CN102127827A - Method for preparing nano-attapulgite modified polyurethane elastic fiber - Google Patents

Method for preparing nano-attapulgite modified polyurethane elastic fiber Download PDF

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CN102127827A
CN102127827A CN2010100010096A CN201010001009A CN102127827A CN 102127827 A CN102127827 A CN 102127827A CN 2010100010096 A CN2010100010096 A CN 2010100010096A CN 201010001009 A CN201010001009 A CN 201010001009A CN 102127827 A CN102127827 A CN 102127827A
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attapulgite
nano
polyurethane elastic
modified polyurethane
elastic fiber
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CN102127827B (en
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杨从登
陈大俊
席青
徐宁
梁红军
李建通
吴国华
吴建儒
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Huafeng Chemical Co ltd
Donghua University
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Donghua University
Zhejiang Huafeng Spandex Co Ltd
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Abstract

本发明提供一种新型纳米凹凸棒土改性聚氨酯弹性纤维的制备方法，采用超声和/或强力机械搅拌以及研磨等措施，使纳米凹凸棒土在低聚二元醇和反应控制剂a的混合溶液中分散形成稳定均匀的胶体，然后分别加入二异氰酸酯、扩链剂、反应控制剂b，嵌段共聚制得聚氨酯弹性纤维。本发明使用原位聚合法制备的聚氨酯弹性纤维具有较好的热稳定性和力学性能。The invention provides a method for preparing novel nano-attapulgite-modified polyurethane elastic fibers. Ultrasound and/or strong mechanical stirring and grinding are used to make nano-attapulgite in a mixed solution of oligomeric glycol and reaction control agent a Disperse to form a stable and uniform colloid, then add diisocyanate, chain extender and reaction control agent b respectively, and block copolymerize to obtain polyurethane elastic fiber. The polyurethane elastic fiber prepared by the in-situ polymerization method of the invention has good thermal stability and mechanical properties.

Description

A kind of nano-attapulgite modification polyurethane elastomer fiber preparation method
Technical field
The invention belongs to macromolecular material from making field, particularly a kind of in-situ preparation method of nano-attapulgite modification polyurethane elastomer fiber.The polyurethane elastomeric fiber of manufacturing of the present invention has heat endurance and mechanical property preferably.
Background technology
Polyurethane elastomeric fiber has plurality of advantages such as light specific gravity, fracture strength height, extension at break height, elasticity height and elastic recovery are good at normal temperatures.But along with the change gradually of polyurethane elastomeric fiber use and range of application is wide, mechanical property to polyurethane elastomeric fiber is more and more higher, the spandex silk is used to make bristlelike monofilament, parachute silk, rope, filter cloth etc., mechanical property to the spandex silk all has higher requirement, and some common spandex silks difficulty reach requirement.And when spandex weave with polyester fiber or knitting textiles in when dyeing, need under 190 ℃ of left and right sides high temperature, finalize the design and under the temperature about 130 ℃, dye for a long time or change colour processing, and its poor heat stability of polyurethane elastomeric fiber, the physical property of its polyurethane elastomeric fiber seriously is damaged, and fiber ruptures.Given this, the use of polyurethane elastomeric fiber is very restricted, and therefore, in recent years, many domestic and international companies, scientific research institutions are engaged in spandex mechanical property and Research on Thermal Stability.
Chinese patent CN03153706.5 public use laminated nano composition intercalation strengthens the method for polyurethane elastomeric fiber mechanical property, Chinese patent 200410009599.1 public use rare earth elements combine with the polyurethane fiber molecular matrix by coordinate bond and improve its mechanical property, but this two method can't improve its heat endurance.U.S. Pat 5879799 and Japan Patent JP 782608; JP 08020625; JP08176268 etc. all disclose and have used 2 of various mol ratios, 4-MDI and 4, and the compound isocyanates of 4-MDI is produced polyurethane elastomeric fiber, and improving its heat endurance, but this method can't improve the mechanical property of elastomer.Chinese patent CN 01109463 has reported a kind of method for preparing the nano imvite compound, improve heat endurance and mechanical property, but undeclared this product is applied in the situation of polyurethane elastomeric fiber.Chinese patent CN 1687173 and CN16933550 disclose respectively and have utilized diamine modified montmorillonoid and quaternary ammonium salt montmorillonite to add in the spandex fiber stoste, and the spandex of strong mechanical performance and high heat stability is produced in modification.But, can produce harmful effect to the spinnability of spinning solution because imvite is laminar structured.
Nano-attapulgite has another name called palygorskite or Palygorskite, be a kind of layer of chain structure contain Shuifu County's zeopan clay mineral.The nano attapulgite clay crystal shape is bar-shaped or fibrous, long 0.15 μ m～5 μ m, diameter 0.01 μ m～0.1 μ m.Nano-attapulgite has unique dispersion, salt tolerant alkali isocolloid character and higher adsorption bleaching ability, has certain plasticity and cohesive force, and it is used widely in all trades and professions.Recent decades, nano attapulgite clay has obtained in fields such as petrochemical industry, daily-use chemical industry, fine chemistry industry, food processing, building material, environmental protection, light textile, catalyst, feed, agricultural chemicals using widely.At present, nano-attapulgite has caused scholar's attention as a kind of silicate clay, it as filler with the consumption that reduces polymeric material with as nucleator at some crystalline polymers.(Peng?ZQ，Chen?DJ.Study?on?thenonisothermal?crystallization?behavior?of?poly(vinyl?alcoh-ol)/attapulgitenanocompositesby?DSC?analysis.J?Polym?Sci?B?Polym?Phys.2006；44：534-540)。
And so far, use the technology of nano attapulgite clay modification spandex not report as yet.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, prepared nano-attapulgite modification polyurethane elastomer fiber by in-situ polymerization, it is characterized in that this invents described nano-attapulgite is club shaped structure, can be dispersed in uniformly in the polyurethane elastomeric fiber, be nano-scale and distribute.The polyurethane elastomeric fiber of manufacturing of the present invention not only has high thermal stability, also has mechanical property preferably.
A kind of in-situ preparation method of nano-attapulgite modification polyurethane elastomer fiber may further comprise the steps:
1 nano-attapulgite original soil after filtration, dissolve, stir, leave standstill, stir again, refilter, grind and dry processing, be added to then with N, N-dimethylacetylamide (DMAC) or N, in the solvent of dinethylformamide (DMF), mixture sonicated 1～5 hour in ultrasonic oscillator, make nano-attapulgite in solvent, be cotton-shaped dispersion, form the dispersion liquid of nano-attapulgite.
2 join nano-attapulgite solution being in the mixed solution of the low poly-dihydric alcohol of solvent and reaction controlling agent a with DMAC, by rotating speed is that 1000～3000 agitator high-speed stirred of changeing disperse to form the stabilized uniform colloid, in solution, add vulcabond then, control thermotonus certain hour prepares prepolymer solution;
Described nano-attapulgite diameter 10-100nm, length is 300-900nm.
Described nano-attapulgite is 0.1%-4% in the mass percent of polyurethane elastomeric fiber.
Described low poly-dihydric alcohol is that number-average molecular weight is 1800～4000 PTMG;
Described reaction controlling agent a is a n-butanol, and addition is equivalent to the amount of the low poly-dihydric alcohol of 0～0.45wt%;
Described vulcabond is 4,4 methyl diphenylene diisocyanates;
38～50 ℃ of described reaction temperatures;
Described reaction time 60～180min;
Described vulcabond is 1.5: 1～1.9: 1 with the ratio of the amount of substance of low poly-dihydric alcohol.
3 prepolymer solution is cooled to 8～15 ℃ after, in 60～150min, progressively add the DMAC solution of amine chain extender and amine reaction controlling agent b; Reaction gained polyurethane solutions its viscosity under 20 ℃ of temperature conditions is 3500～7500 pools; Last add anti-flavescence agent, antioxidant, ultra-violet absorber again, lubricatedly discongest agent to obtain concentration be 28%～35% polyurethane spinning solution, after slaking, filtration, deaeration, dry spinning obtains the polyurethane elastomeric fiber of certain specification.
Described amine chain extender is an ethylenediamine, 1,2-propane diamine, 1, in 3-propane diamine, hexamethylene diamine, the 2 methyl pentamethylenediamine two or more, preferred ethylenediamine and 1, the mixed amine that the 2-propane diamine is formed, ethylenediamine and 1, the ratio of 2-propane diamine amount of substance is (100～75): (0～25), preferred (90～80): (10～20).
Described amine reaction controlling agent b is a diethylamine.
Described amine chain extender, amine reaction controlling agent b use with the form of DMAC solution, and its concentration is 3～9wt% during use.
Described anti-flavescence agent is two (N, N-dimethyl hydrazides amino, 4-phenyl) methane, the manufacturer: the two keys in Taiwan, its consumption is the 0.2wt%～1.5wt% of amount of polymers.
Described antioxidant is a cyamelide, the manufacturer: Taiwan cyanogen spy, its consumption is the 0.5wt%～1.5wt% of amount of polymers.
Described ultraviolet-resistant absorbent is 2-(2 '-hydroxyl-3 ', 5 '-two tertiary pentyls)-benzotriazole, the manufacturer: the two keys in Taiwan, its consumption is the 0.1wt%～1.0wt% of amount of polymers.
Described lubricated to discongest agent be dolomol, and the manufacturer: Japanese grease, its consumption are the 0.1wt%～1.0wt% of amount of polymers.
Described production polyurethane elastomeric fiber, described dry spinning path is square or circular path, temperature is 250 ℃～280 ℃ in the path.
The specific embodiment
Below in conjunction with specific embodiment, further set forth invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values belong to claim institute restricted portion in the appended power of the application equally.
Embodiment 1
1, nano-attapulgite is crossed 200 orders, claim 150g to add deionized water 1000g, mechanical agitation 50 minutes, left standstill 1 hour, incline and supernatant liquid, repetitive operation 3 times, add and add 100mlHCl mechanical agitation 60 minutes again behind the water, be filtered to pH, pour clean pallet natural air drying into to neutral, ball milling 30 minutes, 110 ℃ of vacuumize 2 hours joins in the N,N-dimethylacetamide (DMAC) then, sonicated is 2 hours in ultrasonic oscillator, obtains nano-attapulgite is cotton-shaped distribution in DMAC dispersion liquid.
2, the nano-attapulgite solution of 0.0574Kg is joined in the solution of N,N-dimethylacetamide of the n-butanol of PTMG, 0.0108Kg of 9Kg and 5.293Kg high-speed stirred 2 hours.Be cooled to 28 ℃ then, add 4,4 methyl diphenylene diisocyanates of 2.238Kg, polymerisation is 120 minutes under 45 ℃ of temperature.The N,N-dimethylacetamide that adds 12.723Kg obtains pre-polymer solution.
The concentration of described attapulgite solution is 20wt%, and attapulgite content in the modification polyurethane elastomer fiber is 0.1wt%.
3, prepolymer solution is cooled to 12 ℃ after, in 90min, progressively add 1 of the ethylenediamine contain 0.160kg, 0.079kg, the N of the diethylamine of 2-propane diamine and 0.024kg, the N--dimethylacetamide solution carries out chain extending reaction; Add anti-flavescence agent, antioxidant, ultra-violet absorber at last again and lubricatedly discongest agent and obtain the polyurethane spinning solution; After slaking, filtration, deaeration, dry spinning obtains the polyurethane elastomeric fiber of 40D (Denier).
Embodiment 2
Prepare polyurethane elastomeric fiber according to embodiment 1 is described with quadrat method, difference is that nano-attapulgite content in improved polyurethane fiber is 1.0wt%.
Embodiment 3
Prepare polyurethane elastomeric fiber according to embodiment 1 is described with quadrat method, difference is that nano-attapulgite content in improved polyurethane fiber is 2.0wt%.
Embodiment 4
Prepare polyurethane elastomeric fiber according to embodiment 1 is described with quadrat method, difference is that nano-attapulgite content in improved polyurethane fiber is 4.0wt%.
Comparative Examples 1
1,5.293kg N is housed, the solution of the PTMG of N-dimethylacetamide solvent, 9kg, the n-butanol of 0.0108Kg, add 4 of 94.520kg when cooling to 28 ℃, 4 methyl diphenylene diisocyanate polymerisation 120min, the N,N-dimethylacetamide that adds 12.955Kg prepares prepolymer solution;
2, prepolymer solution is cooled to 12 ℃ after, in 90min, progressively add 1 of the ethylenediamine contain 0.160kg, 0.079kg, the N,N-dimethylacetamide solution of the diethylamine of 2-propane diamine and 0.024kg carries out chain extending reaction; Add anti-flavescence agent, antioxidant, ultra-violet absorber at last again, lubricatedly discongest agent and obtain the polyurethane spinning solution; After slaking, filtration, deaeration, dry spinning obtains the polyurethane elastomeric fiber of 40D (Denier).
By concrete enforcement, obtain the listed different embodiment of following table 1 and table 2 and the mechanical property and the heat endurance of comparative example to top embodiment and Comparative Examples.
Table 1: the mechanical property of different embodiment and comparative example
Physical property DE (％) DS (g) 6DE (％) 6DS (g) 5RER310 (％)
Embodiment 1 582.1 57.9 580.1 61.0 91.4
Embodiment 2 600.2 57.6 601.4 60.8 91.3
Embodiment 3 619.1 58.4 623.4 61.4 91.7
Embodiment 4 596.5 56.8 597.1 60.0 91.4
Comparative Examples 1 565.2 57.7 563.6 60.6 91.6
In the table 1
DE: be elongation at break;
DS: be ultimate strength;
6DE: be the elongation at break of continuous 5 times the 6th stretchings in 300% back that stretch;
6DS: be the ultimate strength of continuous 5 times the 6th stretchings in 300% back that stretch;
5RER310: expression elastic recovery rate.
Figure G2010100010096D00051
The L relaxed length is after stop 30s is returned in the 5th stretching, the relaxed length of sample.
Then the foregoing description and Comparative Examples are carried out heat stabilization test.The heat stabilization test condition is: use different DISPERSE DYES to dye, and dye three times, begin dyeing from room temperature at every turn, rise to 130 ℃ with 1.5 ℃/min temperature after, keeps 130 ℃ to continue the 60min that dye.Before each in addition high-temperature pressure dyeing the spandex silk is carried out pre-setting and handle, treatment conditions are: after 2.385 times of the drawing-offs, and 190 ℃ of typing 1min.
Table 2: the heat endurance of different embodiment and comparative example
Figure G2010100010096D00061
In the table 2:
Figure G2010100010096D00062
The data of analyzing in embodiment 1,2,3,4 and the Comparative Examples 1 can be seen, have added the polyurethane elastomeric fiber of nano-attapulgite, and its elongation at break has raising more significantly.
The data of analyzing in embodiment 1,2,3,4 and the Comparative Examples 1 can see that added the polyurethane elastomeric fiber of nano-attapulgite, its heat endurance improves significantly.

Claims (8)

1.一种纳米凹凸棒土改性聚氨酯弹性纤维的原位制备方法，包括以下步骤：1. an in-situ preparation method of nano-attapulgite modified polyurethane elastic fiber, comprising the following steps: (1)纳米凹凸棒原土经过滤、溶解、搅拌、静置、再搅拌、再过滤、研磨和烘干处理，然后加入溶剂，混合物在超声波振荡器中超声处理1～5小时，使纳米凹凸棒土在溶剂中呈絮状分散，形成纳米凹凸棒土的分散液；(1) The original soil of nano-attapulgite is filtered, dissolved, stirred, left standing, stirred again, filtered again, ground and dried, then a solvent is added, and the mixture is ultrasonically treated in an ultrasonic oscillator for 1 to 5 hours to make the nano-attapulgite The clay is dispersed in flocculent form in the solvent to form a dispersion of nano-attapulgite; (2)使纳米凹凸棒土溶液在低聚二元醇和反应控制剂a的混合溶液中通过机械搅拌分散形成稳定均匀的胶体，然后向溶液中加入二异氰酸酯制备预聚体溶液；(2) making the nano-attapulgite solution in the mixed solution of the oligomeric glycol and the reaction control agent a dispersed by mechanical stirring to form a stable and uniform colloid, and then adding diisocyanate to the solution to prepare a prepolymer solution; (3)冷却所制备预聚体溶液后，向其中逐步加入胺类扩链剂、胺类反应控制剂b的溶液进行扩链反应，得到高分子量的聚合物溶液；(3) After cooling the prepared prepolymer solution, gradually add the solution of amine chain extender and amine reaction control agent b to it to carry out chain extension reaction to obtain high molecular weight polymer solution; (4)向得到的高分子量聚合物溶液中加入防变黄剂、抗氧化剂、紫外线吸收剂和润滑疏解剂，充分混合均匀，制备凹凸棒土改性聚氨酯纺丝原液；(4) Add anti-yellowing agent, antioxidant, ultraviolet absorber and lubricating disintegrating agent in the obtained high molecular weight polymer solution, fully mix uniformly, prepare attapulgite modified polyurethane spinning dope; (5)将所制备凹凸棒土改性聚氨酯纺丝原液通过干法纺丝得到凹凸棒土改性聚氨酯弹性纤维。(5) Dry spinning the prepared attapulgite-modified polyurethane spinning stock solution to obtain attapulgite-modified polyurethane elastic fibers. 2.根据权利要求1所述的纳米凹凸棒土改性聚氨酯弹性纤维的原位制备方法，其特征在于所述的纳米凹凸棒土直径为10-100nm，长度为300-900nm，呈棒状结构。2. The in-situ preparation method of nano-attapulgite-modified polyurethane elastic fibers according to claim 1, characterized in that the nano-attapulgite has a diameter of 10-100 nm, a length of 300-900 nm, and a rod-like structure. 3.根据权利要求1所述的纳米凹凸棒土改性聚氨酯弹性纤维的原位制备方法，其特征在于所述纳米凹凸棒土在改性的聚氨酯弹性纤维中的质量百分比为0.1％-4％。3. The in-situ preparation method of nano attapulgite modified polyurethane elastic fiber according to claim 1, characterized in that the mass percentage of nano attapulgite in the modified polyurethane elastic fiber is 0.1%-4%. 4.根据权利要求1所述的纳米凹凸棒土改性聚氨酯弹性纤维的原位制备方法，其特征在于所述的低聚二元醇为数均分子量1800～4000的聚四氢呋喃醚二醇，反应控制剂a为正丁醇。4. The in-situ preparation method of nano-attapulgite-modified polyurethane elastic fiber according to claim 1, characterized in that said oligomeric glycol is polytetrahydrofuran ether glycol with a number average molecular weight of 1800-4000, and the reaction control agent a is n-butanol. 5.根据权利要求1所述的纳米凹凸棒土改性聚氨酯弹性纤维的原位制备方法，其特征在于所述的二异氰酸酯为4，4’-二苯基甲烷二异氰酸酯。5. the in-situ preparation method of nano attapulgite modified polyurethane elastic fiber according to claim 1, is characterized in that described diisocyanate is 4,4'-diphenylmethane diisocyanate. 6.根据权利要求1所述的纳米凹凸棒土改性聚氨酯弹性纤维的原位制备方法，其特征在于所述的溶剂为N，N-二甲基甲酰胺或N，N-二甲基乙酰胺。6. the in-situ preparation method of nano attapulgite modified polyurethane elastic fiber according to claim 1, is characterized in that described solvent is N, N-dimethylformamide or N, N-dimethylacetamide . 7.根据权利要求1所述的纳米凹凸棒土改性聚氨酯弹性纤维的原位制备方法，其特征在于所述的胺类扩链剂选自乙二胺、1，2-丙二胺、1，3-丙二胺、己二胺、2-甲基戊二胺或二乙撑三胺中的两种或多种，胺类反应控制剂b为二乙胺。7. the in-situ preparation method of nano attapulgite modified polyurethane elastic fiber according to claim 1, is characterized in that described amine chain extender is selected from ethylenediamine, 1,2-propylenediamine, 1, Two or more of 3-propylenediamine, hexamethylenediamine, 2-methylpentamethylenediamine or diethylenetriamine, and the amine reaction control agent b is diethylamine. 8.根据权利要求1所述的纳米凹凸棒土改性聚氨酯弹性纤维的原位制备方法，其特征在于在所述凹凸棒土改性的聚氨酯弹性纤维中，纳米凹凸棒土在聚氨酯弹性纤维中呈纳米尺寸分布。8. The in-situ preparation method of nano-attapulgite-modified polyurethane elastic fiber according to claim 1, characterized in that in the polyurethane elastic fiber modified by attapulgite, nano-attapulgite is in the form of a nanometer in the polyurethane elastic fiber. size distribution.
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CN103924320B (en) * 2014-04-09 2015-12-02 浙江华峰氨纶股份有限公司 A kind of have spandex of long-acting insect protected performance 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
CN106750109A (en) * 2016-12-06 2017-05-31 安徽潜源教学设备有限公司 Good polyurethane plastic runway of a kind of screen resilience and preparation method thereof
CN107880243A (en) * 2017-11-23 2018-04-06 广东元星工业新材料有限公司 A kind of high heat-resistant high-performance polyurethane elastomer and preparation method thereof
CN109749411A (en) * 2019-01-16 2019-05-14 荆晓东 The preparation method of new polyurethane Compiste rope
CN110655635A (en) * 2019-09-09 2020-01-07 浙江凯色丽科技发展有限公司 Polyurethane composite emulsion containing mica-based conductive material and preparation method thereof

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