CN102220653B - Preparation method of heat resistant spandex fiber - Google Patents
Preparation method of heat resistant spandex fiber Download PDFInfo
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- CN102220653B CN102220653B CN 201110127711 CN201110127711A CN102220653B CN 102220653 B CN102220653 B CN 102220653B CN 201110127711 CN201110127711 CN 201110127711 CN 201110127711 A CN201110127711 A CN 201110127711A CN 102220653 B CN102220653 B CN 102220653B
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Abstract
The invention discloses a preparation method of heat resistant spandex fiber, belonging to the technical field of polymer textile material and preparation thereof; the preparation method comprises the following steps of: (1) mixing polyoxytetramethylene and 4,4'-methylenebis(phenyl isocyanate) according to a mole ratio of 1/1.4 to 1/2.5 for reaction to obtain a prepolymer; (2) adding non-protonic polar solvent to the prepolymer prepared in the step (1) so that the prepolymer is dissolved in the non-protonic polar solvent to obtain prepolymer solution; (3) adding a chain extender in the prepolymer solution obtained in the step (2) to obtain spandex spinning fluid with a molecular weight of 20-300 thousands after polymerization reaction, wherein the chain extender is aromatic diamine or the mixture of aromatic diamine and aliphatic diamine; (4) using the spandex spinning fluid prepared in the step (3) to obtain the heat resistant spandex fiber with a solution spinning method. Compared with conventional spandex, the product has obviously improved resistance to heat; moreover, the viscosity stability of the polymer is good.
Description
Technical field:
The present invention relates to a kind of preparation method of heat resistant spandex fiber, belong to high molecule spinning material and preparing technical field thereof, its product spandex fibre is suitable for the textiles manufacturing.
Technical background:
Spandex fibre is that a class contains more carbamate groups (elastomeric polymer NH-CO-O-) at molecular backbone, by soft, the hard segment that replace form-(A-B)-the type segmented copolymer, wherein A is hard section, be generally various isocyanates and small molecule chain extender (dihydroxylic alcohols or diamine) reaction and form, and B normally soft section of the polyethers of molecular weight 500-3000 or polyester polyol.The spandex that forms with the diamine chain extension has more excellent combination property than the product that forms with the dihydroxylic alcohols chain extension, has higher molecular weight and more stable local order microcell, thereby is the common method during present spandex fibre manufacturing is produced.
Common spandex fibre synthetic often first from polyethers HO-[(CH
2)
4-O)]
n-H and aromatic diisocyanate OCN-Ar-NCO begin to be reacted into prepolymer (containing-the NH-CO-O-structure), form soft section part (B), adding ethylenediamine, propane diamine or diethylenetriamine chain extender carries out chain extending reaction and forms the hard section part of polyurethane-urea (A) (containing urea groups-NH-CO-NH-structure) again, the block macromolecular that obtains-(A-B)-because hard section part can form more stable microcell in order regularly, have the high elasticity under the room temperature.Method through the solution spinning can form spandex fibre again, it is a kind of chemical synthetic fiber of excellent performance, has that percentage elongation is large, elastic recovery rate is high, elastic modelling quantity is low, fatigue durability is good, density is little, corrosion-resistant a, sun-proof, the characteristics such as fast light, anti-aging.Spandex has general good affinity to different dyestuffs, and dyeability is good, no matter adopts acidity or plyability dyestuff, disperse dyes, but or the equal even dyeing of metallicity dyestuff.Therefore, it is the very outstanding fiber of a kind of combination property.As long as add a little spandex fibre (mass fraction 2% ~ 25%), be enough to improve the performance of fabric in textiles, the sense comfortable and easy to wear of fabric is significantly improved, the class of fabric also greatly improves.
By mutually forming a large amount of hydrogen bond structures between urea groups-NH-CO-NH-, form more stable local order microcell between the hard section segment in the spandex fibre structure, play the effect of physical crosslinking point.But under higher temperature, hydrogen bond structure destroys easily, and the segment in the hard section is moved, so that physical crosslinking point destroys, the high elasticity of polymer disappears.Under higher temperature, chemical degradation (oxidation) can occur in urea groups and amino ester, and the segment generating unit is divided fracture, and the high elasticity of spandex also reduces.Under normal conditions, common spandex fibre (surpasses 190 ℃) or during higher temperature (130 ℃～135 ℃) long time treatment under hot conditions, formation hard segment part and corresponding physical crosslinking are put easy failure (oxidative degradation), make the fibre property variation, engender the phenomenon that is clamminess.When spandex and polyster fibre interweave blend dyeing, often relate to the high-temp dyeing operation, perhaps need secondary dyeing even three dyeing to match colors, spandex fibre part fracture in the fabric, the phenomenon of turning to be yellow, fluff usually occur during this time, the elasticity of fabric is impaired as a result, it is large that size shape becomes, and this problem is the common issue with of spandex fibre.
The resistance to elevated temperatures of hard segment and soft segment content comparison fiber all has a great impact in the mean molecule quantity of spandex polymer and the molecule.Generally, improve the mean molecule quantity of polymer and the resistance to elevated temperatures that the content of hard section with respect to soft section can improve spandex fibre to a certain extent.In addition, the order degree (degree of crystallinity) that increases in the hard segment also has certain help to improving its resistance to elevated temperatures.But because chemical constitution does not change, urea/ureido functional group does not change, so these methods are for preventing that the oxidative degradation at high temperature of urea/ureido functional group from helping limited.
At present, for the heat resistance that how to improve spandex fibre, other several technological approaches were proposed also.US Patent No. 5879799 reports use 2 of different mol ratio, 4'-methylene (two phenyl isocyanate) (2,4' – MDI) and 4,4'-methylene (two phenyl isocyanate) (4,4'-MDI) mix isocyanates (the former molar content is less than 20%), use simultaneously two kinds of admixtured polyethers, improve the spandex heat resistance.Japan Patent (JP07-82608, JP08-020625, JP08-176253, JP08-176268) is also reported and is adopted identical method to develop high temperature resistant spandex.Chinese patent 200510073397.8 provides the preparation method of a kind of PTMEG modification sodium-based montmorillonite and heat-resisting polyurethane elastomeric fiber, with the imvite-polyether polyol of modification as the flexible polyurethane segment, preparation montmorillonite/polyurethane nano composite polymer, improve heat resistance and the mechanical property of polyurethane elastomeric fiber, find that with thermal weight loss (TGA) analysis the thermal weight loss temperature that contains the spandex of imvite improves 10 than common spandex
oAbout C.Chinese patent 200510073400.6 provides a kind of chain extender during take quaternary ammonium salt modified montmorillonoid as the polyurethane polymerization, synthetic quaternary ammonium salt montmorillonite/polyurethane nano composition polymer, thus improve stable on heating method.Chinese patent 200510073398.2 provide a kind of with organic diamine (the linear aliphatic diamines of the hexamethylene diamine to 18 of 6 a carbon carbon a kind of) modified montmorillonoid the binary chain extender during as the polyurethane polymerization, make the nano composite polymer of diamine montmorillonite/polyurethane, thereby improve stable on heating method.
In addition, Chinese patent 200480024915.0 discloses a kind of preparation method of heat-resisting spandex, and it adds the cellulose acetate of 1%-20% (weight) in the gross weight of polyurethane-urea, this mixture of uniform stirring, do not change other conditions, make heat-resisting fiber.Among the preparation method that Chinese patent 200810190874.2 is described, directly having adopted ethylenediamine is chain extender (need not 1,2-propane diamine), but has improved the ratio of chain extender/prepolymer, and the thermal deformation solidification temperature of result product has improved 10
oAbout C.
Use polycaprolactone glycol and PCDL as the polyalcohol that consists of soft section of polyurethane-urea in Japanese patent application publication No. S58-59213 and the United States Patent (USP) 5,100,999, come so that the crosslinking points of crystal structure is stronger, to improve heat resistance.Yet it is not so good to improve effect, on the contrary, decreases with the polyurethane-urea resilience in comparison response rate of using polyether polyol.Japanese patent application publication No. H1-110520 has proposed to attempt increasing the crosslink density in the hard segment that is included in the urea groups in two amine structures by improving heat resistance with the diamino-diphenyl urea as the diamines of cahin extension agent, to increase heat resistance.Yet, caused crosslinkedly in the pre-spinning polymer solution, cause the time course of spinning solution viscosity to change, stability reduces.US Patent No. 5,362,432 disclose a kind of method, and wherein 1 of the ethylenediamine of 83-92mo1% and 8-17mol%, the mixture of 2-propane diamine is as chain extender.Yet the shortcoming of the method is that the viscosity stability of polymer is not enough owing to used relatively a large amount of ethylenediamines, and the fiber of last gained has lower heat resistance.
In addition, Japanese patent application publication No. H4-100919 has put down in writing a kind of by interpolation before spinning after the polymerization improves stable on heating prior art as additive with triamine.From that time, a lot of polyurethaneurea elastic fiber production company tries by improving heat resistance with triamine as cahin extension agent or additive, but the result is unsatisfactory.Therefore, triamine is only as replenishing the intensity that reduces by the common cahin extension agent that adds, and improving heat settability, and the heat resistance effect is limited.In addition, use excessive triamine meeting so that the viscosity of spinning solution presents unstability inevitably.Adopt the method for triamine to also have Chinese patent 200410001009.0 and 200410001010.3, they are with polytetramethylene ether diol, 4,4'-MDI and n-butanol are that raw material is produced prepolymer, with ethylenediamine, 1, the mixture of 2-propane diamine and diethylamine is chain extender, adds the diethylenetriamines crosslinking agent again.Chinese patent 200910131830.7 (comprises ethylenediamine, 1 by the ratio that changes linear diamines and side chain diamines, 2-propane diamine, 1,3-propane diamine, hexamethylene diamine, 2 methyl pentamethylenediamine, 1, in the 3-butanediamine two kinds and more than), but also make the polyurethane fiber with more crosslinking points, larger hard segment content with diethylenetriamine, improve dyeability.
US Patent No. 20050027094A1 adopts PolyTHF type polyethers and aromatic polyethers (for example ethoxylated bisphenol A) mixture and isocyanates polymerization in prepolymerisation stage, chain extension again, the polyurethane elastomeric fiber that obtains has the advantages that high temperature resistant dyeability is good, elastic recovery rate is good.
Produce with solution spinning technology of spandex except above-mentioned these, also have some specially for adopting melt spinning method to make the heat resistant spandex fiber method, such as Chinese patent 99108972.3,200610009032.3 etc.Because the percentage elongation of the spandex that melt spinning method obtains, elastic recovery rate, production efficiency etc. all can't be compared with solution spinning, so, how a kind of spandex that adopts solution spinning to prepare good heat resistance is provided, be the blank that present industry exists.
Summary of the invention:
The preparation method who the purpose of this invention is to provide a kind of heat resistant spandex fiber, more specifically a kind of method of producing the spandex fibre heat resistant spandex fiber by solution spinning (also being dry spinning).
The technical scheme that the present invention takes for achieving the above object is as follows, and a kind of preparation method of heat resistant spandex fiber may further comprise the steps:
(1), with PolyTHF (PTMEG) and 4,4'-di-2-ethylhexylphosphine oxide (phenyl isocyanate) (4,4'-MDI) mix according to mol ratio 1/1.4～1/2.5, react to get prepolymer;
(2), in the prepolymer of step 1 preparation, add non-proton property polar solvent, so that prepolymer dissolves in non-proton property polar solvent, obtain two ends and contain isocyano (carbamate pre-polymer solution NCO);
(3), in the pre-polymer solution of step 2 acquisition, add chain extender, isocyano is contained at the two ends that generate in the chain extender that adds and the step 2, and (carbamate pre-polymer solution NCO) reacts, aggregate into the spandex spinning fluid of molecular weight 20,000 to 300,000, the apparent viscosity 1000-7000 poise under the room temperature;
(4), with the spandex spinning fluid of step 3 preparation, adopt the method for solution spinning to make heat resistant spandex fiber.
Preferably:
In the step 1: used PolyTHF is that molecular weight is the polyethers HO-[(CH of 800-4000
2)
4-O)]
n-H preferably uses molecular weight to be the polyethers of 1800-2200.The temperature of prepolymerization reaction is 60-80
oC reacted 1.5-4 hours.The temperature of preferred reaction is 70
oC, the time is 2 hours.The prepolymer product is to contain isocyano (carbamate thick liquid NCO).
In the step 2: used non-proton property polar solvent is selected from DMA (DMAc) or DMF (DMF), and non-proton property polar solvent addition is 2～4 times of polyethers volume; Preferred addition is 3 times of polyethers volume.
In the step 3: isocyano is contained at the two ends that generate in the chain extender of adding and the step 2, and (carbamate pre-polymer solution NCO) reacts.Described chain extender is aromatic diamine, perhaps the mixture of aromatic diamine and aliphatic diamine.Wherein: aromatic diamine is selected from m-phenylene diamine (MPD), o-phenylenediamine, p-phenylenediamine (PPD), benzidine, 2,4-diaminotoluene, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diamino-diphenyl sulfone, 3,3'-two chloro-4, in the 4'-diaminodiphenylmethane one or more, preferred 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether or the p-phenylenediamine (PPD) of using.Aromatic diamine in the step 3 can be replaced a part with aliphatic diamine, namely take the mixture of aromatic diamine and aliphatic diamine as chain extender, aliphatic diamine is selected from ethylenediamine, 1,2-propane diamine, 2-methyl isophthalic acid, in the 5-pentanediamine one or more, the preferred ethylenediamine that uses, the ratio of replacement is the 10-90% of the molal quantity of aromatic diamine.
The reaction time of step 3 is 60 minutes-150 minutes, and temperature is 10
oC-40
oC.The preferred reaction time is 120 minutes, and temperature is 20
oC.
The apparent viscosity of the DMA solution of the spandex spinning fluid that step 3 makes is 20
oC is 1000-7000 poise, preferred 2500-6000 poise.
In the step 4: in the solution spinning technique (being dry spinning), the spinning head temperature is 250
oC, spinning speed are 600-750 m/min, and the line density of the elastomer that spinning obtains is 15-70 dtex.
Principle of the present invention and beneficial effect are as follows:
Preparation method and the character of heat resistant spandex fiber of the present invention and conventional spandex fibre have than big difference, although soft section part of macromolecular main chain is identical with conventional spandex, and, hard section part has been introduced two amine structures of rigidity, NH
2-Ar'-X-Ar'-NH
2(X-can be-CH
2-,-O-,-SO
2-etc., Ar' is aromatic rings) or NH
2-Ar'-NH
2, it and isocyanates-Ar-NCO reaction, obtain having rigidity the p-p conjugated structure urea groups-Ar-NH-CO-NH-Ar'-X-Ar'-NH-or-Ar-NH-CO-NH-Ar'-NH-.So hard section part forms more stable orderly regular microcell each other easily.After testing, the spandex fibre of the present invention's preparation has the characteristics such as high-fire resistance energy, high elasticity, high temperature resistant rinsing, is fit to 180
oC to 250
oPrinting and dyeing are used under the high temperature of C, can satisfy the requirement of novel fabric and high-grade fabric, see in detail the specific embodiment.
Beneficial effect of the present invention is as follows:
1, the heat resistance of product of the present invention is compared with conventional spandex, improves obviously.The temperature that conventional spandex fibre may contact when high-temp dyeing is 150
oC-250
oC, in its possibility fracture of this section temperature range, jaundice, and oxidative degradation, adopt synchronous thermal weight loss-differential thermal analysis (TGA-DTA) as seen 300
oOccur below the C phase I because being subjected to the process of thermal weight loss, and with the first exothermic peak 217
oC, and its temperature when the loss in weight 1.0% occurring is 235
oC.If do chain extender enforcement with aromatic diamines fully according to of the present invention, product the first exothermic peak occurs 288
oC improves 71 than conventional spandex
oC, the temperature when the loss in weight 1.0% occurring improves 20 than conventional spandex
oC; Make chain extender according to the mixture of use aromatic diamines of the present invention and ethylenediamine and implement, the first exothermic peak that product occurs is 246
oC improves 29 than conventional spandex
oC, the temperature when the loss in weight 1.0% occurring can improve 24 than conventional spandex
oC-36
oC.So, improved heat resistance effect of the present invention, the polyethers more imvite modified than above-mentioned Chinese patent 200510073397.8 described usefulness made the lifting effect of spandex and (only had 10
oThe raising of C) want obviously, also the effect than above-mentioned use diethylenetriamine additive or use cellulose acetate additive is good.
2, the viscosity stability of polymer is good.The product (in DMAc) of the present invention preparation is placed 4 all slakings, during the phenomenon that viscosity descends or precipitation produces does not occur.Conventional spandex production is reacted with ethylenediamine (or mixture of ethylenediamine and propane diamine, hexamethylene diamine, 2 methyl pentamethylenediamine) chain extender, because reaction speed is too fast, often cause the topical gel phenomenon in the reaction, viscosity raises suddenly, but can descend again after placing, have the unsettled problem of viscosity.The present invention is owing to replace to aromatic diamines with ethylenediamine, and the viscosity of reaction progressively raises, and behind the arrival peak viscosity, does not occur the problem that viscosity descends in the put procedure.
Kind by regulating the aromatic diamine raw material, proportioning, with the ratio of ethylenediamine, can in very large range control structure and the performance of product.
The invention will be further described below in conjunction with the drawings and specific embodiments.
Description of drawings:
Fig. 1 is the x-ray diffraction pattern that the embodiment of the invention vapors away the polymerizate behind the solvent.
Specific embodiments:
Embodiment 1:
(4,4'-MDI) (16 gram) is 70 for PolyTHF PTMEG (molecular weight 1800) (82 gram) and 4,4'-di-2-ethylhexylphosphine oxide (phenyl isocyanate)
oThe C reaction formed performed polymer in 2 hours.The DMAc solvent that adds 200mL in the prepolymer is so that prepolymer dissolves in polar solvent.The mixture chain extender (10/90 mol ratio, 1.55 grams/0.9 gram) that adds 4,4'-diaminodiphenyl ether and ethylenediamine in the prepolymer, making the complete phenyl isocyanate of itself and unreacted is 20 in temperature again
oFurther reacted 120 minutes under the C, until till the viscosity stabilization, aggregate into polyurethane-urea, the apparent viscosity under the room temperature is 3200 poise.With gel permeation chromatography (GPC method) test molecular weight of product, the results are shown in Table 1.
Embodiment 2:
The preparation method is with embodiment 2, and difference is to adopt the mixture chain extender (15/85 mol ratio) of 4,4'-diaminodiphenylmethane and ethylenediamine.Products therefrom at room temperature apparent viscosity is 3850 poise.With GPC method test molecular weight of product, the results are shown in Table 1.
Embodiment 3:
The preparation method uses PolyTHF PTMEG molecular weight 2000 with embodiment 1 when difference is prepolymerization reaction, pre-polymerization finishes only to add in the backward prepolymer p-phenylenediamine (PPD) chain extender (3.4 gram), in temperature 70
o C reaction 2 hours is until till the viscosity stabilization.Products therefrom the results are shown in Table 1 with GPC method test molecule amount.
The manufacturing of Comparative Examples-conventional spandex:
The preparation method is with embodiment 1, and difference is that added diamine chain stretching agent only has ethylenediamine (1.65 gram) in the prepolymer, obtains conventional spandex.Its apparent viscosity at room temperature is 4000 poise.With GPC method test molecule amount, the results are shown in Table 1.
The examination and test of products:
The product of above-described embodiment preparation is measured molecular weight with gel permeation chromatography (GPC method), the results are shown in Table 1.After product at room temperature vapors away solvent, do synchronous thermal weight loss-differential thermal analysis (TGA-DTA method), the results are shown in table 2; Do X-ray diffraction analysis (XRD method), the results are shown in Figure 1.
The molecular weight ratio of table 1, several spandex products.
Table 1 shows: the number-average molecular weight M of product
nWith weight average molecular weight M
w, approach with conventional spandex.The polydispersity index D of product is also approaching with the D of conventional spandex.These data declarations, the molecular weight that the spandex that adopts this method to make has and the difference of conventional spandex are not obvious, and in other words, the use of aromatic amine is very little for the impact of the molecular weight of product.
The heat resistance of table 2, heat-resisting spandex and common spandex is (heating rate 20 relatively
oC/min).
As shown in table 2: the temperature that may contact during owing to high-temp dyeing is 150
oC-250
oC, spandex fibre is in this section temperature range possibility fracture, jaundice, and oxidative degradation is so the heat endurance of spandex is particularly important in this section temperature province.As seen from Table 2, conventional spandex is 300
oOccur below the C phase I because being subjected to the process of thermal weight loss, the first corresponding exothermic peak is 217
oC, and its 1.0% temperature (temperature when also 99.0% weight is residual) when weightless to occur be 235
oC; The first exothermic peak that embodiment 1 and 2 product occur is all 246
oC improves 29 than conventional spandex
oC, the temperature during weight residual 99.0% is respectively 259
oC and 271
oC improves 24 than conventional spandex respectively
oC and 36
oC; The first exothermic peak that the product of embodiment 3 occurs is 288
oC improves 71 than conventional spandex
oC, the temperature during weight residual 99.0% improves 20 than conventional spandex spandex
oC.
Fig. 1 shows that four kinds of different products vapor away the x-ray diffraction pattern of the film behind the solvent.Among Fig. 1, there be not soft section part of chain extending reaction only to present unbodied broad peak (seeing curve 2).Use reacting ethylenediamine in the preparation of conventional spandex (Comparative Examples), 2q=9.3 has appearred in its hard section part
o, 21.2
oWith 29.4
oThe small peak (seeing curve 1) of the ordered structure at place; Use spandex (embodiment 3, curve 3) that aromatic diamine reaction obtains and the spandex (embodiment 1, curve 4) of use 10% aromatic diamines-90% ethylenediamine obvious ordered structure honeybee also to occur in these positions fully, and at 2q=21.2
oThe place the diffraction spike clearly, 17
oAbout locate that obvious acromion is also arranged, prove that the spandex that makes like this can form orderly structure effectively, plays the effect of physical crosslinking point.
Claims (2)
1. the preparation method of a heat resistant spandex fiber may further comprise the steps:
(1), PolyTHF and 4,4'-di-2-ethylhexylphosphine oxide (phenyl isocyanate) are mixed according to mol ratio 1/1.4～1/2.5, react to get prepolymer;
Used PolyTHF is that molecular weight is the polyethers of 1800-2200, and the prepolymerization reaction temperature is 70 ℃, and the reaction time is 2 hours;
(2), in the prepolymer of step (1) preparation, add non-proton property polar solvent, so that prepolymer dissolves the acquisition pre-polymer solution in non-proton property polar solvent;
In the step (2): used non-proton property polar solvent is selected from N, N-dimethylacetylamide (DMAc) or N, dinethylformamide (DMF), non-proton property polar solvent addition is 2～4 times of polyethers volume, obtains two ends after the dissolving and contains isocyano (carbamate pre-polymer solution NCO);
(3), add chain extender in the pre-polymer solution that obtains to step (2), polymerisation gets the spandex spinning fluid of molecular weight 20,000～300,000;
In the step (3): isocyano is contained at the two ends that obtain in the chain extender of adding and the step (2), and (carbamate pre-polymer solution NCO) carries out polymerisation, and polymerization reaction time is 120 minutes, and reaction temperature is 20 ℃;
Described chain extender is the mixture of 4,4'-diaminodiphenyl ether and ethylenediamine, and mol ratio is 10/90; Perhaps
Described chain extender is the mixture of 4,4'-diaminodiphenylmethane and ethylenediamine, and mol ratio is 15/85;
(4), with the spandex spinning fluid of step (3) preparation, adopt the method for solution spinning to make heat resistant spandex fiber.
2. the preparation method of a kind of heat resistant spandex fiber according to claim 1 is characterized in that: the apparent viscosity of the spandex spinning fluid that step (3) makes is 1000-7000 poise at 20 ℃.
3
.The preparation method of a kind of heat resistant spandex fiber according to claim 1 is characterized in that: the solution spinning in the step (4), spinning head temperature are 250 ℃, and spinning speed is 600-750 m/min, and the fiber linear density that spinning obtains is 15-70 dtex.
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| CN102719928B (en) * | 2012-06-12 | 2014-03-26 | 浙江开普特氨纶有限公司 | Preparation method for high-stress high-resilience polyurethane fiber |
| CN104630929B (en) * | 2015-03-16 | 2016-05-11 | 浙江华峰氨纶股份有限公司 | Biological easily degraded spandex and preparation method thereof for paper diaper |
| CN104988624A (en) * | 2015-06-23 | 2015-10-21 | 张家港市华阳针纺织品有限公司 | Spandex yarn preparation method |
| CN105780178B (en) * | 2016-04-28 | 2018-08-24 | 浙江开普特氨纶有限公司 | A kind of preparation method of low melting point spandex fibre |
| CN106757485B (en) * | 2016-11-23 | 2019-07-02 | 华峰重庆氨纶有限公司 | A kind of preparation method of high drawing spandex fibre |
| CN106592008B (en) * | 2016-12-14 | 2019-04-16 | 烟台泰和新材料股份有限公司 | A kind of heat resistant spandex fiber and preparation method thereof |
| CN107287677A (en) * | 2017-08-05 | 2017-10-24 | 合肥梵清电子商务有限公司 | A kind of preparation method of heat resistant spandex fiber |
| CN112725928B (en) * | 2020-12-29 | 2023-01-10 | 宁夏宁东泰和新材有限公司 | Preparation method of high-temperature-resistant polyurethane elastic fiber |
| CN114181373B (en) * | 2022-01-29 | 2023-08-11 | 万华化学集团股份有限公司 | Preparation process of comfortable spandex and prepared spandex |
| WO2023169913A1 (en) * | 2022-03-10 | 2023-09-14 | Basf Se | Polyurethane urea and its preparation method |
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| CN101205286A (en) * | 2007-11-23 | 2008-06-25 | 东华大学 | Synthesis and modification method of thermoplastic polyurethanes for melt-spinning spandex |
| CN101701363A (en) * | 2009-11-20 | 2010-05-05 | 中化国际（苏州）新材料研发有限公司 | Production method of differential polyurethane fiber and polyurethane fiber |
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Address after: 312000 office building 339, Yue Wang Road, Shaoxing, Zhejiang (block A) Co-patentee after: Shaoxing University Patentee after: Zhejiang Zhong Bai special fiber Co., Ltd. Address before: 312000 east two road, Shaoxing, Zhejiang province. Co-patentee before: Shaoxing University Patentee before: Zhejiang Kaipute Spandex Co.,Ltd. |