CN105399920A - Water-soluble and spinnable polyurethane elastomer prepared based on RIM technology - Google Patents
Water-soluble and spinnable polyurethane elastomer prepared based on RIM technology Download PDFInfo
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- CN105399920A CN105399920A CN201510783576.4A CN201510783576A CN105399920A CN 105399920 A CN105399920 A CN 105399920A CN 201510783576 A CN201510783576 A CN 201510783576A CN 105399920 A CN105399920 A CN 105399920A
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- 229920003225 polyurethane elastomer Polymers 0.000 title claims abstract description 23
- 238000005516 engineering process Methods 0.000 title claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000002009 diols Chemical class 0.000 claims abstract description 10
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 42
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 9
- 239000004970 Chain extender Substances 0.000 claims description 8
- 238000003860 storage Methods 0.000 claims description 7
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 5
- 150000003384 small molecules Chemical group 0.000 claims description 4
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 2
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 4
- HBRWOKKTMZCRTK-ARJAWSKDSA-N (z)-4-amino-2-ethyl-4-oxobut-2-enoic acid Chemical compound CC\C(C(O)=O)=C\C(N)=O HBRWOKKTMZCRTK-ARJAWSKDSA-N 0.000 claims 3
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 claims 2
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims 1
- 230000003179 granulation Effects 0.000 claims 1
- 238000005469 granulation Methods 0.000 claims 1
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 claims 1
- 229940051250 hexylene glycol Drugs 0.000 claims 1
- 238000009413 insulation Methods 0.000 claims 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 1
- 239000000835 fiber Substances 0.000 abstract description 13
- 229920001971 elastomer Polymers 0.000 abstract description 8
- 239000000806 elastomer Substances 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 6
- 229920000642 polymer Polymers 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 5
- 238000009987 spinning Methods 0.000 abstract description 5
- 239000002351 wastewater Substances 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 239000005416 organic matter Substances 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 239000003960 organic solvent Substances 0.000 abstract 1
- 229920003169 water-soluble polymer Polymers 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 230000009467 reduction Effects 0.000 description 7
- 229920001410 Microfiber Polymers 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000013585 weight reducing agent Substances 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 239000003658 microfiber Substances 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- -1 polyethylene Polymers 0.000 description 4
- 125000000542 sulfonic acid group Chemical group 0.000 description 4
- XOIJCNLAQGFSAY-ARJAWSKDSA-N (Z)-4-(dihydroxyamino)-2-ethyl-4-oxobut-2-enoic acid Chemical group ON(C(\C=C(/C(=O)O)\CC)=O)O XOIJCNLAQGFSAY-ARJAWSKDSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000002649 leather substitute Substances 0.000 description 2
- 238000002074 melt spinning Methods 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 238000010107 reaction injection moulding Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
- C08G18/3823—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing -N-C=O groups
- C08G18/3825—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing -N-C=O groups containing amide groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/16—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds as constituent
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- 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
- C08G2120/00—Compositions for reaction injection moulding processes
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- Polymers & Plastics (AREA)
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- Polyurethanes Or Polyureas (AREA)
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Abstract
一种基于RIM技术制备的水可溶、可纺聚氨酯弹性体，将含有潜在亲水基团的二元醇组分和二异氰酸酯组分通过RIM技术制备得到线性聚合物。因其含有潜在亲水基团，能在不破坏分子主链的前提下实现水溶与不水溶相互转换：亲水基团释放前为不亲水的弹性体，可用于海岛纤维海组分纺丝；亲水基团释放后为水溶性高分子化合物，可在温和条件下进行减量开纤；封闭亲水基团后不水溶，可在温和条件下实现回收。过程中不产生有机溶剂或含有机物废水排放，有利于环境保护。A water-soluble, spinnable polyurethane elastomer prepared based on RIM technology. The diol component and diisocyanate component containing latent hydrophilic groups are prepared by RIM technology to obtain a linear polymer. Because it contains potential hydrophilic groups, it can realize the conversion between water-soluble and water-insoluble without destroying the main chain of the molecule: before the release of hydrophilic groups, it is an elastomer that is not hydrophilic, and can be used for sea-island fiber sea component spinning ; After the hydrophilic group is released, it becomes a water-soluble polymer compound, which can be reduced in fiber under mild conditions; after the hydrophilic group is blocked, it is insoluble in water and can be recycled under mild conditions. During the process, no organic solvent or waste water containing organic matter is discharged, which is beneficial to environmental protection.
Description
技术领域 technical field
本发明涉及热塑性聚氨酯弹性体领域，特别是指一种基于RIM技术制备的水可溶、可纺聚氨酯弹性体。 The invention relates to the field of thermoplastic polyurethane elastomers, in particular to a water-soluble, spinnable polyurethane elastomer prepared based on RIM technology.
背景技术 Background technique
海岛纤维是将两种不相容的聚合物进行共混纺丝或复合纺丝制造的异形纤维，岛组分聚合物以维系纤维的形式分散于另一种海组分聚合物中，当把海组分去除后，就得到有岛组分行程的超细纤维；超细纤维有纤度细、手感柔软，具有大比表面积和毛细效应，有良好的吸湿散湿性等特点。 The sea-island fiber is a special-shaped fiber made by blending or composite spinning two incompatible polymers. The island component polymer is dispersed in another sea component polymer in the form of maintaining fibers. When the sea After the components are removed, microfibers with island component strokes are obtained; microfibers have the characteristics of fine fineness, soft touch, large specific surface area and capillary effect, and good moisture absorption and dissipation properties.
超细纤维在国民经济中占有重要的地位，仅2014年国内超细纤维合成革的产量近1亿米。国内超细纤维合成革主要使用海岛纤维制备，采用苯减量或碱减量方式进行：苯减量是使用甲苯做溶剂将纤维中的海组份—聚乙烯溶解、去除，苯减量虽然在相对密闭的环境中进行，但减量及聚乙烯回收过程仍然会有大量甲苯（85-150g/1kg纤维）挥发，造成严重污染及资源浪费；碱减量是在10%的氢氧化钠碱液中将海组份—涤纶水解、去除，涤纶水解成为对苯二甲酸盐和乙二醇，同时产生大量含苯二甲酸盐和乙二醇的废水，既不易回收和高附加值利用，又造成废水中COD含量高，不易降解，直接排放亦造成严重的环境污染和资源浪费。 Microfiber plays an important role in the national economy. In 2014 alone, the output of domestic microfiber synthetic leather was nearly 100 million meters. Domestic superfine fiber synthetic leather is mainly prepared from sea-island fibers, and is carried out by benzene reduction or alkali reduction: benzene reduction is to use toluene as a solvent to dissolve and remove the sea component in the fiber—polyethylene, although benzene reduction is in the It is carried out in a relatively closed environment, but a large amount of toluene (85-150g/1kg fiber) will still volatilize in the process of weight reduction and polyethylene recovery, causing serious pollution and waste of resources; alkali weight reduction is done in 10% sodium hydroxide lye Hydrolyze and remove the sea component-polyester, and hydrolyze the polyester into terephthalate and ethylene glycol. At the same time, a large amount of waste water containing phthalate and ethylene glycol is produced, which is not easy to recycle and use with high added value. It also causes high COD content in the wastewater, which is not easy to degrade, and direct discharge also causes serious environmental pollution and waste of resources.
海岛纤维减量造成污染的主要原因是没有适用于熔融纺丝的聚合物弹性体作为海组分，如果这种聚合物弹性体既能纺丝，又能在温和条件下减量并回收利用，则在减量和回收过程中就不会产生有机污染物和大量含有机物的废水，其环境污染问题便可迎刃而解。 The main reason for the pollution caused by the reduction of sea-island fibers is that there is no polymer elastomer suitable for melt spinning as a sea component. If this polymer elastomer can be spun, it can be reduced and recycled under mild conditions. Then in the reduction and recovery process, no organic pollutants and a large amount of waste water containing organic matter will be produced, and the problem of environmental pollution can be easily solved.
发明内容 Contents of the invention
本发明的主要目的在于克服现有技术的缺点，提供一种基于RIM技术制备的水可溶、可纺的聚氨酯弹性体，该弹性体作为海组份与尼龙（PA）复合纺丝可制备具有海岛结构的超细纤维。该弹性体本身含有潜在亲水基团，能在不破坏分子主链的前提下实现水溶与不水溶相互转换，即可在温和条件下将其溶解于水中实现减量、可将减量后溶解于水中的聚氨酯回收再利用，在减量和回收过程中不产生有机废物，减量后的废水也可多次循环利用。 The main purpose of the present invention is to overcome the shortcomings of the prior art and provide a water-soluble, spinnable polyurethane elastomer based on RIM technology. The elastomer can be prepared as a sea component and nylon (PA) by composite spinning. Microfiber with island structure. The elastomer itself contains potential hydrophilic groups, which can realize the conversion between water-soluble and water-insoluble without destroying the main chain of the molecule. It can be dissolved in water under mild conditions to achieve weight reduction, and can be dissolved after weight reduction. Polyurethane in water is recycled and reused, no organic waste is produced in the process of weight reduction and recycling, and the waste water after weight reduction can also be recycled many times.
本发明采用如下的技术方案： The present invention adopts following technical scheme:
采用RIM技术制备水可溶、可纺聚氨酯弹性体，具体通过如下步骤制备： The water-soluble and spinnable polyurethane elastomer is prepared by RIM technology, which is prepared through the following steps:
a.将二元醇组分混合均匀并由保温40-60℃的储罐保存,标记为A料，将二异氰酸酯组分由保温40-60℃的储罐保存，标记为B料； a. Mix the diol component evenly and store it in a storage tank with a temperature of 40-60°C, and mark it as material A; store the diisocyanate component in a storage tank with a temperature of 40-60°C, and mark it as material B;
b.经计量装置按A料与B料中活性基团1：1-1.05摩尔比的比例送至高速混合头混合3-15秒，挤出后将物料置于固化模具中； b. According to the ratio of 1:1-1.05 molar ratio of active groups in material A and material B, the metering device sends it to the high-speed mixing head for mixing for 3-15 seconds, and puts the material in the curing mold after extrusion;
c.将盛有物料的模具在80-110℃的条件下熟化2-10小时后取出物料，造粒，得到水可溶、可纺聚氨酯弹性体。 c. Mature the mold containing the material at 80-110° C. for 2-10 hours, take out the material, and granulate to obtain a water-soluble, spinnable polyurethane elastomer.
A料由（1）低聚二元醇、（2）亲水扩链剂、（3）催化剂及可选（4）小分子扩链剂组成： Material A is composed of (1) oligomeric glycol, (2) hydrophilic chain extender, (3) catalyst and optional (4) small molecule chain extender:
（1）低聚二元醇为耐水解的、相对分子质量100-4000的聚四氢呋喃二元醇中的1种或其组合； (1) The oligomeric diol is one or a combination of polytetrahydrofuran diols with hydrolysis resistance and a relative molecular mass of 100-4000;
（2）亲水扩链剂为N,N-二羟乙基马来酰胺酸或N,N-二羟乙基马来酰胺酸与熔点低于60℃、相对分子质量为500-1500的含磺酸基的二元醇的组合； (2) The hydrophilic chain extender is N,N -dihydroxyethylmaleamic acid or N,N -dihydroxyethylmaleamic acid with a melting point lower than 60°C and a relative molecular mass of 500-1500 containing Combinations of dihydric alcohols with sulfonic acid groups;
（3）催化剂为：有机铋、有机银和/或有机锡中的一种； (3) The catalyst is: one of organic bismuth, organic silver and/or organic tin;
（4）小分子扩链剂为乙二醇、1,4-丁二醇、己二醇、乙二胺、己二胺中的1种或其组合。 (4) The small molecule chain extender is one or a combination of ethylene glycol, 1,4-butanediol, hexanediol, ethylenediamine, and hexamethylenediamine.
二异氰酸酯组分为MDI100、MDI50或液化MDI中的一种。 The diisocyanate component is one of MDI100, MDI50 or liquefied MDI.
水可溶、可纺聚氨酯弹性体中含磺酸基的二元醇及N,N-二羟乙基马来酰胺酸的含量为弹性体总重的15-23%，且含磺酸基的二元醇的含量不超过弹性体总重的3%。 The content of diols containing sulfonic acid groups and N,N -dihydroxyethylmaleamic acid in water-soluble and spinnable polyurethane elastomers is 15-23% of the total weight of the elastomer, and the content of diols containing sulfonic acid groups The content of diol does not exceed 3% of the total weight of the elastomer.
A料的活性基团为羟基和氨基，B料的活性基团为异氰酸酯基团。 The active groups of material A are hydroxyl and amino groups, and the active groups of material B are isocyanate groups.
由上述对本发明的描述可知，与现有技术相比，本发明具有如下有益效果： As can be seen from the above description of the present invention, compared with the prior art, the present invention has the following beneficial effects:
1、水可溶、可纺聚氨酯弹性体含潜在亲水基团，亲水基团未释放时聚氨酯弹性体不亲水，从而其适用熔融纺丝工艺；调整环境的酸碱性来释放和封闭聚氨酯中的亲水基团，可改变聚氨酯弹性体的水溶性，从而可以作为海岛纤维的海组分；作为海岛纤维海组分时，纤维减量过程、海组分回收过程不对水可溶、可纺聚氨酯弹性体的分子主链造成破坏，回收后可以再次利用，不造成资源浪费；过程中无有机物排放，不造成环境污染。 1. Water-soluble and spinnable polyurethane elastomers contain potential hydrophilic groups. When the hydrophilic groups are not released, polyurethane elastomers are not hydrophilic, so they are suitable for melt spinning processes; adjust the acidity and alkalinity of the environment to release and seal The hydrophilic group in polyurethane can change the water solubility of polyurethane elastomer, so that it can be used as the sea component of sea-island fiber; when used as the sea component of sea-island fiber, the process of fiber reduction and sea component recovery is not water-soluble The main molecular chain of the spinnable polyurethane elastomer is damaged, and it can be reused after recycling without causing waste of resources; there is no organic emission in the process and does not cause environmental pollution.
2、采用反应注射成型技术制备水可溶、可纺聚氨酯弹性体，具有反应速度快,加工过程能耗低,成本低等优点。 2. The water-soluble and spinnable polyurethane elastomer is prepared by reaction injection molding technology, which has the advantages of fast reaction speed, low energy consumption during processing, and low cost.
3、作为海岛纤维海组分纺丝时，可使用现有海岛复合纺丝设备进行生产，可为超细纤维行业可持续发展提供方案。 3. When spinning as a sea-island fiber sea component, the existing sea-island composite spinning equipment can be used for production, which can provide a plan for the sustainable development of the ultrafine fiber industry.
具体实施方式 detailed description
下面通过实施例对本发明进行具体描述，有必要在此指出的是以下实施例只是用于对本发明进行进一步的说明，不能理解为对本发明保护范围的限制，该领域的技术熟练人员可以根据上述本发明的内容做出一些非本质的改进和调整，仍属于本发明的保护范围。 The present invention is described in detail by the following examples, it is necessary to point out that the following examples are only used to further illustrate the present invention, and can not be interpreted as limiting the protection scope of the present invention, those skilled in the art can according to the above-mentioned present invention The contents of the invention make some non-essential improvements and adjustments, which still belong to the protection scope of the present invention.
实施例一： Embodiment one:
A料为110重量份PTMG1000、40重量份二羟乙基马来酰胺酸、0.1重量份的有机锡催化剂、8重量份1,4-丁二醇组成的混合物；B料为MDI50。A、B料分别在储罐中40℃保温。经计量装置将A料与B料按活性基团1:1.01的摩尔比送至高速混合头混合10秒，挤出后将物料置于固化模具中，然后将物料及固化模具放于110℃的条件下熟化6小时后取出物料，造粒得到水可溶、可纺聚氨酯弹性体，亲水基团含量为15.5%。 Material A is a mixture consisting of 110 parts by weight of PTMG1000, 40 parts by weight of dihydroxyethylmaleamic acid, 0.1 parts by weight of an organotin catalyst, and 8 parts by weight of 1,4-butanediol; material B is MDI50. Materials A and B are respectively kept at 40°C in storage tanks. Through the metering device, send material A and material B to the high-speed mixing head for mixing for 10 seconds according to the molar ratio of active groups of 1:1.01. After extrusion, the material is placed in the curing mold, and then the material and the curing mold are placed in the After aging for 6 hours under the same conditions, the materials were taken out and granulated to obtain a water-soluble, spinnable polyurethane elastomer with a hydrophilic group content of 15.5%.
实施例二： Embodiment two:
A料为110重量份PTMG1000、6重量份百源3306、56重量份二羟乙基马来酰胺酸、0.2重量份的有机银催化剂；B料为MDI100。A、B料分别在储罐中46℃保温。经计量装置将A料与B料按活性基团1:1.01的摩尔比送至高速混合头混合5秒，挤出后将物料置于固化模具中，然后将物料及固化模具放于90℃的条件下熟化10小时后取出物料，造粒得到水可溶、可纺聚氨酯弹性体，亲水基团含量为22.79%，其中含磺酸基的二元醇含量2.21%。 Material A is 110 parts by weight of PTMG1000, 6 parts by weight of Baiyuan 3306, 56 parts by weight of dihydroxyethylmaleamic acid, and 0.2 parts by weight of organic silver catalyst; material B is MDI100. Materials A and B are respectively kept at 46°C in storage tanks. Through the metering device, send material A and material B to the high-speed mixing head according to the molar ratio of 1:1.01 of the active group and mix for 5 seconds. After extrusion, the material is placed in the curing mold, and then the material and the curing mold are placed in the After aging for 10 hours under the same conditions, the material was taken out and granulated to obtain a water-soluble and spinnable polyurethane elastomer with a hydrophilic group content of 22.79% and a sulfonic acid group-containing glycol content of 2.21%.
实施例三： Embodiment three:
A料为220重量份PTMG2000、58.5重量份二羟乙基马来酰胺酸、0.2重量份的有机铋催化剂；B料为MDI100。A、B料分别在储罐中46℃保温。经计量装置将A料与B料按活性基团1:1.01的摩尔比送至高速混合头混合10秒，挤出后将物料置于固化模具中，然后将物料及固化模具放于100℃的条件下熟化10小时后取出混合料，得到水可溶、可纺聚氨酯弹性体，亲水基团含量为15.46%。 Material A is 220 parts by weight of PTMG2000, 58.5 parts by weight of dihydroxyethylmaleamic acid, and 0.2 parts by weight of organic bismuth catalyst; material B is MDI100. Materials A and B are respectively kept at 46°C in storage tanks. Through the metering device, material A and material B are sent to the high-speed mixing head and mixed for 10 seconds according to the molar ratio of active groups of 1:1.01. After extrusion, the material is placed in the curing mold, and then the material and the curing mold are placed in a 100°C After aging for 10 hours under the same conditions, the mixture was taken out to obtain a water-soluble, spinnable polyurethane elastomer with a hydrophilic group content of 15.46%.
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