CN105155003A - Preparation method for high strength, high modulus and high elastic polyurethane fibers - Google Patents
Preparation method for high strength, high modulus and high elastic polyurethane fibers Download PDFInfo
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- CN105155003A CN105155003A CN201510476522.3A CN201510476522A CN105155003A CN 105155003 A CN105155003 A CN 105155003A CN 201510476522 A CN201510476522 A CN 201510476522A CN 105155003 A CN105155003 A CN 105155003A
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- 229920006306 polyurethane fiber Polymers 0.000 title claims abstract description 106
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000004814 polyurethane Substances 0.000 claims abstract description 78
- 229920002635 polyurethane Polymers 0.000 claims abstract description 78
- 238000005345 coagulation Methods 0.000 claims abstract description 66
- 230000015271 coagulation Effects 0.000 claims abstract description 66
- 238000009987 spinning Methods 0.000 claims abstract description 59
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 28
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 25
- 239000008367 deionised water Substances 0.000 claims abstract description 20
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 58
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 50
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 50
- 229920000570 polyether Polymers 0.000 claims description 50
- 238000003756 stirring Methods 0.000 claims description 39
- 239000011259 mixed solution Substances 0.000 claims description 25
- 229920000728 polyester Polymers 0.000 claims description 23
- 239000004094 surface-active agent Substances 0.000 claims description 19
- 239000003788 bath preparation Substances 0.000 claims description 15
- -1 sulfate ester salt Chemical class 0.000 claims description 15
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 13
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 12
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 8
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical class CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 8
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 7
- 239000001099 ammonium carbonate Substances 0.000 claims description 7
- 239000002798 polar solvent Substances 0.000 claims description 7
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 6
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical group OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 4
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 claims description 4
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 4
- 235000019270 ammonium chloride Nutrition 0.000 claims description 4
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 4
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 4
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 4
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 4
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims 1
- 230000001965 increasing effect Effects 0.000 abstract description 8
- 239000002657 fibrous material Substances 0.000 abstract description 3
- 238000007711 solidification Methods 0.000 abstract description 2
- 230000008023 solidification Effects 0.000 abstract description 2
- 238000000465 moulding Methods 0.000 abstract 1
- 229920002521 macromolecule Polymers 0.000 description 12
- 239000011148 porous material Substances 0.000 description 9
- 229910019142 PO4 Inorganic materials 0.000 description 6
- 239000010452 phosphate Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 239000012071 phase Substances 0.000 description 4
- 230000002787 reinforcement Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 3
- 239000004254 Ammonium phosphate Substances 0.000 description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 3
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 3
- 235000019289 ammonium phosphates Nutrition 0.000 description 3
- 230000002708 enhancing effect Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000005191 phase separation Methods 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Chemical group 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 238000009849 vacuum degassing Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
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Abstract
本发明涉及一种高强高模高弹聚氨酯纤维的制备方法，属于纤维材料技术领域。本发明的一种高强高模高弹聚氨酯纤维的制备方法,将聚氨酯纺丝液经喷丝孔挤出后，以长凝固距离经过由去离子水、铵盐、含酰胺键的有机溶剂、丙酮和低相对分子量阴离子型表面活性剂混合得到的凝固浴中，进行湿法牵伸成型以及热处理，得到高强高模高弹聚氨酯纤维。本发明的制备方法实现了聚氨酯纤维的断裂强度、杨氏模量和断裂伸长率的同时增强，通过本发明制备的聚氨酯纤维断裂强度增加150-280%，断裂伸长率增加60-120%，杨氏模量增加50-160%。本发明的制备方法工艺设备简单，成本较低，对生态环境无污染，可控性高，具有很大的应用前景。The invention relates to a preparation method of high-strength, high-modulus and high-elasticity polyurethane fiber, belonging to the technical field of fiber materials. The preparation method of a high-strength, high-modulus and high-elasticity polyurethane fiber of the present invention is that after the polyurethane spinning solution is extruded through the spinneret holes, the polyurethane spinning solution is passed through deionized water, ammonium salt, organic solvent containing amide bonds, acetone with a long solidification distance. In a coagulation bath mixed with a low relative molecular weight anionic surfactant, wet drawing molding and heat treatment are carried out to obtain high-strength, high-modulus and high-elastic polyurethane fibers. The preparation method of the present invention realizes simultaneous enhancement of the breaking strength, Young's modulus and elongation at break of the polyurethane fiber, and the breaking strength of the polyurethane fiber prepared by the present invention increases by 150-280%, and the elongation at break increases by 60-120% , Young's modulus increased by 50-160%. The preparation method of the invention has simple process equipment, low cost, no pollution to the ecological environment, high controllability and great application prospects.
Description
技术领域 technical field
本发明涉及一种高强高模高弹聚氨酯纤维的制备方法，属于纤维材料技术领域。 The invention relates to a preparation method of high-strength, high-modulus and high-elasticity polyurethane fiber, belonging to the technical field of fiber materials.
背景技术 Background technique
聚氨酯主要是由二异氰酸酯或多异氰酸酯与二羟基或多羟基化合物加聚反应而成。它具有高弹性、耐磨性、耐低温性、耐溶剂性以及耐老化性等优良性能，因而广泛用于国民经济的各个领域。由于聚氨酯材料在N,N-二甲基甲酰胺、N,N-二甲基乙酰胺和二甲基亚砜中具有良好的溶解性，聚氨酯可以通过湿法纺丝的方法制备聚氨酯纤维，广泛的应用在皮革、沙发、鞋帽、汽车内饰、装饰、履带等领域。 Polyurethane is mainly formed by the polyaddition reaction of diisocyanate or polyisocyanate with dihydroxy or polyhydroxy compounds. It has excellent properties such as high elasticity, wear resistance, low temperature resistance, solvent resistance and aging resistance, so it is widely used in various fields of national economy. Due to the good solubility of polyurethane materials in N,N-dimethylformamide, N,N-dimethylacetamide and dimethyl sulfoxide, polyurethane fibers can be prepared by wet spinning, which is widely used. Wide range of applications in leather, sofas, shoes and hats, automotive interiors, decorations, tracks and other fields.
随着聚氨酯纤维应用领域的扩大，人们对聚氨酯纤维的拉伸力学性能提出了更高的要求。因此，聚氨酯纤维拉伸力学性能的增强技术和方法具有重要的应用价值和经济价值。目前，增强聚氨酯纤维拉伸力学性能主要采用如下四个方法：1.通过设计和调节聚氨酯大分子中软硬链段的组分、种类和含量实现聚氨酯纤维拉伸力学性能的调整；2.通过合成的方法，将富含苯环、酯基、碳碳双键或碳碳三键的分子嵌入聚氨酯大分子中，通过引入刚性链段达到增强聚氨酯纤维拉伸力学性能的目的；3.在聚氨酯大分子侧链引入官能团，使分子间形成交联键以实现聚氨酯纤维拉伸力学性能的增强；4.在聚氨酯纤维加工过程中，通过杂化或填充的方法添加无机粉体或纤维状材料，实现聚氨酯纤维拉伸力学性能的增强。 With the expansion of the application field of polyurethane fiber, people put forward higher requirements for the tensile mechanical properties of polyurethane fiber. Therefore, the enhancement technology and method of polyurethane fiber tensile mechanical properties have important application value and economic value. At present, the following four methods are mainly used to enhance the tensile mechanical properties of polyurethane fibers: 1. Realize the adjustment of the tensile mechanical properties of polyurethane fibers by designing and adjusting the components, types and contents of soft and hard segments in polyurethane macromolecules; Synthetic method, embed molecules rich in benzene rings, ester groups, carbon-carbon double bonds or carbon-carbon triple bonds into polyurethane macromolecules, and achieve the purpose of enhancing the tensile mechanical properties of polyurethane fibers by introducing rigid segments; 3. In polyurethane Macromolecular side chains introduce functional groups to form crosslinks between molecules to enhance the tensile mechanical properties of polyurethane fibers; 4. During the processing of polyurethane fibers, inorganic powder or fibrous materials are added by hybridization or filling methods, Realize the enhancement of tensile mechanical properties of polyurethane fibers.
上述增强聚氨酯纤维拉伸力学性能的方法是从分子结构方面、分子间力方面、聚集态方面以及添加增强体方面进行设计和实施的，是将聚氨酯纤维改性成刚性纤维的过程，聚氨酯纤维刚性的增加将会导致其弹性的下降。因此，上述增强聚氨酯纤维拉伸力学性能的方法只能有效地实现其断裂强度和杨氏模量的增加，却难以实现聚氨酯纤维在断裂强度、杨氏模量和断裂伸长率三个力学指标同时增加的目的。针对现有增强聚氨酯纤维拉伸力学性能的缺陷，创新性的制备出一种高强高模高弹的聚氨酯纤维显得非常有意义。 The above method of enhancing the tensile mechanical properties of polyurethane fibers is designed and implemented from the aspects of molecular structure, intermolecular force, aggregation state and adding reinforcements. It is a process of modifying polyurethane fibers into rigid fibers. The rigidity of polyurethane fibers An increase will lead to a decrease in its elasticity. Therefore, the above method of enhancing the tensile mechanical properties of polyurethane fibers can only effectively increase its breaking strength and Young's modulus, but it is difficult to achieve the three mechanical indicators of polyurethane fibers in terms of breaking strength, Young's modulus and elongation at break. Simultaneously increase the purpose. In view of the defects of the tensile mechanical properties of the existing reinforced polyurethane fibers, it is very meaningful to innovatively prepare a polyurethane fiber with high strength, high modulus and high elasticity.
发明内容 Contents of the invention
针对上述问题，本发明的目的在于提供一种高强高模高弹聚氨酯纤维的制备方法，为了实现上述目的，本发明的技术解决方案为， In view of the above problems, the purpose of the present invention is to provide a method for preparing high-strength, high-modulus and high-elasticity polyurethane fiber. In order to achieve the above-mentioned purpose, the technical solution of the present invention is,
一种高强高模高弹聚氨酯纤维的制备方法，所述的方法按以下步骤进行： A preparation method of high-strength high-modulus high-elasticity polyurethane fiber, described method is carried out according to the following steps:
聚氨酯纤维纺丝包括聚氨酯纺丝液制备、凝固浴配制、湿法牵伸成形以及热处理。 Polyurethane fiber spinning includes polyurethane spinning solution preparation, coagulation bath preparation, wet drawing forming and heat treatment.
所述的凝固浴配制是指按如下质量百分比： Described coagulation bath preparation refers to by following mass percentage:
去离子水15～97.5% Deionized water 15～97.5%
铵盐1～70% Ammonium salt 1～70%
含酰胺键的极性溶剂0.5～10% Polar solvent containing amide bond 0.5～10%
丙酮0.9～4.5% Acetone 0.9～4.5%
低相对分子量阴离子型表面活性剂0.1～0.5% Low relative molecular weight anionic surfactant 0.1～0.5%
将铵盐、含酰胺键的有机溶剂、丙酮和低相对分子量阴离子型表面活性剂放入去离子水中得到混合溶液，然后将混合溶液的温度升高至25～90℃并机械搅拌3-5h后得到凝固浴，其中，搅拌速率为800-3000r/min； Put ammonium salt, organic solvent containing amide bonds, acetone and low relative molecular weight anionic surfactant into deionized water to obtain a mixed solution, then raise the temperature of the mixed solution to 25-90°C and mechanically stir for 3-5 hours Obtain a coagulation bath, wherein the stirring rate is 800-3000r/min;
所述的湿法牵伸成形是指将聚氨酯纺丝液经喷丝孔挤出后，以10-80m/min的速率经过温度为25-90℃、凝固距离为8-45m的凝固浴，得到湿法牵伸成形后的聚氨酯纤维。 The wet drawing forming means that after the polyurethane spinning solution is extruded through the spinneret holes, it passes through a coagulation bath with a temperature of 25-90°C and a coagulation distance of 8-45m at a rate of 10-80m/min to obtain Polyurethane fibers formed by wet drawing.
所述的聚氨酯纺丝液是聚醚型聚氨酯纺丝液或聚酯型聚氨酯纺丝液或聚酯-聚醚型聚氨酯纺丝液中的一种，含固量为10-25%，动力粘度为300-20000mPa·s。 The polyurethane spinning solution is one of polyether polyurethane spinning solution or polyester polyurethane spinning solution or polyester-polyether polyurethane spinning solution, with a solid content of 10-25%, dynamic viscosity 300-20000mPa·s.
所述的去离子水的导电率≤16MΩ·cm。 The conductivity of the deionized water is ≤16MΩ·cm.
所述的铵盐是硝酸铵或氯化铵或硫酸铵或硫酸氢铵或碳酸铵或碳酸氢铵或磷酸铵或磷酸氢铵或磷酸二氢铵或磷酸氢二铵中的一种。 The ammonium salt is one of ammonium nitrate or ammonium chloride or ammonium sulfate or ammonium bisulfate or ammonium carbonate or ammonium bicarbonate or ammonium phosphate or ammonium hydrogen phosphate or ammonium dihydrogen phosphate or diammonium hydrogen phosphate.
所述的含酰胺键的极性溶剂是甲酰胺或N,N-二甲基甲酰胺或N,N-二甲基乙酰胺中的一种。 The polar solvent containing amide bonds is one of formamide, N,N-dimethylformamide or N,N-dimethylacetamide.
所述的低相对分子量阴离子型表面活性剂是硫酸酯盐表面活性剂或磺酸盐表面活性剂或磷酸酯盐表面活性剂中的一种，相对分子量为200-1000。 The low relative molecular weight anionic surfactant is one of sulfate ester surfactants, sulfonate surfactants or phosphate ester salt surfactants, with a relative molecular weight of 200-1000.
所述的喷丝孔的直径为65-90μm，长度为1-5mm。 The diameter of the spinneret holes is 65-90 μm and the length is 1-5 mm.
由于采用了以上技术方案，本发明的技术特点在于： Owing to adopting above technical scheme, technical characteristic of the present invention is:
1.本发明的技术方法可以实现聚氨酯纤维的断裂强度、杨氏模量和断裂伸长率的同时增强。 1. The technical method of the present invention can realize the simultaneous reinforcement of the breaking strength, Young's modulus and elongation at break of the polyurethane fiber.
将聚氨酯纺丝液经喷丝孔进入含有铵盐的凝固浴中，经过湿法牵伸成形后，聚氨酯溶液会固化成多孔的纤维结构。在湿法牵伸成形的相转化和液相分离的过程中，聚氨酯纺丝液中的溶剂会扩散至凝固浴中，而凝固浴中的铵盐分子也会随着凝固浴扩散至聚氨酯无定形区的大分子之间和孔洞中，然后聚氨酯纺丝液逐渐固化成聚氨酯纤维，得到溶剂和凝固浴共存的湿法固化聚氨酯纤维。然后，将湿法固化聚氨酯纤维拿出凝固浴并放入干燥箱中进行干燥处理，随着湿法固化聚氨酯纤维中溶剂和凝固浴的挥发，铵盐分子中的铵盐离子会在聚氨酯纤维中无定形区大分子之间以氢键的形式构成微交联结构。同时，铵盐离子也会在聚氨酯纤维的孔洞中形成纳米针状结构和纳米球状结构，且与聚氨酯纤维的大分子之间也形成了较强的氢键力，两者之间的质量比例为8:2-9:1，两者的尺寸均为几十纳米至几百纳米之间，干燥处理后，得到高强高模高弹聚氨酯纤维。当其受到拉伸时，聚氨酯纤维中无定形区大分子之间的微交联结构和聚氨酯纤维孔洞中的纳米针状铵盐结构均可以有效地增加聚氨酯纤维的断裂强度和杨氏模量。同时，聚氨酯纤维孔洞中的纳米针状铵盐结构和纳米球状铵盐结构相互结合并形成了“滑板”结构，该结构可以有效地增加聚氨酯纤维的断裂伸长率。在拉伸力的作用下，以强氢键力围绕在纳米针状铵盐和纳米球状铵盐的聚氨酯大分子可以随着纳米球状铵盐的滚动以及其与纳米针状铵盐之间的相对滑动，增加了聚氨酯大分子之间的滑移位移，从而增加了聚氨酯纤维的断裂伸长率。 The polyurethane spinning solution enters the coagulation bath containing ammonium salt through the spinneret hole, and after wet drawing and forming, the polyurethane solution will solidify into a porous fiber structure. In the process of phase inversion and liquid phase separation during wet drawing, the solvent in the polyurethane spinning solution will diffuse into the coagulation bath, and the ammonium salt molecules in the coagulation bath will also diffuse into the polyurethane amorphous form along with the coagulation bath. Between the macromolecules in the region and in the pores, the polyurethane spinning solution is gradually solidified into polyurethane fibers, and the wet-cured polyurethane fibers in which the solvent and the coagulation bath coexist are obtained. Then, take the wet-cured polyurethane fiber out of the coagulation bath and put it into a drying oven for drying treatment. With the volatilization of the solvent and the coagulation bath in the wet-cured polyurethane fiber, the ammonium salt ions in the ammonium salt molecule will be in the polyurethane fiber. The macromolecules in the amorphous region form a micro-crosslinked structure in the form of hydrogen bonds. At the same time, ammonium salt ions will also form nano-acicular structures and nano-spherical structures in the pores of polyurethane fibers, and also form a strong hydrogen bond with the macromolecules of polyurethane fibers. The mass ratio between the two is 8:2-9:1, the size of both is between tens of nanometers and hundreds of nanometers. After drying, high-strength, high-modulus and high-elastic polyurethane fibers are obtained. When it is stretched, the micro-crosslinked structure between the macromolecules in the amorphous region of the polyurethane fiber and the nano-acicular ammonium salt structure in the pores of the polyurethane fiber can effectively increase the breaking strength and Young's modulus of the polyurethane fiber. At the same time, the nano-acicular ammonium salt structure and the nano-spherical ammonium salt structure in the pores of the polyurethane fiber combine with each other to form a "slider" structure, which can effectively increase the elongation at break of the polyurethane fiber. Under the action of tensile force, the polyurethane macromolecules surrounding the nanoacicular ammonium salt and the nanospherical ammonium salt with strong hydrogen bonding force can roll with the nanospherical ammonium salt and the relative relationship between it and the nanoacicular ammonium salt. Sliding increases the sliding displacement between polyurethane macromolecules, thereby increasing the elongation at break of polyurethane fibers.
2.凝固浴中多种组分的配合使用确保了铵盐分子能够有效地进入聚氨酯纤维中无定形区大分子之间以及聚氨酯纤维的孔洞中。 2. The combined use of various components in the coagulation bath ensures that the ammonium salt molecules can effectively enter between the macromolecules in the amorphous region of the polyurethane fiber and the pores of the polyurethane fiber.
凝固浴中的配比如下：去离子水15～97.5%，铵盐1～70%，含酰胺键的极性溶剂0.5～10%，丙酮0.9～4.5%，低相对分子量阴离子型表面活性剂0.1～0.5%。其中，铵盐是聚氨酯纤维获得高强高模高弹拉伸力学性能的增强体，含酰胺键的极性溶剂和丙酮的使用是为了控制湿法牵伸成形聚氨酯纤维的成形速率、孔洞的尺寸和大小、以及湿法牵伸成形过程中两相的扩散速率，确保铵盐分子能够有效地进入聚氨酯纤维中无定形区大分子之间以及聚氨酯纤维的孔洞中。低相对分子量阴离子型表面活性剂具有阴离子特性，且相对分子量较低，能够与聚氨酯纤维大分子的端基以及大分子链上的酰胺键形成界面结合力，使湿法牵伸成形聚氨酯纤维在干燥热处理过程中，铵盐分子能够有效的形成纳米针状结构和纳米球状结构。 The proportions in the coagulation bath are as follows: deionized water 15-97.5%, ammonium salt 1-70%, polar solvent containing amide bonds 0.5-10%, acetone 0.9-4.5%, low relative molecular weight anionic surfactant 0.1 ~0.5%. Among them, ammonium salt is a reinforcement for polyurethane fibers to obtain high-strength, high-modulus, high-elasticity and tensile mechanical properties. The use of polar solvents and acetone containing amide bonds is to control the forming rate, hole size and size of polyurethane fibers formed by wet drawing. The size and the diffusion rate of the two phases during the wet drawing process ensure that the ammonium salt molecules can effectively enter between the macromolecules in the amorphous region of the polyurethane fiber and the pores of the polyurethane fiber. Low relative molecular weight anionic surfactants have anionic characteristics and relatively low molecular weight, which can form interfacial binding force with the end groups of polyurethane fiber macromolecules and amide bonds on the macromolecular chains, so that the polyurethane fibers formed by wet drawing During heat treatment, the ammonium salt molecules can effectively form nano-acicular structures and nano-spherical structures.
3.在聚氨酯纤维的湿法牵伸成形过程中，采用10-80m/min的速率对聚氨酯纺丝液进行牵伸，并使其经过凝固浴的距离为8-45m，较慢的牵伸速率和较长的凝固浴接触距离能够确保铵盐分子有效地进入聚氨酯纤维中无定形区大分子之间以及聚氨酯纤维的孔洞中。 3. In the wet drawing forming process of polyurethane fiber, the polyurethane spinning solution is drawn at a speed of 10-80m/min, and the distance through the coagulation bath is 8-45m, and the slower drawing speed The longer contact distance with the coagulation bath can ensure that the ammonium salt molecules can effectively enter between the macromolecules in the amorphous region of the polyurethane fiber and into the pores of the polyurethane fiber.
在聚氨酯纤维的湿法牵伸成形过程中，聚氨酯纺丝液与凝固浴之间会发生相转化和相分离，由于聚氨酯纺丝液为细长条形，直径为几十微米，比表面积较大，导致其相转化和相分离具有方向性和取向性，促使聚氨酯纤维形成大量长条形孔洞为主、类圆形孔洞为辅的孔洞结构，从而构建出了大量“滑板”结构。湿法牵伸成形聚氨酯纤维中类圆形孔洞结构和长条状孔洞结构的同时存在，且相互链接，可以为铵盐分子在干燥热处理过程中形成纳米球状结构和纳米针状结构提供场所，有助于形成滑板结构，达到同时增加聚氨酯纤维断裂强度、杨氏模量、断裂伸长率的目的。 During the wet drawing and forming process of polyurethane fibers, phase transformation and phase separation will occur between the polyurethane spinning solution and the coagulation bath. Since the polyurethane spinning solution is in the shape of a long and thin strip, the diameter is tens of microns, and the specific surface area is relatively large. , causing its phase transformation and phase separation to have directionality and orientation, prompting the polyurethane fiber to form a large number of elongated holes and supplemented by circular holes, thus constructing a large number of "skateboard" structures. The simultaneous existence of quasi-circular pore structures and elongated pore structures in wet-drawn polyurethane fibers, and their interconnection, can provide places for ammonium salt molecules to form nano-spherical structures and nano-needle structures during drying and heat treatment. It helps to form a skateboard structure and achieve the purpose of simultaneously increasing the breaking strength, Young's modulus, and breaking elongation of polyurethane fibers.
本发明提供了一种高强高模高弹聚氨酯纤维的制备方法，该方法与现有聚氨酯纤维增强的方法相比，能够同时对聚氨酯纤维的断裂强度、杨氏模量和断裂伸长率实现增强，断裂强度增加150-280%，断裂伸长率增加60-120%，杨氏模量增加50-160%，大幅度提高了聚氨酯纤维的拉伸力学性能，扩宽了聚氨酯纤维的应用领域，该制备方法工艺设备简单，成本较低，对生态环境无污染，可控性高，具有很大的应用前景。 The invention provides a method for preparing high-strength, high-modulus and high-elasticity polyurethane fiber. Compared with the existing polyurethane fiber reinforcement method, the method can simultaneously enhance the breaking strength, Young's modulus and elongation at break of the polyurethane fiber. , the breaking strength increases by 150-280%, the elongation at break increases by 60-120%, and the Young's modulus increases by 50-160%, which greatly improves the tensile mechanical properties of polyurethane fibers and broadens the application fields of polyurethane fibers. The preparation method has simple process equipment, low cost, no pollution to the ecological environment, high controllability and great application prospects.
具体实施方式 Detailed ways
下面结合具体实施例对本发明进行具体详细描述。 The present invention will be described in detail below in conjunction with specific embodiments.
一种高强高模高弹聚氨酯纤维的制备方法，所述制备方法按以下步骤进行： A preparation method of high-strength, high-modulus and high-elasticity polyurethane fiber, described preparation method is carried out according to the following steps:
a聚氨酯纺丝液制备 a Polyurethane spinning solution preparation
将聚醚型聚氨酯或聚酯型聚氨酯或聚酯-聚醚型聚氨酯中的一种放入质量分数为98%～99%的N,N-二甲基甲酰胺中，在室温为8-38℃条件下机械搅拌0.5-1h后真空脱泡，得到含固量为10-25%、动力粘度为300-20000mPa·s的聚醚型聚氨酯纺丝液或聚酯型聚氨酯纺丝液或聚酯-聚醚型聚氨酯纺丝液中的一种，其中，搅拌速率为800-3000r/min。 Put one of polyether polyurethane or polyester polyurethane or polyester-polyether polyurethane into N,N-dimethylformamide with a mass fraction of 98% to 99%, and the room temperature is 8-38 Mechanical stirring at ℃ for 0.5-1h and then vacuum defoaming to obtain polyether type polyurethane spinning solution or polyester type polyurethane spinning solution or polyester type polyurethane spinning solution with solid content of 10-25% and dynamic viscosity of 300-20000mPa·s - One of the polyether polyurethane spinning solutions, wherein the stirring speed is 800-3000r/min.
b凝固浴配制 b coagulation bath preparation
按如下质量百分比： According to the following mass percentage:
去离子水15～97.5% Deionized water 15～97.5%
铵盐1～70% Ammonium salt 1～70%
含酰胺键的极性溶剂0.5～10% Polar solvent containing amide bond 0.5～10%
丙酮0.9～4.5% Acetone 0.9～4.5%
低相对分子量阴离子型表面活性剂0.1～0.5% Low relative molecular weight anionic surfactant 0.1～0.5%
将硝酸铵或氯化铵或硫酸铵或硫酸氢铵或碳酸铵或碳酸氢铵或磷酸铵或磷酸氢铵或磷酸二氢铵或磷酸氢二铵中的一种、甲酰胺或N,N-二甲基甲酰胺或N,N-二甲基乙酰胺中的一种、丙酮和相对分子量为200-1000的硫酸酯盐表面活性剂或磺酸盐表面活性剂或磷酸酯盐表面活性剂中的一种放入导电率≤16MΩ·cm的去离子水中得到混合溶液，然后将混合溶液的温度升高至25～90℃并机械搅拌3-5h后得到凝固浴，其中，搅拌速率为800-3000r/min。 One of ammonium nitrate or ammonium chloride or ammonium sulfate or ammonium bisulfate or ammonium carbonate or ammonium bicarbonate or ammonium phosphate or ammonium hydrogen phosphate or ammonium dihydrogen phosphate or diammonium hydrogen phosphate, formamide or N,N- One of dimethylformamide or N,N-dimethylacetamide, acetone and sulfate surfactants or sulfonate surfactants or phosphate surfactants with a relative molecular weight of 200-1000 One of them is placed in deionized water with a conductivity of ≤16MΩ·cm to obtain a mixed solution, and then the temperature of the mixed solution is raised to 25-90°C and mechanically stirred for 3-5 hours to obtain a coagulation bath, wherein the stirring rate is 800- 3000r/min.
c湿法牵伸成形 c Wet drawing forming
将步骤a制备的聚氨酯纺丝液经直径为65-90μm、长度为1-5mm喷丝孔挤出后，以10-80m/min的速率经过温度为25-90℃、凝固距离为8-45m的凝固浴，得到湿法牵伸成形后的聚氨酯纤维。 After the polyurethane spinning solution prepared in step a is extruded through the spinneret hole with a diameter of 65-90 μm and a length of 1-5 mm, the temperature is 25-90 ° C and the solidification distance is 8-45 m at a rate of 10-80 m/min. coagulation bath to obtain wet-drawn polyurethane fibers.
喷丝孔为纺丝行业常用的喷丝板上的孔，喷丝板通常由金属制成，也可以为高强度塑料或陶瓷，每个喷丝板上喷丝孔的数量为200-3000个。 The spinneret hole is the hole on the spinneret commonly used in the spinning industry. The spinneret is usually made of metal, or it can be high-strength plastic or ceramics. The number of spinneret holes on each spinneret is 200-3000 .
d热处理 dHeat treatment
将经步骤c制备的湿法牵伸成形后的聚氨酯纤维放入温度为80-170℃真空烘箱内干燥处理10-40s后得到高强高模高弹聚氨酯纤维。 Put the wet-drawn polyurethane fiber prepared in step c into a vacuum oven at a temperature of 80-170° C. for 10-40 seconds to obtain a high-strength, high-modulus and high-elasticity polyurethane fiber.
实施例1 Example 1
a聚氨酯纺丝液制备 a Polyurethane spinning solution preparation
将聚醚型聚氨酯放入质量分数为98%的N,N-二甲基甲酰胺中，在室温为8℃条件下机械搅拌0.5h后真空脱泡，得到含固量为10%、动力粘度为300mPa·s的聚醚型聚氨酯纺丝液，其中，搅拌速率为800r/min。 Put the polyether polyurethane into N,N-dimethylformamide with a mass fraction of 98%, mechanically stir it at room temperature for 0.5h, then vacuum degassing to obtain a solid content of 10%, dynamic viscosity 300mPa·s polyether polyurethane spinning solution, wherein the stirring rate is 800r/min.
b凝固浴配制 b coagulation bath preparation
将70g硝酸铵、10g甲酰胺、4.5g丙酮、和0.5g相对分子量为200的硫酸酯盐表面活性剂放入导电率为16MΩ·cm的15g去离子水得到混合溶液，然后将混合溶液的温度升高至25℃并机械搅拌3h后得到凝固浴，其中，搅拌速率为800r/min。 70g ammonium nitrate, 10g formamide, 4.5g acetone, and 0.5g relative molecular weight are put into 15g deionized water with electrical conductivity 16MΩ·cm to obtain mixed solution, then the temperature of mixed solution After raising to 25° C. and stirring mechanically for 3 hours, a coagulation bath was obtained, wherein the stirring rate was 800 r/min.
c湿法牵伸成形 c Wet drawing forming
将步骤a制备的聚醚型聚氨酯纺丝液经直径为65μm、长度为1mm喷丝孔挤出后，以10m/min的速率经过温度为25℃、凝固距离为8m的凝固浴，得到湿法牵伸成形后的聚醚型聚氨酯纤维。 Extrude the polyether polyurethane spinning solution prepared in step a through a spinneret hole with a diameter of 65 μm and a length of 1 mm, and pass through a coagulation bath with a temperature of 25 ° C and a coagulation distance of 8 m at a rate of 10 m/min to obtain a wet process Polyether polyurethane fiber after stretching.
d热处理 dHeat treatment
将经步骤c制备的湿法牵伸成形后的聚醚型聚氨酯纤维放入温度为80℃真空烘箱内干燥处理10s后得到高强高模高弹聚醚型聚氨酯纤维。 Put the wet-drawn polyether polyurethane fiber prepared in step c into a vacuum oven at a temperature of 80° C. for 10 seconds to dry to obtain a high-strength, high-modulus and high-elasticity polyether polyurethane fiber.
实施例2 Example 2
a聚氨酯纺丝液制备 a Polyurethane spinning solution preparation
将聚酯型聚氨酯放入质量分数为99%的N,N-二甲基甲酰胺中，在室温为18℃条件下机械搅拌1h后真空脱泡，得到含固量为15%、动力粘度为3000mPa·s的聚酯型聚氨酯纺丝液，其中，搅拌速率为1200r/min。 Put polyester polyurethane into N,N-dimethylformamide with a mass fraction of 99%, mechanically stir it at room temperature for 1 hour at 18°C, and vacuum defoam to obtain a solution with a solid content of 15% and a dynamic viscosity of 3000mPa·s polyester polyurethane spinning solution, wherein the stirring rate is 1200r/min.
b凝固浴配制 b coagulation bath preparation
将60g氯化铵、8gN,N-二甲基甲酰胺、1.5g丙酮和0.5g相对分子量为400的磺酸盐表面活性剂放入导电率为15MΩ·cm的30g去离子水得到混合溶液，然后将混合溶液的温度升高至50℃并机械搅拌4h后得到凝固浴，其中，搅拌速率为1100r/min。 60g of ammonium chloride, 8gN,N-dimethylformamide, 1.5g of acetone and 0.5g of sulfonate surfactant with a relative molecular weight of 400 were put into 30g of deionized water with a conductivity of 15MΩ·cm to obtain a mixed solution, Then the temperature of the mixed solution was increased to 50° C. and mechanically stirred for 4 hours to obtain a coagulation bath, wherein the stirring rate was 1100 r/min.
c湿法牵伸成形 c Wet drawing forming
将步骤a制备的聚酯型聚氨酯纺丝液经直径为75μm、长度为2mm喷丝孔挤出后，以30m/min的速率经过温度为50℃、凝固距离为15m的凝固浴，得到湿法牵伸成形后的聚酯型聚氨酯纤维。 Extrude the polyester polyurethane spinning solution prepared in step a through a spinneret hole with a diameter of 75 μm and a length of 2 mm, and pass through a coagulation bath with a temperature of 50 ° C and a coagulation distance of 15 m at a rate of 30 m/min to obtain a wet process The polyester polyurethane fiber after drawing and forming.
d热处理 dHeat treatment
将经步骤c制备的湿法牵伸成形后的聚酯型聚氨酯纤维放入温度为100℃真空烘箱内干燥处理20s后得到高强高模高弹聚酯型聚氨酯纤维。 Put the wet-drawn polyester polyurethane fiber prepared in step c into a vacuum oven at a temperature of 100° C. for 20 seconds to dry to obtain a high-strength, high-modulus and high-elastic polyester polyurethane fiber.
实施例3 Example 3
a聚氨酯纺丝液制备 a Polyurethane spinning solution preparation
将聚酯-聚醚型聚氨酯放入质量分数为99%的N,N-二甲基甲酰胺中，在室温为28℃条件下机械搅拌1h后真空脱泡，得到含固量为20%、动力粘度为6000mPa·s的聚酯-聚醚型聚氨酯纺丝液，其中，搅拌速率为1600r/min。 Put polyester-polyether polyurethane into N,N-dimethylformamide with a mass fraction of 99%, mechanically stir for 1 hour at room temperature at 28°C, and vacuum defoam to obtain a solid content of 20%. A polyester-polyether polyurethane spinning solution with a dynamic viscosity of 6000mPa·s, wherein the stirring rate is 1600r/min.
b凝固浴配制 b coagulation bath preparation
将28g硫酸铵、8gN,N-二甲基乙酰胺、3.7g丙酮和0.3g相对分子量为600的磷酸酯盐表面活性剂放入导电率为14MΩ·cm的60g去离子水得到混合溶液，然后将混合溶液的温度升高至75℃并机械搅拌5h后得到凝固浴，其中，搅拌速率为1400r/min。 28g ammonium sulfate, 8gN, N-dimethylacetamide, 3.7g acetone and 0.3g relative molecular weight are phosphate ester salt surfactants of 600 to be put into 60g deionized water with conductivity 14MΩ·cm to obtain mixed solution, then The temperature of the mixed solution was raised to 75° C. and mechanically stirred for 5 hours to obtain a coagulation bath, wherein the stirring rate was 1400 r/min.
c湿法牵伸成形 c Wet drawing forming
将步骤a制备的聚酯-聚醚型聚氨酯纺丝液经直径为85μm、长度为3mm喷丝孔挤出后，以50m/min的速率经过温度为75℃、凝固距离为25m的凝固浴，得到湿法牵伸成形后的聚酯-聚醚型聚氨酯纤维。 Extrude the polyester-polyether polyurethane spinning solution prepared in step a through a spinneret hole with a diameter of 85 μm and a length of 3 mm, and pass through a coagulation bath with a temperature of 75° C. and a coagulation distance of 25 m at a rate of 50 m/min. The polyester-polyether polyurethane fiber formed by wet drawing is obtained.
d热处理 dHeat treatment
将经步骤c制备的湿法牵伸成形后的聚酯-聚醚型聚氨酯纤维放入温度为120℃真空烘箱内干燥处理30s后得到高强高模高弹聚酯-聚醚型聚氨酯纤维。 Put the polyester-polyether polyurethane fiber prepared by wet drawing in step c into a vacuum oven at 120° C. for 30 seconds to dry to obtain a high-strength, high-modulus and high-elastic polyester-polyether polyurethane fiber.
实施例4 Example 4
a聚氨酯纺丝液制备 a Polyurethane spinning solution preparation
将聚醚型聚氨酯放入质量分数为99%的N,N-二甲基甲酰胺中，在室温为38℃条件下机械搅拌1h后真空脱泡，得到含固量为25%、动力粘度为9000mPa·s的聚醚型聚氨酯纺丝液，其中，搅拌速率为2000r/min。 Put polyether polyurethane into N,N-dimethylformamide with a mass fraction of 99%, mechanically stir for 1 hour at room temperature at 38°C, and vacuum defoam to obtain a solid content of 25% and a dynamic viscosity of 9000mPa·s polyether polyurethane spinning solution, wherein the stirring rate is 2000r/min.
b凝固浴配制 b coagulation bath preparation
将5g硫酸氢铵、2g甲酰胺、2.8g丙酮和0.2g相对分子量为800的硫酸酯盐表面活性剂放入导电率为13MΩ·cm的90g去离子水得到混合溶液，然后将混合溶液的温度升高至90℃并机械搅拌3h后得到凝固浴，其中，搅拌速率为1700r/min。 5g ammonium bisulfate, 2g formamide, 2.8g acetone and 0.2g relative molecular weight are put into the 90g deionized water of conductivity 13MΩ·cm that the sulfate ester salt surfactant of 800 obtains mixed solution, then the temperature of mixed solution After raising to 90° C. and stirring mechanically for 3 hours, a coagulation bath was obtained, wherein the stirring rate was 1700 r/min.
c湿法牵伸成形 c Wet drawing forming
将步骤a制备的聚醚型聚氨酯纺丝液经直径为90μm、长度为4mm喷丝孔挤出后，以70m/min的速率经过温度为90℃、凝固距离为35m的凝固浴，得到湿法牵伸成形后的聚醚型聚氨酯纤维。 Extrude the polyether polyurethane spinning solution prepared in step a through a spinneret hole with a diameter of 90 μm and a length of 4 mm, and pass through a coagulation bath with a temperature of 90 ° C and a coagulation distance of 35 m at a rate of 70 m/min to obtain a wet process Polyether polyurethane fiber after stretching.
d热处理 dHeat treatment
将经步骤c制备的湿法牵伸成形后的聚醚型聚氨酯纤维放入温度为150℃真空烘箱内干燥处理40s后得到高强高模高弹聚醚型聚氨酯纤维。 Put the wet-drawn polyether polyurethane fiber prepared in step c into a vacuum oven at a temperature of 150° C. for 40 seconds to dry to obtain a high-strength, high-modulus and high-elastic polyether polyurethane fiber.
实施例5 Example 5
a聚氨酯纺丝液制备 a Polyurethane spinning solution preparation
将聚醚型聚氨酯放入质量分数为99%的N,N-二甲基甲酰胺中，在室温为38℃条件下机械搅拌1h后真空脱泡，得到含固量为25%、动力粘度为12000mPa·s的聚醚型聚氨酯纺丝液，其中，搅拌速率为2400r/min。 Put polyether polyurethane into N,N-dimethylformamide with a mass fraction of 99%, mechanically stir for 1 hour at room temperature at 38°C, and vacuum defoam to obtain a solid content of 25% and a dynamic viscosity of 12000mPa·s polyether polyurethane spinning solution, wherein the stirring rate is 2400r/min.
b凝固浴配制 b coagulation bath preparation
将1g碳酸铵、0.5gN,N-二甲基甲酰胺、0.9g丙酮和0.1g相对分子量为1000的磺酸盐表面活性剂放入导电率为12MΩ·cm的97.5g去离子水得到混合溶液，然后将混合溶液的温度升高至25℃并机械搅拌4h后得到凝固浴，其中，搅拌速率为2000r/min。 Put 1g of ammonium carbonate, 0.5g of N,N-dimethylformamide, 0.9g of acetone and 0.1g of sulfonate surfactant with a relative molecular weight of 1000 into 97.5g of deionized water with a conductivity of 12MΩ·cm to obtain a mixed solution , and then the temperature of the mixed solution was increased to 25° C. and mechanically stirred for 4 hours to obtain a coagulation bath, wherein the stirring rate was 2000 r/min.
c湿法牵伸成形 c Wet drawing forming
将步骤a制备的聚醚型聚氨酯纺丝液经直径为65μm、长度为5mm喷丝孔挤出后，以80m/min的速率经过温度为25℃、凝固距离为45m的凝固浴，得到湿法牵伸成形后的聚醚型聚氨酯纤维。 Extrude the polyether polyurethane spinning solution prepared in step a through a spinneret hole with a diameter of 65 μm and a length of 5 mm, and pass through a coagulation bath with a temperature of 25 ° C and a coagulation distance of 45 m at a rate of 80 m/min to obtain a wet process Polyether polyurethane fiber after stretching.
d热处理 dHeat treatment
将经步骤c制备的湿法牵伸成形后的聚醚型聚氨酯纤维放入温度为170℃真空烘箱内干燥处理40s后得到高强高模高弹聚醚型聚氨酯纤维。 Put the wet-drawn polyether polyurethane fiber prepared in step c into a vacuum oven at a temperature of 170° C. for drying for 40 seconds to obtain a high-strength, high-modulus and high-elastic polyether polyurethane fiber.
实施例6 Example 6
a聚氨酯纺丝液制备 a Polyurethane spinning solution preparation
将聚酯型聚氨酯放入质量分数为98%的N,N-二甲基甲酰胺中，在室温为8℃条件下机械搅拌0.5h后真空脱泡，得到含固量为10%、动力粘度为15000mPa·s的聚酯型聚氨酯纺丝液，其中，搅拌速率为3000r/min。 Put the polyester polyurethane into N,N-dimethylformamide with a mass fraction of 98%, mechanically stir it at room temperature for 0.5h, and then vacuum defoam to obtain a solid content of 10%, dynamic viscosity It is a polyester polyurethane spinning solution of 15000mPa·s, wherein the stirring rate is 3000r/min.
b凝固浴配制 b coagulation bath preparation
将70g碳酸氢铵、10gN,N-二甲基乙酰胺、4.5g丙酮和0.5g相对分子量为200的磷酸酯盐表面活性剂放入导电率为11MΩ·cm的15g去离子水得到混合溶液，然后将混合溶液的温度升高至50℃并机械搅拌5h后得到凝固浴，其中，搅拌速率为2300r/min。 70g ammonium bicarbonate, 10gN, N-dimethylacetamide, 4.5g acetone and 0.5g relative molecular weight are 200 phosphate ester salt surfactants are put into 15g deionized water with a conductivity of 11MΩ cm to obtain a mixed solution, Then the temperature of the mixed solution was increased to 50° C. and mechanically stirred for 5 hours to obtain a coagulation bath, wherein the stirring rate was 2300 r/min.
c湿法牵伸成形 c Wet drawing forming
将步骤a制备的聚酯型型聚氨酯纺丝液经直径为75μm、长度为5mm喷丝孔挤出后，以80m/min的速率经过温度为75℃、凝固距离为45m的凝固浴，得到湿法牵伸成形后的聚酯型型聚氨酯纤维。 After the polyester polyurethane spinning solution prepared in step a is extruded through a spinneret hole with a diameter of 75 μm and a length of 5 mm, it passes through a coagulation bath with a temperature of 75 ° C and a coagulation distance of 45 m at a rate of 80 m/min to obtain a wet The polyester polyurethane fiber after drawing by method.
d热处理 dHeat treatment
将经步骤c制备的湿法牵伸成形后的聚酯型型聚氨酯纤维放入温度为170℃真空烘箱内干燥处理40s后得到高强高模高弹聚酯型型聚氨酯纤维。 Put the wet-drawn polyester polyurethane fiber prepared in step c into a vacuum oven at a temperature of 170° C. for 40 seconds to dry to obtain a high-strength, high-modulus and high-elastic polyester polyurethane fiber.
实施例7 Example 7
a聚氨酯纺丝液制备 a Polyurethane spinning solution preparation
将聚酯型聚氨酯放入质量分数为98%的N,N-二甲基甲酰胺中，在室温为18℃条件下机械搅拌0.5h后真空脱泡，得到含固量为20%、动力粘度为18000mPa·s的聚酯型聚氨酯纺丝液，其中，搅拌速率为800r/min。 Put polyester polyurethane into N,N-dimethylformamide with a mass fraction of 98%, mechanically stir it at room temperature at 18°C for 0.5h, and then vacuum degassing to obtain a solid content of 20%, dynamic viscosity It is a polyester polyurethane spinning solution of 18000mPa·s, wherein the stirring rate is 800r/min.
b凝固浴配制 b coagulation bath preparation
将40g磷酸铵、7g甲酰胺、2.2g丙酮和0.8g相对分子量为400的磷酸酯盐表面活性剂放入导电率为9MΩ·cm的50g去离子水得到混合溶液，然后将混合溶液的温度升高至75℃并机械搅拌3h后得到凝固浴，其中，搅拌速率为2600r/min。 40g ammonium phosphate, 7g formamide, 2.2g acetone and 0.8g relative molecular weight are 400 phosphate ester salt surfactants and put into 50g deionized water with conductivity 9MΩ cm to obtain mixed solution, then the temperature of mixed solution is raised After heating to 75°C and stirring mechanically for 3 hours, a coagulation bath was obtained, wherein the stirring rate was 2600r/min.
c湿法牵伸成形 c Wet drawing forming
将步骤a制备的聚酯型型聚氨酯纺丝液经直径为85μm、长度为2mm喷丝孔挤出后，以30m/min的速率经过温度为90℃、凝固距离为8m的凝固浴，得到湿法牵伸成形后的聚酯型型聚氨酯纤维。 Extrude the polyester polyurethane spinning solution prepared in step a through a spinneret hole with a diameter of 85 μm and a length of 2 mm, and pass through a coagulation bath with a temperature of 90 ° C and a coagulation distance of 8 m at a rate of 30 m/min to obtain wet The polyester polyurethane fiber after drawing by method.
d热处理 dHeat treatment
将经步骤c制备的湿法牵伸成形后的聚酯型型聚氨酯纤维放入温度为80℃真空烘箱内干燥处理10s后得到高强高模高弹聚酯型型聚氨酯纤维。 Put the wet-drawn polyester polyurethane fiber prepared in step c into a vacuum oven at a temperature of 80° C. for 10 seconds to dry to obtain a high-strength, high-modulus and high-elastic polyester polyurethane fiber.
实施例8 Example 8
a聚氨酯纺丝液制备 a Polyurethane spinning solution preparation
将聚酯-聚醚型聚氨酯放入质量分数为98%的N,N-二甲基甲酰胺中，在室温为28℃条件下机械搅拌0.5h后真空脱泡，得到含固量为15%、动力粘度为20000mPa·s的聚酯-聚醚型聚氨酯纺丝液，其中，搅拌速率为1600r/min。 Put the polyester-polyether polyurethane into N,N-dimethylformamide with a mass fraction of 98%, mechanically stir it at room temperature for 0.5h at 28°C, and vacuum defoam to obtain a solid content of 15%. 1. A polyester-polyether polyurethane spinning solution with a dynamic viscosity of 20000mPa·s, wherein the stirring rate is 1600r/min.
b凝固浴配制 b coagulation bath preparation
将20g磷酸氢铵、3gN,N-二甲基甲酰胺、1.5g丙酮和0.5g相对分子量为400的磺酸盐表面活性剂放入导电率为7MΩ·cm的75g去离子水得到混合溶液，然后将混合溶液的温度升高至90℃并机械搅拌4h后得到凝固浴，其中，搅拌速率为3000r/min。 20g of ammonium hydrogen phosphate, 3gN,N-dimethylformamide, 1.5g of acetone and 0.5g of sulfonate surfactant with a relative molecular weight of 400 were put into 75g of deionized water with a conductivity of 7MΩ·cm to obtain a mixed solution, Then the temperature of the mixed solution was increased to 90° C. and mechanically stirred for 4 hours to obtain a coagulation bath, wherein the stirring rate was 3000 r/min.
c湿法牵伸成形 c Wet drawing forming
将步骤a制备的聚酯-聚醚型型聚氨酯纺丝液经直径为90μm、长度为3mm喷丝孔挤出后，以50m/min的速率经过温度为25℃、凝固距离为15m的凝固浴，得到湿法牵伸成形后的聚酯-聚醚型型聚氨酯纤维。 Extrude the polyester-polyether type polyurethane spinning solution prepared in step a through a spinneret hole with a diameter of 90 μm and a length of 3 mm, and pass through a coagulation bath with a temperature of 25 ° C and a coagulation distance of 15 m at a rate of 50 m/min , to obtain polyester-polyether type polyurethane fibers formed by wet drawing.
d热处理 dHeat treatment
将经步骤c制备的湿法牵伸成形后的聚酯-聚醚型型聚氨酯纤维放入温度为120℃真空烘箱内干燥处理20s后得到高强高模高弹聚酯-聚醚型型聚氨酯纤维。 Put the polyester-polyether polyurethane fiber prepared by wet drawing in step c into a vacuum oven at a temperature of 120°C for 20 seconds to dry to obtain a high-strength, high-modulus and high-elastic polyester-polyether polyurethane fiber .
实施例9 Example 9
a聚氨酯纺丝液制备 a Polyurethane spinning solution preparation
将聚酯-聚醚型聚氨酯放入质量分数为98%的N,N-二甲基甲酰胺中，在室温为38℃条件下机械搅拌0.5h后真空脱泡，得到含固量为25%、动力粘度为300mPa·s的聚酯-聚醚型聚氨酯纺丝液，其中，搅拌速率为2400r/min。 Put the polyester-polyether polyurethane into N,N-dimethylformamide with a mass fraction of 98%, mechanically stir at room temperature at 38°C for 0.5h, and then vacuum defoam to obtain a solid content of 25%. 1. A polyester-polyether polyurethane spinning solution with a dynamic viscosity of 300mPa·s, wherein the stirring rate is 2400r/min.
b凝固浴配制 b coagulation bath preparation
将70g磷酸二氢铵、10gN,N-二甲基乙酰胺、4.5g丙酮和0.5g相对分子量为800的磷酸酯盐表面活性剂放入导电率为5MΩ·cm的15g去离子水得到混合溶液，然后将混合溶液的温度升高至25℃并机械搅拌5h后得到凝固浴，其中，搅拌速率为800r/min。 Put 70g of ammonium dihydrogen phosphate, 10g of N,N-dimethylacetamide, 4.5g of acetone and 0.5g of phosphate ester salt surfactant with a relative molecular weight of 800 into 15g of deionized water with a conductivity of 5MΩ cm to obtain a mixed solution , and then the temperature of the mixed solution was increased to 25° C. and mechanically stirred for 5 hours to obtain a coagulation bath, wherein the stirring rate was 800 r/min.
c湿法牵伸成形 c Wet drawing forming
将步骤a制备的聚酯-聚醚型型聚氨酯纺丝液经直径为65μm、长度为4mm喷丝孔挤出后，以70m/min的速率经过温度为75℃、凝固距离为35m的凝固浴，得到湿法牵伸成形后的聚酯-聚醚型型聚氨酯纤维。 Extrude the polyester-polyether polyurethane spinning solution prepared in step a through a spinneret hole with a diameter of 65 μm and a length of 4 mm, and then pass through a coagulation bath with a temperature of 75 ° C and a coagulation distance of 35 m at a rate of 70 m/min , to obtain polyester-polyether type polyurethane fibers formed by wet drawing.
d热处理 dHeat treatment
将经步骤c制备的湿法牵伸成形后的聚酯-聚醚型型聚氨酯纤维放入温度为150℃真空烘箱内干燥处理30s后得到高强高模高弹聚酯-聚醚型型聚氨酯纤维。 Put the polyester-polyether polyurethane fiber prepared by wet drawing in step c into a vacuum oven at a temperature of 150°C for 30 seconds to dry to obtain a high-strength, high-modulus and high-elastic polyester-polyether polyurethane fiber .
实施例10 Example 10
a聚氨酯纺丝液制备 a Polyurethane spinning solution preparation
将聚醚型聚氨酯放入质量分数为99%的N,N-二甲基甲酰胺中，在室温为38℃条件下机械搅拌1h后真空脱泡，得到含固量为25%、动力粘度为20000mPa·s的聚醚型聚氨酯纺丝液，其中，搅拌速率为3000r/min。 Put polyether polyurethane into N,N-dimethylformamide with a mass fraction of 99%, mechanically stir for 1 hour at room temperature at 38°C, and vacuum defoam to obtain a solid content of 25% and a dynamic viscosity of 20000mPa·s polyether polyurethane spinning solution, wherein the stirring rate is 3000r/min.
b凝固浴配制 b coagulation bath preparation
将1g磷酸氢二铵、0.5gN,N-二甲基乙酰胺、0.9g丙酮和0.1g相对分子量为1000的硫酸酯盐表面活性剂放入导电率为16MΩ·cm的97.5g去离子水得到混合溶液，然后将混合溶液的温度升高至90℃并机械搅拌5h后得到凝固浴，其中，搅拌速率为3000r/min。 Put 1g of diammonium hydrogen phosphate, 0.5g of N,N-dimethylacetamide, 0.9g of acetone and 0.1g of a sulfate ester surfactant with a relative molecular weight of 1000 into 97.5g of deionized water with a conductivity of 16MΩ·cm to obtain The solution was mixed, and then the temperature of the mixed solution was raised to 90° C. and mechanically stirred for 5 hours to obtain a coagulation bath, wherein the stirring rate was 3000 r/min.
c湿法牵伸成形 c Wet drawing forming
将步骤a制备的聚醚型型聚氨酯纺丝液经直径为85μm、长度为5mm喷丝孔挤出后，以80m/min的速率经过温度为90℃、凝固距离为45m的凝固浴，得到湿法牵伸成形后的聚醚型型聚氨酯纤维。 Extrude the polyether type polyurethane spinning solution prepared in step a through a spinneret hole with a diameter of 85 μm and a length of 5 mm, and pass through a coagulation bath with a temperature of 90 ° C and a coagulation distance of 45 m at a rate of 80 m/min to obtain a wet The polyether type polyurethane fiber after drawing by method.
d热处理 dHeat treatment
将经步骤c制备的湿法牵伸成形后的聚醚型型聚氨酯纤维放入温度为170℃真空烘箱内干燥处理40s后得到高强高模高弹聚醚型型聚氨酯纤维。 Put the wet-drawn polyether polyurethane fiber prepared in step c into a vacuum oven at a temperature of 170° C. for 40 seconds to dry to obtain a high-strength, high-modulus and high-elastic polyether polyurethane fiber.
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| CN106589279B (en) * | 2017-01-16 | 2021-03-16 | 广东鸿驿聚氨酯科技有限公司 | Production method of graphene polyurethane agricultural machinery track |
| CN108059703A (en) * | 2017-12-18 | 2018-05-22 | 苏州浩洋聚氨酯科技有限公司 | A kind of high-toughness polyurethane synthetic material |
| CN110229353A (en) * | 2019-06-11 | 2019-09-13 | 武汉纺织大学 | A method of improving organic powder-compound polyurethane material interface performance and mechanical property |
| CN110230117A (en) * | 2019-06-11 | 2019-09-13 | 武汉纺织大学 | A method of improving polyurethane fiber strength and strain |
| CN110230117B (en) * | 2019-06-11 | 2022-01-28 | 武汉纺织大学 | Method for improving strength and strain of polyurethane fiber |
| CN110229353B (en) * | 2019-06-11 | 2022-03-04 | 武汉纺织大学 | A method for improving interface properties and mechanical properties of organic powder-polyurethane composites |
| CN113201840A (en) * | 2021-04-27 | 2021-08-03 | 江苏江山红化纤有限责任公司 | Tear-resistant graphene nylon fiber fabric and preparation method thereof |
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