CN115772714A - High-strength high-heat-resistance spandex and preparation method thereof - Google Patents
High-strength high-heat-resistance spandex and preparation method thereof Download PDFInfo
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- CN115772714A CN115772714A CN202211564588.4A CN202211564588A CN115772714A CN 115772714 A CN115772714 A CN 115772714A CN 202211564588 A CN202211564588 A CN 202211564588A CN 115772714 A CN115772714 A CN 115772714A
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- 229920002334 Spandex Polymers 0.000 title claims abstract description 89
- 239000004759 spandex Substances 0.000 title claims abstract description 89
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 58
- 229920000570 polyether Polymers 0.000 claims abstract description 58
- 229920002545 silicone oil Polymers 0.000 claims abstract description 41
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 30
- 150000001412 amines Chemical class 0.000 claims abstract description 28
- 229920000642 polymer Polymers 0.000 claims abstract description 16
- 229920003226 polyurethane urea Polymers 0.000 claims abstract description 15
- 229920000909 polytetrahydrofuran Polymers 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 238000000578 dry spinning Methods 0.000 claims abstract description 9
- 238000009987 spinning Methods 0.000 claims abstract description 8
- -1 polyethylene Polymers 0.000 claims abstract description 7
- 229920001451 polypropylene glycol Polymers 0.000 claims abstract description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims abstract description 4
- 239000004698 Polyethylene Substances 0.000 claims abstract description 4
- 229920000573 polyethylene Polymers 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 29
- 239000000243 solution Substances 0.000 claims description 24
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 13
- 229920002635 polyurethane Polymers 0.000 claims description 13
- 239000004814 polyurethane Substances 0.000 claims description 13
- 125000005442 diisocyanate group Chemical group 0.000 claims description 11
- 239000011550 stock solution Substances 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
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- 238000005516 engineering process Methods 0.000 claims description 8
- 150000002009 diols Chemical class 0.000 claims description 7
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- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 3
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 3
- 150000004985 diamines Chemical class 0.000 claims description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 2
- 239000012948 isocyanate Substances 0.000 abstract description 6
- 150000002513 isocyanates Chemical class 0.000 abstract description 6
- 238000011084 recovery Methods 0.000 abstract description 6
- 229920006306 polyurethane fiber Polymers 0.000 abstract description 2
- 239000013523 DOWSIL™ Substances 0.000 description 8
- 229920013731 Dowsil Polymers 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 5
- 239000004744 fabric Substances 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
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- 230000008569 process Effects 0.000 description 3
- 238000007493 shaping process Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000004984 aromatic diamines Chemical group 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229940113088 dimethylacetamide Drugs 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 210000004177 elastic tissue Anatomy 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000006459 hydrosilylation reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 2
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- LPUQAYUQRXPFSQ-DFWYDOINSA-M monosodium L-glutamate Chemical compound [Na+].[O-]C(=O)[C@@H](N)CCC(O)=O LPUQAYUQRXPFSQ-DFWYDOINSA-M 0.000 description 1
- 235000013923 monosodium glutamate Nutrition 0.000 description 1
- 239000004223 monosodium glutamate Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- 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
- Artificial Filaments (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention provides high-strength high-heat-resistance spandex and a preparation method thereof, wherein the spandex contains 0.05-10% of hydroxyl-terminated polyether silicone oil calculated based on the mass of the spandex; the number average molecular weight of the hydroxyl-terminated polyether silicone oil is 500-5000; the hydroxyl-terminated polyether silicone oil has a polyether structure comprising more than one of polyethylene oxide, polypropylene oxide, polyethylene oxide-propylene oxide or polytetrahydrofuran; the polyurethane fiber is obtained by reacting polyurethane prepolymer containing isocyanate end capping, mixed amine and hydroxyl-terminated polyether silicone oil to obtain a raw material containing polyurethane-urea polymer, and the raw material is taken as spinning solution to obtain the polyurethane-urea polymer through dry spinning; the spandex of the invention has high hard segment content and a regular chain segment structure, the stress concentration phenomenon of the spandex is obviously improved, and the breaking strength, heat resistance and elastic recovery rate of the product are obviously improved.
Description
Technical Field
The invention relates to high-strength high-heat-resistance spandex and a preparation method thereof, belonging to the technical field of polyurethane elastic fibers.
Background
Spandex is used as industrial monosodium glutamate in textile industry, and the comfort and grade of the fabric can be obviously improved by adding a small amount of the non-ammonia non-woven fabric. However, in some fields, such as fabrics interwoven by spandex and polyester, sizing is usually required to be carried out at a temperature of more than 190 ℃, and repeated dyeing is carried out at a temperature of more than 130 ℃, which can greatly deteriorate the mechanical properties of spandex, even lead to fiber breakage, cause the elasticity loss of the fabric and cause defects.
In order to solve the above problems, spandex manufacturers generally adopt physical modification, chemical modification, or improvement of equipment processes to improve the heat resistance and breaking strength of spandex.
Patent CN200480024915.0 is to add 1wt% -20 wt% cellulose acetate into polyurethane or polyurethane urea solution to make physical modification to prepare high modulus, alkali resistance and heat resistance spandex, when the spandex is used for special velvet fabric requiring burnt-out and printing, the fiber will not age, and the fabric state is stably maintained. In patent CN202110943822.3, titanium dioxide modified by silane coupling agent, functional agent and initiator are reacted in styrene-acrylic mixed solution to obtain modified titanium dioxide emulsion, and the modified titanium dioxide emulsion is used for physical modification of spandex, which can significantly improve heat resistance, breaking strength and alkali resistance of spandex. According to the patent CN201611156846.X, meta-aramid fiber is physically added into a spinning solution of spandex to prepare heat-resistant spandex, and the heat deformation temperature of the prepared novel heat-resistant spandex is improved by 5-11 ℃ compared with that of common spandex while the original high elasticity is maintained.
In patent CN201110127711.1, an aromatic diamine chain extender such as 4,4 '-diaminodiphenyl ether, 4,4' -diaminodiphenylmethane and the like is added in the chain extension reaction stage of spandex for chemical modification, so that the temperature of a first exothermic peak of the spandex on a synchronous thermal weight loss-differential thermal analysis curve is increased by more than 20 ℃ compared with that of the conventional spandex. JP2011055950 prepares a high-resilience and high-heat-resistance spandex, which is characterized in that the soft segment of the spandex is copolymerized polyalkylene ether glycol formed by different alkylene ethers with 2-10 carbon atoms, and the hard segment fraction is more than 14% and less than 25%, namely the purpose is achieved by chemical modification of the soft segment and the hard segment.
In patent CN202011589327.9, polytetramethylene ether glycol with different molecular weights is added in the prepolymerization stage, and a microcavity reactor is used to replace a conventional pipeline reactor, so that the problem of heterogeneity in the reaction process is solved; adding a mixture of aromatic diamine, aliphatic diamine, diethylenetriamine and diethylamine in the chain extension stage, and pertinently improving the crystallinity of the molecules; functional substances such as a heat-resistant agent and the like are added in the mixing and curing stage, so that the product performance is further optimized and improved, and the breaking strength and the heat resistance of the spandex prepared by the process are greatly improved compared with those of the conventional spandex.
However, the production process of the prior art is relatively complicated, and even if only simple physical modification is performed, the effect of improving the heat resistance and breaking strength in combination is not satisfactory. When preparing high-strength high-heat-resistance spandex, high hard segment content and regular chain segment structure are generally needed, and in this state, the crystallinity of a hard segment is often too high, so that the polarity difference between soft and hard segments is increased, the compatibility of two phases is poorer, a stress concentration phenomenon can occur at an interface, the number of matrix stress defects is increased, the fiber performance can be greatly changed, and the heat resistance and the breaking strength of a product are seriously deteriorated.
Disclosure of Invention
The technical problem is as follows: in order to solve the problems in the prior art, the invention aims to provide high-strength high-heat-resistance spandex and a preparation method thereof. The spandex prepared by the technology provided by the invention has the advantages that the stress concentration phenomenon of the product is obviously improved, the process technology is simple, and the breaking strength and the heat resistance of the product are obviously improved.
The technical scheme is as follows: in order to achieve the purpose, the invention provides high-strength high-heat-resistance spandex and a preparation method thereof.
The high-strength and high-heat-resistance spandex of the invention contains 0.05-10% of hydroxyl-terminated polyether silicone oil based on the mass of spandex.
The number average molecular weight of the hydroxyl-terminated polyether silicone oil is 500-5000.
The hydroxyl-terminated polyether silicone oil has a polyether structure comprising more than one of polyethylene oxide, polypropylene oxide, polyethylene oxide-propylene oxide or polytetrahydrofuran.
In the preparation method of the high-strength high-heat-resistance spandex, the spandex is subjected to a reaction comprising isocyanate-terminated polyurethane prepolymer, mixed amine and hydroxyl-terminated polyether silicone oil to obtain a raw material containing a polyurethane-urea polymer, and the raw material is used as a spinning solution to obtain the high-strength high-heat-resistance spandex through dry spinning.
The preparation method comprises the following steps:
step 1, carrying out prepolymerization reaction on diisocyanate and polyether diol in the presence of a solvent to prepare an isocyanate-terminated polyurethane prepolymer;
step 2, fully dissolving the polyurethane prepolymer in a solvent to form a polyurethane prepolymer solution;
step 3, reacting the polyurethane prepolymer solution with hydroxyl-terminated polyether silicone oil and mixed amine solution to obtain polyurethane-urea stock solution;
and 4, curing the polyurethane-urea stock solution, and preparing the high-strength high-heat-resistance spandex by a dry spinning technology.
The molar ratio of the diisocyanate to the polyether glycol is 1.65.
The diisocyanate comprises more than one of diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate and/or derivatives and/or modified polymers; the polyether diol comprises polytetramethylene ether glycol with the number average molecular weight of 1000-3000.
The mixed amine comprises monoamine and diamine; does not contain a branched structure.
The mixed amine comprises ethylenediamine and diethylamine, and the molar ratio of the ethylenediamine to the diethylamine is 4-1.
The molar ratio of the total amino of the mixed amine to the isocyanic acid radical of the polyurethane prepolymer is 1.0-1.2.
Has the beneficial effects that: compared with the prior art, the spandex production process is simple in technology, the stress concentration phenomenon of spandex is obviously improved under the condition of high hard segment content and regular chain segment structure, and the breaking strength, heat resistance and elastic recovery rate of a product are obviously improved.
Drawings
FIG. 1 is a scanning electron microscope image of a cross section of spandex prepared in example 1 of the invention;
FIG. 2 is a scanning electron micrograph of a cross section of spandex prepared in comparative example 1 of the present invention.
Detailed Description
The high-strength high-heat-resistance spandex of the invention contains 0.05-10% of hydroxyl-terminated polyether silicone oil calculated based on the mass of the spandex;
further, the content of the hydroxyl-terminated polyether silicone oil is calculated to be 0.1-1% based on the mass of spandex;
the number average molecular weight of the hydroxyl-terminated polyether silicone oil is 500-5000;
preferably, the number average molecular weight of the hydroxyl-terminated polyether silicone oil is 1000-3000;
the polyether structure in the hydroxyl-terminated polyether silicone oil comprises more than one of polyethylene oxide, polypropylene oxide, polyethylene oxide-propylene oxide and polytetrahydrofuran;
preferably, the polyether structure in the hydroxyl-terminated polyether silicone oil comprises polytetrahydrofuran;
the hydroxyl-terminated polyether silicone oil can be obtained by adopting preparation methods such as hydrosilylation reaction, esterification reaction, ring-opening addition reaction and the like;
as an example, hydrogen-containing silicone oil is obtained by hydrosilylation reaction with polyether having terminal alkenyl group in the presence of platinum catalyst;
in the embodiment of the invention, the hydroxyl-terminated polyether silicone oil can be selected from commercial products, such as DOWSIL TM BY16-201、DOWSIL TM SF8427、XIAMETER TM OFX-3667 and the like;
further, the polyurethane elastic fiber is obtained by reacting polyurethane prepolymer containing isocyanate end capping, mixed amine and hydroxyl-terminated polyether silicone oil to obtain a raw material containing polyurethane-urea polymer, and the raw material is used as spinning solution and is obtained by dry spinning;
further, the preparation method of the high-strength high-heat-resistance spandex comprises the following steps:
step 1, carrying out prepolymerization reaction on diisocyanate and polyether diol to prepare an isocyanato-terminated polyurethane prepolymer;
step 2, fully dissolving the polyurethane prepolymer in a solvent to form a polyurethane prepolymer solution;
step 3, reacting the polyurethane prepolymer solution with hydroxyl-terminated polyether silicone oil and a mixed amine solution to obtain a polyurethane polymer stock solution;
and 4, curing the polyurethane polymer stock solution, and preparing the high-strength high-heat-resistance spandex by a dry spinning technology.
In the invention, in the reaction process of the isocyanate end-capped polyurethane prepolymer, the mixed amine and the hydroxyl-terminated polyether silicone oil, a large amount of amine exists in the mixed amine, the reaction activity of the amine and the isocyanate is far greater than that of the hydroxyl, the polyurethane prepolymer preferentially reacts with the amine, the obtained spinning solution raw material contains a certain amount of free hydroxyl-terminated polyether silicone oil, and on the premise of not damaging the molecular structure of a polyurethane-urea polymer and ensuring the high hard segment content and the regular chain segment structure, the hydroxyl-terminated polyether silicone oil with stronger polarity and better compatibility with polyurethane-urea is introduced into the spandex spinning solution, so that stable spinning is realized, and the performances of breaking strength, heat resistance, elastic recovery rate and the like of the product are obviously improved.
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitation of the present invention.
The invention relates to a preparation method of high-strength and high-heat-resistance spandex, which comprises the following steps:
1) Carrying out prepolymerization reaction on diisocyanate and polyether diol at the temperature of 45-100 ℃ for 0.5-5 h to prepare isocyanate end-capped polyurethane prepolymer;
2) Fully dissolving the polyurethane prepolymer in a dimethyl acetamide solvent to form a polyurethane prepolymer solution with the solid content of 30-50%;
3) Reacting the polyurethane prepolymer solution with a mixed amine solution containing hydroxyl-terminated polyether silicone oil to prepare a polyurethane-urea stock solution with the solid content of 25-40%;
4) Curing the polyurethane-urea stock solution, and preparing the polyurethane fiber by a dry spinning technology.
Wherein the molar ratio of the diisocyanate to the polyether glycol is 1.65 to 1.95;
the hydroxyl-terminated polyether silicone oil accounts for 0.05-10% of the weight of the spandex, and preferably accounts for 0.1-1% of the weight of the spandex;
the mixed amine comprises monoamine and diamine;
further, the mixed amine does not contain a branched chain structure;
the mixed amine comprises ethylenediamine and diethylamine.
The molar ratio of the ethylenediamine to the diethylamine is 4;
the concentration of the mixed amine solution is 0.5-10%;
the molar ratio of the total amine groups of the mixed amine to the isocyanate groups of the polyurethane prepolymer is 1.0 to 1.2, preferably 1.02 to 1.10;
other functional additives can be added into the polyurethane stock solution as long as the performance of the product is not deteriorated. Such as lubricants, antioxidants, anti-uv agents, matting agents, dyeing aids, chlorine-resistant aids, and the like.
Further, the reaction is carried out in the presence of a solvent;
preferably, the solvent comprises N, N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF);
by way of example, the solvent is DMAc;
the diisocyanate comprises one or more of diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate and/or derivatives and/or modified polymers;
by way of example, diisocyanates include 4,4' -diphenylmethane diisocyanate;
the polyether diol comprises polytetramethylene ether glycol with the number average molecular weight of 1000-3000;
in the embodiment of the invention, the isocyanate-terminated polyurethane prepolymer is obtained by reacting polytetramethylene ether glycol and 4,4' -diphenylmethane diisocyanate;
in the embodiment of the invention, the hydroxyl-terminated polyether silicone oil can be added into the mixed amine solution and then reacted with the polyurethane prepolymer solution.
The invention also evaluates the key properties of the product by the following methods:
breaking strength: the test method refers to an industry standard FZ/T50006-2013 spandex filament tensile property test method.
Elastic recovery rate: the test method refers to the industry standard FZ/T50007-2012 spandex silk elasticity test method.
Heat resistance: fixing a sample on a shaping support by 2.0 times of drafting, pre-shaping for 1min in a baking oven at 190 ℃, cooling, putting into water, putting into a closed container, processing for 40min at 130 ℃, drying in the air, then putting into the baking oven at 190 ℃ for shaping for 1min, taking out, naturally drying and cooling, and testing the breaking strength, wherein the heat resistance is the breaking strength retention (%) before and after spandex treatment.
Example 1:
step 1): mixing 4,4' -diphenylmethane diisocyanate and polytetramethylene ether glycol with a molecular weight of 1810 according to a molar ratio of 1.75 to 1, and reacting for 2 hours at 90 ℃ to prepare an isocyanate end-capped polyurethane prepolymer;
step 2): fully dissolving the polyurethane prepolymer in a dimethyl acetamide solvent to form a polyurethane prepolymer solution with the solid content of 40%;
and step 3): using 4.5% of silicone oil (DOWSIL) containing end hydroxyl polyether TM SF 8427) to obtain a stock solution of polyurethane-urea with a solid content of 35.0%, wherein DOWSIL is used for chain extension of the polyurethane prepolymer TM SF8427 accounts for 0.5 percent of the weight of spandex, the molar ratio of ethylenediamine to diethylamine in the mixed amine is 5.5;
step 4): hydrotalcite accounting for 4 percent of the weight of the polyurethane polymer is added into the polyurethane stock solution, evenly mixed and cured, and then the 33dtex/3f spandex is prepared by a dry spinning technology.
Example 2:
spandex was prepared according to the same procedures as described in example 1, except that DOWSIL was used TM SF8427 makes up 0.05% by weight of the polyurethane polymer.
Example 3:
spandex was prepared according to the same procedures as described in example 1, except that DOWSIL was used TM SF8427 makes up 1.0% by weight of the polyurethane polymer.
Example 4:
spandex was prepared according to the same procedure as described in example 1, except that DOWSIL was used TM SF8427 makes up 5.0% by weight of the polyurethane polymer.
Example 5:
spandex was prepared according to the same procedures as described in example 1, except that DOWSIL was used TM SF8427 makes up 10% by weight of the polyurethane polymer.
Example 6:
spandex was prepared according to the same procedure as described in example 3, except that the hydroxyl terminated polyether silicone oil added had a polyether segment structure of polypropylene oxide and an average number average molecular weight of 2200.
Example 7:
spandex was prepared according to the same procedure as described in example 3, except that the polyether segment structure in the hydroxyl terminated polyether silicone oil was a copolymer of ethylene oxide and propylene oxide, and the average number average molecular weight was 2200.
Example 8:
spandex was prepared according to the same procedure as described in example 3, except that the polyether segment structure in the hydroxyl terminated polyether silicone oil was polytetrahydrofuran ether, and the average number average molecular weight was 2200.
Example 9:
spandex was prepared according to the same procedure as described in example 1, except that the molar ratio of 4,4' -diphenylmethane diisocyanate to polytetramethylene ether glycol was 1.65.
Example 10:
spandex was prepared according to the same method as described in example 1, except that the molar ratio of 4,4' -diphenylmethane diisocyanate to polytetramethylene ether glycol was 1.95.
Example 11:
spandex was prepared according to the same method as described in example 3, except that the hydroxyl terminated polyether silicone oil was added during the curing in step 4) of the preparation method.
Example 12:
spandex was prepared according to the same method as described in example 5, except that the hydroxyl terminated polyether silicone oil was added during the curing in step 4) of the preparation method.
Example 13:
spandex was prepared according to the same procedure as described in example 1, except that the mixed amine consisted of ethylenediamine, 1, 2-propylenediamine, diethylamine in a molar ratio of 5.4.
Example 14:
spandex was prepared according to the same procedure as described in example 1, except that the mixed amine consisted of 1, 2-propanediamine, diethylamine in a molar ratio of 7.
Example 15:
spandex was prepared according to the same method as described in example 1, except that the hydroxy silicone oil was added.
Example 16:
spandex was prepared according to the same procedure as described in example 1, except that the average number average molecular weight of the hydroxy polyether silicone oil added was less than 500.
Example 17:
spandex was prepared according to the same procedure as described in example 1, except that the average number average molecular weight of the hydroxy polyether silicone oil added was greater than 5000.
Comparative example 1:
spandex was prepared according to the same procedure as described in example 1, except that no hydroxyl terminated polyether silicone oil was added.
The spandex prepared in the above examples and comparative examples was evaluated for breaking strength, elastic recovery, and heat resistance, and the specific results are shown in table 1 below:
TABLE 1 evaluation results of inventive examples and comparative examples
As shown in table 1, spandex prepared by the method of the present invention exhibits high breaking strength, elastic recovery, and heat resistance at a high hard segment content, a regular segment structure.
The spandex and the preparation method thereof of the present invention are illustrated by the above examples, but the present invention is not limited to the above examples, which does not mean that the present invention must be practiced by relying on the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. The high-strength and high-heat-resistance spandex is characterized by comprising 0.05-10% of hydroxyl-terminated polyether silicone oil based on the mass of the spandex.
2. The high tenacity and high heat resistance spandex according to claim 1, wherein the number average molecular weight of the hydroxyl terminated polyether silicone oil is 500 to 5000.
3. The spandex of claim 1, wherein the hydroxyl terminated polyether silicone oil has a polyether structure comprising at least one of polyethylene oxide, polypropylene oxide, polyethylene oxide-propylene oxide, or polytetrahydrofuran.
4. A method for preparing the spandex with high strength and high heat resistance as claimed in claim 1,2 or 3, wherein the spandex is obtained by reacting a prepolymer comprising isocyanate-terminated polyurethane, a mixed amine, and hydroxyl-terminated polyether silicone oil to obtain a raw material comprising a polyurethane-urea polymer, and the raw material is obtained by dry spinning using a spinning solution comprising the raw material.
5. The method for preparing the high-strength high-heat-resistance spandex according to claim 4, comprising the steps of:
step 1, carrying out prepolymerization reaction on diisocyanate and polyether diol in the presence of a solvent to prepare an isocyanate-terminated polyurethane prepolymer;
step 2, fully dissolving the polyurethane prepolymer in a solvent to form a polyurethane prepolymer solution;
step 3, reacting the polyurethane prepolymer solution with hydroxyl-terminated polyether silicone oil and mixed amine solution to obtain polyurethane-urea stock solution;
and 4, curing the polyurethane-urea stock solution, and preparing the high-strength high-heat-resistance spandex by a dry spinning technology.
6. The method for preparing high-strength and high-heat-resistance spandex according to claim 5, wherein the molar ratio of diisocyanate to polyether glycol is 1.65.
7. The method for preparing high tenacity and high heat resistance spandex according to claim 6, wherein the diisocyanate includes one or more of diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, and/or derivatives and/or modified polymers; the polyether diol comprises polytetramethylene ether glycol, and the number average molecular weight is 1000-3000.
8. The method for preparing high tenacity and high heat resistance spandex according to claim 4, wherein the mixed amine includes monoamine and diamine; does not contain a branched structure.
9. The method for preparing spandex with high strength and high heat resistance according to claim 8, wherein the mixed amine comprises ethylenediamine and diethylamine, and the molar ratio of ethylenediamine to diethylamine is 4.
10. The method for preparing the spandex having high strength and high heat resistance as claimed in claim 8, wherein the molar ratio of the total amine groups of the mixed amine to the isocyanate groups of the polyurethane prepolymer is 1.0 to 1.2.
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