CN115772714B - 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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- CN115772714B CN115772714B CN202211564588.4A CN202211564588A CN115772714B CN 115772714 B CN115772714 B CN 115772714B CN 202211564588 A CN202211564588 A CN 202211564588A CN 115772714 B CN115772714 B CN 115772714B
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- 229920002334 Spandex Polymers 0.000 title claims abstract description 79
- 239000004759 spandex Substances 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 56
- 229920000570 polyether Polymers 0.000 claims abstract description 56
- 229920002545 silicone oil Polymers 0.000 claims abstract description 41
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 32
- 150000001412 amines Chemical class 0.000 claims abstract description 27
- 229920002635 polyurethane Polymers 0.000 claims abstract description 25
- 239000004814 polyurethane Substances 0.000 claims abstract description 25
- 229920000642 polymer Polymers 0.000 claims abstract description 17
- 229920003226 polyurethane urea Polymers 0.000 claims abstract description 16
- 229920000909 polytetrahydrofuran Polymers 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 238000000578 dry spinning Methods 0.000 claims abstract description 9
- 238000009987 spinning Methods 0.000 claims abstract description 8
- 239000012948 isocyanate Substances 0.000 claims abstract description 7
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 7
- -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
- 239000000243 solution Substances 0.000 claims description 23
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 19
- 125000005442 diisocyanate group Chemical group 0.000 claims description 11
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 11
- 239000011550 stock solution Substances 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 10
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 9
- 238000005516 engineering process Methods 0.000 claims description 8
- 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 7
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 7
- 125000003277 amino group Chemical group 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 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
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-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
- 238000011084 recovery Methods 0.000 abstract description 6
- 239000013523 DOWSIL™ Substances 0.000 description 8
- 229920013731 Dowsil Polymers 0.000 description 7
- 239000004744 fabric Substances 0.000 description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 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
- 230000000052 comparative effect Effects 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 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
- 238000007385 chemical modification Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000004043 dyeing Methods 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
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000000203 mixture Substances 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
- 230000008569 process Effects 0.000 description 2
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-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
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical group N=C=O OWIKHYCFFJSOEH-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
- 229920004933 Terylene® Polymers 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 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
- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical compound CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 210000004177 elastic tissue Anatomy 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 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
- 239000011259 mixed solution 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
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007142 ring opening reaction 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
- 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
Classifications
-
- 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 a 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 comprises more than one of polyethylene oxide, polypropylene oxide, polyethylene oxide-propylene oxide or polytetrahydrofuran in polyether structure; the polyurethane is obtained by reacting polyurethane prepolymer with isocyanate end, mixed amine and hydroxyl-terminated polyether silicone oil to obtain a raw material containing polyurethane-urea polymer, and dry spinning the raw material serving as spinning solution; the spandex has high hard segment content and regular 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 a high-strength high-heat-resistance spandex and a preparation method thereof, belonging to the technical field of polyurethane elastic fibers.
Background
As industrial monosodium glutamate in textile industry, spandex has the meaning of 'no polyurethane cloth', and the comfort and grade of the fabric can be obviously improved by adding a small amount of spandex. However, in some fields, such as fabric interwoven by spandex and terylene, setting is usually required to be carried out at a temperature above 190 ℃ and repeated dyeing is carried out at a temperature above 130 ℃, which can greatly deteriorate the mechanical properties of the spandex, even lead to fiber breakage, cause elastic loss of the fabric and generate defects.
In order to solve the above problems, polyurethane manufacturers generally adopt physical modification, chemical modification, or improvement of equipment process to improve heat resistance and breaking strength of polyurethane.
The patent CN200480024915.0 prepares the polyurethane with high modulus, alkali resistance and heat resistance by adding 1 to 20wt% of cellulose acetate into polyurethane or polyurethane urea solution for physical modification, when the polyurethane is used for special velvet fabric which needs burnt-out and printing, the fiber cannot age, and the state of the fabric is stably maintained. The modified titanium dioxide emulsion is obtained by reacting the titanium dioxide modified by the silane coupling agent, the functional agent and the initiator in the styrene-acrylic mixed solution, and the modified titanium dioxide emulsion is used for the physical modification of the spandex, so that the heat resistance, the breaking strength and the alkali resistance of the spandex can be remarkably improved. The patent CN20161156846. X adds meta-aramid fiber to the spinning dope of spandex to prepare heat-resistant spandex, while keeping the original high elasticity, the thermal deformation temperature of the prepared novel heat-resistant spandex is improved by 5-11 ℃ compared with that of the common spandex.
The patent CN201110127711.1 is chemically modified by adding an aromatic diamine chain extender such as 4,4 '-diaminodiphenyl ether, 4' -diaminodiphenyl methane and the like in the chain extension reaction stage of spandex, and 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. The patent JP2011055950 prepares a polyurethane with high resilience and high heat resistance, which is characterized in that the soft segment of polyurethane is copolymerized polyalkylene ether glycol formed by different alkylene ethers with carbon numbers of 2-10, and the fraction of the hard segment is more than 14 percent and less than 25 percent, namely the aim is achieved by chemical modification of the soft segment and the hard segment.
Patent CN202011589327.9 adds polytetramethylene ether glycol with different molecular weights in the prepolymerization stage, and simultaneously replaces a conventional pipeline reactor with a microcavity reactor, thereby overcoming the problem of non-uniformity in the reaction process; adding a mixture of aromatic diamine, aliphatic diamine, diethylenetriamine and diethylamine in a chain extension stage, and pertinently improving the crystallinity of molecules; functional substances such as a heat resistant agent are added in the mixed 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 comprehensively improving heat resistance and breaking strength is not ideal. Because when the high-strength high-heat-resistance spandex is prepared, a high hard segment content and a regular chain segment structure are usually required, in this state, the crystallinity of the hard segment tends to be too high, so that the polarity difference between the soft segment and the hard segment becomes large, the compatibility of two phases is poorer, the phenomenon of stress concentration occurs at the interface, the number of stress defects of a matrix is increased, the fiber performance is greatly changed, and the heat resistance and the breaking strength of a product are seriously deteriorated.
Disclosure of Invention
Technical problems: 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 of the invention has the advantages that the stress concentration phenomenon of the product is obviously improved, the 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 above purpose, the invention provides a high-strength high-heat-resistance spandex and a preparation method thereof.
The high-strength high-heat-resistance 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 comprises more than one of polyethylene oxide, polypropylene oxide, polyethylene oxide-propylene oxide or polytetrahydrofuran.
In the preparation method of the high-strength and high-heat-resistance polyurethane, polyurethane is obtained by reacting polyurethane prepolymer with isocyanate end, 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 preparation method comprises the following steps:
step 1, performing prepolymerization reaction on diisocyanate and polyether glycol in the presence of a solvent to obtain isocyanate-terminated polyurethane prepolymer;
step 2, fully dissolving polyurethane prepolymer in a solvent to form polyurethane prepolymer solution;
Step 3, reacting the polyurethane prepolymer solution with hydroxyl-terminated polyether silicone oil and mixed amine solution to prepare polyurethane-urea stock solution;
and 4, curing the polyurethane-urea stock solution, and preparing the high-strength high-heat-resistance spandex through a dry spinning technology.
The mol ratio of the diisocyanate to the polyether glycol is 1.65:1-1.95:1.
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 glycol comprises polytetramethylene ether glycol and has a 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 ethylenediamine to diethylamine is 4:1-10:1.
The molar ratio of the total amino groups of the mixed amine to the isocyanic acid groups of the polyurethane prepolymer is 1.0-1.2.
The beneficial effects are that: compared with the prior art, the spandex production process disclosed by the invention is simple in technology, the stress concentration phenomenon of the 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 the spandex 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 microscope image of a cross section of spandex obtained in comparative example 1 of the invention.
Detailed Description
The high-strength high-heat-resistance spandex contains 0.05 to 10 percent 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 prepared by adopting preparation methods such as hydrosilylation reaction, esterification reaction, ring-opening addition reaction and the like;
As an example, a hydrogen-containing silicone oil is obtained by hydrosilylation reaction with a polyether having an alkenyl group at the end in the presence of a platinum catalyst;
In the examples of the present invention, the hydroxyl-terminated polyether silicone oil may be selected from commercial products such as DOWSIL TMBY16-201、DOWSILTMSF8427、XIAMETERTM OFX-3667 and the like;
further, polyurethane prepolymer, mixed amine and hydroxyl-terminated polyether silicone oil containing isocyanate end are reacted 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;
Further, the preparation method of the high-strength high-heat-resistance spandex comprises the following steps:
Step 1, performing prepolymerization reaction on diisocyanate and polyether glycol to obtain isocyanate-terminated polyurethane prepolymer;
step 2, fully dissolving polyurethane prepolymer in a solvent to form polyurethane prepolymer solution;
step 3, reacting the polyurethane prepolymer solution with hydroxyl-terminated polyether silicone oil and mixed amine solution to prepare polyurethane polymer stock solution;
And 4, curing the polyurethane polymer stock solution, and preparing the high-strength high-heat-resistance spandex through a dry spinning technology.
In the invention, in the reaction process of isocyanate end-capped polyurethane prepolymer, mixed amine and hydroxyl-terminated polyether silicone oil, a large amount of amine groups exist in the mixed amine, and as the reactivity of the amine groups and isocyanate is far greater than that of hydroxyl groups, the polyurethane prepolymer preferentially reacts with the amine groups, and the obtained spinning solution raw material contains a certain amount of free hydroxyl-terminated polyether silicone oil, under the premise of not damaging the molecular structure of polyurethane-urea polymer and ensuring the high hard segment content and regular segment structure, the hydroxyl-terminated polyether silicone oil with stronger polarity and better compatibility with polyurethane-urea is introduced into the polyurethane 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 scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
The invention relates to a preparation method of high-strength high-heat-resistance spandex, which comprises the following steps:
1) Pre-polymerizing diisocyanate and polyether glycol at 45-100 ℃ for 0.5-5 h to obtain isocyanate end-capped polyurethane prepolymer;
2) Fully dissolving polyurethane prepolymer in dimethylacetamide solvent to form polyurethane prepolymer solution with solid content of 30% -50%;
3) Reacting the polyurethane prepolymer solution with a mixed amine solution containing hydroxyl-terminated polyether silicone oil to prepare polyurethane-urea stock solution with the solid content of 25% -40%;
4) And (3) curing the polyurethane-urea stock solution, and preparing the polyurethane through a dry spinning technology.
Wherein the mol ratio of the diisocyanate to the polyether glycol is 1.65:1-1.95:1;
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 structure;
the mixed amine comprises ethylenediamine and diethylamine.
The mol ratio of the ethylenediamine to the diethylamine is 4:1-10:1;
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 1.0-1.2, preferably 1.02-1.10;
Other functional auxiliary agents can be added into the polyurethane stock solution as long as the performance of the product is not degraded. 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 and dimethylformamide DMF;
as an 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 glycol comprises polytetramethylene ether glycol with the number average molecular weight of 1000-3000;
In the examples of the present invention, the isocyanate-terminated polyurethane prepolymer is obtained by reacting polytetramethylene ether glycol, 4' -diphenylmethane diisocyanate;
in the examples of the present invention, hydroxyl-terminated polyether silicone oil may be added to 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 method:
breaking strength: the testing method refers to the industry standard FZ/T50006-2013, spandex yarn tensile property testing method.
Elastic recovery: test methods refer to industry standard FZ/T50007-2012, spandex yarn elasticity test method.
Heat resistance: fixing a sample on a shaping bracket after drawing for 2.0 times, presetting for 1min in a 190 ℃ oven, cooling, putting into water, putting into a closed container, processing for 40min at 130 ℃, airing, putting into the oven for shaping for 1min at 190 ℃, taking out, naturally airing and cooling, and testing 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 molecular weight of 1810 in a molar ratio of 1.75:1, and reacting for 2 hours at 90 ℃ to obtain isocyanate-terminated polyurethane prepolymer;
Step 2): fully dissolving polyurethane prepolymer in dimethylacetamide solvent to form polyurethane prepolymer solution with solid content of 40%;
Step 3): chain extension is carried out on the polyurethane prepolymer by using a mixed amine solution containing hydroxyl-terminated polyether silicone oil (DOWSIL TM SF 8427) with the concentration of 4.5 percent to obtain polyurethane-urea stock solution with the solid content of 35.0 percent, wherein DOWSIL TM SF8427 accounts for 0.5 percent of the weight of spandex, the mol ratio of ethylenediamine to diethylamine in the mixed amine is 5.5:1, and the mol ratio of total amine groups of the mixed amine to isocyanate groups of the polyurethane prepolymer is 1.055:1;
Step 4): hydrotalcite accounting for 4 percent of the weight of the polyurethane polymer is added into the polyurethane stock solution, and after the mixture is uniformly mixed and cured, 33dtex/3f polyurethane is prepared by a dry spinning technology.
Example 2:
Spandex was prepared according to the same method as described in example 1, except that DOWSIL TM SF8427 was 0.05% by weight of polyurethane polymer.
Example 3:
spandex was prepared according to the same method as described in example 1, except that DOWSIL TM SF8427 was 1.0% by weight of polyurethane polymer.
Example 4:
spandex was prepared according to the same method as in example 1, except that DOWSIL TM SF8427 was 5.0% by weight of polyurethane polymer.
Example 5:
Spandex was prepared according to the same method as described in example 1, except that DOWSIL TM SF8427 was 10% by weight of the polyurethane polymer.
Example 6:
spandex was prepared in the same manner as described in example 3, except that the polyether segment structure in the added hydroxyl-terminated polyether silicone oil was polypropylene oxide with an average number average molecular weight of 2200.
Example 7:
Spandex was prepared in the same manner 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 with an average number average molecular weight of 2200.
Example 8:
spandex was prepared in the same manner as described in example 3, except that the polyether segment structure in the hydroxyl-terminated polyether silicone oil was polytetrahydrofuran ether with an average number average molecular weight of 2200.
Example 9:
Spandex was prepared in the same manner as in example 1, except that the molar ratio of 4,4' -diphenylmethane diisocyanate to polytetramethylene ether glycol was 1.65:1.
Example 10:
Spandex was prepared in the same manner as in example 1, except that the molar ratio of 4,4' -diphenylmethane diisocyanate to polytetramethylene ether glycol was 1.95:1.
Example 11:
spandex was prepared according to the same method as described in example 3, except that hydroxyl-terminated polyether silicone oil was added during curing in step 4) of the preparation method.
Example 12:
spandex was prepared according to the same method as in example 5, except that hydroxyl-terminated polyether silicone oil was added during curing in step 4) of the preparation method.
Example 13:
Spandex was prepared according to the same method as in example 1, except that the mixed amine consisted of ethylenediamine, 1, 2-propylenediamine, diethylamine in a molar ratio of 5.4:0.6:1.
Example 14:
spandex was prepared in the same manner as in example 1, except that the mixed amine consisted of 1, 2-propanediamine, diethylamine in a 7:1 molar ratio.
Example 15:
Spandex was prepared in the same manner as in example 1, except that hydroxy silicone oil was added.
Example 16:
spandex was prepared according to the same method as in example 1, except that the average number average molecular weight of the added hydroxy polyether silicone oil was less than 500.
Example 17:
Spandex was prepared according to the same method as in example 1, except that the average number average molecular weight of the added hydroxy polyether silicone oil was greater than 5000.
Comparative example 1:
Spandex was prepared in the same manner 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 examples and comparative examples of the present invention
As shown in Table 1, the 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 present invention is illustrated by the above examples of spandex and its preparation method, but the present invention is not limited to the above examples, i.e., it does not mean that the present invention must be practiced by relying on the above examples. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (9)
1. The high-strength high-heat-resistance spandex is characterized in that the spandex contains 0.05-10% of hydroxyl-terminated polyether silicone oil based on the mass of the spandex; the polyurethane is obtained by reacting polyurethane prepolymer with isocyanate end, mixed amine and hydroxyl-terminated polyether silicone oil to obtain a raw material containing polyurethane-urea polymer, and dry spinning the raw material serving as spinning solution.
2. The high-strength and high-heat-resistance spandex according to claim 1, wherein the hydroxyl-terminated polyether silicone oil has a number average molecular weight of 500-5000.
3. The high-strength and high-heat-resistance spandex according to claim 1, wherein the hydroxyl-terminated polyether silicone oil comprises more than one of polyethylene oxide, polypropylene oxide, polyethylene oxide-propylene oxide or polytetrahydrofuran.
4. A method for preparing the high strength and high heat resistance spandex of claim 1, 2 or 3, comprising the steps of:
step 1, performing prepolymerization reaction on diisocyanate and polyether glycol in the presence of a solvent to obtain isocyanate-terminated polyurethane prepolymer;
step 2, fully dissolving polyurethane prepolymer in a solvent to form polyurethane prepolymer solution;
Step 3, reacting the polyurethane prepolymer solution with hydroxyl-terminated polyether silicone oil and mixed amine solution to prepare polyurethane-urea stock solution;
and 4, curing the polyurethane-urea stock solution, and preparing the high-strength high-heat-resistance spandex through a dry spinning technology.
5. The method for preparing high strength and high heat resistance spandex according to claim 4, wherein the molar ratio of diisocyanate to polyether glycol is 1.65:1-1.95:1.
6. The method for preparing high strength and high heat resistance spandex according to claim 5, wherein 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 glycol comprises polytetramethylene ether glycol and has a number average molecular weight of 1000-3000.
7. The method for preparing high strength and heat resistant spandex of claim 4, wherein the mixed amine comprises monoamine and diamine; does not contain a branched structure.
8. The method for preparing high strength and heat resistant spandex of claim 7, wherein the mixed amine comprises ethylenediamine and diethylamine in a molar ratio of 4:1-10:1.
9. The method for preparing high strength and high heat resistance spandex according to claim 8, wherein the molar ratio of the total amine groups of the mixed amine to the isocyanate groups of the polyurethane prepolymer is 1.0-1.2.
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| US20060135724A1 (en) * | 2004-12-20 | 2006-06-22 | Lawrey Bruce D | Spandex having low heat-set temperature and materials for their production |
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| CN101597864B (en) * | 2009-06-26 | 2011-09-07 | 北京光华纺织集团有限公司 | Polyurethane fiber dry spinning oil agent and preparation method thereof |
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