CN102899739B - 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
- Publication number
- CN102899739B CN102899739B CN201210447405.0A CN201210447405A CN102899739B CN 102899739 B CN102899739 B CN 102899739B CN 201210447405 A CN201210447405 A CN 201210447405A CN 102899739 B CN102899739 B CN 102899739B
- Authority
- CN
- China
- Prior art keywords
- black
- carbon black
- polyurethane
- solution
- situ polymerization
- 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.)
- Active
Links
Landscapes
- Artificial Filaments (AREA)
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 macromolecular material production field, particularly a kind of in-situ polymerization is prepared the method for black polyurethane elastomer.The black polyurethane elastomer of manufacture of the present invention has more lasting black effect, and COLOR FASTNESS is high, and following process does not need to dye again, has good mechanical property simultaneously.
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, there is 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.But due to the molecular structure of polyurethane elastomeric fiber own, under common dyeing condition, the dyeing of polyurethane elastomeric fiber silk is more difficult, the not good polyurethane elastomeric fiber of dyeing is easy in fabric, expose white point, affects the overall quality of fabric; And if dyeing condition is too fierce, the physical property of polyurethane elastomeric fiber can be subject to heavy damage, even ruptures, and then affects the serviceability of fabric.
Carbon black is a kind of important industrial chemicals, mainly by carbon, formed, both can be as reinforcing agent and the filler of elastomeric material, can be used for again coating, 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 black polyurethane elastomer.
Chinese patent CN201010525066.4 and U.S. Pat 7364792B2 openly prepare black polyurethane elastomer with carbon black, the two is all that the dimethylacetamide solution of carbon black is added in polyurethane spinning solution, then by dry spinning, prepares black polyurethane elastomer.But due to the intermolecular powerful van der Waals interaction of nano carbon black, the nano carbon black adding is easily reunited in spinning solution, cause later stage stoste spinnability to decline, carbon black particle is only to have an effect by physical action and fiber simultaneously, and then fibrous mechanical property is also caused to certain negative effect.Even if utilize some dispersants to improve the dispersiveness of carbon black, but improvement effect 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, nano carbon black dispersion liquid is dispersed in oligomer polyol, utilize the activity hydroxy on carbon black particle surface to react with isocyanate group in prepolymer preparation process, make carbon black particle and polyurethane macromolecular interchain form stable chemical bond, play the effect of crosslinking points simultaneously, and then make polyurethane elastomeric fiber there is more lasting black effect, higher COLOR FASTNESS, mechanical property also improves simultaneously.
Technical scheme: the method that in-situ polymerization of the present invention is prepared black polyurethane elastomer comprises following several step:
1) nano carbon black is dried 2～4 hours at 90-120 ℃, then add organic solvent at 20～50 ℃, to grind 3～7 hours, the ultrasonic processing 1～4 hour in ultrasonic oscillator of mixture after grinding, makes nano carbon black dispersed in solvent, forms stable nano carbon black dispersion liquid;
2) nano carbon black dispersion liquid is joined in oligomer polyol by powerful mechanical dispersed with stirring and mix, then add the carbamate prepolymer of vulcabond preparation with-NCO end-blocking, and add solvent fully to dissolve, obtain pre-polymer solution;
3) by after cooling the pre-polymer solution of preparation, add mixed amine solution to carry out chain extending reaction and chain termination reaction, obtain polyurethane urea solutions;
4) to adding antioxidant, ultra-violet absorber, anti-yellowing agent, delustering agent in above-mentioned polyurethane urea solutions and lubricatedly alleviating agent, after being fully uniformly mixed, prepare the black polyurethane spinning solution containing nanometer carbon black;
5), by the black polyurethane spinning solution preparing, by dry spinning system, black polyurethane spinning solution is shootd out, is drawn into silk, and along with solvent evaporates, dry, obtain black polyurethane elastomer.
Described nano carbon black particle diameter is 20nm～500nm, and in nano carbon black dispersion liquid, the mass fraction of carbon black is 10%～40%.
The mass percent of described nano carbon black in black polyurethane elastomer is 0.3%～5.0%.
Described oligomer polyol be the PTMG of number-average molecular weight 1500～3000 or the polypropylene glycol of number-average molecular weight 1500～3000 also or both mixtures.
Described vulcabond is 4,4-MDI or 2,4-MDI, or both mixtures; The solvent adding 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 black polyurethane elastomer that the present invention adopts situ aggregation method to prepare, in prepolymer preparation process, add nanometer carbon black cheap and easy to get, utilize carbon black particle itself with-OH and vulcabond with-NCO radical reaction, thereby make carbon black particle participate in the synthetic reaction of prepolymer.By situ aggregation method, between carbon black particle and polyurethane molecular, form stable chemical bond, carbon black particle plays the effect of chemical crosslinking point simultaneously.
Adopt the present invention to prepare black polyurethane elastomer, stoste good spinning property, fiber has more lasting black effect, and COLOR FASTNESS is high, in following process process, do not need polyurethane elastomeric fiber again to dye, bring great convenience to the processing in polyurethane elastomeric fiber later stage.Meanwhile, the chemical crosslinking point that carbon black particle forms in 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
With example, describe the present invention in detail below, but these examples must not be interpreted as and go up in all senses limitation of the present invention.
(1) nano carbon black is dried 2～4 hours at 90-120 ℃, then add organic solvent at 20～50 ℃, to grind 3～7 hours, the ultrasonic processing 1～4 hour in ultrasonic oscillator of mixture after grinding, makes nano carbon black dispersed in solvent, forms stable carbon black dispersion liquid;
(2) nano carbon black dispersion liquid is joined in oligomer polyol by powerful mechanical dispersed with stirring and mix, then add the carbamate prepolymer of vulcabond preparation with-NCO end-blocking, and add solvent fully to dissolve, obtain pre-polymer solution;
(3) by after cooling the pre-polymer solution of preparation, add mixed amine solution to carry out chain extending reaction and chain termination reaction, obtain polyurethane urea solutions;
(4) to preparing, add antioxidant, ultra-violet absorber, anti-yellowing agent, delustering agent and lubricatedly alleviate agent etc. in polyurethane urea solutions, after being fully uniformly mixed, preparation is containing the black polyurethane spinning solution of nanometer carbon black;
(5), by the black polyurethane spinning solution preparing, by dry spinning system, black polyurethane spinning solution is shootd out, is drawn into silk, and along with solvent evaporates, dry, obtain black polyurethane elastomer.
Described nano carbon black particle diameter is 20nm～500nm, and in dispersion liquid, carbon black mass mark is 10%～40%;
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 the polypropylene glycol of number-average molecular weight 1500～3000 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 of vulcabond ratio;
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 fibre weight 0.5%～1.5%, and anti-yellowing agent consumption is fibre weight 0.2%～1.5%, and ultra-violet absorber consumption is fibre weight 0.1%～1.0%, and lubricated to alleviate agent consumption be 0.1%～1.0% of fibre weight.
Embodiment 1:
By nano carbon black at 110 ℃ dry 2 hours, to get in the DMA (DMAC) that 120g joins 680g, grinder grinds 5 hours; Then by the carbon black solution ultrasonic dispersion 2 hours in ultrasonic oscillator after grinding, obtain stable nano carbon black dispersion liquid, 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 to high-speed stirred 3 hours; Add again 4 of 2.3Kg, 4 '-methyl diphenylene diisocyanate, polymerisation 2 hours at 45 ℃.Add the DMA of 14.68Kg to prepare pre-polymer solution.
Prepolymer solution is cooled to below 15 ℃, progressively adds the DMA solution (concentration of amine is 3%) of the ethylenediamine, the propane diamine of 0.014Kg and the diethylamine of 0.038Kg that contain 0.216Kg to carry out chain extending reaction and chain termination reaction; Then add antioxidant, anti-yellowing agent, ultra-violet absorber and the easypro agent of lubricated solution to obtain polyurethane spinning solution;
Polyurethane spinning solution, after slaking, filtration and deaeration, obtains polyurethane elastomeric fiber through dry spinning.
Embodiment 2:
Nano carbon black is dried to 2 hours at 110 ℃, gets 100g and join in 400g DMA (DMAC), grinder grinds 4 hours; Then by the carbon black solution ultrasonic dispersion 3 hours in ultrasonic oscillator after grinding, obtain stable nano carbon black dispersion liquid, 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 to high-speed stirred 3 hours; Add again 4 of 1.782Kg, 4 '-methyl diphenylene diisocyanate, polymerisation 2 hours at 45 ℃.Add the DMA of 15.144Kg to prepare pre-polymer solution.
Prepolymer solution is cooled to below 15 ℃, progressively adds the DMA solution (concentration of amine is 4%) of the ethylenediamine, the propane diamine of 0.021Kg and the diethylamine of 0.057Kg that contain 0.324Kg to carry out chain extending reaction and chain termination reaction; Then add antioxidant, anti-yellowing agent, ultra-violet absorber and the easypro agent of lubricated solution to obtain polyurethane spinning solution.
Polyurethane spinning solution, after slaking, filtration and deaeration, obtains polyurethane elastomeric fiber through dry spinning.
Embodiment 3:
Nano carbon black is dried to 2 hours at 110 ℃, gets 630g and join in 1170g DMA (DMAC), grinder grinds 7 hours; Then by the carbon black solution ultrasonic dispersion 4 hours in ultrasonic oscillator after grinding, obtain stable nano carbon black dispersion liquid, its concentration is 35%.
The nano carbon black dispersion liquid of 1363g is joined in the DMA solution of 13Kg PTMG and 6.8Kg to high-speed stirred 3 hours; Add again 4 of 2.9Kg, 4-methyl diphenylene diisocyanate, polymerisation 2 hours at 45 ℃.Add the DMA of 22.73Kg to prepare pre-polymer solution.
Prepolymer solution is cooled to below 15 ℃, progressively adds the DMA solution (concentration of amine is 5%) of the ethylenediamine, the propane diamine of 0.046Kg and the diethylamine of 0.061Kg that contain 0.336Kg to carry out chain extending reaction and chain termination reaction; Then add antioxidant, anti-yellowing agent, ultra-violet absorber and the easypro agent of lubricated solution to obtain polyurethane spinning solution.
Polyurethane spinning solution, after slaking, filtration and deaeration, obtains polyurethane elastomeric fiber through dry spinning.
Claims (7)
1. in-situ polymerization is prepared a method for black polyurethane elastomer, it is characterized in that the method comprises following several step:
1) nano carbon black is dried 2～4 hours at 90-120 ℃, then add organic solvent at 20～50 ℃, to grind 3～7 hours, the ultrasonic processing 1～4 hour in ultrasonic oscillator of mixture after grinding, makes nano carbon black dispersed in solvent, forms stable nano carbon black dispersion liquid;
2) nano carbon black dispersion liquid is joined in oligomer polyol by powerful mechanical dispersed with stirring and mix, then add the carbamate prepolymer of vulcabond preparation with-NCO end-blocking, and add solvent fully to dissolve, obtain pre-polymer solution;
3) by after cooling the pre-polymer solution of preparation, add mixed amine solution to carry out chain extending reaction and chain termination reaction, obtain polyurethane urea solutions;
4) to adding antioxidant, ultra-violet absorber, anti-yellowing agent, delustering agent in above-mentioned polyurethane urea solutions and lubricatedly alleviating agent, after being fully uniformly mixed, prepare the black polyurethane spinning solution containing nano carbon black;
5), by the black polyurethane spinning solution preparing, by dry spinning system, black polyurethane spinning solution is shootd out, is drawn into silk, and along with solvent evaporates, dry, obtain black polyurethane elastomer.
2. a kind of in-situ polymerization according to claim 1 is prepared the method for black polyurethane elastomer, it is characterized in that described nano carbon black particle diameter is 20nm～500nm, and in nano carbon black dispersion liquid, the mass fraction of carbon black is 10%～40%.
3. a kind of in-situ polymerization according to claim 1 is prepared the method for black polyurethane elastomer, it is characterized in that the mass percent of described nano carbon black in black polyurethane elastomer is 0.3%～5.0%.
4. a kind of in-situ polymerization according to claim 1 is prepared 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 the polypropylene glycol of number-average molecular weight 1500～3000 also or both mixtures.
5. a kind of in-situ polymerization according to claim 1 is prepared the method for black polyurethane elastomer, it is characterized in that described vulcabond is 4,4MDI or 2,4MDI, or both mixtures; The solvent adding is DMF DMF or DMA DMAC.
6. a kind of in-situ polymerization according to claim 1 is prepared 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 is prepared the method for black polyurethane elastomer, it is characterized in that described organic solvent is DMF DMF or DMA DMAC.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210447405.0A CN102899739B (en) | 2012-11-09 | 2012-11-09 | Method for preparing black polyurethane elastic fiber via in situ polymerization |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210447405.0A CN102899739B (en) | 2012-11-09 | 2012-11-09 | Method for preparing black polyurethane elastic fiber via in situ polymerization |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102899739A CN102899739A (en) | 2013-01-30 |
| CN102899739B true CN102899739B (en) | 2014-04-16 |
Family
ID=47572217
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210447405.0A Active CN102899739B (en) | 2012-11-09 | 2012-11-09 | Method for preparing black polyurethane elastic fiber via in situ polymerization |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102899739B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN104153037B (en) * | 2014-08-13 | 2016-03-02 | 浙江华峰氨纶股份有限公司 | There is the preparation method of the polyurethane elastomeric fiber of humidity absorption and release performance |
| CN104404648B (en) * | 2014-12-17 | 2016-08-24 | 浙江华峰氨纶股份有限公司 | A kind of preparation method of rare earth aluminate blue long afterflow polyurethane elastomeric fiber |
| KR101620573B1 (en) * | 2015-07-31 | 2016-05-13 | 주식회사 효성 | Polyurethanurea elastic fiber with good unwinding performance and method of manufacturing the same |
| CN105483856B (en) * | 2015-12-29 | 2017-10-17 | 浙江华峰氨纶股份有限公司 | A kind of method that in-situ polymerization prepares ageing resistance by ultraviolet light spandex |
| KR101943894B1 (en) * | 2017-11-23 | 2019-01-30 | 태광산업주식회사 | Preparation Method of Black Polyurethaneurea Fiber |
| 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7364792B2 (en) * | 2005-03-19 | 2008-04-29 | Huette Stephan | Spun-dyed polyurethaneurea fibres, a process for their production and their use for producing fabrics |
| CN101326247A (en) * | 2005-12-12 | 2008-12-17 | 东海碳素株式会社 | Surface-modified carbon black and dispersions thereof |
| CN101984158A (en) * | 2010-10-29 | 2011-03-09 | 江苏双良氨纶有限公司 | Method for producing polyether black spandex fibers |
-
2012
- 2012-11-09 CN CN201210447405.0A patent/CN102899739B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7364792B2 (en) * | 2005-03-19 | 2008-04-29 | Huette Stephan | Spun-dyed polyurethaneurea fibres, a process for their production and their use for producing fabrics |
| CN101326247A (en) * | 2005-12-12 | 2008-12-17 | 东海碳素株式会社 | Surface-modified carbon black and dispersions thereof |
| CN101984158A (en) * | 2010-10-29 | 2011-03-09 | 江苏双良氨纶有限公司 | Method for producing polyether black spandex fibers |
Non-Patent Citations (1)
| Title |
|---|
| 陈丽娟.新型聚氨酯/含羟基填料有机/无机杂化材料的制备与性能.《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》.2011,(第3期),第B020-145页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102899739A (en) | 2013-01-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102899739B (en) | Method for preparing black polyurethane elastic fiber via in situ polymerization | |
| CN105420843B (en) | A kind of preparation method of chromophil polyurethane elastic fiber | |
| CN103436983B (en) | High-resilience urethane elastic fiber as well as preparation method thereof | |
| CN103726127B (en) | A kind of black polyurethane urea elastomer adding CNT and preparation method thereof | |
| CN103696038B (en) | A kind of Tingible spandex fiber and preparation method thereof | |
| CN105331274A (en) | Thixotropic bi-compound polyurethane waterproof paint capable of being constructed at high temperature and preparation method thereof | |
| CN105483856B (en) | A kind of method that in-situ polymerization prepares ageing resistance by ultraviolet light spandex | |
| CN101984158B (en) | Method for producing polyether black spandex fibers | |
| CN102010654A (en) | Method for preparing environmental-friendly high-performance polyurethane waterproof paint | |
| CN104559735A (en) | Single-component reactive thixotropic polyurethane waterproof paint and preparation method thereof | |
| CN103710786A (en) | Preparation method of polyurethane raw liquid for high-speed spinning | |
| CN106589459A (en) | Preparation method of polyurethane type graphene and application thereof in polyurethane fibers | |
| CN109881291A (en) | A kind of acid dyes is easily painted the preparation method of spandex | |
| CN102127827B (en) | Method for preparing nano-attapulgite modified polyurethane elastic fiber | |
| CN104153033B (en) | A kind of preparation method of porous easy dyeing spandex | |
| CN108517580B (en) | Method for recycling spandex waste liquid | |
| CN111021093A (en) | Cross-linking type environment-friendly textile coating ink and preparation method and application thereof | |
| CN103898631A (en) | Polyurethane urea rubber composite elastic fiber and preparation method thereof | |
| CN104878463B (en) | A kind of hyper-dispersant and the preparation method without dye polyurethane elastomeric fiber | |
| CN107325246B (en) | Modified polyurethane oligomer, preparation method thereof and application thereof in photocuring digital ink-jet printing | |
| CN109021546A (en) | It is a kind of for making the antistatic macromolecule material preparation method of pu tire | |
| CN104178842A (en) | Silk-like spandex fiber and preparation method thereof | |
| WO2023077679A1 (en) | Preparation method for waterborne polyurethane dispersing agent and use of waterborne polyurethane dispersing agent | |
| CN102534856B (en) | Preparation method of spandex spinning stock solution by PCL dry method | |
| CN110157439A (en) | A kind of modified polyurethane of weatherproof fixes the sand rehabilitating soil agent and preparation method |
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 | ||
| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
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. |