WO2020052360A1 - 一种高强高模聚乙烯纤维的制备方法 - Google Patents

一种高强高模聚乙烯纤维的制备方法 Download PDF

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WO2020052360A1
WO2020052360A1 PCT/CN2019/098640 CN2019098640W WO2020052360A1 WO 2020052360 A1 WO2020052360 A1 WO 2020052360A1 CN 2019098640 W CN2019098640 W CN 2019098640W WO 2020052360 A1 WO2020052360 A1 WO 2020052360A1
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polyethylene
strength
preparing
modulus
molecular weight
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PCT/CN2019/098640
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French (fr)
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叶纯麟
肖明威
李建龙
张振飞
叶晓峰
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上海化工研究院有限公司
上海联濮化工科技有限公司
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Priority to MYPI2021000480A priority Critical patent/MY186481A/en
Publication of WO2020052360A1 publication Critical patent/WO2020052360A1/zh

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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
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/46—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/12—Stretch-spinning methods
    • 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
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties

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  • the invention belongs to the technical field of polymer materials, and particularly relates to a method for preparing high-strength and high-modulus polyethylene fibers.
  • High-performance polyethylene fibers have the characteristics of light weight and high strength, long service life, abrasion resistance, high strength, humidity resistance, and corrosion resistance, and are widely used in Towing rope, negative rope, rescue rope, cut-resistant gloves, etc.
  • high-performance polyethylene fibers can be made into protective clothing, helmets, and bulletproof materials in the military.
  • the high-performance polyethylene fiber composite material also has high strength and strong anti-collision performance.
  • aerospace it is suitable for wingtip structures, spacecraft structures and buoy aircrafts of various aircrafts.
  • the narrow molecular weight distribution polyethylene obtained by single-site catalyst polymerization has caused widespread concern in the industry.
  • the narrow molecular weight distribution polyethylene has a new level of performance compared to the polyethylene obtained by polymerization of traditional Ziegler-Natta and chromium-based catalyst systems because it contains very few low molecular weight parts.
  • the better processing performance than ultra-high molecular weight polyethylene makes metallocene polyethylene show its unique side.
  • the current methods for polyethylene spinning can be divided into three main categories:
  • the first category includes Chinese patent CN200980146604, Chinese patent CN201410264678, International Application Publication No. WO2005 / 066401A1, US Patent US430577, etc.
  • the high molecular weight polyethylene is swollen and dissolved with a solvent, and then extruded into a polyethylene strand. Solvent extraction and drying are performed on the raw silk to remove the solvent, and finally multi-stage drawing is performed to obtain high-strength high-modulus polyethylene fibers. Since the molecular weight of the raw materials used in this method is generally higher than 1.5 million, the strength of the polyethylene fibers obtained is relatively high.
  • the tensile strength of the obtained polyethylene fibers can reach more than 30 cN / dtex.
  • the production process is complicated, the cost is high, and the problems of solvent volatilization and recovery during the production process are difficult to solve and have a large impact on the environment.
  • the second category mainly includes those disclosed in Chinese patent CN201010533593, Chinese patent CN201410416669, Chinese patent CN101230501A, etc.
  • the low molecular weight polyethylene or polyethylene modified masterbatch is blended with ultra-high molecular weight polyethylene to melt and extrude fiber strands, and Multi-stage stretching is performed to obtain polyethylene fibers.
  • the low-molecular-weight polyethylene and modified masterbatch are added in large amounts, and the weight ratio is generally 5% to 10% or even higher.
  • These modified masterbatches also lead to finished products. Defects in mechanical properties, so the fiber strength obtained is not high, usually 15-25cN / dtex. At the same time, the process is more complicated.
  • the third category mainly includes U.S. patent USP4228118, Chinese patent CN03807737, etc. melt extrusion spinning using polyethylene with a weight average molecular weight of less than 300,000. This method does not require the addition of flow-modified masterbatch or low-molecular-weight polyethylene. Low, meanwhile, the temperature control of the post-stretching process is relatively low, so that the mechanical properties of the fibers obtained are also very limited, and the strength is about 15 cN / dtex.
  • the problem to be solved by the present invention is that the current production process of high-strength high-modulus polyethylene is complicated, the production cost is high, and the environment is polluted, and the strength and modulus of the products obtained by the current polyethylene melt spinning method are generally low.
  • a method for preparing high-strength and high-modulus polyethylene fibers is provided.
  • a method for preparing high-strength and high-modulus polyethylene fibers using the following steps:
  • the ratio of the weight average molecular weight to the number average molecular weight of the polyethylene raw material Mw / Mn is less than 3.0, and the number of thousand carbon methyl groups is less than 0.1.
  • the weight of the auxiliary agent is not more than 2% of the weight of the polyethylene raw material.
  • the auxiliary agent is a mixture of an antioxidant and a surface lubricant, and a weight ratio of the antioxidant and the surface lubricant is 1: 1 to 1: 5.
  • the antioxidant is 2,6-di-tert-butyl-p-cresol, 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propanoic stearyl ester, and tetra [ ⁇ - (3, One or more of 5-di-tert-butyl-4-hydroxyphenyl) propionic acid] pentaerythritol ester.
  • the surface lubricant is one or more of titanate-based, fluororubber-based, stearate-based or aluminate-based compounds.
  • the screw of the screw extruder is controlled from the temperature of the feeding section to the temperature of the discharge from 60 ° C to 180 ° C, the rotation speed of the screw is from 10 to 90 rpm, and the diameter of the outlet hole of the extrusion die is 1 to 10 mm.
  • the undrawn filaments are cooled by air or cooling water.
  • the total stretching ratio of the multi-stage stretching is 20 to 120 times, and the temperature of the hot tunnel is 130 ° C to 145 ° C.
  • the invention is a method for preparing high-strength and high-modulus polyethylene fibers. Polyethylene raw materials obtained through the polymerization of a single active site catalyst are blended with an auxiliary agent, and high-strength high-modulus polyethylene fibers are prepared without using a solvent.
  • ultra-high molecular weight polyethylene is generally used for the preparation method of high-strength high-modulus polyethylene fibers, and the performance of polyethylene fibers is improved by increasing the molecular weight of polyethylene.
  • the processability of polyethylene decreases significantly.
  • the processing performance can be increased, and the introduction of the solvent will bring a series of problems such as a large increase in preparation costs and environmental protection issues.
  • the high molecular weight molecular chain part is the key to affecting the processing performance.
  • the invention uses a single-site catalyst polymerization to obtain polyethylene raw materials with a molecular weight of less than 1.2 million, which greatly reduces the content of high molecular weight molecular chains and greatly improves the processing performance of polyethylene.
  • the production of high-strength and high-modulation polyethylene fibers requires very small amounts of additives.
  • the ultra-high molecular weight polyethylene used in solution spinning is mainly obtained by the polymerization of Ziegler-Natta catalyst system.
  • the polymerization process generally uses a kettle reactor to polymerize, and the obtained ultra-high molecular weight polyethylene has a broad molecular weight distribution.
  • Figure 1 is a comparison diagram of the molecular weight distributions of metallocene polyethylene and ultra-high molecular weight polyethylene obtained by polymerization of a solution spinning using a Ziegler-Natta catalyst system.
  • the molecular weight of the ultra-high molecular weight polyethylene is much higher than that of the metallocene polyethylene, the molecular chain part of the low molecular weight is the key to weakening the mechanical properties of the fiber, as shown in Table 2. This is also one of the main reasons for the low strength of the second type of fiber products in the background art.
  • the invention uses polyethylene raw materials with reasonable molecular weight distribution and molecular weight range to maximize the molecular weight of polyethylene in the processable range without adding trace additives that do not affect the performance of the product; it will affect the low mechanical properties of the product.
  • the molecular weight is partially minimized.
  • Figure 1 is a comparison of the molecular weight and distribution of polyethylene obtained by polymerization of ultra-high molecular weight polyethylene with a single-site catalyst.
  • the extruded yarn enters the post-stretching section after being cooled by water.
  • the first-stage stretching temperature is 130 ° C and the stretching is 10 times.
  • the second-stage stretching temperature is 135 ° C, and the stretching is 5 times.
  • the third-stage stretching temperature is 140 ° C, and the stretching is twice. After multi-stage stretching, the strength of the polyethylene fiber was 26.39 cN / dtex, and the modulus was 880 cN / dtex.
  • the extruded yarn enters the post-stretching section after being cooled by water.
  • the first-stage stretching temperature is 131 ° C and the stretching is 12 times.
  • the second-stage stretching temperature is 136 ° C, and the stretching is 5 times.
  • the third-stage stretching temperature is 141 ° C, and the stretching is 2.5 times.
  • the strength of the polyethylene fiber was 29.21 cN / dtex, and the modulus was 920 cN / dtex.
  • the extruded strand enters the post-stretching section after being cooled by air.
  • the first-stage stretching temperature is 132 ° C, and the stretching is 15 times.
  • the second-stage stretching temperature is 136 ° C, and the stretching is 5 times.
  • the third-stage stretching temperature is 142 ° C, and the stretching is 2.5 times.
  • the strength of the polyethylene fiber was 30.92 cN / dtex, and the modulus was 980 cN / dtex.
  • the extruded strand enters the post-stretching section after being cooled by air.
  • the first-stage stretching temperature is 132.5 ° C and the stretching is 16 times.
  • the second-stage stretching temperature is 138 ° C, and the stretching is 6 times.
  • the third-stage stretching temperature is 145 ° C, and the stretching is 4 times.
  • the strength of the polyethylene fiber was 32.11 cN / dtex, and the modulus was 1120 cN / dtex.
  • the extruded yarn enters the post-drawing stage after being cooled by air.
  • the first-stage drawing temperature is 25 ° C and the drawing is 2.8 times.
  • the second-stage stretching temperature was 115 ° C, and the stretching was 5.0 times.
  • the strength of the polyethylene fiber was 18.0 cN / dtex, and the modulus was 820 cN / dtex.
  • the first step is to prepare polyethylene modified masterbatch:
  • LDPE low density polyethylene or LLOPE linear low density polyethylene as raw materials, plus (weight ratio) 7% to 15% POE polyolefin elastomer, 3% to 5% PE foaming agent, and 5% ⁇ 10% EPDM or SEBS with EPDM or SEBS for uniform mixing;
  • the above-mentioned polymer is uniformly mixed and granulated by twin-screw blending: the temperature of each section of the twin-screw is between 150-220 ° C, and the rotation speed of the twin-screw is controlled at 200-250 revolutions per minute to prepare polyethylene modified Masterbatch.
  • the compound polyethylene modified masterbatch has excellent functions such as low melting point, low viscosity, lubricity, good fluidity, and easy dispersion.
  • the screw length-diameter ratio is 1:40
  • the temperature of each section of the screw is 150 °C ⁇ 250 °C
  • the screw extrusion speed is 200 ⁇ 250 rpm
  • spinner melt temperature is controlled at 200 °C ⁇ 220 °C
  • nozzle draft is 5 ⁇ 15m / min
  • sprayed primary fiber is cooled by water bath, water bath temperature is controlled at 20 ⁇ 25 °C
  • the water-bath cooling fiber is rolled into a tube;
  • the rolled fiber is then subjected to two super-stretching, drying, and shaping, and finally made into a finished fiber: super-stretching the first water-stretching, the temperature of the water bath is 80 °C ⁇ 95 °C, The stretching ratio is 5 to 10 times; the second pass is stretched with superheated steam, the steam temperature is 110 ° C to 130 ° C, the stretching ratio is 3 to 6 times; drying after super stretching, drying with hot air circulation, drying temperature It is 120 °C ⁇ 130 °C, and the tension is 1.1 ⁇ 1.2 times; then, after setting, the setting temperature is 130 °C ⁇ 145 °C, and the setting linear speed is 20 ⁇ 40 meters per minute; finally, the ultra-high molecular weight polyethylene finished fiber is made;
  • the fiber strength of the prepared ultra-high molecular weight polyethylene fiber is 15CN / dtex to 25CN / dtex, and the elongation at break is 5% to 8%.
  • a polyethylene having a weight average molecular weight of 121,500 and a Mw / Mn of 5.1 was taken out from a spinneret having a diameter of 0.8 mm and extruded at a rate of 0.5 g / min at a single hole at 270 ° C.
  • the extruded fiber passed through a 15 cm heat-retaining interval, and then was quenched and cooled at 20 ° C and 0.5 m / s, and wound up at a speed of 300 m / min.
  • the extruded yarn enters the post-drawing stage after being cooled by air.
  • the first-stage drawing temperature is 25 ° C, and the drawing is doubled.
  • the second-stage stretching temperature is 100 ° C, and the stretching is 7 times. After multi-stage stretching, the strength of the polyethylene fiber was 12.5 cN / dtex, and the modulus was 503 cN / dtex.
  • a high-density polyethylene having a weight-average molecular weight of 820,000 and a weight-average molecular weight to number-average molecular weight ratio of 2.5 was spun without adding any auxiliary agent. As a result, it was found that the melt viscosity was too high to allow uniform extrusion.
  • this method uses a single active site polyethylene with appropriate molecular weight and distribution to melt the polyethylene, and then adds a certain amount of auxiliary agent to the appropriate stretching process.
  • the polyethylene fiber obtained has excellent mechanical properties.
  • the low-molecular-weight polyethylene used in the comparative example and the melt-spun product of ultra-high-molecular-weight polyethylene fibers obtained by blending with modified masterbatch are far superior in cost and environmental protection to the preparation of ultra-high Method for high-strength and high-molecular-weight polyethylene fibers.

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Abstract

高强高模聚乙烯纤维的制备方法，将重均分子量为60万～120万，由单活性中心催化剂聚合得到的聚乙烯原料与助剂进行共混；共混物经过螺杆挤出机挤出聚乙烯未拉伸粗丝；未拉伸粗丝冷却后进入热甬道进行高温多级拉伸；对多级拉伸后的聚乙烯纤维进行收卷，得到拉伸强度25cN/dtex以上，拉伸模量900cN/dtex以上的聚乙烯纤维。与现有技术相比，所述制备方法生产工艺流程简单、环保节能，安全系数高，生产成本低。

Description

一种高强高模聚乙烯纤维的制备方法 技术领域
本发明属于高分子材料技术领域，尤其是涉及一种高强高模聚乙烯纤维的制备方法。
背景技术
随着科学技术突飞猛进的发展,工程技术界对特种纤维的需求在不断增长，高性能聚乙烯纤维具有轻质高强、使用周期长、耐磨、高强、耐湿、耐腐蚀等特性，而普遍用于拖曳绳、负力绳索、救捞绳、防切割手套等。同时，高性能聚乙烯纤维在军事上可以制成防护衣料、头盔、防弹材料等。高性能聚乙烯纤维的复合材料同样具有高强和极强的防撞击性能，在航空航天方面，适用于各种飞机的翼尖结构、飞船结构和浮标飞机等。在体育用品上，已经制成安全帽、滑雪板、帆轮板、钓竿、球拍及自行车、滑翔板、超轻量飞机零部件等。由于超高分子量聚乙烯纤维复合材料的生物相容性，在医用方面，也可用于牙托、假肢、医用手套等。
近几年，单活性中心催化剂聚合得到的窄分子量分布聚乙烯引起了行业内广泛关注。窄分子量分布的聚乙烯由于仅含有极少的低分子量部分，使其在性能上比传统齐格勒纳塔与铬系催化体系聚合得到的聚乙烯性能上了一个新台阶。而在高强纤维领域，较超高分子量聚乙烯更好的加工性能，使茂金属聚乙烯又展现出了其独特的一面。
目前对于聚乙烯纺丝的方法可以主要分为三大类：
第一类包括是中国专利CN200980146604、中国专利CN201410264678、国际申请公开号第W02005/066401A1、美国专利US430577等公开的以溶剂首先对高分子量聚乙烯进行溶胀溶解后，挤出成聚乙烯原丝。对原丝进行溶剂萃取干燥等步骤除去溶剂，最后进行多级拉伸，得到高强高模聚乙烯纤维。这类方法由于使用的原料分子量一般高于150万，因此所得到的聚乙烯纤维的强度较高，根据分子量的高低的不同，所得的聚乙烯纤维拉伸强度可达30cN/dtex以上。但是生产工艺复杂，成本较高，生产过程中溶剂的挥发回收等问题较难解 决，对环境影响较大。
第二类主要包括中国专利CN201010533593、中国专利CN201410416669、中国专利CN101230501A等公开的，将低分子量聚乙烯或聚乙烯改性母粒与超高分子量聚乙烯进行共混后熔融挤出纤维原丝，并进行多级拉伸得到聚乙烯纤维。该方法为了保证超高分子量聚乙烯的流动性，低分子量的聚乙烯及改性母粒添加量较大，重量比一般在5％～10％甚至更高，这些改性母粒也导致了成品力学性能上的缺陷，因此得到的纤维强度也并不高，通常为15～25cN/dtex。同时工艺流程也较复杂。
第三类主要包括美国专利USP4228118、中国专利CN03807737等使用重均分子量为30万以下的聚乙烯进行熔融挤出纺丝，该方法不用添加流动改性母粒或低分子量聚乙烯，但是由于分子量较低，同时后拉伸工艺的温度控制较低等问题，使其制得的纤维的力学性能也非常有限，强度都在15cN/dtex左右。
发明内容
本发明要解决的问题在于目前高强高模聚乙烯生产工艺复杂，生产成本较高，且对环境污染较大，而现有通过聚乙烯熔融纺丝的方法得到的制品的强度与模量普遍偏低，提供一种高强高模聚乙烯纤维的制备方法。
本发明的目的可以通过以下技术方案来实现：
一种高强高模聚乙烯纤维的制备方法，采用以下步骤：
(1)将重均分子量为60万～120万，由单活性中心催化剂聚合得到的聚乙烯原料与助剂进行共混；
(2)共混物经过螺杆挤出机挤出聚乙烯未拉伸粗丝；
(3)未拉伸粗丝冷却后进入热甬道进行高温多级拉伸；
(4)对多级拉伸后的聚乙烯纤维进行收卷，得到拉伸强度25cN/dtex以上，拉伸模量900cN/dtex以上的聚乙烯纤维。
所述聚乙烯原料重均分子量与数均分子量之比Mw/Mn＜3.0，千碳甲基数＜0.1。
所述助剂加入的重量不大于聚乙烯原料重量的2％。
所述助剂为抗氧剂与表面润滑剂的混合物，抗氧剂与表面润滑剂的重量比为1:1～1:5。
所述抗氧剂为2,6-二叔丁基对甲酚、3-(3,5-二叔丁基-4-羟基苯)丙酸十八烷基酯、四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯中的一种或几种。
所述表面润滑剂为钛酸酯类、氟橡胶类、硬脂酸盐类或铝酸酯类化合物中的一种或几种。
所述螺杆挤出机的螺杆从喂料段温度到出料温度控制为60℃～180℃，螺杆转速为10～90转/min，挤出口模的出丝孔直径为1～10mm。
所述未拉伸粗丝经空气冷却或冷却水冷却。
多级拉伸的总拉伸倍数为20～120倍，热甬道温度为130℃～145℃。
本发明是一种高强高模聚乙烯纤维的制备方法，通过单活性中心催化剂聚合得到的聚乙烯原料与助剂进行共混，在不使用溶剂的工艺下，制得高强高模聚乙烯纤维。
目前对高强高模聚乙烯纤维的制备方法普遍使用超高分子量聚乙烯，通过提高聚乙烯分子量，提升聚乙烯纤维性能。然而随着分子量增加，聚乙烯的加工性能大幅下降。通过在加工过程中引入大量溶剂，可增加其加工性能，而溶剂的引入则会带来制备成本的大幅增加及环保问题等一系列问题。
高分子量的分子链部分是影响加工性能的关键，本发明通过使用单活性中心催化剂聚合得到分子量低于120万的聚乙烯原料，大幅降低高分子量分子链含量，大幅提升聚乙烯的加工性能，只需极微量助剂即可进行高强高模聚乙烯纤维生产。
目前溶液纺丝使用的超高分子量聚乙烯主要以齐格勒纳塔催化体系聚合得到的超高分子量聚乙烯，聚合工艺一般使用釜式反应釜进行聚合，所得超高分子量聚乙烯分子量分布较宽。图1为茂金属聚乙烯与目前溶液纺丝使用齐格勒纳塔催化体系聚合得到的超高分子量聚乙烯分子量分布的对比图。虽然超高分子量聚乙烯分子量远高于茂金属聚乙烯，然而低分子量的分子链部分为削弱纤维力学性能的关键，见表2。这也是背景技术第二类纤维制品强度较低的主要原因之一。
本发明通过使用合理的分子量分布及分子量范围的聚乙烯原料，在添加不 影响制品性能的微量助剂的情况下，使聚乙烯分子量在可加工范围内达到最大化；将影响制品力学性能的低分子量部分最小化。基于以上基本原理，在高强高模聚乙烯纤维制备方法中体现优势如下：
1)纺丝过程中不需要使用溶剂，大幅简化高强高模聚乙烯纤维纺丝流程。
2)大幅降低由于处理溶剂及回收溶剂导致的生产成本。
3)生产过程中处于无溶剂状态，大幅提升了生产过程中的安全系数。
4)生产过程中无危废产生，使高强高模聚乙烯纤维生产过程更环保。
5)生产过程中无溶胀步骤，使生产过程更稳定。
6)制得的高强高模聚乙烯纤维制品力学性能远高于目前其他不使用溶剂进行纺丝制得的聚乙烯纤维。
附图说明
图1为超高分子量聚乙烯与单活性中心催化剂聚合得到的聚乙烯分子量及分布的对比。
具体实施方式
下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明，但不以任何形式限制本发明。应当指出的是，对本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进。这些都属于本发明的保护范围。
实施例中聚乙烯原料的表征数据由以下方法获得：
拉伸性能
采用《ASTM D885M》的方法与设备，对成品丝的拉伸强度以及拉伸模量进行测试。
实施例1
取重均分子量为60万，Mw/Mn为2.8，千碳甲基数＜0.1的聚乙烯与抗氧剂1010以99.8％与0.2％的比例加入混合釜共混3min后喂入双螺杆挤出机中。双螺杆从喂料段温度到出料温度为60℃～180℃，转速90转/min，挤出口模的孔径为2mm。
挤出的原丝通过水冷后进入后拉伸环节，第一级拉伸温度130℃，拉伸10倍。第二级拉伸温度为135℃，拉伸5倍。第三级拉伸温度为140℃，拉伸2倍。多级拉伸后得到聚乙烯纤维强度为26.39cN/dtex，模量为880cN/dtex。
实施例2
取重均分子量为80万，Mw/Mn为2.9，千碳甲基数＜0.1的聚乙烯与抗氧剂2,6-二叔丁基对甲酚及氟橡胶以99.6％与0.2％、0.2％的比例加入混合釜共混5min后喂入双螺杆挤出机中。双螺杆从喂料段温度到出料温度为60℃～180℃，转速80转/min，挤出口模的孔径为3mm。
挤出的原丝通过水冷后进入后拉伸环节，第一级拉伸温度131℃，拉伸12倍。第二级拉伸温度为136℃，拉伸5倍。第三级拉伸温度为141℃，拉伸2.5倍。多级拉伸后得到聚乙烯纤维强度为29.21cN/dtex，模量为920cN/dtex。
实施例3
取重均分子量为100万，Mw/Mn为2.5，千碳甲基数＜0.1的聚乙烯与抗氧剂1076及硬脂酸钙以99.4％与0.2％、0.4％的比例加入混合釜共混5min后喂入双螺杆挤出机中。双螺杆从喂料段温度到出料温度为60℃～180℃，转速60转/min，挤出口模的孔径为5mm。
挤出的原丝通过空气冷却后进入后拉伸环节，第一级拉伸温度132℃，拉伸15倍。第二级拉伸温度为136℃，拉伸5倍。第三级拉伸温度为142℃，拉伸2.5倍。多级拉伸后得到聚乙烯纤维强度为30.92cN/dtex，模量为980cN/dtex。
实施例4
取重均分子量为120万，Mw/Mn为2.9，千碳甲基数＜0.1的聚乙烯、抗氧剂1076、硬脂酸钙、硬脂酸锌、钛酸酯以99.1％与0.2％、0.2％、0.3％、0.4％的比例加入混合釜共混5min后喂入双螺杆挤出机中。双螺杆从喂料段温度到出料温度为60℃～180℃，转速20转/min，挤出口模的孔径为6mm。
挤出的原丝通过空气冷却后进入后拉伸环节，第一级拉伸温度132.5℃，拉伸16倍。第二级拉伸温度为138℃，拉伸6倍。第三级拉伸温度为145℃，拉伸4倍。多级拉伸后得到聚乙烯纤维强度为32.11cN/dtex，模量为1120cN/dtex。
对比例1
取重均分子量为11.5万，Mw/Mn为2.3的聚乙烯、1000个碳具有0.4个含 5个以上碳的长度的支链的高密度聚乙烯，由构成为φ0.8mm的喷丝头，290℃下，以单孔喷出量0.5g/min的度挤出。挤出纤维通过15cm的保温区间，之后以20℃、0.5m/s的淬火冷却，以300m/min速度收卷。
挤出的原丝通过空气冷却后进入后拉伸环节，第一级拉伸温度25℃，拉伸2.8倍。第二级拉伸温度为115℃，拉伸5.0倍。多级拉伸后得到聚乙烯纤维强度为18.0cN/dtex，模量为820cN/dtex。
对比例2
选用分子量为150～200万的超高分子量聚乙烯粉状树脂为原料,加3％～8％(重量比)聚乙烯改性母粒,经长径比1∶40螺杆熔融挤压纺丝及超倍拉伸获得高强度、高延伸的聚乙烯纤维,纤维强度为15CN/dtex～25CN/dtex,断裂伸长率5％～8％。
具体生产工艺实施步骤如下：
第一步聚乙烯改性母粒制备：
1.选用LDPE低密度聚乙烯或LLOPE线性低密度聚乙烯为原料,加(重量比)7％～15％的POE聚烯烃弹性体、3％～5％的发PE发泡剂,以及5％～10％的发三元乙丙橡胶EPDM或SEBS进行均匀混配；
2.将已均匀混配上述聚合物经双螺杆共混炼造粒：双螺杆各段温度在150～220℃之间,双螺杆转速控制在每分钟200～250转,制备成聚乙烯改性母粒。
其复配聚乙烯改性母粒具有熔点低、粘度低、润滑性、流动性好、易分散等优异功能。
第二步超高分子量聚乙烯熔融纺丝制备：
1.选用分子量为150～200万的超高分子量聚乙烯树脂,加3％～8％(重量比)的已复配的聚乙烯改性母粒均匀混合；
2.将上述混合料输送入螺杆挤压熔融纺丝：螺杆长径比为1∶40,螺杆各段温度为150℃～250℃,螺杆挤出速度为200～250转/分,喷丝板100～150孔,孔径0.5～0.8mm,喷丝熔体温度控制在200℃～220℃,喷头牵伸5～15m/分；喷出的初纤维经水浴冷却,水浴槽温度控制在20～25℃；水浴冷却纤维进行收卷成筒装；
3.再将已收卷成筒的纤维进行两道超倍拉伸、干燥、定型,最后制成成品纤维：超倍拉伸第一道用水浴拉伸,水浴温度为80℃～95℃,拉伸倍数为5～10倍； 第二道用过热蒸气拉伸,蒸气温度为110℃～130℃,拉伸倍数为3～6倍；超倍拉伸后干燥,使用热风循环干燥,干燥温度为120℃～130℃,张力为1.1～1.2倍；再经定型,定型温度130℃～145℃,定型线速度每分钟20～40米；最后制成超高分子量聚乙烯成品纤维；收卷。所制成的超高分子量聚乙烯纤维的纤维强力15CN/dtex～25CN/dtex,断裂伸长率为5％～8％。
对比例3
取重均分子量为12.15万，Mw/Mn为5.1的聚乙烯，由构成为φ0.8mm的喷丝头，270℃下，以单孔喷出量0.5g/min的度挤出。挤出纤维通过15cm的保温区间，之后以20℃、0.5m/s的淬火冷却，以300m/min速度收卷。
挤出的原丝通过空气冷却后进入后拉伸环节，第一级拉伸温度25℃，拉伸2倍。第二级拉伸温度为100℃，拉伸7倍。多级拉伸后得到聚乙烯纤维强度为12.5cN/dtex，模量为503cN/dtex。
对比例4
取重均分子量82万且重均分子量与数均分子量之比为2.5的高密度聚乙烯,不添加任何助剂进行纺丝，其结果发现由于熔融粘度过高，无法均匀挤出。
表1
Figure PCTCN2019098640-appb-000001
由上表可知，本方法通过使用合适分子量大小及分布的单活性中心聚乙烯熔融挤出后，添加一定量的助剂,以合适的拉伸工艺，制得的聚乙烯纤维在力学性能上优于对比例中使用的低分子量聚乙烯及通过与改性母粒共混得到超高分 子量聚乙烯纤维的熔融纺丝制品，而且在成本以及环保方面都远优于使用溶液溶解的方法制备超高分子量聚乙烯高强高模纤维的方法。
表2单活性中心高分子量聚乙烯与低分子量聚乙烯共混后溶液纺丝得到制品的力学性能对比(百分比为重量比)
HDPE(7万PD5.0) MPE(80万PD2.8) 拉伸强度(cN/dtex)
0％ 100％ 34.2
1％ 99％ 31.1
5％ 95％ 23.3
10％ 90％ 18.9
以上对本发明的具体实施例进行了描述。需要理解的是，本发明并不局限于上述特定实施方式，本领域技术人员可以在权利要求的范围内做出各种变形或修改，这并不影响本发明的实质内容。

Claims (10)

  1. 一种高强高模聚乙烯纤维的制备方法，其特征在于，该方法采用以下步骤：
    (1)将重均分子量为60万～120万，由单活性中心催化剂聚合得到的聚乙烯原料与助剂进行共混；
    (2)共混物经过螺杆挤出机挤出聚乙烯未拉伸粗丝；
    (3)未拉伸粗丝冷却后进入热甬道进行高温多级拉伸；
    (4)对多级拉伸后的聚乙烯纤维进行收卷，得到拉伸强度25cN/dtex以上，拉伸模量900cN/dtex以上的聚乙烯纤维。
  2. 根据权利要求1所述的一种高强高模聚乙烯纤维的制备方法，其特征在于，所述聚乙烯原料重均分子量与数均分子量之比Mw/Mn＜3.0，千碳甲基数＜0.1。
  3. 根据权利要求1所述的一种高强高模聚乙烯纤维的制备方法，其特征在于，所述助剂加入的重量不大于聚乙烯原料重量的2％。
  4. 根据权利要求1或3所述的一种高强高模聚乙烯纤维的制备方法，其特征在于，所述助剂为抗氧剂与表面润滑剂的混合物。
  5. 根据权利要求4所述的一种高强高模聚乙烯纤维的制备方法，其特征在于，所述抗氧剂为2,6-二叔丁基对甲酚、3-(3,5-二叔丁基-4-羟基苯)丙酸十八烷基酯、四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯中的一种或几种。
  6. 根据权利要求4所述的一种高强高模聚乙烯纤维的制备方法，其特征在于，所述表面润滑剂为钛酸酯类、氟橡胶类、硬脂酸盐类或铝酸酯类化合物中的一种或几种。
  7. 根据权利要求4所述的一种高强高模聚乙烯纤维的制备方法，其特征在于，所述抗氧剂与表面润滑剂的重量比为1:1～1:5。
  8. 根据权利要求1所述的一种高强高模聚乙烯纤维的制备方法，其特征在于，所述螺杆挤出机的螺杆从喂料段温度到出料温度控制为60℃～180℃，螺杆转速为10～90转/min，挤出口模的出丝孔直径为1～10mm。
  9. 根据权利要求1所述的一种高强高模聚乙烯纤维的制备方法，其特征在 于，所述未拉伸粗丝经空气冷却或冷却水冷却。
  10. 根据权利要求1所述的一种高强高模聚乙烯纤维的制备方法，其特征在于，多级拉伸的总拉伸倍数为20～120倍，热甬道温度为130℃～145℃。
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CN109306541A (zh) * 2018-09-14 2019-02-05 上海化工研究院有限公司 一种高强高模聚乙烯纤维的制备方法

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TWI819389B (zh) * 2020-10-08 2023-10-21 南韓商可隆股份有限公司 具有改善收縮率的高強度聚乙烯紗線以及其製造方法
CN115369519A (zh) * 2022-01-04 2022-11-22 东华大学 一种熔纺高性能聚乙烯纤维及其制备方法
CN115369519B (zh) * 2022-01-04 2024-04-26 东华大学 一种熔纺高性能聚乙烯纤维及其制备方法
CN115573054A (zh) * 2022-10-26 2023-01-06 宁波市旭马吊索工具有限公司 一种高强度吊装带纤维及其制备方法
CN116463746A (zh) * 2023-05-05 2023-07-21 盐城优和博新材料有限公司 一种高韧性高强聚乙烯复合纤维及生产方法

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