender comprise N-methyl ethylenediamine, NEED, N-isopropyl-1,3-propane diamine one or more, its content is 20 % by mole ~ 80 % by mole of chain extender.
Described chain extender also comprise in ethylenediamine, 1,2-propane diamine, 1,3-propane diamine, hexamethylene diamine or 2 methyl pentamethylenediamine one or more;
One or both of described amine reaction controlling agent diethylamine and monoethanolamine, its addition is the 0.2wt% ~ 0.8wt% of PTMG.
The DMAC solution of described chain extender and the agent of amine reaction controlling, its concentration is 3 ~ 9wt%.
3 in the heavy polymer solution obtained, add anti-flavescence agent, antioxidant, ultra-violet absorber, lubrication discongest agent, fully mix, prepare polyurethane spinning solution;
Described anti-flavescence agent is two (N, N-dimethyl-hydrazine is amino, 4-phenyl) methane, and manufacturer: Taiwan double bond, its consumption is the 0.2wt% ~ 1.5wt% of amount of polymers.
Described antioxidant is cyamelide, manufacturer: Taiwan cyanogen is special, and its consumption is the 0.5wt% ~ 1.5wt% of amount of polymers.
Described ultraviolet-resistant absorbent is 2-(2 '-hydroxyl-3 ', 5 '-two tertiary pentyl)-benzotriazole, manufacturer: Taiwan double bond, its consumption is the 0.1wt% ~ 1.0wt% of amount of polymers.
It is dolomol that described lubrication discongests agent, manufacturer: Japanese grease, and its consumption is the 0.1wt% ~ 1.0wt% of amount of polymers.
Described polyurethane dope viscosity is 3000-10000piose.
Described polyurethane spinning solution concentration is 28 ~ 40%
Prepared polyurethane spinning solution is obtained polyurethane elastomeric fiber by dry spinning by 4.
Described dry-spinning spinning shaft temperature is 245 ~ 260 DEG C;
Described dry-spinning spinning speed is 500 ~ 1000m/min, preferably 600 ~ 800m/min.
Describe its production process of the present invention in detail by embodiment below, but these embodiments must not be interpreted as the limitation of the present invention gone up in all senses.
Embodiment 1:
In the reactor that agitator is housed, add PTMG and the 5.5kgDMAC mixing that 9.0kg number-average molecular weight is 1810, add the MDI of 2.486kg, after reactive polymeric 135min, then add 12.8kgDMAC and reconcile prepolymer concentration.
Then add containing 84.8g(0.962mol) NEED, 231g(3.850mol) ethylenediamine and the DMAC solution of diethylamine of 23.4g carry out chain extending reaction, finally add 0.7 % by weight anti-flavescence agent, 1.0 % by weight antioxidants, 0.35 % by weight ultra-violet absorber, 0.3 % by weight lubrication discongest agent and obtain spinning solution, its original liquid concentration is 35%, after slaking, deaeration, filtration, form spandex thread by dry spinning.Dry spinning is spun into the polyurethane elastomeric fiber of 20D (Denier).Then its heat-set efficiency is detected.
Heat-set efficiency detection mode: by polyurethane elastomeric fiber drawing-off 100%(from 150mm to 300mm) after, at 150 DEG C, dry heat-setting 1 minute, is then cooled to room temperature by fiber, measures its fibre length, and according to its heat-set efficiency of following formulae discovery:
Heat-set efficiency (%)={ (length-initial length after heat setting)/(length-initial length after drawing-off) } * 100%
Embodiment 2
Same method according to embodiment 1 prepares polyurethane elastomeric fiber, and difference is to add 212.1g(2.406mol) NEED, 144.4g(2.406mol) ethylenediamine and the DMAC solution of diethylamine of 23.4g carry out chain extending reaction.
Embodiment 3
Same method according to embodiment 1 prepares polyurethane elastomeric fiber, and difference is to add 339.4g(3.850mol) NEED, 57.7g(0.962mol) ethylenediamine and the DMAC solution of diethylamine of 23.4g carry out chain extending reaction.
Embodiment 4
Same method according to embodiment 1 prepares polyurethane elastomeric fiber, and difference is to add 212.1g(2.406mol) NEED, 72.2g(1.203mol) ethylenediamine, 89g(1.203mol) 1, the DMAC solution of the diethylamine of 2-propane diamine and 23.4g carries out chain extending reaction.
Embodiment 5 to 8 and comparative example 1 to 3
Same method according to embodiment 1 prepares polyurethane elastomeric fiber, and difference is that the molar percentage (mol%) of MDI/PTMG mol ratio as shown in table 1 and chain extender and kind there occurs change.
Table 1:
Shown in upper table 1: the heat-set efficiency being polyurethane elastomeric fiber prepared by chain extender with the N-methyl ethylenediamine of 20 % by mole ~ 80 % by mole, NEED, N-isopropyl-1,3-propane diamine has and significantly improves.
Claims (1)
1. a preparation method for the polyurethane elastomeric fiber of applicable low temperature setting, is characterized in that the method comprises the following steps:
A). polytetramethylene ether diol PTMG and 4,4-diphenyl methane MDI reacts in solvent DMA DMAC, preparation prepolymer solution;
B). after prepolymer solution is cooled to 8 ~ 15 DEG C, the DMAC solution adding chain extender and reaction controlling agent in prepolymer solution carries out chain extending reaction, obtains the polymer solution of high molecular;
C). in the heavy polymer solution obtained, add anti-flavescence agent, antioxidant, ultra-violet absorber, lubrication discongest agent, fully mix, prepare polyurethane spinning solution;
D). prepared polyurethane spinning solution is obtained polyurethane elastomeric fiber by dry spinning;
The mol ratio of described MDI and PTMG is 1.8:1 ~ 2.2:1;
Described chain extender comprises two parts, Part I comprise N-methyl ethylenediamine, NEED, N-isopropyl-1,3-propane diamine one or more, this content is 20% ~ 80% of chain extender total mole number; The Part II of described chain extender comprise in ethylenediamine, 1,2-propane diamine, 1,3-propane diamine, hexamethylene diamine or 2 methyl pentamethylenediamine one or more;
Described reaction controlling agent comprises one or both mixture of diethylamine and monoethanolamine, and its addition is the 0.2wt% ~ 0.8wt% of polytetramethylene ether diol PTMG.
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103590138B (en) * | 2013-11-06 | 2015-09-30 | 浙江华峰氨纶股份有限公司 | A kind of preparation method of flame-retardant polyurethane elastic fiber |
| CN103668544B (en) * | 2013-12-11 | 2016-01-13 | 浙江华峰氨纶股份有限公司 | A kind of polyurethane elastomeric fiber with multielement functionality and preparation method thereof |
| CN103710786B (en) * | 2013-12-18 | 2015-08-12 | 浙江华峰氨纶股份有限公司 | A kind of preparation method of the polyurethane stock solution for high speed spinning |
| CN104726960A (en) * | 2013-12-20 | 2015-06-24 | 浙江华峰氨纶股份有限公司 | Polyurethane elastic fiber with improved heat-setting performance, and preparation method thereof |
| CN104278354A (en) * | 2014-10-28 | 2015-01-14 | 浙江华峰氨纶股份有限公司 | Preparation method of flesh-colored spandex |
| CN104651974B (en) * | 2015-03-13 | 2017-01-04 | 浙江华峰氨纶股份有限公司 | A kind of super fine denier spandex fibre and preparation method thereof |
| CN105603583B (en) * | 2015-12-30 | 2017-10-24 | 浙江华峰氨纶股份有限公司 | A kind of spandex with endurance and fusible characteristic and preparation method thereof |
| CN105506777A (en) * | 2016-01-26 | 2016-04-20 | 浙江华峰氨纶股份有限公司 | Polyurethane elastic fiber easy to adhere and preparation method thereof |
| CN109610039B (en) * | 2018-12-04 | 2021-05-25 | 华峰化学股份有限公司 | Preparation method of polyurethane urea elastic fiber with high heat setting efficiency |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4973647A (en) * | 1989-05-31 | 1990-11-27 | E. I. Du Pont De Nemours And Company | Fiber from polyether-based spandex |
| CN1176967A (en) * | 1996-07-24 | 1998-03-25 | 晓星T＆C株式会社 | Process of mfg. improved polyurethane fiber polymer |
| CN101495683A (en) * | 2006-07-31 | 2009-07-29 | 株式会社晓星 | A polyurethane elastic fiber with high heat settable property |
| CN101849048A (en) * | 2007-11-06 | 2010-09-29 | 株式会社晓星 | Method for preparing polyurethaneurea elastic fiber with improved heat settability and polyurethaneurea elastic fiber prepared by the same |
| CN102899740A (en) * | 2012-11-09 | 2013-01-30 | 浙江华峰氨纶股份有限公司 | Method for preparing low-temperature finalizing polyurethane elastic fiber |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4973647A (en) * | 1989-05-31 | 1990-11-27 | E. I. Du Pont De Nemours And Company | Fiber from polyether-based spandex |
| CN1176967A (en) * | 1996-07-24 | 1998-03-25 | 晓星T＆C株式会社 | Process of mfg. improved polyurethane fiber polymer |
| CN101495683A (en) * | 2006-07-31 | 2009-07-29 | 株式会社晓星 | A polyurethane elastic fiber with high heat settable property |
| CN101849048A (en) * | 2007-11-06 | 2010-09-29 | 株式会社晓星 | Method for preparing polyurethaneurea elastic fiber with improved heat settability and polyurethaneurea elastic fiber prepared by the same |
| CN102899740A (en) * | 2012-11-09 | 2013-01-30 | 浙江华峰氨纶股份有限公司 | Method for preparing low-temperature finalizing polyurethane elastic fiber |
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Address after: No. 1788, Dongshan Economic Development Zone, Ruian, Wenzhou, Zhejiang Patentee after: Huafeng Chemical Co.,Ltd. Address before: No. 1788, Dongshan Economic Development Zone, Ruian, Wenzhou, Zhejiang Patentee before: ZHEJIANG HUAFENG SPANDEX Co.,Ltd. |
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