WO2013023432A1 - 一种高强度、高模量、高熔点pva纤维及其制造方法 - Google Patents

一种高强度、高模量、高熔点pva纤维及其制造方法 Download PDF

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Publication number
WO2013023432A1
WO2013023432A1 PCT/CN2012/000871 CN2012000871W WO2013023432A1 WO 2013023432 A1 WO2013023432 A1 WO 2013023432A1 CN 2012000871 W CN2012000871 W CN 2012000871W WO 2013023432 A1 WO2013023432 A1 WO 2013023432A1
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pva
modulus
strength
spinning
fiber
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PCT/CN2012/000871
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English (en)
French (fr)
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吴福胜
高祖安
李康荣
季学勇
崔明发
黄荣海
冯加芳
姜家保
陈思鹏
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安徽皖维高新材料股份有限公司
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Priority to EP12824445.6A priority Critical patent/EP2746434A4/en
Priority to BR112013016774A priority patent/BR112013016774A2/pt
Publication of WO2013023432A1 publication Critical patent/WO2013023432A1/zh

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    • 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
    • D01D1/00—Treatment of filament-forming or like material
    • D01D1/02—Preparation of spinning solutions
    • 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
    • D01D5/06—Wet 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
    • 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
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/14—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated alcohols, e.g. polyvinyl alcohol, or of their acetals or ketals

Definitions

  • the invention relates to a synthetic fiber and a preparation method thereof, in particular to a polyvinyl alcohol (PVA) fiber and a preparation method thereof, and more particularly to a high strength, high modulus, high melting point PVA fiber and a preparation method thereof.
  • PVA polyvinyl alcohol
  • PVA fibers are closely related to their properties such as strength, modulus and melting point. Fibers with a strength of 3 ⁇ 5CN/dtex, a modulus of 60 ⁇ 80CN/dtex, and an initial melting point of 85 ⁇ 90°C are mostly used for civil use; the strength is 10 ⁇ llCN/dtex, the modulus is 220 ⁇ 250CN/dtex, and the initial melting point is 10 (TC fiber). It is reinforced with general cement products; the PVA fiber with better performance is not only used for reinforcement of cement products, but also for reinforcement of high performance concrete, highway asphalt, plastic and rubber.
  • the PVA fiber can be produced by a conventional wet method, a dry-wet method, a gel method, a boron-containing wet method, or the like.
  • Ordinary wet method and dry-wet method have low fiber quality index, the strength is 3 ⁇ 5CN/dtex, the modulus is 60 ⁇ 80CN/dte X , and the initial melting point is 85 ⁇ 90 ⁇ . Because the initial melting point is low, the fiber must be treated by formalization to meet the requirements. Application requirements, this fiber is mainly used to replace cotton as a civilian raw material. With the rise of petrochemical industry, synthetic fibers such as polyester in the 1980s have developed rapidly.
  • PVA fiber Due to the inherent defects of PVA fiber, such as poor dyeability, low elasticity, poor dimensional stability, and poor scratchability, it is automatically withdrawn from the field of application.
  • the fiber is excellent in acid and alkali resistance, light resistance, weather resistance and corrosion resistance, and its application in the industrial field will be more extensive as long as there is a major breakthrough in strength and modulus.
  • PVA As a polymer material, PVA itself is a flexible chain polymer linear macromolecule with a planar sawtooth structure.
  • the theoretical strength and theoretical modulus of PVA are 210 CN/dtex and 1900 CN/dtex.
  • the spinning method is suitable, overcoming the excessive entanglement of the fibers during the initial molding process, the hydrogen bond can be excessively entangled.
  • the gel method and the boron-containing wet method can improve the PVA macromolecular entanglement at the initial stage of fiber formation.
  • the gel method has difficulties such as solvent recovery, and there is currently no large industrial device. In the existing boron-containing wet process, the average degree of polymerization is used? X
  • PVA resin 1700 PVA resin is used as raw material.
  • a certain amount of boron additive is added.
  • the total stretching ratio of fiber post-treatment is 10.0 ⁇ 11.0 times, the fiber strength is about llCN/dtex, and the modulus is 230 ⁇ 280CN/dtex.
  • the initial melting point is 100 ⁇ 103°C, but such products are difficult to meet the needs of special fields.
  • the present invention is directed to the deficiencies of the prior art and the needs of the application field, and aims to provide a bismuth strength, high modulus, high melting point PVA fiber, and the technical problem to be solved is to improve the boron-containing wet spinning manufacturing method, and further improve the nascent life.
  • the molecular structure of the fiber avoids the entanglement of PVA macromolecules at the initial stage of fiber formation to improve the quality of the PVA fiber.
  • the high-strength, high-modulus, high-melting PVA fiber referred to in the present invention refers to the strength ⁇ 13.5 CN / dtex, modulus PVA fiber ⁇ 320CN/dtex, initial melting point ⁇ 108 ⁇ .
  • the high-strength, high-modulus, high-melting PVA fiber is produced by a boron-containing gel wet spinning process, including preparation, filtration, defoaming, spinning and post-treatment of a spinning dope, and existing boron-containing wet
  • the difference between the spinning method is that the spinning dope is different from the spinning coagulation bath.
  • the spinning dope is prepared by using a PVA resin with an average polymerization degree of 1700-2000 and an additive of boric acid and copper sulfate in water at 90-100 ° C.
  • the spinning dope is prepared, and the PVA content in the spinning dope is 15-17 wt% (mass percentage, the same below), the boric acid (3 ⁇ 4B0 3 ) content is 1.2-1.6 wt%, and the copper sulfate (CuS0 4 ) content is 0.05-0.1 wt%;
  • the nascent fiber sprayed from the raw liquid through the spinneret enters a spinning coagulation bath (one bath) containing sodium hydroxide (NaOH) 15-50 g/L and sodium sulfate (Na 2 S0 4 ) 300. -390 g/L, H 3 B0 3 5-15 g/L.
  • the treatment after one bath is followed by the wet treatment with boron.
  • the method selects PVA with polymerization degree ⁇ 1700 as raw material, adjusts the content of H 3 B0 3 to 1.2-1.6wt% when preparing the spinning dope, and adds 0.05-0.1wt% CuSO 4 to make the kinematic viscosity of the spinning dope From the original 4-5Pa's to 6-8Pa s; when the nascent fiber is ejected at the spinneret, it immediately reacts with a specific coagulation bath to produce a gel, which means that the coagulation bath strengthens the gel effect of the nascent fiber.
  • the total draw ratio of fiber post-treatment was increased from the existing 10.0-11.0 times to 13.0-14.5 times.
  • the boron-containing gel wet spinning manufacturing method aims to improve the quality of the PVA fiber by improving the molecular structure of the nascent fiber and avoiding PVA macromolecular entanglement at the initial stage of fiber formation.
  • the invention produces a single boron-containing wet spinning method for PVA fibers, and extends to a boron-containing gel wet spinning method, thereby effectively increasing the total stretching ratio of the nascent fibers, and obtaining the PVA fiber strength and modulus.
  • the amount and melting point are obviously better than those of the PVA fiber obtained by the boron-containing wet spinning method.
  • the high-strength high-modulus PVA fiber produced by the method of the invention has a product with an average strength of ⁇ 13.5CN/dtex and a modulus of >320CN/dtex and an initial melting point of ⁇ 108 ⁇ .
  • Figure 1 is a process flow diagram of a process for producing PVA fibers of the present invention.
  • the process includes preparation, filtration, defoaming, spinning and post-treatment of the spinning dope.
  • the spinning dope is prepared by feeding, washing and dissolving.
  • the post-treatment described is neutralization, wet drawing, water washing, drying, preheating, high elongation, cooling, cutting, packing, and the like.
  • the parameter settings of the respective processes are as follows: Raw material PVA: polymerization degree 1700 ⁇ 2000, residual acetate 0.2 ⁇ 0.5%, sodium acetate 0.2-0.5% after washing; additive preparation: H 3 B0 3 1.2 ⁇ 1.6wt%, CuSO 4 0.05 ⁇ 0.1wt%;
  • Dissolution dissolution temperature 95 ⁇ 100°C, dissolution time 90 ⁇ 120 minutes, stock solution concentration 15 ⁇ 17wt%, kinematic viscosity 6 ⁇ 8Pa.s; defoaming: defoaming temperature 98 ⁇ 100'C, defoaming time 4 ⁇ 6 Hour
  • Neutralization, wet drawing Neutralization, wet drawing coagulation bath Na 2 SO 4 300 ⁇ 390g/l, H 2 SO 4 5 ⁇ 50g/l, wet heat stretching 2.0 ⁇ 2.8 times, wet heat stretching 80 ⁇ 95° C ;
  • Preheating and extension preheating temperature 210 ⁇ 235°C, extension dry stretching 2.0 ⁇ 4.0 times, extension temperature 210 ⁇ 235'C ;
  • Cooling The temperature of the tow after the cooling of the roller is 25 ⁇ 45°C.
  • Raw material PVA polymerization degree 1720, residual acetate 0.21%, sodium acetate 0.23% after washing; additive preparation: H 3 B0 3 1.35%, CuSO 4 0.05% ; dissolution: dissolution temperature 97 ° C, dissolution time 110 minutes, stock concentration 16.8%; defoaming: defoaming temperature 98 ° C, defoaming time 4 hours; spinning: spinning coagulation bath NaOH 18g / l, Na 2 SO 4 310g / l, H 3 BO 3 5.5g / l, negative in the bath Stretching -20.8%, spinning air bath stretching 2.08 times; Neutralization, wet drawing: Neutralization, wet drawing coagulation bath Na 2 SO 4 310g/l, H 2 S0 4 12g/l, wet heat stretching 2.3 Double, wet heat stretching 85 ° C; preheating, extension: preheating temperature 225 ° C, extended dry stretching 2.93 times, extended oven temperature 212 ° C ;
  • Example 1 The main technical quality indicators of PVA fiber are as follows:
  • Raw material PVA degree of polymerization 1820, residual acetate 0.35%, sodium acetate 0.2% after washing; additive preparation: H 3 B0 3 1.52%, CuSO 4 0.05%; Dissolution: dissolution temperature 98 ° C, dissolution time 120 minutes, stock solution concentration 16.0%; defoaming: defoaming temperature 98 ° C, defoaming time 4.5 hours; spinning: spinning coagulation bath NaOH 35g / l, Na 2 SO 4 330g / l, H 3 B0 3 6.5g / l, negative tensile - 30.8% in the bath, 2.08 times stretching in the spinning air bath; neutralization, wet drawing: neutralization, wet drawing coagulation bath Na 2 SO 4 330g / l, 3 ⁇ 4SO 4 40g / l, wet heat stretching 2.0 times, wet heat stretching 88 ° C ; preheating, stretching: preheating temperature 225 ° C, extended dry stretching 3.44 times, extended oven temperature 228 ° C
  • Example 2 The main technical quality indicators of PVA fiber are as follows:
  • Raw material PVA polymerization degree 1950, residual acetate 0.28%, sodium acetate 0.40% after washing; additive configuration: H 3 B0 3 1.25%, CuSO 4 0.08%; Dissolution: dissolution temperature 99 'C, dissolution time 120 minutes, stock concentration 15.8%; defoaming: defoaming temperature 99 ° C, defoaming time 5 hours; spinning: spinning coagulation bath NaOH 45g / L, Na 2 SO 4 330 g / L, H 3 B0 3 6g / L, negative in the bath Stretching -29.9%, spinning air bath stretching 2.06 times; Neutralization, wet drawing: Neutralization, wet drawing coagulation bath Na 2 SO 4 340 g / L, H 2 SO 4 50g / L, wet heat stretching 2.5 times, wet heat drawing 92 °C; preheating, extension: preheating temperature 230 ° C, extended dry stretching 2.8 times, extended oven temperature 220 ° C;
  • Example 3 The main technical quality indicators of PVA fiber are as follows:

Abstract

一种高强度、高模量、高熔点PVA纤维是由含硼凝胶湿法纺丝法制造的、强度≥13.5CN/dtex、模量≥320CN/dtex、初熔点≥108°C总拉伸倍数达13.0-14.5倍的PVA纤维。本产品性能优良，用途广泛，适用于高端工业领域的应用。还公开了该纤维的制造方法。

Description

一种高强度、 高模量、 高熔点 PVA纤维及其制造方法 一、技术领域
本发明涉及一种合成纤维及其制备方法， 特别涉及聚乙烯醇（PVA)纤维及其制备方法， 更具体地说是一种高强度、 高模量、 高熔点 PVA纤维及其制造方法。
二、 背景技术
PVA 纤维的用途与其性能如强度、 模量、 熔点密切相关。 强度 3~5CN/dtex、 模量 60~80CN/dtex、初熔点 85~90°C的纤维多用于民用；强度 10~llCN/dtex、模量 220~250CN/dtex、 初熔点 10(TC的纤维多用一般水泥制品增强； 更髙性能的 PVA纤维不仅用于水泥制品增强， 而且可用于高性能混凝土、 高速公路沥青、 塑料、 橡胶的增强。
PVA纤维的制造方法有普通湿法、 干湿法、 凝胶法、 含硼湿法等。 普通湿法及干湿法得 到纤维的质量指标低， 其强度 3~5CN/dtex、 模量 60~80CN/dteX、 初熔点 85~90Ό， 由于初熔 点低， 纤维必须经过缩甲醛处理才能满足应用要求， 此纤维主要用于代替棉花作民用原料。 随着石油化工的崛起， 80年代涤纶等合成纤维得到迅猛的发展， 由于 PVA纤维固有的缺陷， 如染色性差、 弹性低、 尺寸稳定性差、 挺刮性差等， 使其自动退出服用领域。 但该纤维耐酸 碱性、 耐光性、 耐气候性、 耐腐蚀性极佳， 只要强度、 模量上有重大的突破， 其在工业领域 的应用会更加广泛。
作为高分子材料 PVA本身是是柔性链聚合物线性大分子， 有平面锯齿型结构。 PVA的理 论强度和理论模量为 210 CN/dtex和 1900 CN/dtex， 只要纺丝方法适宜， 克服纤维在初期成型 过程中大分子之间氢键作用而发生过度的缠结现象，就可以进行高倍率拉伸， 从而得到强度、 模量更髙的纤维。 采用凝胶法、 含硼湿法可以改善纤维成型初期 PVA大分子缠结现象。 凝胶 法存在溶剂回收等困难，目前无大工业化装置。在已有的含硼湿法工艺中，使用平均聚合度？ X
=1700的 PVA树脂为原料， 在配制纺丝原液时添加一定量的硼添加剂， 纤维后处理总拉伸倍 数达 10.0~11.0倍， 纤维强度达 llCN/dtex左右、 模量 230~280CN/dtex、 初熔点 100~103°C， 但这样的产品还难以满足特殊领域的需求。
三、 发明内容
本发明针对现有技术的不足以及应用领域的需求， 旨在提供一种髙强度、 高模量、 高熔 点 PVA纤维， 所要解决的技术问题是改进含硼湿法纺丝制造方法， 进一步改善初生纤维的分 子结构， 避免纤维成型初期 PVA大分子缠结， 以提高 PVA纤维品质。
本发明所称的高强度、 高模量、 高熔点 PVA 纤维是指强度≥13.5CN/dtex、 模量 ≥320CN/dtex、 初熔点≥108Ό的 PVA纤维。
本高强度、 高模量、 高熔点 PVA纤维的制造方法是含硼凝胶湿法纺丝法， 包括纺丝原液 的制备、 过滤、 脱泡、 纺丝和后处理， 与现有含硼湿法纺丝法的区别是纺丝原液和紡丝凝固 浴不同， 所述的纺丝原液的制备是选用平均聚合度 1700-2000的 PVA树脂以及添加剂硼酸和 硫酸铜于 90-100°C的水中配制纺丝原液， 纺丝原液中 PVA含量 15-17wt% (质量百分比， 下 同）、 硼酸（¾B03)含量 1.2-1.6wt%、 硫酸铜 (CuS04)含量 0.05-0.1wt%； 纺丝原液经喷丝 头喷出的初生纤维进入纺丝凝固浴 （一浴）， 所述的纺丝凝固浴中含氢氧化钠 （NaOH) 15-50g/L、硫酸钠（Na2S04) 300-390g/L、 H3B035-15g/L。一浴以后的处理同含硼湿法后处理。
本方法选用聚合度≥1700 的 PVA 为原料， 在配制纺丝原液时调整了 H3B03的含量为 1.2-1.6wt%, 同时添加了 0.05-0.1wt%CuSO4， 使纺丝原液运动粘度由原来的 4-5Pa's提高到 6-8Pa s; 当初生纤维在喷丝头喷出瞬间， 立即与特定的凝固浴反应产生凝胶， 也就是说本凝 固浴强化了初生纤维的凝胶效应， 同时弱化了初生纤维的凝固作用， 使纤维成型初期 PVA大 分子缠结现象明显减少， 而耦合几率大大增加。 纤维后处理总拉伸倍数由现有的 10.0-11.0倍 提高到 13.0-14.5倍。
本含硼凝胶湿法纺丝制造方法通过改善初生纤维的分子结构、避免纤维成型初期 PVA大 分子缠结实现提高 PVA纤维品质的发明目的。
与己有含硼湿法纺丝法相比， 本发明有益效果体现在：
1、 本发明将 PVA纤维制造单一的含硼湿法纺丝方法， 延伸到含硼凝胶湿法纺丝方法， 从而有效地提高了初生纤维总拉伸倍数， 制得的 PVA纤维强度、 模量、 熔点明显优于含硼湿 法纺丝方法得到的 PVA纤维质量。
2、 利用本发明方法所生产的高强高模 PVA 纤维,其平均强度≥13.5CN/dtex、 模量 >320CN/dtex 初熔点≥108Ό的产品。
四、 附图说明
图 1是本发明 PVA纤维制造方法的工艺流程图。
五、 具体实施方式
结合附图， 非限定实施例叙述如下：
本工艺流程包括纺丝原液的配制、 过滤、 脱泡、 纺丝和后处理。
所述的纺丝原液的配制即图中投料、 水洗和溶解。
所述的后处理即图中中和、 湿牵伸、 水洗、 干燥、 预热、 高倍延伸、 冷却、 切断、 打包 等。
所述各工序的参数设置分别为： 原料 PVA: 聚合度 1700~2000、 残余醋酸根 0.2~0.5%、 水洗后醋酸钠 0.2-0.5%； 添加剂配制： H3B031.2~1.6wt%、 CuSO40.05~0.1wt%;
溶解：溶解温度 95~100°C、溶解时间 90~120分钟、原液浓度 15~17wt%、运动粘度 6~8Pa.s; 脱泡： 脱泡温度 98~100'C、 脱泡时间 4~6小时；
纺丝： 纺丝凝固浴 NaOH15~50g/l、 Na2SO4300~390g/K H3B035~15 g/K 浴中负拉伸 -15~ -40%、 纺丝空气浴拉伸 2~3倍；
中和、湿牵伸： 中和、湿牵伸凝固浴 Na2SO4300~390g/l、 H2SO45~50g/l、湿热拉伸 2.0~2.8 倍、 湿热拉伸 80~95°C ;
水洗： 软水温度 30~45°C ;
预热、 延伸： 预热温度 210〜235°C、 延伸干拉伸 2.0~4.0倍、 延伸温度 210~235'C ;
冷却： 罗拉冷却后的丝束温度 25~45°C。
实施例 1 :
原料 PVA: 聚合度 1720、 残余醋酸根 0.21%、 水洗后醋酸钠 0.23%; 添加剂配制： H3B031.35%、 CuSO40.05%; 溶解： 溶解温度 97°C、 溶解时间 110分钟、 原液浓度 16.8%;脱 泡:脱泡温度 98°C、脱泡时间 4小时；纺丝：纺丝凝固浴 NaOH18g/l、Na2SO4310g/l、H3BO35.5g/l、 浴中负拉伸 -20.8%、纺丝空气浴拉伸 2.08倍； 中和、湿牵伸： 中和、湿牵伸凝固浴 Na2SO4310g/l、 H2S0412g/l、 湿热拉伸 2.3倍、 湿热拉伸 85°C ; 预热、 延伸： 预热温度 225°C、 延伸干拉伸 2.93倍、 延伸烘箱温度 212°C ;
实施例 1PVA纤维主要技术质量指标如下:
Figure imgf000005_0001
实施例 2:
原料 PVA: 聚合度 1820、 残余醋酸根 0.35%、 水洗后醋酸钠 0.2%; 添加剂配制: H3B031.52%、 CuSO40.05%; 溶解： 溶解温度 98°C、 溶解时间 120分钟、 原液浓度 16.0%; 脱泡： 脱泡温度 98°C、 脱泡时间 4.5小时； 纺丝： 纺丝凝固浴 NaOH35g/l、 Na2SO4330g/l、 H3B036.5g/l、 浴中负拉伸 -30.8%、 纺丝空气浴拉伸 2.08倍； 中和、 湿牵伸： 中和、 湿牵伸凝固 浴 Na2SO4330g/l、 ¾SO440g/l、湿热拉伸 2.0倍、湿热拉伸 88°C ; 预热、延伸：预热温度 225°C、 延伸干拉伸 3.44倍、 延伸烘箱温度 228°C；
实施例 2PVA纤维主要技术质量指标如下:
Figure imgf000006_0001
实施例 3:
原料 PVA: 聚合度 1950、 残余醋酸根 0.28%、 水洗后醋酸钠 0.40%; 添加剂配置： H3B031.25%、 CuSO40.08%; 溶解： 溶解温度 99 'C、 溶解时间 120分钟、 原液浓度 15.8%; 脱泡： 脱泡温度 99°C、 脱泡时间 5小时； 纺丝： 纺丝凝固浴 NaOH45g/L、 Na2SO4330 g/L、 H3B036g/L、 浴中负拉伸 -29.9%、 纺丝空气浴拉伸 2.06倍； 中和、 湿牵伸： 中和、 湿牵伸凝固 浴 Na2SO4340 g/L、H2SO450g/L、湿热拉伸 2.5倍、湿热拉伸 92 °C ;预热、延伸：预热温度 230°C、 延伸干拉伸 2.8倍、 延伸烘箱温度 220 °C ;
实施例 3PVA纤维主要技术质量指标如下:
指标名称 单位 指标
断裂强度 CN/dtex 14.01
難 CN/dtex 348.33
初熔温度 °C 111.23
纤度 dtex 2.01
伸长率 % 6.08

Claims

一种高强度、高模量、高熔点 PVA纤维，其特征在于：本 PVA纤维强 ≥13.5CN/dtex、 模量≥320CN/dtex、 初熔点≥108°C。
2、 一种如权利要求 1所述的高强度、 高模量、 高熔点 PVA纤维的制造方法， 包括 PVA 纺丝原液制备、 过滤、 脱泡、 纺丝和后处理， 其特征在于： 所述的纺丝原液的制备是选用平 均聚合度 1700-2000的 PVA树脂以及添加剂硼酸和硫酸铜于 90-100°C的水中配制纺丝原液， 纺丝原液中 PVA含量 15-17wt%、 硼酸含量 1.2-1.6wt%、 硫酸铜含量 0.05-0.1wt%； 纺丝凝固 浴中含氢氧化钠 15-50g/L、 硫酸钠 300-390g/L、 硼酸 5-15g/L。
PCT/CN2012/000871 2011-08-18 2012-06-25 一种高强度、高模量、高熔点pva纤维及其制造方法 WO2013023432A1 (zh)

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