CN111534883A - High-elastic polyurethane urea fiber, preparation method thereof and fabric - Google Patents

High-elastic polyurethane urea fiber, preparation method thereof and fabric Download PDF

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Publication number
CN111534883A
CN111534883A CN202010073075.8A CN202010073075A CN111534883A CN 111534883 A CN111534883 A CN 111534883A CN 202010073075 A CN202010073075 A CN 202010073075A CN 111534883 A CN111534883 A CN 111534883A
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molecular weight
prepolymer
weight polyol
fiber
diisocyanate
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Inventor
乔建强
田东伟
荆建林
张永旗
崔跃伟
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ZHENGZHOU ZHONGYUAN SPANDEX ENGINEERING TECHNOLOGY CO LTD
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ZHENGZHOU ZHONGYUAN SPANDEX ENGINEERING TECHNOLOGY CO LTD
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Priority to CN202010073075.8A priority Critical patent/CN111534883A/en
Publication of CN111534883A publication Critical patent/CN111534883A/en
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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
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation 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
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • 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
    • C08G18/42—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
    • 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
    • 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
    • C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • 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
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • 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
    • D01F1/10—Other agents for modifying properties

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Artificial Filaments (AREA)

Abstract

The application relates to a high-elasticity polyurethane urea fiber which is formed by reacting high molecular weight polyol, low molecular weight polyol and diisocyanate to form a prepolymer and polymerizing the prepolymer and an amine chain extender. The polyurethane urea fiber has high tensile modulus, and the tensile modulus and the definite elongation recovery modulus after multiple times of stretching are both higher than those of the conventional spandex, so that the elasticity of the fabric using the spandex is more sufficient. The application also relates to a method for preparing the polyurethane urea fiber and a fabric using the fiber.

Description

High-elastic polyurethane urea fiber, preparation method thereof and fabric
Technical Field
The invention relates to the field of spandex fibers, in particular to a high-elasticity polyurethane urea fiber, a preparation method thereof and a fabric using the fiber.
Background
Spandex is a special fiber for textiles, and has been widely used in knitted and woven elastic fabrics. Aiming at high gram weight requirements of high-grade warp knitted fabrics and jean fabrics and high elasticity requirements after dyeing and finishing, the current situation is that the denier of spandex yarn is increased to meet the requirements, but the gram weight of the fabrics is higher.
The traditional method for improving the mechanical property of polyurethane fiber mainly selects a chain extender capable of forming a high-rigidity hard segment in the chain extension stage of spandex prepolymer, or carries out crosslinking modification in the forming stage and post-processing stage of spandex polymer. CN103757741B adds 10-15% aromatic heterocyclic chain extender UPy (2-ureido-4 [1H ] -pyrimidone) type diamino compound in the chain extender to replace part of the traditional symmetric diamine chain extender and short-chain branched diamine chain extender, introduces aromatic heterocyclic rigid structure into the polyurethane urea molecular chain, and is used for improving the elasticity of spandex yarn. However, the chain extender selected by the method is a chain extender which is easy to yellow, the synthesis is difficult and the price is high, and the yellowing speed of spandex in the prior art is increased and the cost is greatly increased. CN102277649A uses a twin-screw extruder to mix polyurethane chips with a chlorine-resistant cross-linking agent to introduce a cross-linked structure into spandex polymer molecules, thereby improving the elasticity of melt-spun spandex. However, the introduction of such cross-linked structures can result in polymer viscosities that are enormous and only suitable for melt-spun spandex production processes using twin-screw extruders. The polymer has huge viscosity, so that the polymer cannot be dissolved in aprotic solvents such as N, N '-dimethylformamide, N' -dimethylacetamide, N-methylpyrrolidone or dimethyl sulfoxide and the like used in the conventional dry method, and is not suitable for the production process of spandex in the dry method. CN103789864B adds an organic peroxide initiator into the polymer solution, and in the course of channel spinning or the heating course of the next user, the organic peroxide releases free radicals to initiate the cross-linking action between molecules and improve the elasticity of the spandex, but the diphenylmethylene groups in the chemical structure of the spandex and the alpha-bond methylene near the ether-oxygen bond are degraded and yellowed when meeting the free radicals. In order to avoid the attack of free radicals to the molecular structure of spandex filaments, antioxidants and anti-yellowing agents are added in the general spandex polymer formula to eliminate and passivate the free radicals so as to avoid yellowing degradation caused by the free radicals. Obviously, although the technical scheme improves the elasticity of the spandex yarn, the technical scheme can bring a new problem that free radicals cause yellowing and degradation of the spandex. Therefore, there is a need to develop a new method which is low in cost, suitable for the existing production process and does not bring about the reduction of other qualities of spandex yarn.
Disclosure of Invention
Embodiments of the present application provide a highly elastic polyurethaneurea fiber, a method of preparing the same, and a fabric using the polyurethaneurea fiber.
In a first aspect, embodiments herein provide an elastomeric polyurethaneurea fiber that can be formed by first reacting a high molecular weight polyol, a low molecular weight polyol, and a diisocyanate to form a prepolymer, and then polymerizing the prepolymer with an amine-based chain extender. Specifically, the prepolymer may be formed by first mixing a high molecular weight polyol and a low molecular weight polyol to form a mixture, and then reacting a diisocyanate with the mixture, wherein preferably the low molecular weight polyol may be present in the mixture in an amount of 0.01% to 10%, more preferably 0.5% to 7%, and most preferably 0.2% to 5% by mass.
In one embodiment, the prepolymer may be formed using bulk polymerization; in another embodiment, the prepolymer may be solution polymerized in an aprotic solvent, which may be selected from the group consisting of N, N '-Dimethylformamide (DMF), N' -dimethylacetamide (DMAc), N-methylpyrrolidone, or dimethylsulfoxide.
In yet another embodiment, the high molecular weight polyol may have a number average molecular weight of 650 to 5000. The high molecular weight polyol is preferably selected from polyether diols, polyester diols, polyesteramide diols, polycarbonate diols, polyacrylic diols or mixtures or copolymers thereof and the like, more preferably from one or more of polytetrahydrofuran diol, polypropylene diol, polybutylene adipate diol, and copolymer diols obtained by reacting tetrahydrofuran with monomers such as ethylene oxide, propylene oxide, 2-methyltetrahydrofuran or 3-methyltetrahydrofuran.
In yet another embodiment, the low molecular weight polyol may have a number of carbon atoms of 2 to 20, preferably selected from one or more of ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 4-butanediol, diethylene glycol, trimethylolpropane, 1, 6-hexanediol.
In yet another embodiment, the diisocyanate may be selected from 4,4 '-diphenylmethane diisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate or 4, 4' -dicyclohexyl diisocyanate.
In yet another embodiment, the amine chain extender may be a multifunctional amine, preferably selected from one or more of ethylenediamine, 1, 2-propanediamine, 1, 3-propanediamine, 1, 4-butanediamine, 2, 3-butanediamine, 1, 5-pentanediamine, 2-methylpentanediamine, 1, 6-hexanediamine, 1, 4-cyclohexanediamine.
In a second aspect, embodiments of the present application provide a method of preparing a highly elastic polyurethaneurea fiber, which may comprise the steps of:
(1) reacting a high molecular weight polyol, a low molecular weight polyol, and a diisocyanate to form a prepolymer; and
(2) and polymerizing the prepolymer with an amine chain extender and a terminator.
In one embodiment, the high molecular weight polyol and the low molecular weight polyol may be mixed together to form a mixture in step (1), and then the diisocyanate is reacted with the mixture to form the prepolymer, wherein the low molecular weight polyol may be preferably present in the mixture in an amount of 0.01% to 10%, more preferably 0.5% to 7%, and most preferably 0.2% to 5% by mass.
In one embodiment, the molar ratio of diisocyanate to the mixture in step (1) may be from 1.6 to 2.5, preferably the diisocyanate is reacted with the mixture at 70 to 90 ℃ for 90 to 240 minutes.
In yet another embodiment, the prepolymer in step (1) may be solution polymerized in an aprotic solvent.
In still another embodiment, the prepolymer may be dissolved in the aprotic solvent in step (2) to form a prepolymer solution with a mass percentage of 40 to 60%, and then an amine-based chain extender and a terminator are added to perform polymerization, thereby obtaining a polyurethaneurea solution with a mass concentration of 30 to 45%, wherein the polyurethaneurea may have a number average molecular weight of 2 to 30 ten thousand.
In yet another embodiment, the aprotic solvent may be selected from N, N '-dimethylformamide, N' -dimethylacetamide, N-methylpyrrolidone, or dimethylsulfoxide.
In yet another embodiment, the high molecular weight polyol may have a number average molecular weight of 650 to 5000. The high molecular weight polyol is preferably selected from polyether diols, polyester diols, polyesteramide diols, polycarbonate diols, polyacrylic diols or mixtures or copolymers thereof and the like, more preferably from one or more of polytetrahydrofuran diol, polypropylene diol, polybutylene adipate diol, and copolymer diols obtained by reacting tetrahydrofuran with monomers such as ethylene oxide, propylene oxide, 2-methyltetrahydrofuran or 3-methyltetrahydrofuran.
In yet another embodiment, the low molecular weight polyol may have a number of carbon atoms of 2 to 20, preferably selected from one or more of ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 4-butanediol, diethylene glycol, trimethylolpropane, 1, 6-hexanediol.
In yet another embodiment, the diisocyanate may be selected from 4,4 '-diphenylmethane diisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate or 4, 4' -dicyclohexyl diisocyanate.
In yet another embodiment, the amine chain extender may be a multifunctional amine, preferably selected from one or more of ethylenediamine, 1, 2-propanediamine, 1, 3-propanediamine, 1, 4-butanediamine, 2, 3-butanediamine, 1, 5-pentanediamine, 2-methylpentanediamine, 1, 6-hexanediamine, 1, 4-cyclohexanediamine.
In yet another embodiment, the method may further comprise step (3): and (3) adding additives such as an anti-ultraviolet agent, an anti-yellowing agent, a dyeing assistant, a lubricant, a delustering agent and the like into the polyurethane urea solution obtained in the step (2), uniformly mixing, and curing at 40-60 ℃ for 30-60 hours to obtain a spandex spinning stock solution.
In yet another embodiment, the method may further comprise step (4): and (4) extruding the spandex spinning stock solution obtained in the step (3) through a spinneret plate, and obtaining the high-elasticity polyurethane urea fiber through dry spinning.
In a third aspect, embodiments herein provide a fabric at least a portion of which uses the above-described polyurethaneurea fiber.
Detailed Description
Based on the requirements on the gram weight and high elasticity of spandex, the invention adopts a method of enabling low molecular weight polyol to participate in prepolymerization reaction, thereby changing the structure of the final polyurethane urea molecular chain, and further adopting dry spinning to prepare high-stress and high-resilience polyurethane fiber.
Specifically, the polyurethane urea fiber of the present invention can be formed by first reacting a high molecular weight polyol, a low molecular weight polyol, and a diisocyanate to form a prepolymer, and then polymerizing the prepolymer with an amine-based chain extender. This is clearly distinguished from conventional urethanization techniques: in the present invention, low molecular weight polyol is additionally involved in the prepolymerization reaction, and the prepolymer thus formed may include, in addition to the conventional product A1 of high molecular weight polyol and diisocyanate, the product A2 of low molecular weight polyol and diisocyanate, as well as the product of A1 further reacted with low molecular weight polyol and the product of A2 further reacted with high molecular weight polyol.
From the viewpoint of process implementation, it is preferable that the high molecular weight polyol and the low molecular weight polyol are first mixed uniformly to form a mixture, and then the diisocyanate is reacted with the mixture to form the prepolymer. In fact, whether the high molecular weight polyol is added first to react with the diisocyanate and then the low molecular weight polyol, or the low molecular weight polyol is added first to react with the diisocyanate and then the high molecular weight polyol, the process may continue due to the high product viscosity. However, these solutions are theoretically available and are therefore within the scope of the present invention. According to the invention, the low molecular weight polyol may be present in the mixture in a mass content ranging from 0.01% to 10%, preferably from 0.5% to 7%, more preferably from about 0.2% to 5%.
As the high molecular weight polyol, high molecular weight polyols known in the art to be suitable for use in the synthesis of polyurethanes can be used in the present invention, and the number average molecular weight of the polyol is preferably 650 to 5000. The high molecular weight polyol in the present invention may be selected from polyether diols, polyester diols, polyesteramide diols, polycarbonate diols, polyacrylic diols or mixtures or copolymers thereof, and the like; more preferably, it is selected from one or more of polytetrahydrofuran glycol, polypropylene glycol, polybutylene adipate glycol, and copolymer glycols obtained by reacting tetrahydrofuran with monomers such as ethylene oxide, propylene oxide, 2-methyltetrahydrofuran or 3-methyltetrahydrofuran.
The low molecular weight polyol used in the present invention may contain 2 to 20 carbon atoms, and is preferably one or more selected from the group consisting of ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 4-butanediol, diethylene glycol, trimethylolpropane, and 1, 6-hexanediol.
Examples of the diisocyanate include aliphatic, alicyclic and aromatic diisocyanates. For example, 4,4 '-diphenylmethane diisocyanate, 2, 4-and 2, 6-toluene diisocyanate, m-and p-xylene diisocyanate, alpha', α ' -tetramethyl-xylene diisocyanate, 4 ' -diphenyl ether diisocyanate, 4 ' -dicyclohexyl diisocyanate, 1, 3-and 1, 4-cyclohexylene diisocyanate, 3- (. alpha. -isocyanatoethyl) phenyl isocyanate, 1, 6-hexamethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, isophorone diisocyanate, or a mixture thereof or a copolymer thereof, and the like. 4, 4' -diphenylmethane diisocyanate is preferred.
The prepolymer in the present invention may be formed by bulk polymerization. However, the prepolymer may also be prepared by solution polymerization in an aprotic solvent, i.e., a mixture of a high molecular weight polyol and a low molecular weight polyol is dissolved in an aprotic solvent, and then diisocyanate is added to react; alternatively, the diisocyanate, which has been dissolved in an aprotic solvent, may be added to the mixture to carry out the reaction. The aprotic solvent may be selected from N, N '-Dimethylformamide (DMF), N' -dimethylacetamide (DMAc), dimethylsulfoxide or N-methylpyrrolidone. They are all common solvents for urethanization reactions.
In the prepolymerization, the molar ratio of diisocyanate to the mixture can be controlled to be 1.6 to 2.5. Reacting a diisocyanate with the mixture at a temperature of 70 to 90 ℃ for 90 to 240 minutes, thereby obtaining a prepolymer.
In order to obtain the polyurethaneurea of the present invention, the prepolymer is then polymerized with an amine chain extender and a terminator. The prepolymer may be dissolved in an aprotic solvent to form a prepolymer solution with a mass percentage of 40 to 60%, and then an amine-based chain extender and a terminator may be added to perform polymerization, thereby obtaining a polyurethaneurea solution with a mass concentration of 30 to 45%, wherein the polyurethaneurea may have a number average molecular weight of 2 to 30 ten thousand.
The amine chain extender may be a polyfunctional amine, and for example, ethylenediamine, 1, 2-propylenediamine, 1, 3-propylenediamine, 1, 2-butylenediamine, 1, 4-butylenediamine, 2, 3-butylenediamine, 1, 5-pentylenediamine, 2-methyl-1, 5-pentylenediamine, triethylenediamine, m-xylylenediamine, piperazine, o-phenylenediamine, m-phenylenediamine, and p-phenylenediamine, 1, 3-diaminocyclohexane, 1, 4-cyclohexanediamine, 1, 6-hexamethylenediamine, N' - (methylenebis-4, 1-phenylene) bis [2- (ethylamino) -urea ], and the like can be used. They may be used alone or in combination.
The terminator may be a small molecule monofunctional amine, and for example, monoalkylamines such as isopropylamine, n-butylamine, t-butylamine, 2-ethylhexylamine, cyclohexylamine, and the like, and dialkylamines such as diethylamine, dimethylamine, di-n-butylamine, di-t-butylamine, di-isobutylamine, di-2-ethylhexylamine, diisopropylamine, and the like can be used. They may be used alone or in combination.
Further, additives such as an anti-ultraviolet agent, an anti-yellowing agent, a dyeing assistant, a lubricant, a delustering agent and the like are added into the polyurethane urea solution obtained above, and after being uniformly mixed, the polyurethane urea solution is aged for 30 to 60 hours at the temperature of 40 to 60 ℃ to obtain a spandex spinning stock solution. And extruding the spandex spinning stock solution through a spinneret plate, and obtaining the high-elasticity polyurethane urea fiber through dry spinning. These other additive components and dry spinning may be those well known in the art and are not intended to be limiting.
Generally, the urea-based hard segments have better elasticity and recovery than the urethane hard segments in the polyurethane. Therefore, in order to improve the elasticity of the polyurethane fiber, the content of the urea hard segment in the polyurethane fiber can be increased as much as possible. However, this concept is not technically feasible in practice, since the viscosity of the reaction product becomes high and the solubility becomes poor when the urea hard segment content is increased to a certain extent. On the other hand, since the low molecular weight polyol is easy to absorb water and may have a side reaction causing cross-linking, and the process conditions are not easy to control, the skilled person would not think of increasing the content of the urethane hard segment by adding the low molecular weight polyol, thereby increasing the elasticity of the polyurethane fiber. However, the present inventors have unexpectedly found that by allowing a low molecular weight polyol to participate in a prepolymerization reaction together with a high molecular weight polyol, the above-mentioned problems of the low molecular weight polyol can be overcome, and the elasticity of the final polyurethaneurea can be improved as well.
On the other hand, since the product of polyol and diisocyanate tends to have high viscosity, even in the case where it is necessary to add low molecular weight polyol to improve specific properties of polyurethane such as heat resistance, it is common practice in the art to continue polymerization by adding low molecular weight polyol as an additional chain extender to the prepolymer solution after the prepolymerization reaction of high molecular weight polyol and diisocyanate is completed. Obviously, this practice is clearly different from the present invention, and the order of addition of the low molecular weight polyols also results in fundamental differences in the structure of the segments of the final polyurethaneurea, and the resulting polyurethaneurea fibers also differ greatly in their properties.
It can be seen that the method for preparing the highly elastic polyurethaneurea fiber of the present invention may comprise the steps of:
(1) reacting a high molecular weight polyol, a low molecular weight polyol, and a diisocyanate to form a prepolymer; specifically, the high molecular weight polyol and the low molecular weight polyol are uniformly mixed to form a mixture, and then the diisocyanate and the mixture react to form a prepolymer;
(2) polymerizing the prepolymer with an amine chain extender and a terminator;
(3) adding an additive into the polyurethane urea solution obtained in the step (2), uniformly mixing, and curing at 40-60 ℃ for 30-60 hours to obtain a polyurethane fiber spinning solution; and
(4) and extruding the spandex spinning stock solution through a spinneret plate, and obtaining the high-elasticity polyurethane urea fiber through dry spinning.
The tensile modulus and the recovery modulus of the polyurethane urea fiber are obviously improved. As the mechanical properties of the fibers are improved, the same denier fiber can be used to provide higher stretch to meet the stretch requirements of the fabric; spandex filaments having a lower denier may also be used in conventional applications in place of spandex filaments having a higher denier, thereby reducing the cost of spandex fabrics.
Examples
The present invention is described in more detail below by way of examples, in which the properties of the polyurethaneurea filaments in the examples and comparative examples are measured by using a MTS (Meits) CMT6102 universal tensile tester. The tensile stress, elongation at break and breaking strength were obtained by testing a polyurethane urea fiber yarn having a length of 50cm at a tensile rate of 500 m/min; the fifth 200% recovery force in the five-cycle tensile test was obtained by cycle testing a polyurethaneurea filament having a length of 50cm five times at a constant elongation rate of 0 to 300% at a tensile rate of 500 m/min. "stress stretched 300% times" means the stress when stretched four times its original length.
Example 1:
4000g of polytetrahydrofuran diol having a number average molecular weight of about 1800 was taken, mixed with 100g of 1, 4-butanediol homogeneously in a reaction vessel, and 1250g of 4, 4' -diphenylmethane diisocyanate were then added to the reaction vessel. Mixing and stirring are carried out for 5min at about 45 ℃, then the temperature is raised to about 90 ℃, and the reaction is continued for about 2 hours to obtain viscous prepolymer.
The prepolymer temperature was lowered to about 40 ℃ and then 6809g of DMAc was added for dilution to obtain a prepolymer solution. To this was added a chain extender and terminator solution comprising 88.66g of ethylenediamine, 19.01g of 2-methylpentamethylenediamine, 11.99g of diethylamine and 3348.86g of DMAc. After the chain extension reaction, a polymer solution with a solid content of about 35% by weight and a viscosity of about 4500 poise is obtained. Stirring the mixture for 30 minutes, adding functional assistant slurry of 0.3 wt% of anti-ultraviolet agent Tinuivn234, 0.5 wt% of anti-yellowing agent HN150, 0.3 wt% of dyeing assistant SAS, 0.3 wt% of lubricant MgSt and 0.3 wt% of flatting agent TDO, and curing to obtain the polyurethane urea stock solution. And then carrying out dry spinning on the polyurethane urea stock solution to obtain the polyurethane urea fiber.
The fiber specification is 40D, the stress of 300% times of stretching is about 14.5cN, the elongation at break is 490%, and the breaking strength is about 48 cN; the fifth 200% recovery force in the five cycle tensile test was about 1.32 cN.
Example 2:
4000g of polytetrahydrofuran diol having a number average molecular weight of about 1800 was taken, mixed with 40g of 1, 4-butanediol homogeneously in a reaction vessel, and 1065g of 4, 4' -diphenylmethane diisocyanate was then added to the reaction vessel. Mixing and stirring are carried out for 5min at about 45 ℃, then the temperature is raised to about 90 ℃, and the reaction is continued for about 2 hours to obtain viscous prepolymer.
The prepolymer temperature was lowered to about 40 ℃ and then 6497g DMAc was added for dilution to give a prepolymer solution. To this was added a chain extender and terminator solution comprising 84.74g of ethylenediamine, 18.17g of 2-methylpentamethylenediamine, 11.46g of diethylamine and 3195.87g of DMAc. After the chain extension reaction, a polymer solution having a solid content of about 35% by weight and a viscosity of about 4200 poise was obtained. Stirring the mixture for 30 minutes, adding functional assistant slurry of 0.3 wt% of anti-ultraviolet agent Tinuivn234, 0.5 wt% of anti-yellowing agent HN150, 0.3 wt% of dyeing assistant SAS, 0.3 wt% of lubricant MgSt and 0.3 wt% of flatting agent TDO, and curing to obtain the polyurethane urea stock solution. And then carrying out dry spinning on the polyurethane urea stock solution to obtain the polyurethane urea fiber.
The fiber specification is 40D, the stress at 300% times of stretching is about 13.8cN, the elongation at break is 495%, and the breaking strength is about 50 cN; the fifth 200% recovery force in the five cycle tensile test was about 1.26 cN.
Example 3:
4000g of polytetrahydrofuran diol having a number average molecular weight of about 1800 was taken, mixed with 100g of ethylene glycol in a reaction vessel, and 1387g of 4, 4' -diphenylmethane diisocyanate was added to the reaction vessel. The mixture was stirred at about 45 ℃ and then heated to about 90 ℃ to continue the reaction for about 2 hours to obtain a viscous prepolymer.
The prepolymer temperature was lowered to about 40 ℃ and then 6983.45g of DMAc was added for dilution to give a prepolymer solution. To this was added a chain extender and terminator solution comprising 91.11g of ethylenediamine, 19.54g of 2-methylpentamethylenediamine, 12.32g of diethylamine and 3435.07g of DMAc. After the chain extension reaction, a polymer solution with a solid content of about 35% by weight and a viscosity of about 4600 poise was obtained. Stirring the mixture for 30 minutes, adding functional assistant slurry of 0.3 wt% of anti-ultraviolet agent Tinuivn234, 0.5 wt% of anti-yellowing agent HN150, 0.3 wt% of dyeing assistant SAS, 0.3 wt% of lubricant MgSt and 0.3 wt% of flatting agent TDO, and curing to obtain the polyurethane urea stock solution. And then carrying out dry spinning on the polyurethane urea stock solution to obtain the polyurethane urea fiber.
The fiber specification is 40D, the 300% time stretch stress is about 16cN, the elongation at break is 483%, and the breaking strength is about 47 cN; the fifth 200% recovery force in the five cycle tensile test was about 1.36 cN.
Comparative example 1：
4000g of polytetrahydrofuran diol (number average molecular weight: about 1800) was charged into the reaction vessel, and 941g of 4, 4' -diphenylmethane diisocyanate was further added. Mixing and stirring are carried out for 5min at about 45 ℃, then the temperature is raised to about 90 ℃, and the reaction is continued for about 2 hours to obtain viscous prepolymer.
The prepolymer temperature was lowered to about 40 ℃ and then 6288.55g of DMAc was added for dilution to give a prepolymer solution. To this was added a chain extender and terminator solution comprising 81.99g of ethylenediamine, 17.58g of 2-methylpentamethylenediamine, 11.09g of diethylamine and 3093.12g of DMAc. After the chain extension reaction, a polymer solution with the solid content of about 35 percent by weight and the viscosity of about 4000 poise is obtained. Stirring the mixture for 30 minutes, adding functional assistant slurry of 0.3 wt% of anti-ultraviolet agent Tinuivn234, 0.5 wt% of anti-yellowing agent HN150, 0.3 wt% of dyeing assistant SAS, 0.3 wt% of lubricant MgSt and 0.3 wt% of flatting agent TDO, and curing to obtain the polyurethane urea stock solution. And then carrying out dry spinning on the polyurethane urea stock solution to obtain the polyurethane urea fiber.
The fiber specification is 40D, the stress at 300% times of stretching is about 12.5cN, the elongation at break is 530%, and the breaking strength is about 53 cN; the fifth 200% recovery force in the five cycle tensile test was about 1.15 cN.
Example 4:
4000g of polytetrahydrofuran diol having a number average molecular weight of about 1800 was taken, mixed with 8g of 1, 4-butanediol in a reaction vessel to homogeneity, and 966g of 4, 4' -diphenylmethane diisocyanate was then added to the reaction vessel. Mixing and stirring are carried out for 5min at about 45 ℃, then the temperature is raised to about 90 ℃, and the reaction is continued for about 2 hours to obtain viscous prepolymer.
The prepolymer temperature was lowered to about 40 ℃ and then 6330.54g of DMAc was added for dilution to give a prepolymer solution. To this was added a chain extender and terminator solution comprising 82.59g of ethylenediamine, 17.71g of 2-methylpentamethylenediamine, 11.17g of diethylamine and 3113.89g of DMAc. After the chain extension reaction, a polymer solution with a solid content of about 35% by weight and a viscosity of about 4600 poise was obtained. Stirring the mixture for 30 minutes, adding functional assistant slurry of 0.3 wt% of anti-ultraviolet agent Tinuivn234, 0.5 wt% of anti-yellowing agent HN150, 0.3 wt% of dyeing assistant SAS, 0.3 wt% of lubricant MgSt and 0.3 wt% of flatting agent TDO, and curing to obtain the polyurethane urea stock solution. And then carrying out dry spinning on the polyurethane urea stock solution to obtain the polyurethane urea fiber.
The fiber specification is 40D, the stress of 300% times of stretching is about 13cN, the elongation at break is 515%, and the breaking strength is about 49.6 cN; the fifth 200% recovery force in the five cycle tensile test was about 1.18 cN.
Example 5:
4000g of polytetrahydrofuran diol having a number average molecular weight of about 1800 was taken, mixed with 200g of 1, 4-butanediol in a reaction vessel to homogeneity, and 1560g of 4, 4' -diphenylmethane diisocyanate was added to the reaction vessel. Mixing and stirring are carried out for 5min at about 45 ℃, then the temperature is raised to about 90 ℃, and the reaction is continued for about 2 hours to obtain viscous prepolymer.
The prepolymer temperature was lowered to about 40 ℃ and then 7330.91g of DMAc was added for dilution to give a prepolymer solution. To this was added a chain extender and terminator solution comprising 95.54g of ethylenediamine, 20.49g of 2-methylpentamethylenediamine, 12.91g of diethylamine and 3605.72g of DMAc. After the chain extension reaction, a polymer solution with a solid content of about 35% by weight and a viscosity of about 5300 poise is obtained. Stirring the mixture for 30 minutes, adding functional assistant slurry of 0.3 wt% of anti-ultraviolet agent Tinuivn234, 0.5 wt% of anti-yellowing agent HN150, 0.3 wt% of dyeing assistant SAS, 0.3 wt% of lubricant MgSt and 0.3 wt% of flatting agent TDO, and curing to obtain the polyurethane urea stock solution. And then carrying out dry spinning on the polyurethane urea stock solution to obtain the polyurethane urea fiber.
The fiber specification is 40D, the stress of 300% times of stretching is about 20cN, the elongation at break is 478%, and the breaking strength is about 56 cN; the fifth 200% recovery force in the five cycle tensile test was about 1.42 cN.
Example 6:
4000g of polybutylene adipate diol having a number average molecular weight of about 2000 were taken, and mixed with 200g of 1, 4-butanediol in a reaction vessel to obtain a uniform mixture, and then 1500g of 4, 4' -diphenylmethane diisocyanate was added to the reaction vessel. Mixing and stirring at about 45 ℃ for 5min, then heating to about 90 ℃, and continuing the reaction for about 2 hours to obtain a viscous prepolymer.
The prepolymer temperature was lowered to about 40 ℃ and then 7254.54g of DMAc was added for dilution to give a prepolymer solution. To this was added a chain extender and terminator solution comprising 94.61g of ethylenediamine, 20.29g of 2-methylpentamethylenediamine, 12.79g of diethylamine and 3568.31g of DMAc. After the chain extension reaction, a polymer solution with a solid content of about 35% by weight and a viscosity of about 4100 poise is obtained. Stirring the mixture for 30 minutes, adding functional assistant slurry of 0.3 wt% of anti-ultraviolet agent Tinuivn234, 0.5 wt% of anti-yellowing agent HN150, 0.3 wt% of dyeing assistant SAS, 0.3 wt% of lubricant MgSt and 0.3 wt% of flatting agent TDO, and curing to obtain the polyurethane urea stock solution. And then carrying out dry spinning on the polyurethane urea stock solution to obtain the polyurethane urea fiber.
The fiber specification is 40D, the stress of 300% times of stretching is about 18cN, the elongation at break is 512%, and the breaking strength is about 52 cN; the fifth 200% recovery force in the five cycle tensile test was about 1.32 cN.
Comparative example 2：
4000g of polybutylene adipate diol (number average molecular weight: about 2000) was charged into the reaction vessel, followed by 880g of 4, 4' -diphenylmethane diisocyanate. Mixing and stirring at about 45 ℃ for 5min, then heating to about 90 ℃, and continuing the reaction for about 2 hours to obtain a viscous prepolymer.
The prepolymer temperature was lowered to about 40 ℃ and then 6210.90g of DMAc was added for dilution to give a prepolymer solution. To this was added a chain extender and terminator solution comprising 80.84g of ethylenediamine, 17.33g of 2-methylpentamethylenediamine, 10.93g of diethylamine and 3054.59g of DMAc. After the chain extension reaction, a polymer solution with the solid content of about 35 percent by weight and the viscosity of about 4000 poise is obtained. Stirring the mixture for 30 minutes, adding functional assistant slurry of 0.3 wt% of anti-ultraviolet agent Tinuivn234, 0.5 wt% of anti-yellowing agent HN150, 0.3 wt% of dyeing assistant SAS, 0.3 wt% of lubricant MgSt and 0.3 wt% of flatting agent TDO, and curing to obtain the polyurethane urea stock solution. And then carrying out dry spinning on the polyurethane urea stock solution to obtain the polyurethane urea fiber.
The fiber specification is 40D, the stress at 300% times of stretching is about 11cN, the elongation at break is 560%, and the breaking strength is about 49 cN; the fifth 200% recovery force in the five cycle tensile test was about 1.08 cN.

Claims (10)

1. A high-elasticity polyurethane-urea fiber is prepared through the reaction between high-molecular polyol, low-molecular polyol and diisocyanate to obtain prepolymer, and polymerizing the prepolymer with amine chain extender.
2. The fiber of claim 1, characterized in that the prepolymer is formed by first mixing a high molecular weight polyol with a low molecular weight polyol to form a mixture and then reacting a diisocyanate with the mixture, wherein preferably the low molecular weight polyol is present in the mixture in an amount of 0.01% to 10%, more preferably 0.5% to 7%, most preferably 0.2% to 5% by mass.
3. The fiber of claim 1 or 2, wherein the prepolymer is formed by bulk polymerization or solution polymerization in an aprotic solvent.
4. The fiber according to any of claims 1 to 3, characterized in that the high molecular weight polyol has a number average molecular weight of 650 to 5000; the high molecular weight polyol is preferably selected from polyether diols, polyester amide diols, polycarbonate diols, polyacrylic diols or mixtures or copolymers thereof; more preferably one or more selected from polytetrahydrofuran glycol, polypropylene glycol, polybutylene adipate glycol, and copolymer glycols obtained by reacting tetrahydrofuran with the monomer ethylene oxide, propylene oxide, 2-methyltetrahydrofuran or 3-methyltetrahydrofuran.
5. The fiber according to any of claims 1 to 4, characterized in that the low molecular weight polyol has a number of carbon atoms of 2 to 20, preferably selected from one or more of ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, diethylene glycol, trimethylolpropane, 1, 6-hexanediol.
6. The fiber according to any of claims 1 to 5, characterized in that the amine chain extender is a multifunctional amine, preferably selected from one or more of ethylene diamine, 1, 2-propane diamine, 1, 3-propane diamine, 1, 4-butane diamine, 2, 3-butane diamine, 1, 5-pentane diamine, 2-methyl pentane diamine, 1, 6-hexane diamine, 1, 4-cyclohexane diamine.
7. A method for preparing a highly elastic polyurethaneurea fiber comprising the steps of:
(1) reacting a high molecular weight polyol, a low molecular weight polyol, and a diisocyanate to form a prepolymer; and
(2) and polymerizing the prepolymer with an amine chain extender and a terminator.
8. A process according to claim 7, characterised in that in step (1) the high molecular weight polyol is first mixed homogeneously with the low molecular weight polyol to form a mixture and the diisocyanate is then reacted with the mixture to form the prepolymer, wherein preferably the low molecular weight polyol is present in the mixture in an amount of from 0.01% to 10%, more preferably from 0.5% to 7%, most preferably from 0.2% to 5% by weight.
9. The process according to claim 7 or 8, characterized in that in step (1) the molar ratio of diisocyanate to the mixture is from 1.6 to 2.5, preferably the diisocyanate is reacted with the mixture at from 70 to 90 ℃ for from 90 to 240 minutes.
10. A fabric using the polyurethaneurea fiber according to any one of claims 1 to 6 or the polyurethaneurea fiber prepared by the method according to any one of claims 7 to 9.
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CN112210860A (en) * 2020-10-12 2021-01-12 郑州中远氨纶工程技术有限公司 Preparation method of anti-skidding spandex core-spun yarn suitable for denim fabric
CN115197391A (en) * 2022-08-15 2022-10-18 河北邦泰氨纶科技有限公司 Fiber-grade polyurethane slice and preparation method and application thereof
WO2024110903A1 (en) * 2022-11-25 2024-05-30 Toray Opelontex Co., Ltd. Polyurethane elastic fiber

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CN112210860A (en) * 2020-10-12 2021-01-12 郑州中远氨纶工程技术有限公司 Preparation method of anti-skidding spandex core-spun yarn suitable for denim fabric
CN115197391A (en) * 2022-08-15 2022-10-18 河北邦泰氨纶科技有限公司 Fiber-grade polyurethane slice and preparation method and application thereof
CN115197391B (en) * 2022-08-15 2023-10-31 河北邦泰氨纶科技有限公司 Fiber-grade polyurethane slice and preparation method and application thereof
WO2024110903A1 (en) * 2022-11-25 2024-05-30 Toray Opelontex Co., Ltd. Polyurethane elastic fiber

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