CN102899739A - Method for preparing black polyurethane elastic fiber via in situ polymerization - Google Patents
Method for preparing black polyurethane elastic fiber via in situ polymerization Download PDFInfo
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Abstract
The invention relates to a method for preparing a black polyurethane elastic fiber via in situ polymerization, comprising the following steps: (1) evenly dispersing nanometer carbon black particles in low-polymer polyhydric alcohol by using a grinding or ultrasonic and powerful mechanical stirring method so as to form a stable mixture, (2) adding diisocyanate in the polyhydric alcohol containing the carbon black particles for full reaction and adding a solvent for full dissolution to obtain NCO end capped prepolymer polyurethane formic ether solution; (3) carrying out chain extension and chain termination on the prepolymer solution by using mixed amine solution to generate polyurethane urea solution, and (4) curing the polyurethane urea solution and spinning the polyurethane urea solution into the black polyurethane elastic fiber by means of a dry spinning system. The polyurethane elastic fiber prepared via an in situ polymerization method is lasting in black effect and high in color fastness, so that the subsequent processing is free of dyeing; and at the same time, the polyurethane elastic fiber has relatively good mechanical property.
Description
Technical field
The invention belongs to the macromolecular material production field, particularly a kind of in-situ polymerization prepares the method for black polyurethane elastomer.The black polyurethane elastomer of manufacturing of the present invention has more lasting black effect, and COLOR FASTNESS is high, and following process does not need to dye again, has simultaneously preferably mechanical property.
Background technology
Polyurethane elastomeric fiber is called spandex in China, it is by 85%(percentage by weight at least) the large molecule that forms of polyurethane segment, have the advantages such as high fracture strength, high extension at break and elastic recovery rate are good, and the range of application of polyurethane elastomeric fiber is also becoming wide gradually.Yet because the molecular structure of polyurethane elastomeric fiber own, under common dyeing condition, the dyeing of polyurethane elastomeric fiber silk is difficult, and the not good polyurethane elastomeric fiber of dyeing is easy to expose white point in fabric, affects the overall quality of fabric; And if dyeing condition is too fierce, then the physical property of polyurethane elastomeric fiber can be subject to heavy damage, even fracture, and then affects the serviceability of fabric.
Carbon black is a kind of important industrial chemicals, mainly formed by carbon, both can be as reinforcing agent and the filler of elastomeric material, can be used for again coating, printing ink etc., wherein carbon black is as colouring agent, a kind of best black pigment, and cheap being easy to get, be the desirable feedstock of producing the black polyurethane elastomer.
Chinese patent CN201010525066.4 and US Patent No. 7364792B2 are open to prepare the black polyurethane elastomer with carbon black, the two all is that dimethylacetamide solution with carbon black adds in the polyurethane spinning solution, then prepares the black polyurethane elastomer by dry spinning.But because the intermolecular powerful van der Waals interaction of nano carbon black, the nano carbon black that adds is easily reunited in spinning solution, cause later stage stoste spinnability to descend, carbon black particle only is to have an effect by physical action and fiber simultaneously, and then fibrous mechanical property is also caused certain negative effect.Even utilize some dispersants to improve the dispersiveness of carbon black, but improvement effect and not obvious.
Summary of the invention
Technical problem: the object of the invention is to solve above-mentioned the deficiencies in the prior art, provide a kind of in-situ polymerization to prepare the method for black polyurethane elastomer, the nano carbon black dispersion liquid is dispersed in the oligomer polyol, utilize the activity hydroxy on carbon black particle surface in the prepolymer preparation process, to react with isocyanate group, so that carbon black particle and polyurethane macromolecular interchain form stable chemical bond, play simultaneously the effect of crosslinking points, and then make polyurethane elastomeric fiber have more lasting black effect, higher COLOR FASTNESS, mechanical property also improves simultaneously.
Technical scheme: the method that in-situ polymerization of the present invention prepares the black polyurethane elastomer comprises following several step:
1) nano carbon black is lower dry 2～4 hours at 90-120 ℃, then add organic solvent 20～50 ℃ of lower grindings 3～7 hours, the ultrasonic processing 1～4 hour in ultrasonic oscillator of mixture after the grinding makes nano carbon black Uniform Dispersion in solvent, forms stable nano carbon black dispersion liquid;
2) the nano carbon black dispersion liquid is joined in the oligomer polyol by powerful mechanical dispersed with stirring and mix, then add the vulcabond preparation with the carbamate prepolymer of-NCO end-blocking, and add solvent and fully dissolve, obtain pre-polymer solution;
3) after the pre-polymer solution cooling with preparation, add mixed amine solution and carry out chain extending reaction and chain termination reaction, obtain polyurethane urea solutions;
4) add antioxidant, ultra-violet absorber, anti-yellowing agent, delustering agent and lubricatedly alleviate agent in the above-mentioned polyurethane urea solutions, after fully mixing, prepare the black polyurethane spinning solution that contains nanometer carbon black;
5) with the black polyurethane spinning solution for preparing, by the dry spinning system, the black polyurethane spinning solution is shootd out, is drawn into silk, and along with solvent evaporates, drying, namely obtain the black polyurethane elastomer.
Described nano carbon black particle diameter is 20nm～500nm, and the mass fraction of carbon black is 10%～40% in the nano carbon black dispersion liquid.
The mass percent of described nano carbon black in the black polyurethane elastomer is 0.3%～5.0%.
Described oligomer polyol be the PTMG of number-average molecular weight 1500～3000 or number-average molecular weight 1500～3000 polypropylene glycol also or both mixtures.
Described vulcabond is 4,4-MDI or 2,4-MDI, or both mixtures; The solvent that adds is DMF DMF or DMA DMAC.
Described mixed amine solution is chain extender and chain terminating agent mixed solution, and chain extender is selected from ethylenediamine, propane diamine, hexamethylene diamine or 2 methyl pentamethylenediamine, or its mixture; Chain terminating agent is diethylamine, di-n-propylamine, monoethanolamine or n-hexylamine, or its mixture.
Described organic solvent is N, N-METHYLFORMAMIDE DMF or N, N-methylacetamide DMAC.
Beneficial effect: the present invention adopts the black polyurethane elastomer of situ aggregation method preparation, in the prepolymer preparation process, add nanometer carbon black cheap and easy to get, utilize carbon black particle itself with-OH and vulcabond with-the NCO radical reaction, thereby make carbon black particle participate in the synthetic reaction of prepolymer.By situ aggregation method, form stable chemical bond between carbon black particle and polyurethane molecular, carbon black particle plays the effect of chemical crosslinking point simultaneously.
Adopt the present invention to prepare the black polyurethane elastomer, stoste good spinning property, fiber have more lasting black effect, and COLOR FASTNESS is high, do not need in the following process process polyurethane elastomeric fiber is dyeed again, bring great convenience for the processing in polyurethane elastomeric fiber later stage.Simultaneously, the chemical crosslinking point that carbon black particle forms in the polyurethane macromolecular chain makes carbon black particle play the effect of reinforcement, and the black polyurethane elastomer of preparation has more excellent mechanical property.
The specific embodiment
The below describes the present invention in detail with example, but these examples must not be interpreted as and go up in all senses limitation of the present invention.
(1) nano carbon black is lower dry 2～4 hours at 90-120 ℃, then add organic solvent 20～50 ℃ of lower grindings 3～7 hours, the ultrasonic processing 1～4 hour in ultrasonic oscillator of mixture after the grinding makes nano carbon black Uniform Dispersion in solvent, forms stable carbon black dispersion liquid;
(2) the nano carbon black dispersion liquid is joined in the oligomer polyol by powerful mechanical dispersed with stirring and mix, then add the vulcabond preparation with the carbamate prepolymer of-NCO end-blocking, and add solvent and fully dissolve, obtain pre-polymer solution;
(3) after the pre-polymer solution cooling with preparation, add mixed amine solution and carry out chain extending reaction and chain termination reaction, obtain polyurethane urea solutions;
(4) alleviate agent etc. to preparing to add antioxidant, ultra-violet absorber, anti-yellowing agent, delustering agent in the polyurethane urea solutions and lubricate, after fully mixing, preparation contains the black polyurethane spinning solution of nanometer carbon black;
(5) with the black polyurethane spinning solution for preparing, by the dry spinning system, the black polyurethane spinning solution is shootd out, is drawn into silk, and along with solvent evaporates, drying, namely obtain the black polyurethane elastomer.
Described nano carbon black particle diameter is 20nm～500nm, and the carbon black mass mark is 10%～40% in the dispersion liquid;
The mass fraction of described nano carbon black in polyurethane elastomeric fiber is 0.3%～5%;
Described oligomer polyol be the PTMG of number-average molecular weight 1500～3000 or number-average molecular weight 1500～3000 polypropylene glycol also or both mixtures;
Described vulcabond be 4,4-methyl diphenylene diisocyanate or 2,4-methyl diphenylene diisocyanate also or both mixtures;
40～50 ℃ of reaction temperatures, reaction time 90～180min;
Described oligomer polyol is 1:1.4～1:1.85 with the amount ratio of vulcabond;
Described mixed amine solution is mixing DMAC solution or the DMF solution of chain extender diamines and chain terminating agent monoamine, and concentration is 3%～9%;
Described chain extender diamines is ethylenediamine, propane diamine, hexamethylene diamine, 2 methyl pentamethylenediamine or its mixture, and chain terminating agent is diethylamine, di-n-propylamine, monoethanolamine, n-hexylamine or its mixture;
Described antioxidant consumption is 0.5%～1.5% of fibre weight, and the anti-yellowing agent consumption is 0.2%～1.5% of fibre weight, and the ultra-violet absorber consumption is 0.1%～1.0% of fibre weight, and lubricated to alleviate the agent consumption be 0.1%～1.0% of fibre weight.
Embodiment 1:
With nano carbon black 110 ℃ lower dry 2 hours, get in the DMA (DMAC) that 120g joins 680g, grinder ground 5 hours; Then the ultrasonic dispersion 2 hours in ultrasonic oscillator of the carbon black solution after will grinding obtains stable nano carbon black dispersion liquid, and its concentration is 15%.
The nano carbon black dispersion liquid of 420g is joined in the solution of DMA of 10Kg PTMG and 5.385Kg high-speed stirred 3 hours; Add 4 of 2.3Kg, 4 '-methyl diphenylene diisocyanate was 45 ℃ of lower polymerisations 2 hours again.The DMA that adds 14.68Kg is prepared pre-polymer solution.
Prepolymer solution is cooled to below 15 ℃, and the DMA solution (concentration of amine is 3%) that progressively adds the diethylamine of the propane diamine of the ethylenediamine contain 0.216Kg, 0.014Kg and 0.038Kg carries out chain extending reaction and chain termination reaction; Then add antioxidant, anti-yellowing agent, ultra-violet absorber and the easypro agent of lubricated solution and obtain the polyurethane spinning solution;
The polyurethane spinning solution obtains polyurethane elastomeric fiber through dry spinning after slaking, filtration and deaeration.
Embodiment 2:
Nano carbon black was descended dry 2 hours at 110 ℃, get 100g to join in the 400g DMA (DMAC), grinder ground 4 hours; Then the ultrasonic dispersion 3 hours in ultrasonic oscillator of the carbon black solution after will grinding obtains stable nano carbon black dispersion liquid, and its concentration is 20%.
The nano carbon black dispersion liquid of 485g is joined in the DMA solution of 7.5Kg PTMG and 4.038Kg high-speed stirred 3 hours; Add 4 of 1.782Kg, 4 '-methyl diphenylene diisocyanate was 45 ℃ of lower polymerisations 2 hours again.The DMA that adds 15.144Kg is prepared pre-polymer solution.
Prepolymer solution is cooled to below 15 ℃, and the DMA solution (concentration of amine is 4%) that progressively adds the diethylamine of the propane diamine of the ethylenediamine contain 0.324Kg, 0.021Kg and 0.057Kg carries out chain extending reaction and chain termination reaction; Then add antioxidant, anti-yellowing agent, ultra-violet absorber and the easypro agent of lubricated solution and obtain the polyurethane spinning solution.
The polyurethane spinning solution obtains polyurethane elastomeric fiber through dry spinning after slaking, filtration and deaeration.
Embodiment 3:
Nano carbon black was descended dry 2 hours at 110 ℃, get 630g to join in the 1170g DMA (DMAC), grinder ground 7 hours; Then the ultrasonic dispersion 4 hours in ultrasonic oscillator of the carbon black solution after will grinding obtains stable nano carbon black dispersion liquid, and its concentration is 35%.
The nano carbon black dispersion liquid of 1363g is joined in the DMA solution of 13Kg PTMG and 6.8Kg high-speed stirred 3 hours; Add 4 of 2.9Kg, the 4-methyl diphenylene diisocyanate was 45 ℃ of lower polymerisations 2 hours again.The DMA that adds 22.73Kg is prepared pre-polymer solution.
Prepolymer solution is cooled to below 15 ℃, and the DMA solution (concentration of amine is 5%) that progressively adds the diethylamine of the propane diamine of the ethylenediamine contain 0.336Kg, 0.046Kg and 0.061Kg carries out chain extending reaction and chain termination reaction; Then add antioxidant, anti-yellowing agent, ultra-violet absorber and the easypro agent of lubricated solution and obtain the polyurethane spinning solution.
The polyurethane spinning solution obtains polyurethane elastomeric fiber through dry spinning after slaking, filtration and deaeration.
Claims (7)
1. an in-situ polymerization prepares the method for black polyurethane elastomer, it is characterized in that the method comprises following several step:
1) nano carbon black is lower dry 2～4 hours at 90-120 ℃, then add organic solvent 20～50 ℃ of lower grindings 3～7 hours, the ultrasonic processing 1～4 hour in ultrasonic oscillator of mixture after the grinding makes nano carbon black Uniform Dispersion in solvent, forms stable nano carbon black dispersion liquid;
2) the nano carbon black dispersion liquid is joined in the oligomer polyol by powerful mechanical dispersed with stirring and mix, then add the vulcabond preparation with the carbamate prepolymer of-NCO end-blocking, and add solvent and fully dissolve, obtain pre-polymer solution;
3) after the pre-polymer solution cooling with preparation, add mixed amine solution and carry out chain extending reaction and chain termination reaction, obtain polyurethane urea solutions;
4) add antioxidant, ultra-violet absorber, anti-yellowing agent, delustering agent and lubricatedly alleviate agent in the above-mentioned polyurethane urea solutions, after fully mixing, prepare the black polyurethane spinning solution that contains nanometer carbon black;
5) with the black polyurethane spinning solution for preparing, by the dry spinning system, the black polyurethane spinning solution is shootd out, is drawn into silk, and along with solvent evaporates, drying, namely obtain the black polyurethane elastomer.
2. a kind of in-situ polymerization according to claim 1 prepares the method for black polyurethane elastomer, it is characterized in that described nano carbon black particle diameter is 20nm～500nm, and the mass fraction of carbon black is 10%～40% in the nano carbon black dispersion liquid.
3. a kind of in-situ polymerization according to claim 1 prepares the method for black polyurethane elastomer, it is characterized in that the mass percent of described nano carbon black in the black polyurethane elastomer is 0.3%～5.0%.
4. a kind of in-situ polymerization according to claim 1 prepares the method for black polyurethane elastomer, it is characterized in that described oligomer polyol be the PTMG of number-average molecular weight 1500～3000 or number-average molecular weight 1500～3000 polypropylene glycol also or both mixtures.
5. a kind of in-situ polymerization according to claim 1 prepares the method for black polyurethane elastomer, it is characterized in that described vulcabond is 4,4MDI or 2,4MDI, or both mixtures; The solvent that adds is DMF DMF or DMA DMAC.
6. a kind of in-situ polymerization according to claim 1 prepares the method for black polyurethane elastomer, it is characterized in that described mixed amine solution is chain extender and chain terminating agent mixed solution, chain extender is selected from ethylenediamine, propane diamine, hexamethylene diamine or 2 methyl pentamethylenediamine, or its mixture; Chain terminating agent is diethylamine, di-n-propylamine, monoethanolamine or n-hexylamine, or its mixture.
7. a kind of in-situ polymerization according to claim 1 prepares the method for black polyurethane elastomer, it is characterized in that described organic solvent is DMF DMF or DMA DMAC.
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| CN103147160A (en) * | 2013-03-21 | 2013-06-12 | 江苏华天通科技有限公司 | Modified polyurethane fiber material and nano-modification and coloring method thereof |
| CN103498209A (en) * | 2013-10-21 | 2014-01-08 | 浙江华峰氨纶股份有限公司 | Manufacturing method of high-temperature-resistant and alkali-resistant polyurethane elastic fibers |
| CN104153037A (en) * | 2014-08-13 | 2014-11-19 | 浙江华峰氨纶股份有限公司 | Preparation method of polyurethane elastic fiber with moisture absorption and moisture liberation performance |
| CN104404648A (en) * | 2014-12-17 | 2015-03-11 | 浙江华峰氨纶股份有限公司 | Preparation method of rare earth aluminate polyurethane elastic fiber capable of emitting long blue afterglow |
| CN105483856A (en) * | 2015-12-29 | 2016-04-13 | 浙江华峰氨纶股份有限公司 | Method for preparing ultraviolet aging resistant spandex through in situ polymerization |
| CN108138373A (en) * | 2015-07-31 | 2018-06-08 | 株式会社晓星 | Polyurethane-urea elastomeric yarns with excellent unwinding and preparation method thereof |
| CN108823674A (en) * | 2018-07-12 | 2018-11-16 | 武汉轻工大学 | A kind of polyurethane/carbon black fibre and preparation method thereof at charcoal and electric conductivity |
| CN109825894A (en) * | 2017-11-23 | 2019-05-31 | 泰光产业株式会社 | The preparation method of chlorine resistance black polyurethane urea elastomer |
| CN114276581A (en) * | 2021-12-31 | 2022-04-05 | 江苏卧尔康家居用品有限公司 | Polyurethane additive and polyurethane prepared by using same |
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| CN103147160A (en) * | 2013-03-21 | 2013-06-12 | 江苏华天通科技有限公司 | Modified polyurethane fiber material and nano-modification and coloring method thereof |
| CN103147160B (en) * | 2013-03-21 | 2015-11-18 | 江苏华天通科技有限公司 | A kind of improved polyurethane fiber material and nano modification thereof and colorize method |
| CN103498209A (en) * | 2013-10-21 | 2014-01-08 | 浙江华峰氨纶股份有限公司 | Manufacturing method of high-temperature-resistant and alkali-resistant polyurethane elastic fibers |
| CN103498209B (en) * | 2013-10-21 | 2015-10-28 | 浙江华峰氨纶股份有限公司 | There is the preparation method of high temperature resistant and alkaline-resisting polyurethane elastomeric fiber |
| CN104153037A (en) * | 2014-08-13 | 2014-11-19 | 浙江华峰氨纶股份有限公司 | Preparation method of polyurethane elastic fiber with moisture absorption and moisture liberation performance |
| CN104404648A (en) * | 2014-12-17 | 2015-03-11 | 浙江华峰氨纶股份有限公司 | Preparation method of rare earth aluminate polyurethane elastic fiber capable of emitting long blue afterglow |
| CN108138373A (en) * | 2015-07-31 | 2018-06-08 | 株式会社晓星 | Polyurethane-urea elastomeric yarns with excellent unwinding and preparation method thereof |
| CN105483856A (en) * | 2015-12-29 | 2016-04-13 | 浙江华峰氨纶股份有限公司 | Method for preparing ultraviolet aging resistant spandex through in situ polymerization |
| CN109825894A (en) * | 2017-11-23 | 2019-05-31 | 泰光产业株式会社 | The preparation method of chlorine resistance black polyurethane urea elastomer |
| CN108823674A (en) * | 2018-07-12 | 2018-11-16 | 武汉轻工大学 | A kind of polyurethane/carbon black fibre and preparation method thereof at charcoal and electric conductivity |
| CN108823674B (en) * | 2018-07-12 | 2020-11-20 | 武汉轻工大学 | Polyurethane/carbon black fiber with carbon forming and conductivity and preparation method thereof |
| CN114276581A (en) * | 2021-12-31 | 2022-04-05 | 江苏卧尔康家居用品有限公司 | Polyurethane additive and polyurethane prepared by using same |
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Address after: No. 1788, Dongshan Economic Development Zone, Wenzhou City, Zhejiang Province Patentee after: Huafeng Chemical Co.,Ltd. Address before: No. 1788, Dongshan Economic Development Zone, Wenzhou City, Zhejiang Province Patentee before: ZHEJIANG HUAFENG SPANDEX Co.,Ltd. |