CN101736432B - Production method of anti-yellowing polyurethane elastic fiber - Google Patents
Production method of anti-yellowing polyurethane elastic fiber Download PDFInfo
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- CN101736432B CN101736432B CN200910259780A CN200910259780A CN101736432B CN 101736432 B CN101736432 B CN 101736432B CN 200910259780 A CN200910259780 A CN 200910259780A CN 200910259780 A CN200910259780 A CN 200910259780A CN 101736432 B CN101736432 B CN 101736432B
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Abstract
The invention discloses a production method of anti-yellowing polyurethane elastic fiber, comprising the following steps of: mixing and reacting by using polymerized polybasic alcohol and diisocyanate matters as raw materials to obtain a prepolymer end-capped by isocyanate; dissolving the prepolymer by using an amide compound, then mixing and reacting with an amine chain extender to obtain a polyurethane-urea solution; adding an additive in the generated polyurethane-urea solution to obtain a polyurethane fiber spinning solution which takes polyurethane and a polyurethane-urea compound as a repeating unit; and ageing the polyurethane fiber spinning solution and then spinning in a dry method to obtain polyurethane fiber. The production method has the advantages that: the polymer yellowing trend due to the existence of unsaturated double bonds and the influence of ultraviolet irradiation and oxidation is reduced; meanwhile, the compatibility between the additive and the polymer does not exist as the molecular structure of the polymer is modified.
Description
Technical field
The invention belongs to the chemical fibre technical field, be specifically related to a kind of production method of anti-yellowing polyurethane elastic fiber.
Background technology
Polyurethane elastomeric fiber is compiled or is interweaved, the weaving face fabric that enriches is provided for people through handing over other fiber.But, polyurethane elastomeric fiber when long-term storage or be exposed under the more intense environment of illumination, cause xanthochromia and problem such as aging easily.For preventing that the polyurethane elastomeric fiber xanthochromia from being purpose with wearing out; The means that the technical staff takes generally all are in polymerization stoste, to add Hinered phenols antioxidant; Reach BTA and ultra-violet absorbers such as benzophenone or septichen and mix, with the anti-xanthochromia that improves elastomer, ageing-resistant performance.Shortcomings such as but all there is additive in these class methods and the polymer phase capacitive is poor, separate out easily; In actual application, yellowing resistance is not so good; In addition, because additive is separated out from fiber, also possibly cause polyurethane elastomeric fiber mixing problems such as stopping up knitting needle when knitting with other fibers.
Summary of the invention
The objective of the invention is to make polyurethane elastomeric fiber to have the production method of good yellowing resistance.
The preparation method of the spandex fibre of anti-xanthochromia the of the present invention comprises the steps:
Using polymerized polyalcohol and 4,4 of IPDI that is equivalent to isocyanates total amount 0.5-10% and 90-99.5% '-methyl diphenylene diisocyanate is that the raw materials mix reaction obtains isocyanate-terminated prepolymer;
Prepolymer is obtained polyurethane urea solutions with amide compound dissolving back with the amine chain extender hybrid reaction;
In the polyurethane urea solutions that generates, add additive, obtaining with polyurethanes and polyurethanes carbamide compound is the spandex fiber stoste of repetitive;
With carrying out the dry-spinning method spinning after the ageing of spandex fiber stoste, obtain spandex fibre;
The preparation method of the elastic spandex fiber of anti-xanthochromia the of the present invention, wherein the mol ratio of diisocyanates material and polymerized polyalcohol is 1.55: 1-2.15: 1.
The preparation method of the elastic spandex fiber of anti-xanthochromia the of the present invention, wherein polymerized polyalcohol is that molecular weight is the 1800-2000 polymeric dihydric alcohol.
The preparation method of the elastic spandex fiber of anti-xanthochromia the of the present invention, wherein the solid content of polyurethane urea solutions is 25%-35%.
The preparation method of the elastic spandex fiber of anti-xanthochromia the of the present invention, wherein amide compound is selected from dimethyl formamide, dimethylacetylamide.
The preparation method of the elastic spandex fiber of anti-xanthochromia the of the present invention, the wherein mixture formed by the material of following molar ratio of amine chain extender: ethylenediamine 50-85; 2 methyl pentamethylenediamine or propane diamine 15-50; Wherein chain extender also comprises at least a single functionality chain terminating agent, and said terminator is selected from one of primary amine or secondary amine, diethylamine, two-n-butylamine, n-butylamine, n-hexylamine, cyclohexylamine, monoethanolamine of single functionality or its mixture etc., wherein preferred diethylamine or monoethanolamine.
The preparation method of the elastic spandex fiber of anti-xanthochromia the of the present invention, wherein digestion time is 30-60 hour.
The preparation method of the elastic spandex fiber of anti-xanthochromia the of the present invention, wherein use in the dry-spinning method hot nitrogen or air in circular or square path to the spinning solution oven dry, through drawing-off, oil, reel and process spandex fibre.
The preparation method of the elastic spandex fiber of anti-xanthochromia the of the present invention, wherein additive comprises TITANIUM DIOXIDE DELUSTRANT, magnesium stearate lubricant.
Beneficial effect of the present invention is in the prepolymerization reaction process; Add 4,4 of the IPDI be equivalent to isocyanates total amount 0.5-10% and 90-99.5% '-methyl diphenylene diisocyanate and carry out chain extending reaction generation polyether polyols with reduced unsaturation with amine chain extender again with the prepolymer that polyether Glycols fully reacts, generates.Because containing a certain amount of aliphatic hydrocarbon chemical constitution, reduced the unsaturated double-bond quantity that phenyl ring has in the middle of the polymer macromolecule chain reduces polymer because of having unsaturated double-bond, receiving the influence of ultraviolet ray irradiation and oxidation to cause the polymer flavescence to be inclined to.Simultaneously, because be modification that polymer molecular structure is carried out, do not have a problem of the compatibility of additive and polymer yet.
Specify anti-yellowing polyurethane elastic fiber of the present invention below in conjunction with specific embodiment.
The specific embodiment
Embodiment 1
Polyether Glycols 3500 grams and 4; 4 '-methyl diphenylene diisocyanate 865 restrains and IPDI 5 grams react 120min at 85 ℃; Obtain the prepolymer that two ends have NCO, add 6871 gram dimethylacetylamide dissolvings and form solution.Add the 71 gram ethylenediamines, 39 gram 2 methyl pentamethylenediamines, the 10 gram monoethanolamines that are dissolved in the 2070 gram dimethylacetamide solutions while stirring fast, carry out chain extending reaction, the polyurethane urea solutions that obtains.Add then and contain TiO
2: 8 grams; Dolomol: the dispersion liquid of 10 grams, dimethylacetylamide (DMAC) 200 grams; Obtain spinning solution after mixing, the spinning solution ageing used hot nitrogen or air in circular or square path, spinning solution to be dried after 30 hours; Through drawing-off, oil, reel, just can make the spandex silk.
Embodiment 2
Polyether Glycols 3500 grams and 4; 4 '-methyl diphenylene diisocyanate 775 restrains and IPDI 85 grams react 120min at 85 ℃; Obtain the prepolymer that two ends have NCO, add 6871 gram dimethylacetylamide dissolvings and form solution.Add the 71 gram ethylenediamines, 39 gram 2 methyl pentamethylenediamines, the 10 gram monoethanolamines that are dissolved in the 2070 gram dimethylacetamide solutions while stirring fast, carry out chain extending reaction, the polyurethane urea solutions that obtains.Add then and contain TiO
2: 8 grams; Dolomol: 10 grams, the dispersion liquid of dimethylacetylamide (DMAC) 200g obtains spinning solution after mixing; After the spinning solution ageing 30 hours; Use hot nitrogen or air in circular or square path to the spinning solution oven dry, through drawing-off, oil, reel, just can make the spandex silk.
Embodiment 3
Polyether Glycols 3500 grams and 4; 4 '-methyl diphenylene diisocyanate 835 restrains and IPDI 35 grams react 120min at 85 ℃; Obtain the prepolymer that two ends have NCO, add 6853 gram dimethylacetylamide dissolvings and form solution.Add the 72 gram ethylenediamines, 40 gram 2 methyl pentamethylenediamines, the 11 gram monoethanolamines that are dissolved in the 2090 gram dimethylacetamide solutions while stirring fast, carry out chain extending reaction, the polyurethane urea solutions that obtains.Add then and contain TiO
2: 8 grams; Dolomol: 10 grams, the dispersion liquid of dimethylacetylamide (DMAC) 200 gram g obtains spinning solution after mixing; After the spinning solution ageing 30 hours; Use hot nitrogen or air in circular or square path to the spinning solution oven dry, through drawing-off, oil, reel, just can make the spandex silk.
Embodiment 4
Polyether Glycols 3500 grams and 4; 4 '-methyl diphenylene diisocyanate 795 restrains and IPDI 70 grams react 120min at 85 ℃; Obtain the prepolymer that two ends have NCO, add 6846 gram dimethylacetylamide dissolvings and form solution.Add fast while stirring 72 the gram ethylenediamines, 40 the gram 2 methyl pentamethylenediamines, 11 the gram monoethanolamines be dissolved in 2086 the gram dimethylacetylamides in formed solution, carry out chain extending reaction, the polyurethane urea solutions that obtains.Add then and contain TiO
2: 8 grams, dolomol: 10 grams, the dispersion liquid of DMAC:200g; Obtain spinning solution after mixing, the spinning solution ageing used hot nitrogen or air in circular or square path, spinning solution to be dried after 30 hours; Through drawing-off, oil, reel, just can make the spandex silk.
Test Example spandex xanthochromia detects contrast test
Instrument: Ultra Scan Pro Usp1136 computerized color matching instrument (Huntlab)
LFY-302 light fastness tester (instrument research institute of institute of section is spun by the Shandong Province)
Experimental technique:
1. the spandex silk of getting among each embodiment deoils in right amount;
2. the spandex silk 5g that takes by weighing after deoiling puts in the light fastness tester;
3. 25 ℃ of temperature are set, and humidity 60% was with xenon lamp Continuous irradiation 76 hours;
4. with the whiteness of computerized color matching appearance test experiments silk, the result sees table:
Spandex xanthochromia experimental data table
| Sample | IPDI content (%) | Pre-irradiation whiteness value WICIE D65/10 | Irradiation back whiteness value WICIE D65/10 | Whiteness difference WICIE D65/10 behind the pre-irradiation |
| Embodiment 1 | 0.5 | 40.81 | 28.61 | 12.20 |
| Embodiment 2 | 10.0 | 42.56 | 35.06 | 7.50 |
| Embodiment 3 | 4.0 | 40.52 | 32.52 | 8.00 |
| Embodiment 4 | 8.0 | 41.81 | 34.01 | 7.80 |
Add a certain amount of IPDI, can effectively improve the anti-yellowing property of polyurethane elastomeric fiber from the anti-xanthochromia data, the prepolymerization reaction that detect; But; Addition surpasses after 4%, and the whiteness difference before and after the xenon lamp photo-irradiation treatment does not significantly change.
The above embodiment only is that preferred implementation of the present invention is described; Be not that scope of the present invention is limited; Design under the prerequisite of spirit not breaking away from the present invention; Various distortion and improvement that the ability those of ordinary skill is made technical scheme of the present invention all should fall in the definite protection domain of claims of the present invention.
Claims (6)
1. the preparation method of the elastic spandex fiber of anti-the xanthochromia comprises the steps:
Use polymerized polyalcohol and diisocyanates material to obtain isocyanate-terminated prepolymer as the raw materials mix reaction;
Prepolymer is obtained polyurethane urea solutions with amide compound dissolving back with the amine chain extender hybrid reaction;
In the polyurethane urea solutions that generates, add additive, obtaining with polyurethanes and polyurethanes carbamide compound is the spandex fiber stoste of repetitive;
With carrying out the dry-spinning method spinning after the ageing of spandex fiber stoste, obtain spandex fibre;
It is characterized in that the mixture that said diisocyanates material is made up of following substances in parts by weight: 4,4-methyl diphenylene diisocyanate 90-99.5; IPDI 10-0.5; The mol ratio of said diisocyanates material and polymerized polyalcohol is 1.55: 1-2.15: 1; Said polymerized polyalcohol is that molecular weight is the 1800-2000 polymeric dihydric alcohol; The mixture that said amine chain extender is made up of the material of following molar ratio: ethylenediamine 50-85; 2 methyl pentamethylenediamine or propane diamine 15-50; Said chain extender also comprises at least a single functionality chain terminating agent, and said terminator is selected from one of primary amine or secondary amine, dimethylamine, diethylamine, two-n-butylamine, n-butylamine, n-hexylamine, cyclohexylamine, monoethanolamine of single functionality or its mixture.
2. the preparation method of the elastic spandex fiber of anti-xanthochromia the according to claim 1 is characterized in that the solid content of said polyurethane urea solutions is 25%-35%.
3. like the preparation method of the said elastic spandex fiber of anti-xanthochromia of claim 2, it is characterized in that said amide compound is selected from dimethyl formamide, dimethylacetylamide.
4. like the preparation method of the said elastic spandex fiber of anti-xanthochromia of claim 3, it is characterized in that said digestion time is 30-60 hour.
5. like the preparation method of the said elastic spandex fiber of anti-xanthochromia of claim 4, it is characterized in that, use in the said dry-spinning method hot nitrogen or air in circular or square path to the spinning solution oven dry, through drawing-off, oil, reel and process spandex fibre.
6. like the preparation method of the said elastic spandex fiber of anti-xanthochromia of claim 5, it is characterized in that said additive comprises TITANIUM DIOXIDE DELUSTRANT, magnesium stearate lubricant.
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102534857A (en) * | 2010-12-16 | 2012-07-04 | 烟台泰和新材料股份有限公司 | Polyurethane elastic fiber preparation method for improving unwinding performance |
| KR101219986B1 (en) * | 2010-12-29 | 2013-01-08 | 주식회사 효성 | Polyurethaneurea Elastic Fiber having high Adhesive Power among Multi-Filament Yarn and Preparing method |
| CN105113045B (en) * | 2015-09-28 | 2017-05-10 | 倪士勇 | Fiber, method for manufacturing same and fabric with fiber |
| 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 |
| CN108342833A (en) * | 2017-12-31 | 2018-07-31 | 广州海鑫无纺布实业有限公司 | A kind of preparation method of the high-hydroscopicity silk fiber non-woven fabrics of color inhibition |
| CN109487361B (en) * | 2018-11-23 | 2021-07-23 | 万华化学集团股份有限公司 | Spandex fiber with good heat resistance and low-temperature setting property and preparation method thereof |
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| CN101096778A (en) * | 2007-07-06 | 2008-01-02 | 烟台氨纶股份有限公司 | Process for producing polyether type comfortable spandex fibre |
| CN101096782A (en) * | 2007-07-06 | 2008-01-02 | 烟台氨纶股份有限公司 | method for preparing polyurethane snapback fibre with solution polymerization |
| CN101096779A (en) * | 2007-07-06 | 2008-01-02 | 烟台氨纶股份有限公司 | Process for producing polyether type easy dyeing spandex fiber |
| CN101096780A (en) * | 2007-07-06 | 2008-01-02 | 烟台氨纶股份有限公司 | Process for producing colorful spandex fiber |
| CN101260272A (en) * | 2007-03-08 | 2008-09-10 | 关西涂料株式会社 | Water-based single-component paint and multilayer film forming method |
| CN101469463A (en) * | 2008-07-15 | 2009-07-01 | 烟台氨纶股份有限公司 | Preparation of polyether type high resilience spandex fibre and product produced thereby |
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| CN101260272A (en) * | 2007-03-08 | 2008-09-10 | 关西涂料株式会社 | Water-based single-component paint and multilayer film forming method |
| CN101096778A (en) * | 2007-07-06 | 2008-01-02 | 烟台氨纶股份有限公司 | Process for producing polyether type comfortable spandex fibre |
| CN101096782A (en) * | 2007-07-06 | 2008-01-02 | 烟台氨纶股份有限公司 | method for preparing polyurethane snapback fibre with solution polymerization |
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Address after: 264006 No. 10, Heilongjiang Road, Yantai economic and Technological Development Zone, Yantai, Shandong Patentee after: Taihe New Material Group Co.,Ltd. Address before: 264006 No. 10, Heilongjiang Road, Yantai economic and Technological Development Zone, Yantai, Shandong Patentee before: YANTAI TAYHO ADVANCED MATERIALS Co.,Ltd. |