CN114230753A - Preparation method of polyether ester type melt-spun spandex slice - Google Patents
Preparation method of polyether ester type melt-spun spandex slice Download PDFInfo
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- CN114230753A CN114230753A CN202111503754.5A CN202111503754A CN114230753A CN 114230753 A CN114230753 A CN 114230753A CN 202111503754 A CN202111503754 A CN 202111503754A CN 114230753 A CN114230753 A CN 114230753A
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- polyether
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- caprolactone
- polyol
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- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 45
- 229920000570 polyether Polymers 0.000 title claims abstract description 45
- 229920002334 Spandex Polymers 0.000 title claims abstract description 39
- 239000004759 spandex Substances 0.000 title claims abstract description 39
- 150000002148 esters Chemical class 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229920005862 polyol Polymers 0.000 claims abstract description 60
- 150000003077 polyols Chemical class 0.000 claims abstract description 40
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000012948 isocyanate Substances 0.000 claims abstract description 11
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 11
- 239000004970 Chain extender Substances 0.000 claims abstract description 9
- 239000003999 initiator Substances 0.000 claims abstract description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 57
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 22
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 21
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 18
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 16
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical group C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 230000018044 dehydration Effects 0.000 claims description 6
- 238000006297 dehydration reaction Methods 0.000 claims description 6
- RLJWTAURUFQFJP-UHFFFAOYSA-N propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)O.CC(C)O.CC(C)O RLJWTAURUFQFJP-UHFFFAOYSA-N 0.000 claims description 6
- VXUYXOFXAQZZMF-UHFFFAOYSA-N tetraisopropyl titanate Substances CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 229920001451 polypropylene glycol Polymers 0.000 claims description 5
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims description 2
- 230000000977 initiatory effect Effects 0.000 claims 1
- 150000003384 small molecules Chemical group 0.000 claims 1
- 238000005469 granulation Methods 0.000 abstract description 12
- 230000003179 granulation Effects 0.000 abstract description 12
- 229920001610 polycaprolactone Polymers 0.000 abstract description 12
- 239000004814 polyurethane Substances 0.000 abstract description 7
- 229920002635 polyurethane Polymers 0.000 abstract description 7
- 238000009826 distribution Methods 0.000 abstract description 5
- 238000001125 extrusion Methods 0.000 abstract description 3
- 238000002464 physical blending Methods 0.000 abstract description 3
- 229920000728 polyester Polymers 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 description 15
- 238000004806 packaging method and process Methods 0.000 description 10
- 238000002074 melt spinning Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- -1 epsilon-caprolactone polyol Chemical class 0.000 description 5
- 238000002156 mixing Methods 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000000578 dry spinning Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000003908 quality control method Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 206010040007 Sense of oppression Diseases 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
-
- 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
- D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a preparation method of polyether ester type melt-spun spandex slices, which comprises the steps of firstly using polyether polyol as an initiator to initiate epsilon-caprolactone to open-loop and polymerize into polyether-epsilon-caprolactone polyol, then adding the polyether-epsilon-caprolactone polyol, a micromolecular chain extender and isocyanate into a double-screw reaction extruder, and carrying out extrusion granulation to obtain the polyether ester type melt-spun spandex slices. The melt-spun spandex slice prepared by the invention has the comprehensive advantages of polyester type polyurethane and polyether type polyurethane, the reaction process is uniform, the controllability is strong, the product has the characteristics of high molecular weight and narrow molecular weight distribution, the problems of poor compatibility, uneven reaction rate and the like in physical blending and use of poly epsilon-caprolactone polyol and polyether polyol are solved, the melt-spun spandex filament has the characteristics of high molecular weight and narrow molecular weight distribution, and the spandex filament melt-spun by the slice has high strength, good resilience and good heat resistance.
Description
Technical Field
The invention relates to the field of spandex preparation, in particular to a preparation method of a polyether ester type melt-spun spandex slice.
Background
Spandex as a high-elasticity fiber has the characteristics of quick rebound, high elastic recovery rate and strong adaptability, and can be combined with other fibers to be made into various elastic fabrics. The clothes made of the elastic cloth are comfortable to wear, do not have oppression and constraint feeling on bodies, have good shape retention, drapability and wrinkle resistance, and are widely applied to the textile industry.
The spandex can be prepared by dry spinning and melt spinning, wherein the melt spinning process flow is relatively simple, the equipment investment is small, the production efficiency is high, and particularly, the spandex has the characteristics of environmental protection without a solvent, and is widely concerned under the condition that the requirements of environmental protection and sustainable development are continuously improved at present.
However, the high temperature of the melt spinning process results in poorer heat resistance and elasticity of the melt spun spandex than the dry spandex, which limits the application. On the premise of keeping the melt fluidity requirement of the melt spinning process, the key is to improve the heat resistance and the mechanical property of the melt spinning spandex slice. In the prior art, a cross-linking agent, a nano powder auxiliary agent and the like are added in a melt-spun spandex slice formula to improve the strength of the melt-spun spandex, but the problems of uneven dispersion and difficult quality control exist.
Polyurethane materials synthesized by poly epsilon-caprolactone polyol have excellent mechanical strength and heat resistance, and currently, scientific researchers adopt a method of physically mixing poly epsilon-caprolactone polyol and polyether polyol to prepare melt-spun spandex slices. For example, in patent application CN109868524, poly-epsilon-caprolactone polyol and polyether polyol are first blended, and then added into a reaction extruder together with isocyanate and a chain extender to prepare melt-spun spandex chips. The poly epsilon-caprolactone polyol component mainly improves the strength and heat resistance of melt spinning spandex, while the polyether polyol component reduces the Vicat softening point and provides processing fluidity, and the prepared product has the advantages of polyester polyurethane and polyether polyurethane, and the index is close to that of dry spinning spandex. However, polyether polyols and poly-epsilon-caprolactone polyol with different molecular weights have poor compatibility when simply mixed and react with isocyanate at different reaction rates, so that the uniformity and controllability of a reaction system cannot be ensured, the wide molecular weight distribution is easily caused, the mechanical strength, the heat resistance and the rebound resilience are reduced, and the product quality control is not facilitated.
Disclosure of Invention
The invention aims to provide a preparation method of a polyether ester type melt-spun spandex slice, which overcomes the defects in the prior art and can be used for preparing melt-spun spandex filaments with high strength, good heat resistance and narrow molecular weight distribution.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of polyether ester type melt-spun spandex slices comprises the steps of firstly using polyether polyol as an initiator to initiate epsilon-caprolactone to open loop and polymerize to form polyether-epsilon-caprolactone polyol, and then extruding, granulating and drying the polyether-epsilon-caprolactone polyol, a small molecular chain extender and isocyanate according to a molar ratio of 1 (0.5-3.7) to 1.5-5.3.
Further, the number average molecular weight of the polyether-epsilon-caprolactone polyol is 1000-3000.
Further, the preparation method of the polyether-epsilon-caprolactone polyol comprises the following steps:
A. carrying out vacuum dehydration on polyether polyol at 100-150 ℃, and carrying out vacuum dehydration on an epsilon-caprolactone raw material at 90-110 ℃ until the water content is below 500 ppm;
B. adding the dehydrated polyether polyol and epsilon-caprolactone into a reactor, uniformly stirring at 120 ℃, adding 50-500 ppm of catalyst, introducing nitrogen, and heating to 160-190 ℃ for reaction;
C. reacting for 4-24 h at 160-190 ℃, reducing the acid value to below 1.0mgKOH/g, starting to vacuumize, and further reducing the acid value to below 0.5mgKOH/g to obtain the polyether-epsilon-caprolactone polyol.
Furthermore, the mole ratio of the dehydrated polyether polyol to the epsilon-caprolactone is 1 (3-18).
Further, the polyether polyol comprises one of polytetrahydrofuran ether glycol, polyethylene glycol and polypropylene glycol.
Further, the catalyst is one of stannous octoate, tetrabutyl titanate and tetraisopropyl titanate.
Further, the micromolecular chain extender is one of ethylene glycol, 1, 4-butanediol and 1, 6-hexanediol.
Further, the isocyanate is 4, 4' -diphenylmethane diisocyanate.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention adopts polyether polyol as an initiator, initiates epsilon-caprolactone ring-opening polymerization under the action of a catalyst to prepare polyether-epsilon-caprolactone polyol, and then reacts with isocyanate and a chain extender to prepare melt-spun spandex slices through extrusion. The polyether polyol initiator and the epsilon-caprolactone are chemically bonded to form a polyether ester polyol structure with a uniform molecular structure, so that the problems of poor physical blending compatibility of the polyether polyol and the epsilon-caprolactone polyol, uneven reaction rate with isocyanate and the like are solved, and a reaction system for synthesizing the melt-spun spandex slice is uniform and has strong controllability. The melt-spun spandex slice prepared by the method can better exert the comprehensive advantages of polyester type polyurethane and polyether type polyurethane, has the characteristics of high molecular weight and narrow molecular weight distribution, and the melt-spun yarn has high mechanical strength, strong heat resistance and good rebound resilience.
Detailed Description
The invention is further described below.
A preparation method of a polyether ester type melt-spun spandex slice comprises the steps of firstly using polyether polyol as an initiator to initiate epsilon-caprolactone to open loop and polymerize to form polyether-epsilon-caprolactone polyol, then adding the polyether-epsilon-caprolactone polyol slice and micromolecular chain extender and isocyanate into a double-screw reaction extruder according to a molar ratio of 1 (0.5-3.7) to (1.5-5.3), and carrying out extrusion, granulation and drying to obtain the polyether ester type melt-spun spandex slice.
Wherein the number average molecular weight of the polyether-epsilon-caprolactone polyol is 1000-3000; the preparation method of the polyether-epsilon-caprolactone polyol comprises the following steps:
A. and (3) carrying out vacuum dehydration on polyether polyol at the temperature of 100-150 ℃, and carrying out vacuum dehydration on the epsilon-caprolactone raw material at the temperature of 90-110 ℃ until the moisture content is below 500 ppm.
B. Adding polyether polyol and epsilon-caprolactone which are dehydrated in a molar ratio of 1 (3-18) into a reactor, uniformly stirring at 120 ℃, adding 50-500 ppm of catalyst, introducing nitrogen, and heating to 160-190 ℃ for reaction.
C. Reacting for 4-24 h at 160-190 ℃, reducing the acid value to below 1.0mgKOH/g, starting to vacuumize, and further reducing the acid value to below 0.5mgKOH/g to obtain the polyether-epsilon-caprolactone polyol.
Wherein the polyether polyol comprises one of polytetrahydrofuran ether glycol, polyethylene glycol and polypropylene glycol; the catalyst is one of stannous octoate, tetrabutyl titanate and tetraisopropyl titanate; the micromolecular chain extender is one of ethylene glycol, 1, 4-butanediol and 1, 6-hexanediol; the isocyanate is 4, 4' -diphenylmethane diisocyanate.
The present invention will be described in detail with reference to examples. It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict.
The following detailed description is illustrative of the embodiments and is intended to provide further details of the invention. Unless otherwise defined, all technical terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention.
The test methods or test methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials, unless otherwise indicated, are conventionally obtained commercially or prepared by conventional methods.
The molecular weight in the invention is number average molecular weight. The raw materials were dewatered under reduced pressure until the water content was 500ppm or less before use, and the following examples all used parts by mass.
Example 1
65 parts of polytetrahydrofuran ether glycol (molecular weight 650) and 35 parts of epsilon-caprolactone, adding the polytetrahydrofuran ether glycol and 35 parts of epsilon-caprolactone into a reactor, uniformly stirring at 120 ℃, adding 50ppm of tetrabutyl titanate, introducing nitrogen, heating to 160 ℃, reacting for 4 hours, wherein the acid value is 0.45mgKOH/g, vacuumizing for 4 hours, and then the acid value is 0.12mgKOH/g, and obtaining the polytetrahydrofuran ether-epsilon-caprolactone glycol with the molecular weight of 1000 after the reaction is finished.
And injecting 70 parts of the obtained polytetrahydrofuran ether-epsilon-caprolactone diol, 3.8 parts of 1, 6-hexanediol and 26.2 parts of 4, 4' -diphenylmethane diisocyanate into a double-screw extruder by using a metering pump, extruding at 190 ℃, and then carrying out underwater granulation, drying and packaging to obtain the product.
Comparative example 1
65 parts of polytetrahydrofuran ether glycol (molecular weight is 1000) and 35 parts of poly-epsilon-caprolactone glycol (molecular weight is 1000), and uniformly blending to obtain the mixed polyol. And (3) taking 70 parts of the mixed polyol, 3.8 parts of 1, 6-hexanediol and 26.2 parts of 4, 4' -diphenylmethane diisocyanate, injecting the mixture into a double-screw extruder by using a metering pump, extruding at 190 ℃, and then carrying out underwater granulation, drying and packaging to obtain the product.
Example 2
20 parts of polyethylene glycol (molecular weight 400) and 80 parts of epsilon-caprolactone, adding the mixture into a reactor, uniformly stirring the mixture at 120 ℃, adding 200ppm of tetraisopropyl titanate, introducing nitrogen, heating the mixture to 180 ℃, reacting for 24 hours, wherein the acid value is 0.82mgKOH/g, vacuumizing the reactor for 6 hours, and then obtaining the polyethylene glycol-epsilon-caprolactone glycol with the molecular weight of 2000, wherein the acid value is 0.16 mgKOH/g.
Injecting 67 parts of the obtained polyethylene glycol-epsilon-caprolactone diol, 6.4 parts of 1, 4-butanediol and 26.6 parts of 4, 4' -diphenylmethane diisocyanate into a double-screw extruder by using a metering pump, extruding at 190 ℃, and then carrying out underwater granulation, drying and packaging to obtain the product.
Comparative example 2
32.5 parts of polyethylene glycol (molecular weight 2000) and 67.5 parts of poly-epsilon-caprolactone diol (molecular weight 2000), and uniformly blending to obtain the mixed polyol. And (3) injecting 67 parts of the mixed polyol, 6.4 parts of 1, 4-butanediol and 26.6 parts of 4, 4' -diphenylmethane diisocyanate into a double-screw extruder by using a metering pump, extruding at 190 ℃, and then carrying out underwater granulation, drying and packaging to obtain the product.
Example 3
33.3 parts of polypropylene glycol (with the molecular weight of 1000) and 66.7 parts of epsilon-caprolactone, adding the mixture into a reactor, uniformly stirring the mixture at 120 ℃, adding 200ppm of stannous octoate, introducing nitrogen, heating the mixture to 190 ℃, reacting for 24 hours, wherein the acid value is 0.75mgKOH/g, vacuumizing the reactor for 6 hours, and then obtaining the polypropylene glycol-epsilon-caprolactone glycol with the molecular weight of 3000, wherein the acid value is 0.11 mgKOH/g.
Injecting the obtained polypropylene glycol-epsilon-caprolactone diol 66 parts, 1, 4-butanediol 6.7 parts and 27.3 parts of 4, 4' -diphenylmethane diisocyanate into a double-screw extruder by using a metering pump, extruding at 190 ℃, and then carrying out underwater granulation, drying and packaging to obtain the product.
Comparative example 3
21.6 parts of polypropylene glycol (with the molecular weight of 3000) and 78.4 parts of poly-epsilon-caprolactone glycol (with the molecular weight of 3000) are evenly blended to obtain the mixed polyol. And (3) injecting 66 parts of the mixed polyol, 6.7 parts of 1, 4-butanediol and 27.3 parts of 4, 4' -diphenylmethane diisocyanate into a double-screw extruder by using a metering pump, extruding at 190 ℃, and then carrying out underwater granulation, drying and packaging to obtain the product.
Example 4
50 parts of polytetrahydrofuran ether glycol (molecular weight is 1000) and 50 parts of epsilon-caprolactone, adding the mixture into a reactor, uniformly stirring the mixture at 120 ℃, adding 500ppm of tetraisopropyl titanate, introducing nitrogen, heating the mixture to 190 ℃, reacting for 14 hours, wherein the acid value is 0.82mgKOH/g, vacuumizing the reactor for 5 hours, and then obtaining the polytetrahydrofuran ether-epsilon-caprolactone glycol with the molecular weight of 2000, wherein the acid value is 0.16 mgKOH/g.
Injecting 67 parts of the obtained polytetrahydrofuran ether-epsilon-caprolactone diol, 6.4 parts of 1, 4-butanediol and 26.6 parts of 4, 4' -diphenylmethane diisocyanate into a double-screw extruder by using a metering pump, extruding at 190 ℃, and then carrying out underwater granulation, drying and packaging to obtain the product.
Comparative example 4
50 parts of polytetrahydrofuran ether glycol (molecular weight 2000) and 50 parts of poly epsilon-caprolactone glycol (molecular weight 2000) are evenly blended to obtain the mixed polyol. And (3) injecting 67 parts of the mixed polyol, 6.4 parts of 1, 4-butanediol and 26.6 parts of 4, 4' -diphenylmethane diisocyanate into a double-screw extruder by using a metering pump, extruding at 190 ℃, and then carrying out underwater granulation, drying and packaging to obtain the product.
Example 5
33.3 parts of polytetrahydrofuran ether glycol (molecular weight is 1000) and 66.7 parts of epsilon-caprolactone, adding the polytetrahydrofuran ether glycol and the epsilon-caprolactone into a reactor, stirring the mixture evenly at 120 ℃, adding 500ppm of tetraisopropyl titanate, introducing nitrogen, heating the mixture to 190 ℃, reacting the mixture for 16 hours, wherein the acid value is 0.75mgKOH/g, vacuumizing the mixture for 5 hours, the acid value is 0.11mgKOH/g, and obtaining the polytetrahydrofuran ether-epsilon-caprolactone glycol with the molecular weight of 3000 after the reaction is finished.
Injecting the obtained polytetrahydrofuran ether-epsilon-caprolactone glycol 66 parts, ethylene glycol 5 parts and 29 parts of 4, 4' -diphenylmethane diisocyanate into a double-screw extruder by using a metering pump, extruding at 190 ℃, and then carrying out underwater granulation, drying and packaging to obtain the product.
Comparative example 5
33.3 parts of polytetrahydrofuran ether glycol (molecular weight of 3000) and 66.7 parts of poly-epsilon-caprolactone glycol (molecular weight of 3000) are uniformly blended to obtain the mixed polyol. And (3) injecting 66 parts of mixed polyol, 5 parts of ethylene glycol and 29 parts of 4, 4' -diphenylmethane diisocyanate into a double-screw extruder by using a metering pump, extruding at 190 ℃, and then carrying out underwater granulation, drying and packaging to obtain the product.
The formulations of the examples are shown in Table 1 and the mechanical properties are shown in Table 2.
TABLE 1 formula table of polyether ester type melt-spun spandex slice
TABLE 2 mechanics performance table of polyether ester type melt-spinning spandex slice
As can be seen from Table 2, the melt-spun spandex slice prepared by the polyether-epsilon-caprolactone polyol synthesized by the method has excellent comprehensive mechanical properties compared with the melt-spun spandex slice product prepared by the physical blending of the polyether/poly-epsilon-caprolactone polyol with the same molecular weight and the same proportion.
It will be appreciated by those skilled in the art that the invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The embodiments disclosed above are therefore to be considered in all respects as illustrative and not restrictive. All changes which come within the scope of or equivalence to the invention are intended to be embraced therein.
Claims (8)
1. A preparation method of polyether ester type melt-spun spandex slices is characterized by comprising the steps of initiating ring-opening polymerization of epsilon-caprolactone to obtain polyether-epsilon-caprolactone polyol by taking polyether polyol as an initiator, and then extruding, granulating and drying the polyether-epsilon-caprolactone polyol, a small-molecular chain extender and isocyanate according to a molar ratio of 1 (0.5-3.7) to 1.5-5.3.
2. The method for preparing the polyether ester type melt-spun spandex chip as claimed in claim 1, wherein the number average molecular weight of the polyether-epsilon-caprolactone polyol is 1000-3000.
3. The method for preparing the polyether ester type melt-spun spandex chip as claimed in claim 1, wherein the method for preparing the polyether-epsilon-caprolactone polyol comprises the following steps:
A. carrying out vacuum dehydration on polyether polyol at 100-150 ℃, and carrying out vacuum dehydration on an epsilon-caprolactone raw material at 90-110 ℃ until the water content is below 500 ppm;
B. adding the dehydrated polyether polyol and epsilon-caprolactone into a reactor, uniformly stirring at 120 ℃, adding 50-500 ppm of catalyst, introducing nitrogen, and heating to 160-190 ℃ for reaction;
C. reacting for 4-24 h at 160-190 ℃, reducing the acid value to below 1.0mgKOH/g, starting to vacuumize, and further reducing the acid value to below 0.5mgKOH/g to obtain the polyether-epsilon-caprolactone polyol.
4. The method for preparing the polyether ester type melt-spun spandex chip according to claim 3, wherein the mole ratio of the polyether polyol and epsilon-caprolactone which are subjected to water removal is 1 (3-18).
5. The method of claim 3, wherein the polyether polyol comprises one of polytetrahydrofuran ether glycol, polyethylene glycol and polypropylene glycol.
6. The method of claim 3, wherein the catalyst is one of stannous octoate, tetrabutyl titanate and tetraisopropyl titanate.
7. The method for preparing the polyether ester type melt-spun spandex chip according to claim 1, wherein the small-molecule chain extender is one of ethylene glycol, 1, 4-butanediol and 1, 6-hexanediol.
8. A process for preparing a melt-spun spandex chip of the polyether ester type according to claim 1, characterized in that the isocyanate is 4, 4' -diphenylmethane diisocyanate.
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