CN109322008B - Method for improving performance stability of spandex product - Google Patents
Method for improving performance stability of spandex product Download PDFInfo
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- CN109322008B CN109322008B CN201811172376.5A CN201811172376A CN109322008B CN 109322008 B CN109322008 B CN 109322008B CN 201811172376 A CN201811172376 A CN 201811172376A CN 109322008 B CN109322008 B CN 109322008B
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- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/16—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds as constituent
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- 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
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- 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
- C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
- C08G18/423—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing cycloaliphatic groups
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- 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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- 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
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- 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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- 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
- D01F1/106—Radiation shielding agents, e.g. absorbing, reflecting agents
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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
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Abstract
The invention discloses a method for improving the performance stability of spandex products, which comprises the steps of synthesizing alicyclic polyester polyols containing different molecular weights, carrying out prepolymerization on the alicyclic polyester polyols and polyether polyols respectively with diisocyanate and carrying out chain extension reaction on prepolymerization reactants to generate a high molecular compound, mixing the high molecular compound generated by the chain extension reaction according to the mass ratio of 1-40% to form a stock solution, adding prepared slurry containing various auxiliaries into the prepared stock solution, forming a uniform spinning stock solution by a stirring method, and preparing the spinning stock solution into spandex fibers by a dry spinning method. The invention effectively solves the influence of environmental temperature and humidity change on the stability of spandex products by changing the structural composition of soft and hard sections of spandex and introducing units with different structures into spandex high molecular compounds, and has very important significance for reducing the production cost of spandex and improving the economic benefit of spandex enterprises.
Description
Technical Field
The invention relates to a preparation method for improving the performance stability of spandex products, and belongs to the technical field of spandex fibers. More particularly, the invention relates to a preparation technology and a method for improving the performance stability of spandex products.
Background
The spandex is polyurethane elastic fiber, is called 'monosodium glutamate' in textile fiber, is small in dosage, generally accounts for 6-8% of textile, but is very excellent in performance and very wide in application, is used in single clothes in the past, is expanded to the fields of clothes external application, medical use and the like, is more and more popular with improvement of living standard of people, and can provide comfort and fabric stiffness which are not possessed by other fibers such as terylene, chinlon and the like.
In the processes of high-temperature curing molding, storage and the like, spandex is influenced by internal factors (chemical composition and structure) and external factors (temperature and humidity), so that the performance of spandex is changed, which is generally called as the aging phenomenon of a high polymer material. I.e. a process in which the material properties change from good to bad over time, which process can be divided into reversible and irreversible, i.e. physical and chemical changes. The aging of the polymer material is usually a chemical change, and becomes a key difficulty for limiting the further development and application of the polymer material. In the using process of spandex, the main factors causing the performance change, namely aging, such as temperature and humidity, are often acted simultaneously, the caused harm is larger than the independent action of any one factor, and under different environmental conditions, polyurethane polymers are aged to different degrees, and the performance of the polyurethane polymers is also changed differently.
Some hydrophilic groups with strong polarity, such as carbamate groups, carbamido groups and the like, exist in the internal structure of the spandex polymer, so that water molecules can easily perform chemical reaction with the hydrophilic groups in the spandex structure, and chemical bonds in the molecules are broken to be degraded, thereby directly reducing the mechanical strength. The polyurethane belongs to polyether polyurethane, ether bonds in a soft segment structure of the polyurethane initiate free radical chain reaction under the combined action of high temperature and oxygen in air, so that the polyurethane material is degraded, the thermochemical degradation process is carried out on carbon atoms close to the ether bonds, peroxide reaction occurs, the chemical bonds of the polymer are broken, and the physical properties are reduced. Meanwhile, under the environment with higher humidity, the glass transition temperature of the spandex can be reduced, so that the temperature section of the elastomer of the spandex is advanced, and the strength is reduced. Therefore, solving the influence of environmental temperature and humidity change on the performance stability of spandex products becomes an important problem to be solved urgently in spandex manufacturing industry.
Patent CN 105504212A discloses a preparation method of a moisture-heat aging resistant polyurethane elastomer, which comprises mixing diphenylmethane diisocyanate and hexamethylene diisocyanate at a certain ratio to obtain a composite isocyanate component, mixing polyester diol and polyether diol at a certain ratio to obtain a composite polyol component, and mixing the prepolymer with aromatic diamine to obtain a block copolymerization polyurethane elastomer. The obtained polyurethane elastomer has good hydrolysis resistance and stability, but the obtained product has low strength and influences the performance of spandex products.
The patent CN 108359072A discloses a polyester-type polyurethane resin for sofa leather with high temperature resistance, humidity and heat aging resistance, a chemical reaction modification method is adopted, a special dimer acid modified polyester polyol, hydroxyl-terminated organic silicon, isocyanate and a chain extender are mixed and reacted according to a certain proportion to obtain a polymer X, the polyester polyol, the isocyanate and the chain extender are mixed and reacted according to a certain proportion to obtain a polymer Y, and the high humidity and heat aging resistance polyester-type polyurethane adhesive layer resin for sofa leather is finally obtained by a blending method of the two. The invention replaces polyether polyurethane resin, solves the defect of poor hydrolysis resistance of the traditional polyester polyurethane resin, has the advantage of good heat resistance compared with the polyether polyurethane resin, but has complex production process and difficult product performance adjustment.
Patent CN 107663671A discloses a heat-resistant polyurethane elastic fiber and a preparation method thereof, diisocyanate and hydroxyl-terminated polyether are mixed and then performed with prepolymer 1, diisocyanate, amine-terminated polyether and alkali metal are mixed and then performed with prepolymer 2, prepolymer solutions 1 and 2 are obtained after respective dissolution, and a chain extender and a terminator are added into the mixed two solutions to perform chain extension reaction to obtain a polyurethane solution; the heat-resistant polyurethane elastic fiber is obtained by spinning, and the main chain simultaneously contains two hard segment structures, so that the heat-resistant polyurethane elastic fiber has excellent heat resistance while ensuring excellent elastic performance, but no relevant research is made on the environment humidity resistance.
The invention discloses a preparation method for improving the stability of spandex products, which is a basic theory of the invention and is based on the basic research idea of changing the structural composition of soft and hard sections of spandex, applying basic chemical raw materials and introducing units with different structures into a macromolecular compound to improve the intermolecular acting force and the microphase separation degree of polymer molecules. The invention not only can effectively solve the influence of environmental temperature and humidity change on the stability of spandex products, but also has important significance in reducing the production cost of spandex and improving the economic benefit of spandex enterprises.
Disclosure of Invention
The technical problem is as follows: the influence of the change of the environmental temperature and humidity on the performance stability of spandex products is an important problem to be solved urgently in spandex manufacturing industry, but related literature reports are lacked at present. The invention discloses a preparation method for improving the performance stability of spandex products, which is guided by the basic theory of improving intermolecular acting force and improving the degree of microphase separation among polymer molecules according to the structural characteristics of spandex molecules. The invention not only can effectively solve the influence of environmental temperature and humidity change on the performance stability of spandex products, but also has important significance for reducing the production cost of spandex and improving the economic benefit of spandex enterprises.
The technical scheme is as follows: the method comprises the steps of respectively carrying out prepolymerization on synthesized alicyclic polyester polyol and polyether polyol with different molecular weights and diisocyanate, carrying out chain extension reaction on respectively generated prepolymerization reactants to generate a high molecular compound solution A and a high molecular compound solution B, then carrying out blending on the high molecular compound solution A and the high molecular compound solution B generated by chain extension according to the mass ratio of 1-40% to form a stock solution, adding prepared slurry containing various auxiliaries into the prepared stock solution, forming uniform spinning stock solution by a stirring method, and preparing the spinning stock solution into spandex fibers by a dry spinning method;
the alicyclic polyester polyol PEP is prepared from micromolecular alicyclic dihydric alcohol and aliphatic polybasic acid through a copolycondensation method, the molecular weight of the alicyclic polyester polyol PEP is 1000-3000, the micromolecular alicyclic dihydric alcohol is 1, 4-cyclohexanedimethanol CHDM, and the aliphatic polybasic acid is succinic acid BDA, glutaric acid GA or adipic acid AA.
Wherein the content of the first and second substances,
the polyether polyol is polyether glycol, and the molecular weight of the polyether glycol is polytetrahydrofuran glycol PTMG of 1000-3000.
The method comprises the following steps of carrying out prepolymerization on alicyclic polyester polyol and diisocyanate, carrying out bulk polymerization reaction on alicyclic polyester polyol PEP and diisocyanate at the reaction temperature of 50-90 ℃ to generate a prepolymer, dissolving the generated prepolymer in a solvent, and carrying out chain extension reaction at the reaction temperature of 20-70 ℃ to generate a high molecular compound solution A.
The polyether glycol and the diisocyanate are subjected to prepolymerization, the polyether glycol and the diisocyanate are subjected to bulk polymerization at the reaction temperature of 40-70 ℃ to generate a prepolymer, the generated prepolymer is dissolved in a solvent, and chain extension reaction is performed at the reaction temperature of 20-60 ℃ to generate a high molecular compound solution B.
And dissolving the generated prepolymer in a solvent, wherein the solvent is one or a mixture of N, N-dimethylformamide DMF and N, N-dimethylacetamide DMAc, and the mass concentration of the prepolymer PP in the solvent is 15-40%.
The polymer compound solution A is characterized in that the molar ratio of diisocyanate to alicyclic polyester polyol PEP is 1.5-2.7; the molar ratio of diisocyanate to polyether glycol in the polymer compound solution B is 1.5-2.7.
The chain extender used in the chain extension reaction comprises: one or more mixtures of 1, 2-Ethylenediamine (EDA), 1, 2-Propylenediamine (PDA), Diethylenetriamine (DETA), Diethanolamine (DEA) or 2-methyl-1, 5-pentylenediamine (MPDA); the chain terminator comprises: one or more of diethylamine DEA, ethanol EtOH or n-butanol NBA.
The chain extender and the chain terminator are dissolved in one or a mixture of N, N-dimethylformamide DMF or N, N-dimethylacetamide DMAc, the mass concentration is 2.5-5.0%, and the ratio of 2 multiplied by the mole number of the chain extender to the mole number of the chain terminator is (12-18): 1.
Has the advantages that: the invention discloses a preparation method for improving the performance stability of spandex products by improving the acting force among macromolecules and improving the microphase separation degree among polymer molecules according to the structural characteristics of spandex molecules. The invention effectively solves the problem that the environmental temperature and humidity change affects the performance stability of the spandex product, and has important significance for reducing the production cost of the spandex and improving the economic benefit of spandex enterprises.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. Other advantages and capabilities of the present invention will be understood and appreciated by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention. It should be understood that the following examples are only intended to further illustrate the present invention and are not intended to limit the scope of the present invention.
Preparation of high molecular polymer stock solution by polyether polyol and diisocyanate compound
Adding a certain mass of polyether glycol into a first reactor protected by inert gas, starting a stirrer, and controlling the temperature of the reactor to be 40-70 ℃; weighing a certain mass of diisocyanate, slowly dropwise adding the diisocyanate into a reactor, and carrying out bulk polymerization reaction on polyether glycol and the diisocyanate for 2-3 hours to generate a prepolymer containing a certain excessive terminal group-NCO group.
Under the protection of inert gas, adding a certain amount of N, N-Dimethylformamide (DMF) or N, N-dimethylacetamide (DMAc) into a second reactor, starting a stirrer, controlling the temperature of the reactor to be 20-40 ℃, transferring the prepolymer generated in the first reactor into the second reactor, and stirring for 1-3 hours to fully and uniformly mix the prepolymer and the solvent.
Slowly dripping the prepared solution containing the chain extender and the chain terminator with a certain concentration into a second reactor, wherein the ratio of the sum of the moles of the end groups of the chain extender to the sum of the moles of the end groups of the chain terminator is (12-18): 1, and the ratio of the sum of the moles of the end groups of the chain extender and the chain terminator to the moles of the prepolymer-NCO active groups in the second reactor is (1.01-1.10): 1, and carrying out chain extension reaction for 1-2 hours at the reaction temperature of 20-60 ℃ to generate a high polymer stock solution.
And (3) transferring the high molecular polymer stock solution generated by the second reactor to a curing tank protected by inert gas, starting a stirrer, and controlling the temperature of the curing tank to be 50-70 ℃.
Preparation of high-molecular polymer stock solution from alicyclic polyester polyol (PEP) and diisocyanate compound
Adding a certain mass of alicyclic polyester polyol (PEP) into a first reactor protected by inert gas, starting a stirrer, and controlling the temperature of the reactor to be 50-90 ℃; weighing a certain mass of diisocyanate, slowly dropwise adding the diisocyanate into a reactor, and carrying out bulk polymerization reaction on alicyclic polyester polyol (PEP) and the diisocyanate for 2-3 hours to generate a prepolymer containing a certain excessive end group-NCO group; .
Under the protection of inert gas, adding a certain amount of N, N-Dimethylformamide (DMF) or N, N-dimethylacetamide (DMAc) into a second reactor, starting a stirrer, controlling the temperature of the reactor to be 20-60 ℃, transferring the prepolymer generated in the first reactor into the second reactor, and stirring for 1-3 hours to fully and uniformly mix the prepolymer and the solvent.
Slowly dripping the prepared solution containing the chain extender and the chain terminator with a certain concentration into a second reactor, wherein the ratio of the sum of the moles of the end groups of the chain extender to the sum of the moles of the end groups of the chain terminator is (14-16): 1, and the ratio of the sum of the moles of the end groups of the chain extender and the chain terminator to the moles of the prepolymer-NCO active groups in the second reactor is (1.03-1.08): 1, and carrying out chain extension reaction for 1-2 hours at the reaction temperature of 20-60 ℃ to generate a high polymer stock solution.
Transferring the stock solution of the high molecular polymer generated by the alicyclic polyester polyol and the diisocyanate compound into a curing tank of the stock solution of the high molecular polymer generated by the prepared polyether polyol and the diisocyanate compound, and stirring and mixing the materials uniformly.
Preparation of spinning dope and spandex spinning product
Adding the prepared functional auxiliary agent containing the antioxidant, the anti-hydrolysis agent, the lubricant, the delustering agent, the ultraviolet absorbent and the anti-blocking agent with certain mass concentration into the curing tank, curing for 20-40 hours at the temperature of 50-70 ℃ and at a proper stirring speed to obtain a spinning stock solution with uniform performance, and preparing a spandex spinning product by adopting a dry spinning method.
Example 1:
(1) polytetramethylene ether glycol with molecular weight of 1810 and mass of 12.0Kg is added with N2Starting a stirrer in a first reactor under gas protection, and controlling the temperature of the reactor to be 45 ℃; 2.80Kg of 4, 4-diphenylmethane diisocyanate was weighed and slowly added dropwise into the reactor, and the bulk polymerization was carried out for 2 hours to obtain a bulk prepolymer.
(2) Under the protection of inert gas, 20.5Kg of N, N-dimethylacetamide (DMAc) is added into the second reactor, the stirrer is started, the temperature of the reactor is controlled to be 30 ℃, the prepolymer generated in the step 1 is transferred to the second reactor, and the prepolymer and the solvent are stirred for 1.5 hours to be fully and uniformly mixed.
(3) 7.97Kg of a solution containing chain extenders, 1, 2-Ethylenediamine (EDA), 1, 2-Propylenediamine (PDA) and chain terminator Diethylamine (DEA), at a mass concentration of 4.0%, was slowly dropped into the second reactor, wherein (mole of EDA + mole of PDA) × 2/DEA is 14.50, and a chain extension reaction was carried out at a reaction temperature of 30 ℃ for 1.5 hours to give a polymer stock solution.
(4) Transferring the stock solution of the high molecular polymer generated in the second reactor to a curing tank protected by inert gas, starting a stirrer, and controlling the temperature of the curing tank to be 55 ℃. And (3) adding the prepared functional auxiliary agent containing the antioxidant, the anti-hydrolysis agent, the lubricant, the delustering agent, the ultraviolet absorbent and the anti-blocking agent into the curing tank in the step (3), and curing for 25 hours at the temperature of 55 ℃ and at a proper stirring speed to obtain the spinning stock solution with uniform performance.
(5) Spinning by adopting a dry spinning method to prepare the product with the required specificationThe spinning sample of 40D without cycloaliphatic polyester polyol compound is abbreviated as blank sample. The main spinning process parameters are as follows: the temperatures of the upper channel and the lower channel are respectively 258 ℃ and 185 ℃, the spinning speed is 750M/min, and the air inlet quantity is 11.5M3Min, air flow ratio 60/40.
Example 2:
(1) polytetramethylene ether glycol with mass of 9.85Kg is added to N2Starting a stirrer in a first reactor under gas protection, and controlling the temperature of the reactor to be 45 ℃; 2.27Kg of 4, 4-diphenylmethane diisocyanate was weighed and slowly added dropwise into the reactor, and bulk polymerization was carried out for 2 hours to obtain a bulk prepolymer.
(2) Under the protection of inert gas, 16.5Kg of N, N-dimethylacetamide (DMAc) is added into the second reactor, the stirrer is started, the temperature of the reactor is controlled to be 30 ℃, the prepolymer generated in the step 1 is transferred to the second reactor, and the prepolymer and the solvent are stirred for 1.5 hours to be fully and uniformly mixed.
(3) 6.48Kg of a solution containing chain extenders, 1, 2-Ethylenediamine (EDA), 1, 2-Propylenediamine (PDA) and chain terminator Diethylamine (DEA), at a mass concentration of 4.0%, was slowly dropped into the second reactor, and a chain extension reaction was carried out at a reaction temperature of 30 ℃ for 1.5 hours to produce a polymer dope.
(4) Transferring the stock solution of the high molecular polymer generated in the second reactor to a curing tank protected by inert gas, starting a stirrer, and controlling the temperature of the curing tank to be 55 ℃.
(5) Adding alicyclic polyester polyol with the mass of 0.520Kg into a first reactor protected by inert gas, starting a stirrer, and controlling the temperature of the reactor to be 65 ℃; then, 0.195Kg of 4, 4-diphenylmethane diisocyanate was slowly dropped into the reactor, and bulk polymerization was carried out for 2.5 hours to obtain a prepolymer.
(6) Under the protection of inert gas, 0.73Kg of N, N-dimethylacetamide (DMAc) is added into the second reactor, the stirrer is started, the temperature of the reactor is controlled to be 35 ℃, the prepolymer generated in the first reactor is transferred to the second reactor, and the prepolymer and the solvent are stirred for 2.0 hours to be fully and uniformly mixed.
(7) 0.65Kg of a 3.5% by mass solution containing chain extender 1, 2-Ethylenediamine (EDA) and chain terminator Diethylamine (DEA) was slowly added dropwise to the second reactor, wherein the molar ratio of 2 XEDA/DEA was 15.80, and the chain extension reaction was carried out at 35 ℃ for 1.5 hours to give a polymer stock solution.
(8) Transferring the polymer stock solution generated in the step 7 to the polyether type polymer stock solution generated in the step 4 in a curing tank, stirring and mixing uniformly, and keeping the temperature of the curing tank at 55 ℃.
(9) Adding the prepared functional auxiliary agent containing the antioxidant, the anti-hydrolysis agent, the lubricant, the delustering agent, the ultraviolet absorbent and the anti-blocking agent into the curing tank in the step 8, and curing for 25 hours at the temperature of 55 ℃ and at a proper stirring speed to obtain the spinning solution with uniform performance.
(10) Spinning is carried out by adopting a dry spinning method, and a spinning sample with the alicyclic polyester polyol/polytetramethylene ether glycol mass ratio of 40D, namely 5/95, is prepared, and is referred to as a comparative sample 1. The main spinning process parameters are as follows: the temperatures of the upper channel and the lower channel are respectively 258 ℃ and 185 ℃, the spinning speed is 750M/min, and the air inlet quantity is 11.5M3/min, air flow rate 60/40
Example 3:
in a similar manner to example 2, a spinning sample of 10/90 mass ratio of alicyclic polyester polyol/polytetramethylene ether glycol having a specification of 40D, referred to as comparative sample 2, was prepared.
Example 4:
in a similar manner to example 2, a spinning sample of 15/85 mass ratio of alicyclic polyester polyol/polytetramethylene ether glycol having a specification of 40D, referred to as comparative sample 3, was prepared.
Example 5:
in a similar manner to example 2, a spinning sample of 20/80 mass ratio of alicyclic polyester polyol/polytetramethylene ether glycol having a specification of 40D, referred to as comparative sample 4, was prepared.
The quality of the rebound resilience of the high polymer material is usually expressed by internal power consumption, when the spandex filament is stretched and retracted, the work done by external force on the spandex and the retraction work done by the spandex on the external force are respectively equivalent to the areas covered under a stretching curve and a retraction curve, so the energy consumed in one stretching and retraction cycle is equivalent to the difference between the two areas, the two curves form a closed loop called a hysteresis loop, and the area contained by the hysteresis loop is the internal power consumption of the spandex filament.
By comparing the change conditions of internal work consumption of the spandex filament processed under different temperature and humidity conditions, the stability of the spandex filament can be reflected, and the smaller the change of the internal work consumption is, the better the stability of the spandex filament is. Table 1 compares the blank samples with the samples of examples 2-5, wherein the experimental conditions of the temperature and humidity effect are as follows: the treatment was carried out at 80 ℃ and a relative humidity RH of 80% for 24 hours.
TABLE 1 comparison of creep characteristics of comparative samples of inventive examples and blank samples
The experimental data in table 1 show that the alicyclic polyester polyol and the diisocyanate high molecular polymer are added into the spinning solution, so that the performance of the spandex filament against the influence of the environmental temperature and humidity is effectively improved. The data of the comparative examples show that under the conditions that the mass ratio of the alicyclic polyester polyol to the polytetramethylene ether glycol is 10/90 and 15/85 respectively, the spandex yarn has the best performance of resisting the influence of the environmental temperature and humidity after being treated for 24 hours under the conditions that the temperature is 80 ℃ and the relative humidity RH is 80 percent, and meanwhile, other physical indexes of the spandex yarn are not obviously different. The invention effectively solves the problem of influence of environmental temperature and humidity change on the performance stability of spandex products, and has important significance for reducing the production cost of spandex and improving the economic benefit of spandex enterprises.
In light of the above teachings, those skilled in the art will readily appreciate that the materials and methods illustrated herein are capable of performing the present invention and that the upper and lower limits, ranges, and values of the materials and processes are capable of performing the present invention and are not intended to limit the scope of the present invention.
In practice, the technical personnel according to the invention make improvements and modifications, which still belong to the protection scope of the invention. Furthermore, it is to be understood that one or more method steps mentioned in the present invention does not exclude that other method steps may also be present before or after the combined steps or that other method steps may also be inserted between these explicitly mentioned steps, unless otherwise indicated; the numbering of the method steps is only a convenient tool for identifying the method steps, and is not intended to limit the arrangement order of the method steps or the range of the method steps, and the relative relationship between the method steps and the range can be changed or adjusted without substantially changing the technical content.
Claims (8)
1. A method for improving the performance stability of spandex products is characterized in that the method comprises the steps of respectively carrying out prepolymerization on synthesized alicyclic polyester polyol and polyether polyol with different molecular weights and diisocyanate, carrying out chain extension reaction on respectively generated prepolymerization reactants to generate a high molecular compound solution A and a high molecular compound solution B, then carrying out blending on the high molecular compound solution A and the high molecular compound solution B generated by chain extension according to the mass ratio of 1-40% to form a stock solution, adding prepared slurry containing various auxiliaries into the prepared stock solution, forming a uniform spinning stock solution by a stirring method, and preparing the spinning stock solution into spandex fibers by a dry spinning method;
the alicyclic polyester polyol PEP is prepared from micromolecular alicyclic dihydric alcohol and aliphatic polybasic acid through a copolycondensation method, the molecular weight of the alicyclic polyester polyol PEP is 1000-3000, the micromolecular alicyclic dihydric alcohol is 1, 4-cyclohexanedimethanol CHDM, and the aliphatic polybasic acid is succinic acid BDA, glutaric acid GA or adipic acid AA.
2. The method for improving the performance stability of spandex products according to claim 1, wherein the polyether polyol is polyether glycol, and the molecular weight of the polyether glycol is polytetrahydrofuran diol PTMG of 1000-3000.
3. The method for improving the performance stability of the spandex product according to claim 1, wherein the alicyclic polyester polyol and the diisocyanate are subjected to prepolymerization, the alicyclic polyester polyol PEP and the diisocyanate are subjected to bulk polymerization at a reaction temperature of 50-90 ℃ to generate a prepolymer, the generated prepolymer is dissolved in a solvent, and chain extension reaction is performed at a reaction temperature of 20-70 ℃ to generate a polymer compound solution A.
4. The method for improving the performance stability of spandex products according to claim 1, wherein the polyether polyol and the diisocyanate are prepolymerized, the polyether diol and the diisocyanate are subjected to bulk polymerization at a reaction temperature of 40-70 ℃ to form a prepolymer, the prepolymer is dissolved in a solvent, and a chain extension reaction is performed at a reaction temperature of 20-60 ℃ to form a polymer compound solution B.
5. The method for improving the performance stability of spandex products according to claim 3 or 4, characterized in that the generated prepolymer is dissolved in a solvent, the solvent is one or a mixture of N, N-dimethylformamide DMF and N, N-dimethylacetamide DMAc, and the mass concentration of the prepolymer PP in the solvent is 15-40%.
6. The method for improving the performance stability of spandex products according to claim 1, wherein the molar ratio of diisocyanate to alicyclic polyester polyol PEP in the polymer compound solution A is 1.5-2.7; the molar ratio of diisocyanate to polyether glycol in the polymer compound solution B is 1.5-2.7.
7. The method for improving the performance stability of spandex products according to claim 1 or 4, wherein the chain extender used in the chain extension reaction comprises: one or more mixtures of 1, 2-Ethylenediamine (EDA), 1, 2-Propylenediamine (PDA), Diethylenetriamine (DETA), Diethanolamine (DEA) or 2-methyl-1, 5-pentylenediamine (MPDA); the chain terminator comprises: one or more of diethylamine DEA, ethanol EtOH or n-butanol NBA.
8. The method for improving the performance stability of spandex products according to claim 7, wherein the chain extender and the chain terminator are dissolved in one or a mixture of N, N-dimethylformamide DMF or N, N-dimethylacetamide DMAc, the mass concentration is 2.5-5.0%, and the ratio of 2 x the number of moles of the chain extender to the number of moles of the chain terminator is (12-18): 1.
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| CN113551990A (en) * | 2021-06-29 | 2021-10-26 | 滁州市玉林聚氨酯有限公司 | Method for detecting internal heat generation of polyurethane material |
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