CN113862822B - Deodorizing spandex and preparation method thereof - Google Patents

Deodorizing spandex and preparation method thereof Download PDF

Info

Publication number
CN113862822B
CN113862822B CN202111217336.XA CN202111217336A CN113862822B CN 113862822 B CN113862822 B CN 113862822B CN 202111217336 A CN202111217336 A CN 202111217336A CN 113862822 B CN113862822 B CN 113862822B
Authority
CN
China
Prior art keywords
spandex
deodorizing
phenyl
acid
dihydroxybenzoic acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202111217336.XA
Other languages
Chinese (zh)
Other versions
CN113862822A (en
Inventor
孙振波
王建伟
张斌
李春花
祁倩
曾登
蒋叶群
刘培强
俞德帮
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ldz New Aoshen Spandex Co ltd
Original Assignee
Ldz New Aoshen Spandex Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ldz New Aoshen Spandex Co ltd filed Critical Ldz New Aoshen Spandex Co ltd
Priority to CN202111217336.XA priority Critical patent/CN113862822B/en
Publication of CN113862822A publication Critical patent/CN113862822A/en
Application granted granted Critical
Publication of CN113862822B publication Critical patent/CN113862822B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348—Hydroxycarboxylic acids
    • 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
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
    • Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear

Landscapes

  • 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)
  • Artificial Filaments (AREA)

Abstract

The invention relates to a deodorizing spandex, which belongs to the technical field of new materials, and is mainly positioned in a molecular chain in a block form and at the tail end of the molecular chain by introducing a phenyl-ammonium carboxylate group on the molecular chain of the spandex. The invention also discloses a preparation method of the deodorizing spandex, which comprises the steps of pre-polymerization reaction, preparation of a phenyl-ammonium carboxylate terminator, chain extension and termination, adding an auxiliary agent to obtain a spinning solution, and preparing the deodorizing spandex by a dry spinning system after the spinning solution is cured. According to the invention, by utilizing the principle that ammonia is adsorbed by carboxyl, the phenyl-ammonium carboxylate groups are introduced into the molecular chain of the spandex, and are mainly positioned in the molecular chain in a block form and at the tail end of the molecular chain, the deodorizing spandex is prepared by in-situ polymerization, so that the ammonia can be quickly adsorbed, the washability is good, the problem of deodorizing the spandex is well solved, and the physical index of the fiber is not influenced.

Description

Deodorizing spandex and preparation method thereof
Technical Field
The invention relates to spandex, in particular to deodorizing spandex, and also relates to a preparation method of the deodorizing spandex, belonging to the technical field of new materials.
Background
The polyurethane elastic fiber has excellent elasticity, high strength and good chemical resistance, and is used for making elastic knitted fabrics or textiles, such as various underwear, ski wear, sports wear, swimwear, aerospace wear and the like. The deodorizing spandex can effectively adsorb or decompose common odor in life such as ammonia, acetic acid and the like in the taking process, so that the requirements of people on healthy and clean daily necessities are met.
The related prior art shows that: the inorganic deodorant is added into the spandex polymer to improve the deodorizing property of the spandex. Chinese patent publication CN 110291236A discloses that an inorganic deodorant composed of zirconium phosphate (Zr-phosphate) and metal oxides of Zn, si and the like is added to a spandex polymer. Chinese laid-open patent CN 110644070a mixes a polyurethane prepolymer having unreacted terminal isocyanate groups in a polyurethane urea polymer and a slurry of a mixture of silver particles and metal hydroxide to eliminate ammonia gas and hydrogen sulfide gas. The Chinese published patent document CN 102268752B adds octacarboxyl-containing metal phthalocyanine into spandex to solve formaldehyde elimination in the textile using process and the surrounding environment. However, the poor compatibility of the inorganic particles with the spandex polymer causes the deterioration of the physical properties of the fiber, thereby affecting the quality of the spandex.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the deodorizing spandex which can quickly adsorb peculiar smell gas and has good washability without influencing the physical index of fibers.
The invention aims to solve another technical problem of providing a method for preparing the deodorizing spandex. The method introduces phenyl-ammonium carboxylate groups on the molecular chain of spandex to prepare the deodorizing spandex.
The technical problems to be solved by the invention are realized by the following technical proposal. The invention relates to a deodorizing spandex, which is characterized in that a phenyl-ammonium carboxylate group is introduced into a molecular chain of the spandex, and the deodorizing spandex has a general formula:
wherein,,
a1 is:
a2 is:
a is:
r is:
any one of them;
NR1 is: triethylamine, pyridine or N, N-diisopropylethylamine;
r2 is:
or->Or a mixture of both;
r3 is:
x, y, m is the degree of polymerization, x=2-13, y=1-11, m=20-45.
The invention also discloses a preparation method of the deodorizing spandex, which is characterized by comprising the following steps:
(1) Prepolymerization reaction: adding a solvent into a reactor, adding polytetramethylene ether glycol, a diisocyanate compound and dihydroxybenzoic acid into the reactor in proper proportion under the condition of stirring, reacting for 90-120min at 89-109 ℃ to form a prepolymer containing phenyl-ammonium carboxylate, and adding tertiary amine and the solvent to dissolve to form a prepolymer solution;
(2) Preparation of a phenyl-ammonium carboxylate terminator: under the condition of solvent and stirring, tertiary amine and amino-phthalic acid are put into a reactor to react for 15-45min at 30-50 ℃;
(3) Chain extension and termination: cooling the prepolymer to 8-10 ℃, and adding mixed amine under stirring to perform chain extension reaction and chain termination reaction to form a high-viscosity polymer;
(4) Adding an auxiliary agent: adding one or more of an appropriate amount of anti-yellowing agent, matting agent, antioxidant, magnesium stearate or other auxiliary agents;
(5) Spinning: and curing the spinning solution, and preparing the deodorizing spandex by a dry spinning system.
The preparation method of the deodorizing spandex comprises the following further preferred technical scheme that in the step (1): the tertiary amine is selected from triethylamine or pyridine or N, N-diisopropylethylamine; the dihydroxybenzoic acid is selected from 3, 5-dihydroxybenzoic acid or 2, 3-dihydroxybenzoic acid; the diisocyanate compound is 4,4-MDI or 2,4-MDI.
The preparation method of the deodorizing spandex comprises the following further preferred technical scheme that in the step (1): the molecular weight of polytetramethylene ether glycol is 1800-3000, and the isocyanate of diisocyanate compound: the total hydroxyl mole ratio of the polytetramethylene ether glycol and the dihydroxybenzoic acid is 1.6-2.2, and the hydroxyl mole ratio of the polytetramethylene ether glycol and the dihydroxybenzoic acid is 1-5; the carboxyl group molar ratio of the tertiary amine to the dihydroxybenzoic acid is 1:1.
The preparation method of the deodorizing spandex comprises the following further preferred technical scheme that: the tertiary amine is selected from triethylamine or pyridine or N, N-diisopropylethylamine; the amino-phthalic acid is selected from 4-aminophthalic acid or 5-aminoisophthalic acid.
The preparation method of the deodorizing spandex comprises the following further preferred technical scheme that: the molar ratio of tertiary amine to carboxyl of amino-phthalic acid is 1:1.
The preparation method of the deodorizing spandex comprises the following further preferred technical scheme that in the step (3): the mixed amine consists of a chain extender and a terminator, wherein the chain extender is selected from ethylenediamine or pentylene diamine or a mixture thereof.
The preparation method of the deodorizing spandex comprises the following further preferred technical scheme that in the step (3): the terminator comprises a phenyl-ammonium carboxylate terminator and one or a mixture of a plurality of diethylamine, dipropylamine, cyclohexylamine, n-butanol and ethanolamine.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, by utilizing the principle that ammonia is adsorbed by carboxyl, phenyl-ammonium carboxylate functional groups are introduced into a molecular chain of spandex, and are mainly positioned in the molecular chain in a block form and at the tail end of the molecular chain, the deodorizing spandex is prepared by in-situ polymerization, so that the ammonia can be quickly adsorbed, the washability is good, the problem of deodorizing the spandex is well solved, and the physical index of the fiber is not influenced.
Detailed Description
In examples 1-3 below, the general formula of the deodorizing spandex is:
wherein,,
a1 is:
a2 is:
a is:
r is:
any one of them;
NR1 is: triethylamine, pyridine or N, N-diisopropylethylamine;
r2 is:
or->Or a mixture of both;
r3 is:
x, y, m is the degree of polymerization, x=2-13, y=1-11, m=20-45.
Example 1, the process for preparing deodorizing spandex, comprising the steps of:
(1) Preparation of a prepolymer: poly (tetramethylene ether glycol) 4305g with molecular weight of 2000, 4-MDI 1001g and 2, 5-dihydroxybenzoic acid 32g react at 90 ℃ for 130min to obtain isocyanate groups at two ends, 49g triethylamine and 9005g N, N-dimethylacetamide are added to dissolve the prepolymer, and the temperature is reduced to 10 ℃.
(2) Preparation of a phenyl-ammonium carboxylate terminator: 11g of triethylamine and 10g of 4-aminophthalic acid are reacted at 50g of N, N-dimethylacetamide under stirring at 50℃for 25min.
(3) Chain extension reaction: 93g of ethylenediamine, 12g of diethylamine and 2030g of N, N-dimethylacetamide are added to the solution of the step of ammonium diphenyl-carboxylate and mixed to obtain a mixed ammonia solution, and the mixed ammonia solution is added to the prepolymer cooled to 10 ℃ while stirring, so that a high-viscosity stable polymer is finally obtained.
(4) Preparation of spinning dope: to the polymer solution were added 8.74g of a yellowing inhibitor, 17.86g of titanium dioxide as a matting agent, 4.76g of an antioxidant, and 21.6g of magnesium stearate to obtain a spinning dope.
(5) Spinning: the spinning dope is cured at 40 ℃ and then treated by a dry spinning system to prepare the deodorizing spandex through the processes of liquid discharge, spitting, stretching, false twisting, oiling and the like.
Example 2: the preparation method of the deodorizing spandex comprises the following steps:
(1) Preparation of a prepolymer: 4202g of polytetramethylene ether glycol with molecular weight of 2000, 1001g of 4,4-MDI and 67g of 2, 3-dihydroxybenzoic acid are reacted at 90℃for 130min to give a prepolymer having isocyanate groups at both ends, 103g of triethylamine and 9005g of N, N-dimethylacetamide are added to dissolve the prepolymer, and the mixture is cooled to 10 ℃.
(2) Preparation of a phenyl-ammonium carboxylate terminator: 22g of pyridine and 25g of 4-aminophthalic acid are reacted at 50g of N, N-dimethylacetamide under stirring for 25min at 50 ℃.
(3) Chain extension reaction: 93g of ethylenediamine, 8g of diethylamine and 2030g of N, N-dimethylacetamide are added to the solution of the step of ammonium diphenyl-carboxylate and mixed to obtain a mixed ammonia solution, and the mixed ammonia solution is added to the prepolymer cooled to 10 ℃ while stirring, so that a high-viscosity stable polymer is finally obtained.
(4) Preparation of spinning dope: to the polymer solution were added 8.74g of a yellowing inhibitor, 17.86g of titanium dioxide as a matting agent, 4.76g of an antioxidant, and 21.6g of magnesium stearate to obtain a spinning dope.
(5) Spinning: the spinning dope is cured at 40 ℃ and then treated by a dry spinning system to prepare the deodorizing spandex through the processes of liquid discharge, spitting, stretching, false twisting, oiling and the like.
Example 3: the preparation method of the deodorizing spandex comprises the following steps:
(1) Preparation of a prepolymer: poly (tetramethylene ether glycol) 4305g with molecular weight 2500, 4-MDI 1001g and 3, 5-dihydroxybenzoic acid 248g react at 90 ℃ for 130min to obtain isocyanate groups at two ends, 127g pyridine and 9005g N, N-dimethylacetamide are added to dissolve prepolymer, and the temperature is reduced to 10 ℃.
(2) Preparation of a phenyl-ammonium carboxylate terminator: 18g of N, N-diisopropylethylamine and 10g of 5-aminoisophthalic acid were reacted under 50g of N, N-dimethylacetamide with stirring at 50℃for 25 minutes.
(3) Chain extension reaction: 103g of ethylenediamine, 13g of diethylamine and 2030g of N, N-dimethylacetamide are added to the solution of the step of ammonium diphenyl-carboxylate and mixed to obtain a mixed ammonia solution, and the mixed ammonia solution is added to a prepolymer cooled to 10 ℃ while stirring, so that a high-viscosity stable polymer is finally obtained.
(4) Preparation of spinning dope: to the polymer solution were added 8.74g of a yellowing inhibitor, 17.86g of titanium dioxide as a matting agent, 4.76g of an antioxidant, and 21.6g of magnesium stearate to obtain a spinning dope.
(5) Spinning: the spinning dope is cured at 40 ℃ and then treated by a dry spinning system to prepare the deodorizing spandex through the processes of liquid discharge, spitting, stretching, false twisting, oiling and the like.
Comparative example 1: the preparation method of the spandex comprises the following steps:
(1) Preparation of a prepolymer: 4305g of polytetramethylene ether glycol with the molecular weight of 2000 and 1001g of 4,4-MDI are heated to 90 ℃ for reaction for 130min, isocyanate groups are arranged at two ends of the reaction product, 9005g of N, N-dimethylacetamide is added for dissolving the prepolymer, and the temperature is reduced and the reaction product is cooled to 10 ℃.
(2) Chain extension reaction: 93g of ethylenediamine and 15g of diethylamine are added into 2080g of N, N-dimethylacetamide to be mixed to obtain a mixed ammonia solution, and the mixed ammonia solution is added into a prepolymer cooled to 10 ℃ while stirring, so as to finally obtain the high-viscosity stable polymer.
(4) Preparation of spinning dope: to the polymer solution were added 8.74g of a yellowing inhibitor, 17.86g of titanium dioxide as a matting agent, 4.76g of an antioxidant, and 21.6g of magnesium stearate to obtain a spinning dope.
(5) Spinning: the polyurethane fiber is prepared by the processes of liquid discharge, spitting, stretching, false twisting, oiling and the like by a dry spinning system after the spinning solution is cured at the temperature of 40 ℃.
Comparative example 2: the preparation method of the spandex comprises the following steps:
(1) Preparation of a prepolymer: poly (tetramethylene ether glycol) 4305g with molecular weight of 2000, 4-MDI 1001g and dimethylolpropionic acid 28g react at 90 ℃ for 130min to obtain isocyanate groups at both ends, 49g triethylamine and 9005g N, N-dimethylacetamide are added to dissolve the prepolymer, and the temperature is lowered to 10 ℃.
(2) Chain extension reaction: 93g of ethylenediamine and 15g of diethylamine are added into 2080g of N, N-dimethylacetamide to be mixed to obtain a mixed ammonia solution, and the mixed ammonia solution is added into a prepolymer cooled to 10 ℃ while stirring, so as to finally obtain the high-viscosity stable polymer.
(4) Preparation of spinning dope: to the polymer solution were added 8.74g of a yellowing inhibitor, 17.86g of titanium dioxide as a matting agent, 4.76g of an antioxidant, and 21.6g of magnesium stearate to obtain a spinning dope.
(5) Spinning: the polyurethane fiber is prepared by the processes of liquid discharge, spitting, stretching, false twisting, oiling and the like by a dry spinning system after the spinning solution is cured at the temperature of 40 ℃.
Comparative example 3: the preparation method of the spandex comprises the following steps:
(1) Preparation of a prepolymer: 4305g of polytetramethylene ether glycol with the molecular weight of 2000 and 1001g of 4,4-MDI are heated to 90 ℃ for reaction for 130min, isocyanate groups are arranged at two ends of the reaction product, 9005g of N, N-dimethylacetamide is added for dissolving the prepolymer, and the temperature is reduced and the reaction product is cooled to 10 ℃.
(2) Chain extension reaction: 93g of ethylenediamine and 15g of diethylamine are added into 2080g of N, N-dimethylacetamide to be mixed to obtain a mixed ammonia solution, and the mixed ammonia solution is added into a prepolymer cooled to 10 ℃ while stirring, so as to finally obtain the high-viscosity stable polymer.
(4) Preparation of spinning dope: 32g of 2, 5-dihydroxybenzoic acid, 10g of 4-aminophthalic acid and 60g of triethylamine are mixed to obtain deodorant auxiliary materials, and 8.74g of anti-yellowing agent, 17.86g of delustering agent titanium dioxide, 4.76g of antioxidant, 21.6g of magnesium stearate and the deodorant auxiliary materials are added into the polymer solution to obtain spinning stock solution.
(5) Spinning: the polyurethane fiber is prepared by the processes of liquid discharge, spitting, stretching, false twisting, oiling and the like by a dry spinning system after the spinning solution is cured at the temperature of 40 ℃.
The spandex prepared in examples and comparative examples was tested and compared:
the detection method comprises the following steps:
1. and (3) stretching detection: FZ/T54010-2014 spandex filament
2. Deodorizing and detecting: determination of deodorizing Properties of textiles after 30 Water washes according to GB/T33610.2-2017 part 2: the detection tube method detects ammonia and acetic acid reduction rate of spandex.
The detection results are as follows:
as can be seen from the comparative experiments above: according to the invention, the phenyl-ammonium carboxylate groups are introduced into the molecular chain of the spandex through in-situ polymerization, so that ammonia can be quickly adsorbed, the washability is good, and the physical index of the fiber is not influenced.
Example 4, a deodorizing spandex, comprising a molecular chain of spandex and an ammonium phenyl-carboxylate group, has the general formula:
wherein,,
a1 is:
a2 is:
a is:
r is:
any one of them;
NR1 is: triethylamine, pyridine or N, N-diisopropylethylamine;
r2 is:
or->Or a mixture of both;
r3 is:
x, y, m is the degree of polymerization, x=2-13, y=1-11, m=20-45.
The preparation method of the deodorizing spandex comprises the following steps:
(1) Prepolymerization reaction: adding a solvent into a reactor, adding polytetramethylene ether glycol, a diisocyanate compound and dihydroxybenzoic acid into the reactor in proper proportion under the condition of stirring, reacting for 105min at the temperature of 99 ℃ to form a prepolymer containing phenyl-ammonium carboxylate, and adding tertiary amine and the solvent to dissolve to form a prepolymer solution; the tertiary amine is selected from triethylamine or pyridine or N, N-diisopropylethylamine; the dihydroxybenzoic acid is selected from 3, 5-dihydroxybenzoic acid or 2, 3-dihydroxybenzoic acid; the diisocyanate compound is 4,4-MDI or 2,4-MDI. The molecular weight of polytetramethylene ether glycol is 1800-3000, and the isocyanate of diisocyanate compound: the total hydroxyl mole ratio of polytetramethylene ether glycol and dihydroxybenzoic acid is 2, and the hydroxyl mole ratio of polytetramethylene ether glycol and dihydroxybenzoic acid is 3; the carboxyl group molar ratio of the tertiary amine to the dihydroxybenzoic acid is 1:1.
(2) Preparation of a phenyl-ammonium carboxylate terminator: under the condition of solvent and stirring, tertiary amine and amino-phthalic acid are put into a reactor to react for 30min at 40 ℃; the tertiary amine is selected from triethylamine or pyridine or N, N-diisopropylethylamine; the amino-phthalic acid is selected from 4-aminophthalic acid or 5-aminoisophthalic acid. The molar ratio of tertiary amine to carboxyl of amino-phthalic acid is 1:1.
(3) Chain extension and termination: after the prepolymer is cooled to 9 ℃, adding mixed amine to perform chain extension reaction and chain termination reaction under the stirring condition to form a high-viscosity polymer; the mixed amine consists of a chain extender and a terminator, wherein the chain extender is selected from ethylenediamine or pentylene diamine or a mixture thereof. The terminator comprises a mixture of one of diethyl amine, dipropyl amine, cyclohexane, n-butanol and ethanolamine.
(4) Adding an auxiliary agent: adding one or more of an appropriate amount of anti-yellowing agent, matting agent, antioxidant or magnesium stearate;
(5) Spinning: and curing the spinning solution, and preparing the deodorizing spandex by a dry spinning system.
The above embodiments of the present invention are only examples, and therefore, the scope of the present invention is not limited thereto, but all changes, modifications, substitutions and variations made by the present invention are included in the scope of the present invention.

Claims (7)

1. The deodorizing spandex is characterized in that a phenyl-ammonium carboxylate group is introduced into a molecular chain of the spandex, and the deodorizing spandex has a general formula:
wherein,,
a1 is:
a2 is:
a is:
r is:
any one of them;
NR1 is: any one of triethylamine, pyridine or N, N-diisopropylethylamine;
r2 is:
or->Or a mixture of both;
r3 is:
x, y, m is the degree of polymerization, x=2-13, y=1-11, m=20-45.
2. A method for preparing the deodorizing spandex according to claim 1, which comprises the following steps:
(1) Prepolymerization reaction: adding a solvent into a reactor, adding polytetramethylene ether glycol, a diisocyanate compound and dihydroxybenzoic acid into the reactor in proper proportion under the condition of stirring, reacting for 90-120min at 89-109 ℃ to form a prepolymer containing phenyl-ammonium carboxylate, and adding tertiary amine and the solvent to dissolve to form a prepolymer solution;
(2) Preparation of a phenyl-ammonium carboxylate terminator: under the condition of solvent and stirring, tertiary amine and amino-phthalic acid are put into a reactor to react for 15-45min at 30-50 ℃;
(3) Chain extension and termination: after the prepolymer solution is cooled to 8-10 ℃, adding mixed amine under the stirring condition to perform chain extension reaction and chain termination reaction to form a high-viscosity polymer; the mixed amine consists of a chain extender and a terminator, wherein the chain extender is selected from ethylenediamine or pentylene diamine or a mixture thereof;
(4) Adding an auxiliary agent: adding one or more of an appropriate amount of anti-yellowing agent, a delustring agent, an antioxidant, magnesium stearate or other auxiliary agents into the polymer obtained in the step (3) to form a spinning solution;
(5) Spinning: and curing the spinning solution, and preparing the deodorizing spandex by a dry spinning system.
3. The method for producing deodorizing spandex according to claim 2, wherein in step (1): the tertiary amine is selected from triethylamine or pyridine or N, N-diisopropylethylamine; the dihydroxybenzoic acid is selected from 3, 5-dihydroxybenzoic acid or 2, 3-dihydroxybenzoic acid; the diisocyanate compound is 4,4-MDI or 2,4-MDI.
4. The method for producing deodorizing spandex according to claim 2, wherein in step (1): the molecular weight of polytetramethylene ether glycol is 1800-3000, and the isocyanate of diisocyanate compound: the total hydroxyl mole ratio of the polytetramethylene ether glycol and the dihydroxybenzoic acid is 1.6-2.2, and the hydroxyl mole ratio of the polytetramethylene ether glycol and the dihydroxybenzoic acid is 1-5; the carboxyl group molar ratio of the tertiary amine to the dihydroxybenzoic acid is 1:1.
5. The method for producing deodorizing spandex according to claim 2, wherein in step (2): the tertiary amine is selected from triethylamine or pyridine or N, N-diisopropylethylamine; the amino-phthalic acid is selected from 4-aminophthalic acid or 5-aminoisophthalic acid.
6. The method for producing deodorizing spandex according to claim 2, wherein in step (2): the molar ratio of tertiary amine to carboxyl of amino-phthalic acid is 1:1.
7. The method for producing deodorizing spandex according to claim 2, wherein in step (3): the terminator comprises a phenyl-ammonium carboxylate terminator and one or a mixture of a plurality of diethylamine, dipropylamine, cyclohexylamine, n-butanol and ethanolamine.
CN202111217336.XA 2021-10-19 2021-10-19 Deodorizing spandex and preparation method thereof Active CN113862822B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111217336.XA CN113862822B (en) 2021-10-19 2021-10-19 Deodorizing spandex and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111217336.XA CN113862822B (en) 2021-10-19 2021-10-19 Deodorizing spandex and preparation method thereof

Publications (2)

Publication Number Publication Date
CN113862822A CN113862822A (en) 2021-12-31
CN113862822B true CN113862822B (en) 2023-07-28

Family

ID=79000449

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111217336.XA Active CN113862822B (en) 2021-10-19 2021-10-19 Deodorizing spandex and preparation method thereof

Country Status (1)

Country Link
CN (1) CN113862822B (en)

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3684269B2 (en) * 1996-05-31 2005-08-17 東洋紡績株式会社 Deodorant fiber products
CN101918046B (en) * 2008-02-15 2014-09-24 东丽奥培隆特士株式会社 Deodorizing material
JP2012202012A (en) * 2011-03-28 2012-10-22 Asahi Kasei Fibers Corp Improved deodorant fabric
JP6061245B2 (en) * 2011-11-25 2017-01-18 東レ・オペロンテックス株式会社 Polyurethane elastic fiber and method for producing the same
JP2015196102A (en) * 2014-03-31 2015-11-09 東邦化工建設株式会社 Adsorbent element for deodorization and production method thereof
WO2016104573A1 (en) * 2014-12-26 2016-06-30 東レ・オペロンテックス株式会社 Fiber structure and production method for same
KR102030355B1 (en) * 2018-06-27 2019-10-10 태광산업주식회사 Preparation Method of Antibacterial and deodorized Polyurethaneurea Elastic Fiber and Polyurethaneurea Elastic Fiber thereby

Also Published As

Publication number Publication date
CN113862822A (en) 2021-12-31

Similar Documents

Publication Publication Date Title
CN106757485B (en) A kind of preparation method of high drawing spandex fibre
CN107740278B (en) Comb-shaped polyurethane flame-retardant water-repellent finishing agent and preparation method and application thereof
CN109487361B (en) Spandex fiber with good heat resistance and low-temperature setting property and preparation method thereof
CN102517688B (en) Preparation method of polyurethane elastomeric fiber possessing excellent heat setting performance
KR100780434B1 (en) Polyurethaneurea elastic fiber and method for preparation thereof
US6639041B2 (en) Spandex having low set at low temperatures
CN112778540B (en) Lignin-based polyol for synthesizing polyurethane and preparation method thereof
CN112359439A (en) Preparation method of high-elongation low-modulus polyurethane elastic fiber
CN114016155A (en) Antibacterial regenerated polyester fiber and preparation method thereof
CN105483856B (en) A kind of method that in-situ polymerization prepares ageing resistance by ultraviolet light spandex
CN113862822B (en) Deodorizing spandex and preparation method thereof
CN101736432B (en) Production method of anti-yellowing polyurethane elastic fiber
CA2085578C (en) Elastic polyurethane fiber
CN113622050B (en) Preparation method of high-resilience chlorine-resistant spandex fiber and application of high-resilience chlorine-resistant spandex fiber in diaper
CN101130603A (en) Modified poly- p-benzene dicarboxylic acid trimethylene glycol ester and method for producing the same
JP4264912B2 (en) Polyurethane urea composition and polyurethane elastic fiber
CN110079888B (en) Polyurethane elastic fiber with flame retardant function and preparation method thereof
EP0843032A1 (en) Elastic polyurethane-urea fibers
KR101180508B1 (en) Polyurethane composition for high tenacity spandex fiber, and spandex fiber prepared using the polyurethane composition
KR20200024053A (en) Elastic fiber having improved dying property
KR100397704B1 (en) Stabilized spandex
KR20080060507A (en) Polyurethane elastic fiber having improved resistance of discoloration
CN110241473B (en) Preparation method of spandex with lasting aging resistance
EP3696301B1 (en) Polyurethane urea elastic yarn having improved dyeability and manufacturing method therefor
CN114575163A (en) Anti-fouling and crease-resistant garment fabric

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant