CN104153033B - A kind of preparation method of porous easy dyeing spandex - Google Patents

A kind of preparation method of porous easy dyeing spandex Download PDF

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CN104153033B
CN104153033B CN201410395720.2A CN201410395720A CN104153033B CN 104153033 B CN104153033 B CN 104153033B CN 201410395720 A CN201410395720 A CN 201410395720A CN 104153033 B CN104153033 B CN 104153033B
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spandex
solution
reactor
prepolymer
polyurea
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CN104153033A (en
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温作杨
李燕
刘亚辉
池晓智
梁红军
费长书
席青
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Huafeng Chemical Co ltd
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Zhejiang Huafeng Spandex Co Ltd
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Abstract

The present invention relates to a kind of preparation method of porous easy dyeing spandex, the method is at the first reactor 1stIn Reactor, add polytetramethylene ether diol PTMG, 4 simultaneously, 4-'-diphenylmethane diisocyanate 4,4-MDI, fully carries out prepolymerization reaction, obtains the prepolymer PP with-NCO end-blocking; In high speed dissolving machine Dissolver, adopt DMA DMAC as solvent, to prepolymer, PP fully dissolves, the pre-polymer solution PPs of contained-NCO end-blocking; At the second reactor 2ndIn Reactor, adopt the mixed amine DMAC solution that contains Diamines chain extender, monoamine terminator and hydramine to carry out chain growth, chain termination to PPs simultaneously, prepare end with-OH polyurea based formic acid esters solution; Then, add antioxidant, lubricant, delustering agent, ultraviolet absorber and polyvinylpyrrolidone PVP, dispersed with stirring; Finally, by dry spinning system, the polyurea based formic acid esters solution that contains auxiliary agent is sprayed to silk a stretching, high temperature drying, finish oil, coiling and molding, just obtain easy pore, chromatophilia can spandex.

Description

Preparation method of porous easy-to-dye spandex
Technical Field
The invention relates to a preparation method of porous easily-dyed spandex, belonging to the technical field of polyurethane elastic fiber material manufacturing.
Background
Polyurethane elastic fiber is commonly called spandex, and the chemical structure of the polyurethane elastic fiber generally consists of two parts of soft forging and hard forging. The soft forging is generally polyether, polyester or the like, and the hard forging is generally composed of isocyanate and a chain extender (mostly diamine). Due to the thermodynamic incompatibility between the soft forging and the hard forging, separate domains are formed by dispersion and aggregation and exhibit respective glass transition temperatures, having excellent elastic tensile properties and breaking strength. Spandex is compared with the industrial monosodium glutamate of textiles, and is blended with non-elastic fibers to obtain fabric cloth, so that the comfort and the attractiveness of the fabric to be worn can be greatly improved, and the spandex becomes one of indispensable textile raw materials.
In recent years, with the improvement of living standard, people continuously pursue clothes (such as color, hand feeling, evenness of strips, grain uniformity and the like), the content of spandex of some varieties is higher, and the spandex is woven in a naked yarn form, so that higher requirements are provided for the dyeing performance of the spandex, otherwise, the fabric is easy to generate a white exposure phenomenon under a high drafting condition, and the attractiveness of the clothes is influenced. At present, the dyeing performance of spandex is mainly limited by the following two factors: firstly, the heat resistance of the spandex is poor, and when the spandex is dyed at high temperature (130 ℃ and above), the spandex performance is degraded, and the elasticity and resilience performance are partially lost, so that the spandex cannot be dyed at high temperature; ② the polyurethane has many imino (-NH-) in the chemical structure, which is easy to form firmer hydrogen bond with urethane carbonyl, urea carbonyl, ester carbonyl and ether bond, thus preventing the biological hydrogen bond association between dye molecule and polyurethane molecule, therefore, the best dyeing effect can not be achieved.
So far, there are few reports on spandex dyeing, wherein the nicotai spandex company discloses a special end-capping agent in patent No. cn9611599.x, respectivelyPreparing polyether easy-dyeing spandex. The Nicoti urethane elastic fiber company also discloses a special chain extender adopted in the patent CN200710015248.5Preparing polyether easy-dyeing spandex. Huafeng spandex company discloses in patent CN200910131830.7 that a polyurethane elastic fiber with high temperature resistance and easy dyeing is prepared by using dihydric alcohol and diisocyanate as raw materials and respectively using n-butyl alcohol and diethylamine as reaction control agents in a prepolymerization process and a chain extension process.
Through our research, we found that: patent CN9611599.X, applicationThe methods of patent CN200910131830.7 and patent CN200910131830.7 respectively adopt n-butyl alcohol and diethylamine as terminating agents, and the improvement range of the dyeing performance of spandex is not large. Patent CN200710015248.5 adoptedThe preparation method of the chain extender can effectively improve the dyeing property of spandex under acid dyes, but the dyeing property of the disperse dyes which are commonly adopted at present is not greatly improved.
Disclosure of Invention
The technical problem is as follows: the invention aims to solve the defects of the prior art and provides a preparation method of porous spandex easy to dye.
The technical scheme is as follows: the preparation method of the porous easily-dyed spandex comprises the following steps:
step 1. in the first reactor 1stAdding polytetramethylene ether glycol (PTMG) and 4, 4-diphenylmethane diisocyanate (4, 4-MDI) into a Reactor at the same time, and fully performing prepolymerization reaction to obtain prepolymer PP capped by-NCO;
step 2, in a high-speed Dissolver Dissoller, N-Dimethylacetamide (DMAC) is used as a solvent to fully dissolve the prepolymer PP to obtain prepolymer solution PPs containing-NCO end capping;
step 3. in the second reactor 2ndIn Reactor, adopting mixed amine DMAC solution containing diamine chain extender, monoamine terminator and alcohol amine to simultaneously carry out chain extension and chain termination on PPs, and preparing polyurea formic ether solution with-OH at the tail end;
step 4, adding an antioxidant, a lubricant, a delustering agent, an ultraviolet absorbent and polyvinylpyrrolidone (PVP) into the polyurea formate solution with the-OH at the tail end obtained in the step 3, and fully stirring, dispersing and curing to obtain a polyurea formate spinning solution;
and 5, carrying out spinning stretching, high-temperature drying, oiling with an oil agent, and winding forming on the polyurea-formate spinning solution by virtue of a dry spinning system and a dry spinning process to obtain the spandex with easy pore-forming and easy dyeing properties.
The prepolymerization reaction temperature is 60-90 ℃.
The molecular weight of the polytetramethylene ether glycol PTMG is 1500-3000.
The content of-NCO end group in the prepolymer PP is 2.00 wt% -2.60 wt%.
Diamine in the diamine chain extender is one or more of ethylenediamine, 1, 2-propanediamine, 2-methyl-1, 5-pentanediamine and tetramethyl ethylenediamine; monoamines in the monoamine terminators are dimethylamine, diethylamine, dipropylamine, one or more; the alcohol amine is ethanolamine, diethanolamine, diethylene glycol alcohol amine or isopropanolamine.
The mole ratio of the addition amount of the chain extender diamine in the mixed amine DMAC solution to the addition amounts of the chain terminator monoamine and the alcohol amine is 5-10; the addition amount of the monoamine and the alcohol amine in the chain terminator is 0.5-10 in molar ratio.
The concentration of the mixed amine DMAC solution is 3-8 wt%; the concentration of the polyurethane solution is 30 wt% to 40 wt%.
The addition amount of the polyvinylpyrrolidone PVP accounts for 0.5 wt% -5 wt% of the proportion of the bare spandex filament.
The molecular weight of the polyvinylpyrrolidone PVP is 300000-1300000.
The oiling weight of the oiling agent in the step 5 accounts for 5-10 wt% of the proportion of the spandex.
Has the advantages that: compared with other preparation methods, the method has the following advantages that: (1) since the-OH end groups in ethanolamine are very reactive with the-NCO end groups in the prepolymer, it is found that the reactivity is very low at 2ndThe Reactor has low bulk temperature (generally lower than 90 ℃) and almost no reaction of-OH end group and-NCO end group under the condition that a large amount of-NH 2 end group with high reaction activity exists; and the polymer is in the subsequent high-temperature channel due to the fast spinning speed(generally 900m/min or above), the probability of generating OH end groups and-NCO end groups (the-NCO is obtained by dropping off the monoamine end capping under the high temperature condition) is small, and then a solution with partial-OH polyurea-based formate can be prepared, so that the hydrophilic performance of the polymer can be increased, the hydrogen bond association capacity between the polymer and dye molecules is improved, and the dyeing performance of spandex is improved. (2) The PVP has excellent biocompatibility and hydrophilicity due to the special structure, and can improve the coloring performance of spandex; because PVP has good water solubility, PVP with certain molecular weight and addition amount is added in spandex, a porous structure can be formed on the surface of spandex filaments in the high-temperature dyeing process of the spandex, the specific surface area of the spandex can be improved, so that the dyeing effect of the spandex can be improved, and PVP with different molecular weights or addition amounts can be adopted to achieve the target dyeing performance. Due to the advantages, the aim of preparing the porous easily-dyed spandex can be fulfilled.
Drawings
FIG. 1 Spandex surface morphology before dyeing.
FIG. 2 shows the surface morphology of spandex after dyeing.
Detailed Description
The invention is described in detail below with reference to examples, which are not to be construed as limiting the invention in any way.
Example 1
Step 1, simultaneously feeding 395.16kg of polytetramethylene ether glycol (molecular weight 1800) and 89.97kg of 4, 4-diphenylmethane diisocyanate into a first reactor, and reacting for 2hr at 80 ℃ to obtain a prepolymer (PP);
step 2, simultaneously conveying 469.97kg of prepolymer and 573.91kg of N, N-Dimethylacetamide (DMAC) solvent to a high-speed dissolving machine, and fully dissolving PP under the action of high-speed shearing force to obtain Prepolymer Solution (PPs);
step 3, 1043.88kg of prepolymer solution and 286.57kg of mixed amine DMAC solution (comprising 1.02kg of propylene diamine, 7.72kg of ethylene diamine, 0.99kg of diethylamine and 0.42kg of isopropanolamine) are subjected to chain extension and chain termination simultaneously under the condition of rapid stirring to prepare polyurea-formate polymer solution;
step 4, adding 27.48kg of PVP (polyvinylpyrrolidone) containing an antioxidant, a lubricant, a flatting agent and an ultraviolet absorbent and polyvinylpyrrolidone (PVP accounts for 3.0 wt% of the spandex) into the polyurea-formate solution obtained in the step 3, and fully stirring, dispersing and curing to obtain a polyurea-formate spinning solution;
and 5, performing spinning stretching, high-temperature drying, oiling with an oiling agent (the oiling agent accounts for 7 percent of the proportion of the spandex) and winding forming on the polyurea formate spinning solution by virtue of a dry spinning system to obtain the spandex with easy pore-forming and dyeing properties.
Example 2
Step 1, simultaneously feeding 402.50kg of polytetramethylene ether glycol (molecular weight 1800) and 90.17kg of 4, 4-diphenylmethane diisocyanate into a first reactor, and reacting for 2hr at 80 ℃ to obtain a prepolymer (PP);
step 2, simultaneously conveying 487.12kg of prepolymer and 574.42kg of N, N-Dimethylacetamide (DMAC) solvent to a high-speed dissolving machine, and fully dissolving PP under the action of high-speed shearing force to obtain Prepolymer Solution (PPs);
step 3, 1051.45kg of prepolymer solution and 287.23kg of mixed amine DMAC solution (comprising 1.03kg of propylene diamine, 7.69kg of ethylene diamine, 0.97kg of diethylamine and 0.45kg of isopropanolamine) are subjected to chain extension and chain termination simultaneously under the condition of rapid stirring to prepare polyurea-formate polymer solution;
step 4, adding 16.91kg of PVP (polyvinylpyrrolidone) containing an antioxidant, a lubricant, a flatting agent and an ultraviolet absorbent and polyvinylpyrrolidone (PVP accounts for 1.5 wt% of the spandex) into the polyurea-formate solution obtained in the step 3, and fully stirring, dispersing and curing to obtain a polyurea-formate spinning solution;
and 5, performing spinning stretching, high-temperature drying, oiling with an oiling agent (the oiling agent accounts for 6.5 percent of the proportion of the spandex) and winding forming on the polyurea-formate spinning solution by virtue of a dry spinning system to obtain the spandex with easy pore-forming and easy dyeing properties.
Example 3
Step 1, simultaneously feeding 375.87kg of polytetramethylene ether glycol (molecular weight is 1800) and 83.52kg of 4, 4-diphenylmethane diisocyanate into a first reactor, and reacting for 2hr at 80 ℃ to obtain a prepolymer (PP);
step 2, simultaneously conveying 452.43kg of prepolymer and 554.82kg of N, N-Dimethylacetamide (DMAC) solvent to a high-speed dissolving machine, and fully dissolving PP under the action of high-speed shearing force to obtain Prepolymer Solution (PPs);
step 3, preparing a polyurea-urethane polymer solution by simultaneously carrying out chain growth and chain termination on 1043.88kg of prepolymer solution and 273.27kg of mixed amine DMAC solution (comprising 0.97kg of propylene diamine, 7.12kg of ethylene diamine, 0.94kg of diethylamine and 0.52kg of isopropanolamine) under the condition of rapid stirring;
step 4, adding 14.44kg of PVP (polyvinylpyrrolidone) (PVP accounts for 1.0 wt% of spandex) containing antioxidant, lubricant, flatting agent and ultraviolet absorbent into the polyurea-formate solution obtained in the step 3, and fully stirring, dispersing and curing to obtain polyurea-formate spinning solution;
and 5, performing spinning stretching, high-temperature drying, oiling with an oiling agent (the oiling agent accounts for 6.5 percent of the proportion of the spandex) and winding forming on the polyurea-formate spinning solution by virtue of a dry spinning system to obtain the spandex with easy pore-forming and easy dyeing properties.
Example 4
Step 1, simultaneously feeding 375.81kg of polytetramethylene ether glycol (molecular weight is 1800) and 83.49kg of 4, 4-diphenylmethane diisocyanate into a first reactor, and reacting for 2hr at 80 ℃ to obtain a prepolymer (PP);
step 2, simultaneously conveying 452.12kg of prepolymer and 555.29kg of N, N-Dimethylacetamide (DMAC) solvent to a high-speed dissolving machine, and fully dissolving PP under the action of high-speed shearing force to obtain Prepolymer Solution (PPs);
step 3, 1045.51kg of prepolymer solution and 274.12kg of mixed amine DMAC solution (comprising 0.99kg of propylene diamine, 7.31kg of ethylene diamine, 0.92kg of diethylamine and 0.68kg of isopropanolamine) are subjected to chain extension and chain termination simultaneously under the condition of rapid stirring to prepare polyurea-formate polymer solution;
step 4, adding 12.00kg of PVP (polyvinylpyrrolidone) containing an antioxidant, a lubricant, a flatting agent and an ultraviolet absorbent and polyvinylpyrrolidone (PVP accounts for 0.5 wt% of the spandex) into the polyurea-formate solution obtained in the step 3, and fully stirring, dispersing and curing to obtain a polyurea-formate spinning solution;
and 5, carrying out spinning stretching, high-temperature drying, oiling of an oil agent (the oil agent accounts for 5 percent of the proportion of the spandex) and winding forming on the polyurea formate spinning solution by virtue of a dry spinning system, so as to obtain the spandex with easy pore-forming and easy dyeing properties.

Claims (4)

1. A preparation method of porous easily-dyed spandex is characterized by comprising the following steps:
step 1. in the first reactor 1stAdding polytetramethylene ether glycol (PTMG) and 4, 4-diphenylmethane diisocyanate (4, 4-MDI) into a Reactor at the same time, and fully performing prepolymerization reaction to obtain prepolymer PP capped by-NCO;
step 2, in a high-speed Dissolver Dissoller, N-Dimethylacetamide (DMAC) is used as a solvent to fully dissolve the prepolymer PP to obtain prepolymer solution PPs containing-NCO end capping;
step 3. in the second reactor 2ndIn Reactor, adopting mixed amine DMAC solution containing diamine chain extender, monoamine terminator and alcohol amine to simultaneously carry out chain extension and chain termination on PPs, and preparing polyurea formic ether solution with-OH at the tail end;
step 4, adding an antioxidant, a lubricant, a delustering agent, an ultraviolet absorbent and polyvinylpyrrolidone (PVP) into the polyurea formate solution with the-OH at the tail end obtained in the step 3, and fully stirring, dispersing and curing to obtain a polyurea formate spinning solution;
step 5, with the help of a dry spinning system and a dry spinning process, carrying out spinning stretching, high-temperature drying, oiling with an oil agent, and winding forming on the polyurea-formate spinning solution to obtain spandex with easy pore-forming and easy dyeing properties;
wherein,
the molecular weight of the polytetramethylene ether glycol PTMG is 1500-3000;
the content of-NCO end group in the prepolymer PP is 2.00 wt% -2.60 wt%;
diamine in the diamine chain extender is one or more of ethylenediamine, 1, 2-propanediamine, 2-methyl-1, 5-pentanediamine and tetramethyl ethylenediamine; monoamines in the monoamine terminators are one or more of dimethylamine, diethylamine and dipropylamine; the alcohol amine is ethanolamine, diethanolamine, diethylene glycol alcohol amine or isopropanolamine;
the mole ratio of the addition amount of the chain extender diamine in the mixed amine DMAC solution to the addition amounts of the chain terminator monoamine and the alcohol amine is 5-10; the adding amount of the monoamine and the alcohol amine in the chain terminator is 0.5-10 in molar ratio;
the concentration of the mixed amine DMAC solution is 3-8 wt%; the concentration of the polyurethane solution is 30-40 wt%;
the addition amount of the polyvinylpyrrolidone PVP accounts for 0.5 wt% -5 wt% of the proportion of the bare spandex filament.
2. The method for preparing porous dyeable spandex according to claim 1, wherein the prepolymerization temperature is 60 ℃ to 90 ℃.
3. The method for preparing porous spandex easy to dye according to claim 1, wherein the molecular weight of polyvinylpyrrolidone (PVP) is 300000-1300000.
4. The method for preparing porous spandex that is easy to dye according to claim 1, wherein the oil applied in step 5 accounts for 5-10 wt% of the spandex specific gravity.
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CN105177755B (en) * 2015-07-30 2017-05-17 浙江华峰氨纶股份有限公司 High-concentration polyurethane-urea spinning solution and preparation method therefor
CN105442083B (en) * 2015-12-29 2017-09-12 浙江华峰氨纶股份有限公司 A kind of preparation method of reactive dye easy dyeing spandex
CN106702526B (en) * 2016-12-15 2019-08-20 浙江华峰氨纶股份有限公司 A kind of disperse dyeable and the excellent spandex and preparation method thereof of high temperature resistance
CN109537092B (en) * 2018-11-26 2021-01-05 华峰重庆氨纶有限公司 Preparation method of multifunctional polyurethane elastic fiber
CN110923844B (en) * 2019-12-16 2022-06-03 华峰化学股份有限公司 Preparation method of spandex easy to unwind
CN111424332B (en) * 2020-04-28 2022-07-22 华峰化学股份有限公司 Special spandex for mask belt and preparation method thereof
CN116377614B (en) * 2023-02-08 2025-02-18 华峰化学股份有限公司 A kind of high resilience active dyeable polyurethane urea elastic fiber

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