CN111379045A - Elasticity-controllable spandex and preparation method thereof - Google Patents

Elasticity-controllable spandex and preparation method thereof Download PDF

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Publication number
CN111379045A
CN111379045A CN202010412405.1A CN202010412405A CN111379045A CN 111379045 A CN111379045 A CN 111379045A CN 202010412405 A CN202010412405 A CN 202010412405A CN 111379045 A CN111379045 A CN 111379045A
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spandex
alcohol
controllable
aliphatic
elasticity
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CN111379045B (en
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魏朋
娄贺娟
张一风
章伟
郭正
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Zhongyuan University of Technology
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Zhongyuan University of Technology
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/94—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
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    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
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    • C08G18/428—Lactides
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6648—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
    • C08G18/6651—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
    • C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/07—Addition of substances to the spinning solution or to the melt for making fire- or flame-proof filaments
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
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    • D01F1/02—Addition of substances to the spinning solution or to the melt
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    • D01F1/00—General methods for the manufacture of artificial filaments or the like
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    • D01F1/00—General methods for the manufacture of artificial filaments or the like
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Abstract

The invention belongs to the field of high polymer materials, and particularly relates to elasticity-controllable spandex and a preparation method thereof. Isocyanate and polydihydric alcohol react in polar amide solution to prepare isocyanate end-capped prepolymer, then chain extension is carried out by amine or alcohol chain extender, and spandex polymer with the weight-average molecular weight more than 8 ten thousand is obtained after the end-capping reaction is terminated by the end-capping agent; then the spandex fiber with the fineness of 5-40D is prepared by dry spinning, and finally the adjustable and controllable elongation at break is within 100-500 percent. The spandex polymer related by the invention also has excellent thermal stability and mechanical property, and compared with the conventional spandex polymer, the thermal decomposition temperature is higher than 240 ℃, and the strength is higher than 1.2 cN/dtex.

Description

Elasticity-controllable spandex and preparation method thereof
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to elasticity-controllable spandex and a preparation method thereof.
Background
The spandex has excellent elastic performance which is not possessed by other fibers, the elongation at break of the spandex is generally 400-700%, and the elastic recovery rate after 300% of elongation can reach more than 95%. Because the spandex 6-8% is added into the fabric, the fabric has good elasticity, the fabric can be endowed with comfort which other fibers do not have, and the grade of clothes is greatly improved, the spandex is generally known as 'monosodium glutamate in textile fibers', and is an indispensable special fiber for developing high-grade elastic textiles. However, because of its high elasticity, it is necessary to strictly control the tension of spandex during weaving and dyeing, and it is generally necessary to further process bare spandex yarn into core yarn, covering yarn or twisted yarn, etc., to be mixed with natural fiber and chemical fiber in different proportions, and to form various forms of elastic fabrics by knitting or weaving. On the other hand, the elasticity of the spandex fiber is within 500 percent, so that the requirement of taking can be met; while generally high elasticity means lower strength, modulus and heat resistance. Therefore, how to control the elasticity of spandex fibers and realize the adjustability and controllability of the elasticity within a certain range is very necessary to improve the physical properties and the processing and forming properties of the spandex fibers.
Disclosure of Invention
The invention provides elasticity-controllable spandex and a preparation method thereof, and solves the problem that spandex fibers in the prior art are not favorable for obtaining excellent physical properties and forming processing due to overlarge elasticity and uncontrollable elasticity.
The technical scheme of the invention is realized as follows:
a preparation method of elasticity-controllable spandex comprises the following steps:
(1) dissolving diisocyanate and polydihydric alcohol in polar amide solution, and reacting at 80-100 ℃ for 80-120min to prepare isocyanate end-capped prepolymer solution;
(2) dissolving a chain extender and a monofunctional alcohol end-capping reagent in DMF (dimethyl formamide) to prepare a mixed solution;
(3) adding the mixed solution obtained in the step (2) into the prepolymer solution obtained in the step (1), and continuously reacting to obtain a polyurethane solution with the weight-average molecular weight of more than 8 ten thousand;
(4) and (3) adding the additive into the polyurethane solution obtained in the step (3) after ball milling, refining and dispersing, curing to obtain a spinning solution, and performing dry spinning to obtain the elasticity-controllable spandex.
The mass ratio of diisocyanate to polydiol in the step (1) is (52-68): (32-48).
The diisocyanate comprises one or the combination of two of 1, 5-naphthalene diisocyanate, 4 '-diisocyanato-3, 3' -dimethyl biphenyl, m-phenylene diisocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate, 4 '-methylene bis (phenyl isocyanate), toluene diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane 4,4' -diisocyanate and isophorone diisocyanate.
The polydiol is aliphatic polydiol and biphenyl structure dihydric alcohol with the molecular weight of 100-2000, and the mass ratio of the aliphatic polydiol to the biphenyl structure dihydric alcohol is as follows: (40-100): (0-60); wherein the aliphatic poly-diol is any one of polycaprolactone diol, polyethylene glycol, polycarbonate diol, polytetrahydrofuran ether glycol, polylactide diol, polyethylene oxide diol, polybutylene succinate diol, polyhexamethylene adipate diol and polyhexamethylene succinate diol; the structural formula of the dihydric alcohol with the biphenyl structure is as follows:
Figure 935757DEST_PATH_IMAGE001
(wherein, n and m are integers of 2-12);
the polar amide solution is DMF or DMAc.
The mass fraction of the chain extender and the monofunctional alcohol end-capping reagent in the mixed solution in the step (2) is 1-10%;
wherein the chain extender is one or the combination of two of an amine chain extender and an alcohol chain extender with the functionality of more than or equal to 2, and the using amount of the chain extender with the functionality of 2 accounts for 50-90%;
wherein the monofunctional alcohol blocking agent is aliphatic alcohol with 1-10 carbon atoms or dialkyl amine with 4-10 carbon atoms, wherein the aliphatic alcohol with 1-10 carbon atoms is any one of methanol, ethanol, propanol or butanol, and the dialkyl amine with 4-10 carbon atoms is any one of diethylamine, N-ethyl-N-propylamine, diisopropylamine, N-tert-butyl-N methylamine and N-tert-butyl-N isopropylamine.
The amine chain extender is aliphatic diamine, triamine, quaternary amine, aromatic diamine and tertiary amine compounds with the carbon number of 2-16; wherein the aliphatic diamine compound is any one of ethylenediamine, propylenediamine, methylcyclohexanediamine, pentylenediamine, hexylenediamine, and polyetherdiamine; the aliphatic triamine is any one of 3,3' -diamino dipropylamine and diethylenetriamine; the aliphatic quaternary amine is one of pentamine, triethylene tetramine and triethylene tetramine; the aromatic diamine is any one of m-phenylenediamine, biphenyldiamine, p-phenylenediamine, diethyltoluenediamine, dimethylthiotoluenediamine, 4' -methylenebis (6-methyl-2-ethylaniline), 4' -methylenebis (2-ethyl) aniline and 4,4' -bis-sec-butylaminodiphenylmethane; the aromatic triamine is any one of N, N ', N ' ' -triphenyl-1, 3, 5-benzene triamine and sym-benzene triamine; the alcohol chain extender is aliphatic dihydric alcohol, trihydric alcohol, tetrahydric alcohol and aromatic dihydric alcohol compounds with the carbon atom number of 2-12; wherein the aliphatic dihydric alcohol is any one of ethylene glycol, butanediol, hexanediol, diethylene glycol, tripropylene glycol or propylene glycol; the aliphatic trihydric alcohol is any one of glycerol and trimethylolpropane; the aliphatic tetrahydric alcohol is pentaerythritol; the aromatic diol is any one of hydroquinone dihydroxyethyl ether, resorcinol bis (2-hydroxyethyl) ether and 3-hydroxyethyloxyethyl-1-hydroxyethyl benzene diether.
The molar ratio of the sum of the number of amino groups and hydroxyl groups in the mixed solution in the step (2) in the step (3) to the isocyanate groups in the prepolymer solution in the step (1) is (1-3): 1.
The amount of the additive in the step (4) is 0.1-5% of the mass fraction of the polyurethane solution obtained in the step (3); the additive is two or more of antioxidant, uvioresistant agent, antibacterial agent, flame retardant, pigment, nano-particles, stabilizer and luminescent agent.
The spandex fiber prepared by the method has the fineness of 5-40D, and the breaking elongation of the spandex fiber is adjustable and controllable between 100 and 500 percent.
The invention has the following beneficial effects:
(1) isocyanate and polydihydric alcohol react in polar amide solution to prepare isocyanate end-capped prepolymer, then chain extension is carried out by amine or alcohol chain extender, and spandex polymer with the weight-average molecular weight more than 8 ten thousand is obtained after the end-capping reaction is terminated by the end-capping agent; then the spandex fiber with the fineness of 5-40D is prepared by dry spinning, and finally the adjustable and controllable elongation at break is within 100-500 percent. The mass fraction of soft segment polydihydric alcohol is reduced by selecting polydihydric alcohol with shorter molecular chain, namely low molecular weight, and biphenyl structure dihydric alcohol is introduced to regulate the proportion of soft segments and soft segments, so that the structure of hard segment molecular chain with high mass ratio is designed, and meanwhile, the movement capability of the soft segment coil molecular structure can be effectively reduced by regulating the density of cross-linking points, and the adjustable and controllable elongation at break (namely elasticity) of 100-500 percent is realized.
(2) The spandex polymer related by the invention also has excellent thermal stability and mechanical property, and compared with the conventional spandex polymer, the thermal decomposition temperature is higher than 240 ℃, and the strength is higher than 1.2 cN/dtex.
(3) Through the use of the additive, the performance of the spandex fiber such as antibacterial property, flame retardance, antistatic property, luminescence and the like can be endowed, and the application range of the spandex fiber is expanded.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is an infrared spectrum of spandex of example 1.
FIG. 2 is a graph of the thermal weight loss of spandex in examples 1-3.
Figure 3 is a microscope image (magnification 1000 x) of the apparent morphology of spandex in example 1.
Fig. 4 is a graph of thermal weight loss and a graph of DTG of spandex in comparative example.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
The preparation method of the elasticity-controllable spandex of the embodiment comprises the following steps:
adding isophorone diisocyanate and polycaprolactone diol into N, N-Dimethylformamide (DMF) to react for 90min at 80 ℃ to obtain isocyanate end-capped prepolymer, wherein the mass ratio of the diisocyanate to the diol is 55: 45; dissolving chain extender ethylenediamine and 3,3' -diamino dipropylamine into DMF (dimethyl formamide) together with end-capping reagent methanol according to a molar ratio of 5:5 to prepare a mixed solution with the mass fractions of 2% and 1%, and adding the mixed solution into the prepolymer solution to continuously react (in a reaction system, the molar ratio of the sum of the number of amino groups and hydroxyl groups to isocyanic acid radical is 1: 1) to obtain a polyurethane solution with the molecular weight of 82685; adding an antioxidant, an uvioresistant agent and an antibacterial agent into a polyurethane solution (the total mass fraction of the additive is 5%) after ball milling refinement and dispersion, curing to obtain a spinning solution, and performing dry spinning to obtain the spandex fiber with the fineness of 10D. The breaking strength of the fiber is 1.3cN/dtex, the elongation at break is 500%, the infrared spectrogram of the spandex fiber is shown in figure 1, the thermal weight loss curve is shown in figure 2, the thermal decomposition temperature is 248 ℃, and the microscope picture of the apparent morphology with the magnification of 1000x is shown in figure 3.
Example 2
The preparation method of the elasticity-controllable spandex of the embodiment comprises the following steps:
adding 1, 5-naphthalene diisocyanate, 4,4' -diisocyanato-3, 3' -dimethylbiphenyl and polytetrahydrofuran ether glycol (Mw 1000), and reacting 4,4' -bis (6-hydroxyhexaneoxy) biphenyl in N, N-dimethylacetamide (DMAc) at 85 ℃ for 100min to obtain an isocyanate end-capped prepolymer, wherein the mass ratio of diisocyanate to dihydric alcohol is 60:40, and the polytetrahydrofuran ether glycol accounts for 50% of the dihydric alcohol; dissolving chain extender propylene diamine and pentaerythritol tetraamine and end-capping reagent diethylamine in DMF according to the molar ratio of 6:4 to prepare a mixed solution with the mass fraction of both being 5%, adding the mixed solution into the prepolymer solution for continuous reaction (in the reaction system, the molar ratio of the sum of the number of amino groups and hydroxyl groups to isocyanic acid radical is 1: 1) to obtain a polyurethane solution with the molecular weight of 120800; adding an antioxidant and a stabilizer into a polyurethane solution (the total mass fraction of the additive is 1.8%) after ball milling, refining and dispersing, curing to obtain a spinning solution, and performing dry spinning to obtain the spandex fiber with the fineness of 15D. The breaking strength of the fiber is 1.6cN/dtex, the elongation at break is 296%, the thermal weight loss curve is shown in figure 2, and the thermal decomposition temperature is 270 ℃.
Example 3
The preparation method of the elasticity-controllable spandex of the embodiment comprises the following steps:
adding 4,4 '-methylenebis (phenyl isocyanate) and polytetrahydrofuran ether glycol (Mw 2000), 4,4' -bis (6-hydroxyhexyloxy) biphenyl into N, N-dimethylacetamide (DMAc) to react for 120min at 95 ℃ to obtain isocyanate end-capped prepolymer, wherein the mass ratio of diisocyanate to dihydric alcohol is 55:45, and the polytetrahydrofuran ether glycol accounts for 60% of the dihydric alcohol; dissolving chain extender methyl cyclohexanediamine and N, N ', N ' ' -triphenyl-1, 3, 5-benzene triamine and end capping agent ethanol in DMAc according to a molar ratio of 9:1 to prepare mixed solutions with the mass fractions of 3% and 1%, respectively, adding the mixed solutions into the prepolymer solution to continue reacting (in a reaction system, the molar ratio of the sum of the number of amino groups and hydroxyl groups to isocyanic acid groups is 1.5: 1) to obtain a polyurethane solution with the molecular weight of 119260; adding an antioxidant, a stabilizer and carbon nano tubes into a polyurethane solution (the total mass fraction of the additive is 4%) after ball milling, refining and dispersing, curing to obtain a spinning solution, and performing dry spinning to obtain the spandex fiber with the fineness of 12D. The breaking strength of the fiber is 1.5cN/dtex, the elongation at break is 260%, and the thermal weight loss curve is shown in figure 2, and the thermal decomposition temperature is 261 ℃.
Example 4
The preparation method of the elasticity-controllable spandex of the embodiment comprises the following steps:
adding m-xylylene diisocyanate, 4,4' -diisocyanato-3, 3' -dimethyl biphenyl and polyethylene glycol (Mw 200), and reacting 4,4' -bis (6-hydroxyhexyloxy) biphenyl in DMF at 85 ℃ for 110min to obtain isocyanate end-capped prepolymer, wherein the mass ratio of diisocyanate to dihydric alcohol is 65:35, and the polyethylene glycol accounts for 70% of the dihydric alcohol; dissolving chain extender pentanediamine and glycerol and end-capping reagent N-ethyl-N-propylamine in DMF according to the molar ratio of 8:2 to prepare mixed solution with the mass fractions of 8% and 3%, adding the mixed solution into the prepolymer solution for continuous reaction (in a reaction system, the molar ratio of the sum of the number of amino groups and hydroxyl groups to isocyanic acid radical is 1.9: 1) to obtain a polyurethane solution with the molecular weight of 140830; adding an antioxidant and a stabilizer into a polyurethane solution (the total mass fraction of the additive is 0.5%) after ball milling, refining and dispersing, curing to obtain a spinning solution, and performing dry spinning to obtain the spandex fiber with the fineness of 20D. The breaking strength of the fiber is 1.8cN/dtex, the elongation at break is 170%, and the thermal decomposition temperature is 274 ℃.
Example 5
The preparation method of the elasticity-controllable spandex of the embodiment comprises the following steps:
adding p-phenylene diisocyanate and polycarbonate diol (Mw 860), 4,4' -bis (6-hydroxyhexyloxy) biphenyl into DMF, and reacting at 85 ℃ for 100min to obtain isocyanate end-capped prepolymer, wherein the mass ratio of the diisocyanate to the diol is 55:45, and the polycarbonate diol accounts for 80% of the diol; dissolving chain extender hexamethylene diamine and pentaerythritol and end-capping reagent N-ethyl-N-propylamine in DMF according to the molar ratio of 7:3 to prepare mixed solution with the mass fractions of 9% and 2%, and adding the mixed solution into the prepolymer solution for continuous reaction (in a reaction system, the molar ratio of the sum of the number of amino groups and hydroxyl groups to isocyanic acid radical is 2: 1) to obtain a polyurethane solution with the molecular weight of 126250; adding an antioxidant, a stabilizer and graphene into a polyurethane solution (the total mass fraction of additives is 1.6%) after ball milling, refining and dispersing, curing to obtain a spinning solution, and performing dry spinning to obtain the spandex fiber with the fineness of 25D. The breaking strength of the fiber is 1.5cN/dtex, the elongation at break is 320 percent, and the thermal decomposition temperature is 283 ℃.
Example 6
The preparation method of the elasticity-controllable spandex of the embodiment comprises the following steps:
toluene diisocyanate and polylactide diol (Mw 620), 4,4' -bis (6-hydroxyhexyloxy) biphenyl are added into DMAc to react for 120min at 80 ℃ to obtain isocyanate end-capped prepolymer, wherein the mass ratio of the diisocyanate to the diol is 65:35, and the content of the polylactide diol in the diol is 40%; dissolving butanediol and pentaerythritol serving as chain extenders and methanol serving as an end-capping reagent in DMAc according to a molar ratio of 5:5 to prepare a mixed solution with the mass fractions of 1% and 9%, adding the mixed solution into a prepolymer solution, and continuously reacting (in a reaction system, the molar ratio of the sum of the number of amino groups and hydroxyl groups to isocyanic acid radical is 1.9: 1) to obtain a polyurethane solution with the molecular weight of 82090; adding an antioxidant, a stabilizer and titanium dioxide into a polyurethane solution (the total mass fraction of the additive is 3%) after ball milling and refining and dispersion, curing to obtain a spinning solution, and performing dry spinning to obtain the spandex fiber with the fineness of 40D. The breaking strength of the fiber is 1.9cN/dtex, the elongation at break is 100 percent, and the thermal decomposition temperature is 295 ℃.
Example 7
The preparation method of the elasticity-controllable spandex of the embodiment comprises the following steps:
adding 4,4 '-methylene bis (phenyl isocyanate) and polyethylene oxide dihydric alcohol (Mw 1500), and adding 4,4' -bis- (6-hydroxyhexyloxy) biphenyl into DMAc to react for 100min at 80 ℃ to obtain isocyanate-terminated prepolymer, wherein the mass ratio of diisocyanate to dihydric alcohol is 52:48, and the content of polylactide dihydric alcohol in the dihydric alcohol is 50%; dissolving a chain extender of hydroquinone dihydroxyethyl ether and pentaerythritol tetraamine and an end capping agent of diisopropylamine in DMAc according to a molar ratio of 6:4 to prepare a mixed solution with the mass fraction of both being 8%, adding the mixed solution into a prepolymer solution for continuous reaction (in a reaction system, the molar ratio of the sum of the number of amino groups and hydroxyl groups to isocyanic acid radicals is 1.6: 1) to obtain a polyurethane solution with the molecular weight of 92600; adding an antioxidant, a stabilizer and clay into a polyurethane solution (the total mass fraction of the additive is 2.5%) after ball milling and refining and dispersion, curing to obtain a spinning solution, and performing dry spinning to obtain the spandex fiber with the fineness of 30D. The breaking strength of the fiber is 1.6cN/dtex, the elongation at break is 162 percent, and the thermal decomposition temperature is 280 ℃.
Example 8
The preparation method of the elasticity-controllable spandex of the embodiment comprises the following steps:
adding m-xylylene diisocyanate and poly (butylene succinate) dihydric alcohol (Mw 1800) and 4,4' -bis- (6-hydroxyhexyloxy) biphenyl into DMF, and reacting at 90 ℃ for 90min to obtain an isocyanate end-capped prepolymer, wherein the mass ratio of the diisocyanate to the dihydric alcohol is 68:32, and the poly (butylene succinate) dibasic content in the dihydric alcohol is 80%; dissolving chain extender resorcinol bis (2-hydroxyethyl) ether and trimethylolpropane and end capping agent N-tert-butyl-N-methylamine in DMF according to a molar ratio of 8:2 to prepare mixed solutions with mass fractions of 7% and 1%, and adding the mixed solutions into the prepolymer solution for continuous reaction (in a reaction system, the molar ratio of the sum of the number of amine groups and hydroxyl groups to isocyanic acid radicals is 2: 1) to obtain a polyurethane solution with the molecular weight of 146150; adding the antioxidant and the pigment into a polyurethane solution (the total mass fraction of the additive is 0.5%) after ball milling, refining and dispersing, curing to obtain a spinning solution, and performing dry spinning to obtain the 25D-fineness spandex fiber. The breaking strength of the fiber is 1.4cN/dtex, the elongation at break is 240 percent, and the thermal decomposition temperature is 260 ℃.
Example 9
The preparation method of the elasticity-controllable spandex of the embodiment comprises the following steps:
adding 4,4' -diisocyanato-3, 3' -dimethylbiphenyl, p-phenylene diisocyanate and poly (hexamethylene adipate) diol (Mw 800), and adding 4,4' -bis (6-hydroxyhexyloxy) biphenyl into DMF to react at 90 ℃ for 110min to obtain an isocyanato-terminated prepolymer, wherein the mass ratio of diisocyanate to diol is 60:40, and the proportion of poly (hexamethylene adipate) diol in diol is 40%; dissolving chain extender methylcyclohexanediamine and trimethylolpropane and end-capping reagent N-tert-butyl-N isopropylamine in DMF according to the molar ratio of 5:5 to prepare mixed solutions with the mass fractions of 6% and 2%, respectively, adding the mixed solutions into the prepolymer solution to continue reacting (in a reaction system, the molar ratio of the sum of the number of amino groups and hydroxyl groups to isocyanic acid radicals is 1.5: 1) to obtain a polyurethane solution with the molecular weight of 88260; adding the antioxidant and the antibacterial agent into a polyurethane solution (the total mass fraction of the additive is 0.5%) after ball milling, refining and dispersing, curing to obtain a spinning solution, and performing dry spinning to obtain the spandex fiber with the fineness of 20D. The breaking strength of the fiber is 1.6cN/dtex, the elongation at break is 178 percent, and the thermal decomposition temperature is 271 ℃.
Example 10
The preparation method of the elasticity-controllable spandex of the embodiment comprises the following steps:
adding toluene diisocyanate and poly (hexamethylene succinate) (Mw 600), 4,4' -bis- (6-hydroxyhexyloxy) biphenyl into DMF, and reacting at 80 ℃ for 100min to obtain isocyanate end-capped prepolymer, wherein the mass ratio of the diisocyanate to the dihydric alcohol is 55:45, and the proportion of the poly (hexamethylene succinate) in the dihydric alcohol is 70%; dissolving chain extender diethylene glycol and triethylene tetramine and end-capping reagent propanolamine in DMF according to a molar ratio of 7:3 to prepare mixed solutions with mass fractions of 7% and 3%, respectively, adding the mixed solutions into the prepolymer solution to continue reaction (in a reaction system, the molar ratio of the sum of the number of amino groups and hydroxyl groups to isocyanic acid radical is 3: 1) to obtain a polyurethane solution with the molecular weight of 105400; the antioxidant and the luminous agent are added into a polyurethane solution (the total mass fraction of the additive is 4%) after ball milling, refining and dispersion, then a spinning solution is obtained after curing, and the spandex fiber with the fineness of 15D is obtained through dry spinning. The breaking strength of the fiber is 1.2cN/dtex, the elongation at break is 428%, and the thermal decomposition temperature is 257 ℃.
Example 11
The preparation method of the elasticity-controllable spandex of the embodiment comprises the following steps:
adding 1, 5-naphthalene diisocyanate and polyethylene oxide dihydric alcohol (Mw 100), 4,4' -bis- (6-hydroxyhexyloxy) biphenyl into DMAc to react for 100min at 100 ℃ to obtain isocyanate end-capped prepolymer, wherein the mass ratio of diisocyanate to dihydric alcohol is 56:44, and the ratio of poly (hexylene glycol succinate) in the dihydric alcohol is 80%; dissolving chain extender propylene glycol and pentaerythritol as well as end-capping reagent triethanolamine in DMAc according to the molar ratio of 8:2 to prepare mixed solution with the mass fractions of 10% and 4%, adding the mixed solution into the prepolymer solution for continuous reaction (in a reaction system, the molar ratio of the sum of the number of amino groups and hydroxyl groups to isocyanic acid radical is 2.6: 1) to obtain a polyurethane solution with the molecular weight of 141800; adding an antioxidant and a stabilizer into a polyurethane solution (the total mass fraction of the additive is 5%) after ball milling, refining and dispersing, curing to obtain a spinning solution, and performing dry spinning to obtain the 25D-fineness spandex fiber. The breaking strength of the fiber is 1.8cN/dtex, the elongation at break is 112 percent, and the thermal decomposition temperature is 287 ℃.
Example 12
The preparation method of the elasticity-controllable spandex of the embodiment comprises the following steps:
adding 4,4 '-methylene bis (phenyl isocyanate), hexamethylene diisocyanate and polytetrahydrofuran ether glycol (Mw 800), and reacting 4,4' -bis (6-hydroxyhexyloxy) biphenyl in DMAc at 90 ℃ for 110min to obtain isocyanate end-capped prepolymer, wherein the mass ratio of diisocyanate to dihydric alcohol is 60:40, and the polytetrahydrofuran ether glycol in the dihydric alcohol accounts for 40%; dissolving chain extender ethylenediamine and diethylenetriamine and end capping agent butanol amine in a molar ratio of 9:1 in DMAc to prepare a mixed solution with the mass fraction of both being 10%, adding the mixed solution into the prepolymer solution for continuous reaction (in a reaction system, the molar ratio of the sum of the number of amino groups and hydroxyl groups to isocyanic acid radical is 2: 1) to obtain a polyurethane solution with the molecular weight of 104000; adding an antioxidant, a flame retardant and a stabilizer into a polyurethane solution (the total mass fraction of the additive is 2%) after ball milling and refining and dispersion, curing to obtain a spinning solution, and performing dry spinning to obtain the spandex fiber with the fineness of 30D. The breaking strength of the fiber is 1.7cN/dtex, the elongation at break is 166 percent, and the thermal decomposition temperature is 274 ℃.
Comparative example
The preparation method of the elasticity-controllable spandex of the embodiment comprises the following steps:
adding 4,4' -methylene bis (phenyl isocyanate) and polytetrahydrofuran ether glycol (Mw 4000) into N, N-Dimethylformamide (DMF) according to the mass ratio of 40:55-50:50, and reacting at 80 ℃ for 95min to obtain isocyanate end-capped prepolymer; dissolving chain extender ethylenediamine and end-capping reagent diethylamine in DMF to prepare mixed solution with mass fraction of 6%, adding the mixed solution into the prepolymer solution to continue reaction to obtain polyurethane solution with molecular weight of 82000-93000; adding an antioxidant and an uvioresistant agent (the mass fraction is 1%) into a polyurethane solution after ball milling refinement and dispersion, curing to obtain a spinning solution, and performing dry spinning to obtain the spandex fiber with the fineness of 20D. The breaking strength of the fiber is 0.8-1.5cN/dtex, the elongation at break is 520-680 percent, and the thermal decomposition temperature is 225-234 ℃. FIG. 4 is a thermal weight loss curve of spandex prepared according to the above method, and the thermal decomposition temperature is 230 ℃ and is lower than 240 ℃.
Examples of the effects of the invention
In the comparative example, the conventional molecular composition and chain extension method of spandex has the advantages that the soft segment proportion is too high, the molecular chain of the soft segment is longer and lacks crosslinking sites, so the breaking elongation is more than 500 percent, the elasticity is higher, the breaking length is not more than 1.5cN/dtex, and the thermal decomposition temperature is less than 240 ℃. According to the invention, through the molecular structure design, the proportion of a hard segment is improved, the length of a soft segment molecular chain is reduced, and the aromatic chain extender and the crosslinking site are introduced, so that the adjustability and controllability of the breaking elongation rate within 100-500% are effectively realized, and the strength can reach 1.9cN/dtex at most.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (9)

1. A preparation method of elasticity-controllable spandex is characterized by comprising the following steps:
(1) dissolving diisocyanate and polydihydric alcohol in polar amide solution, and reacting at 80-100 ℃ for 80-120min to prepare isocyanate end-capped prepolymer solution;
(2) dissolving a chain extender and a monofunctional alcohol end-capping reagent in DMF (dimethyl formamide) to prepare a mixed solution;
(3) adding the mixed solution obtained in the step (2) into the prepolymer solution obtained in the step (1), and continuously reacting to obtain a polyurethane solution with the weight-average molecular weight of more than 8 ten thousand;
(4) and (3) adding the additive into the polyurethane solution obtained in the step (3) after ball milling, refining and dispersing, curing to obtain a spinning solution, and performing dry spinning to obtain the elasticity-controllable spandex.
2. The method for preparing the elasticity-controllable spandex according to claim 1, characterized in that: the mass ratio of diisocyanate to polydiol in the step (1) is (52-68): (32-48).
3. The method for preparing the elasticity-controllable spandex according to claim 2, characterized in that: the diisocyanate comprises one or the combination of two of 1, 5-naphthalene diisocyanate, 4 '-diisocyanato-3, 3' -dimethyl biphenyl, m-phenylene diisocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate, 4 '-methylene bis (phenyl isocyanate), toluene diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane 4,4' -diisocyanate and isophorone diisocyanate.
4. The process for preparing an elastic controlled spandex according to claim 3, characterized in that: the polymeric dualismThe alcohol is aliphatic polyglycol with molecular weight of 100-2000 and biphenyl structure dihydric alcohol, and the mass ratio of the aliphatic polyglycol to the biphenyl structure dihydric alcohol is as follows: (40-100): (0-60); wherein the aliphatic poly-diol is any one of polycaprolactone diol, polyethylene glycol, polycarbonate diol, polytetrahydrofuran ether glycol, polylactide diol, polyethylene oxide diol, polybutylene succinate diol, polyhexamethylene adipate diol and polyhexamethylene succinate diol; the structural formula of the dihydric alcohol with the biphenyl structure is as follows:
Figure DEST_PATH_IMAGE001
(wherein, n and m are integers of 2-12); the polar amide solution is DMF or DMAc.
5. The method for preparing the elasticity-controllable spandex according to claim 1, characterized in that: the mass fraction of the chain extender and the monofunctional alcohol end-capping reagent in the mixed solution in the step (2) is 1-10%;
wherein the chain extender is one or the combination of two of an amine chain extender and an alcohol chain extender with the functionality of more than or equal to 2, and the using amount of the chain extender with the functionality of 2 accounts for 50-90%;
wherein the monofunctional alcohol blocking agent is aliphatic alcohol with 1-10 carbon atoms or dialkyl amine with 4-10 carbon atoms, wherein the aliphatic alcohol with 1-10 carbon atoms is any one of methanol, ethanol, propanol or butanol, and the dialkyl amine with 4-10 carbon atoms is any one of diethylamine, N-ethyl-N-propylamine, diisopropylamine, N-tert-butyl-N methylamine and N-tert-butyl-N isopropylamine.
6. The method for preparing the elasticity-controllable spandex according to claim 5, characterized in that: the amine chain extender is aliphatic diamine, triamine, quaternary amine, aromatic diamine and tertiary amine compounds with the carbon number of 2-16; wherein the aliphatic diamine compound is any one of ethylenediamine, propylenediamine, methylcyclohexanediamine, pentylenediamine, hexylenediamine, and polyetherdiamine; the aliphatic triamine is any one of 3,3' -diamino dipropylamine and diethylenetriamine; the aliphatic quaternary amine is one of pentamine, triethylene tetramine and triethylene tetramine; the aromatic diamine is any one of m-phenylenediamine, biphenyldiamine, p-phenylenediamine, diethyltoluenediamine, dimethylthiotoluenediamine, 4' -methylenebis (6-methyl-2-ethylaniline), 4' -methylenebis (2-ethyl) aniline and 4,4' -bis-sec-butylaminodiphenylmethane; the aromatic triamine is any one of N, N ', N ' ' -triphenyl-1, 3, 5-benzene triamine and sym-benzene triamine; the alcohol chain extender is aliphatic dihydric alcohol, trihydric alcohol, tetrahydric alcohol and aromatic dihydric alcohol compounds with the carbon atom number of 2-12; wherein the aliphatic dihydric alcohol is any one of ethylene glycol, butanediol, hexanediol, diethylene glycol, tripropylene glycol or propylene glycol; the aliphatic trihydric alcohol is any one of glycerol and trimethylolpropane; the aliphatic tetrahydric alcohol is pentaerythritol; the aromatic diol is any one of hydroquinone dihydroxyethyl ether, resorcinol bis (2-hydroxyethyl) ether and 3-hydroxyethyloxyethyl-1-hydroxyethyl benzene diether.
7. The method for preparing the elasticity-controllable spandex according to claim 1, characterized in that: the molar ratio of the sum of the number of amino groups and hydroxyl groups in the mixed solution in the step (2) in the step (3) to the isocyanate groups in the prepolymer solution in the step (1) is (1-3): 1.
8. The method for preparing the elasticity-controllable spandex according to claim 1, characterized in that: the amount of the additive in the step (4) is 0.1-5% of the mass fraction of the polyurethane solution obtained in the step (3); the additive is two or more of antioxidant, uvioresistant agent, antibacterial agent, flame retardant, pigment, nano-particles, stabilizer and luminescent agent.
9. An elastic controlled spandex prepared by the method of any one of claims 1-8, characterized in that: the fineness of the spandex fiber is 5-40D, and the breaking elongation is adjustable and controllable between 100 and 500 percent.
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