WO2010066095A1

WO2010066095A1 - Conductive macromolecule resin and sheath-core composite structure dyeable antistatic fiber

Info

Publication number: WO2010066095A1
Application number: PCT/CN2009/001349
Authority: WO
Inventors: 黄哲军
Original assignee: 苏州贤聚新材料科技有限公司
Priority date: 2008-12-08
Filing date: 2009-11-30
Publication date: 2010-06-17
Also published as: CN101434739A; CN101434739B

Abstract

A conductive macromolecule resin comprises (weight percent) polyether ester amide (10-60), base resin (30-80), and salt (more than 0-10). The base resin is polybutylene terephthalate, polyethylene terephthalate, polypropylene terephthalate, polyamide, polypropylene, polyether ester, polyethylene and/or polyacrylonitrile. The salt comprises lithium bis(trifluoromethylsulfonyl)imide, lithium 1,1,1-trifluoro-C-[(trifluoromethyl)sulfonyl]methanesulfonamide, lithium perchlorate, lithium trifluoromethanesulfonate, lithium tetrafluoroborate, sodium tetrafluoroborate, sodium triflate, lithium bis(trifluoromethanesulfonyl)imide, sodium 1,1,1-trifluoro-C-[(trifluoromethyl)sulfonyl]methanesulfonamide, sodium perchlorate, potassium borofluoride, potassium perchlorate, potassium hexafluoroborate, potassium perfluorobutanylsulfonate, calcium perchlorate, calcium hexafluoroborate, calcium trifluoromethanesulfonate, zinc perchlorate, magnesium perchlorate and/or magnesium trifluoromethanesulfonate. A sheath-core composite structure dyeable antistatic fiber comprises (weight percent) skin layer (5-50), and core layer (50-95), where the skin layer is the conductive macromolecule resin and the core layer is polybutylene terephthalate, polyethylene terephthalate, polypropylene terephthalate, polyamide, polypropylene, polyether ester, polyethylene and/or polyacrylonitrile.

Description

一种导电高分子树脂以及皮芯复合结构可染色抗静电纤维技术领域 Conductive polymer resin and sheath-core composite structure capable of dyeing antistatic fiber

本发明属于高分子合成纤维技术领域，具体涉及一种导电高分子树脂以及由该树脂制得的一种皮芯复合结构可染色抗静电纤雉。 The invention belongs to the technical field of polymer synthetic fibers, and particularly relates to a conductive polymer resin and a sheath-core composite structure prepared from the resin, which can dye antistatic fibers.

背景技术 Background technique

聚对苯二曱酸丁二醇酯（ polybutylene terephthalate, PBT )、聚对苯二曱酸乙二醇酯（ polyethylene terephthalate， PET )、聚对苯二曱酸丙二醇酯 ( polytrimethylene terephthalate , PTT )、聚酰胺（Polyamide , PA )、聚丙烯 ( polypropylene , PP )、聚醚酯（ Polyetherester， PEET )、聚醚酰胺 ( Polyetheramide> PEA )、聚醚酯酰胺（ Polyetheresteramide, PEEA )、聚乙烯 ( polyethylene, PE )、聚丙烯腈（ polyacrylonitrile, PAN )等纤维是目前广泛使用的合成纤维，但普遍存在的缺点是: 本身并不抗静电，需要经过后期处理才能获得抗静电性能，而通过后处理的合成歼维，抗静电性能并不持久，在多次洗涤之后很容易丧失抗静电性能。 Polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), poly Amide (Polyamide, PA), polypropylene (polypropylene, PP), polyetherester (PEET), polyetheramide (PEA), polyetheresteramide (PEEA), polyethylene (polyethylene) Polyacrylonitrile (PAN) and other fibers are widely used synthetic fibers, but the common disadvantages are: they are not antistatic, they require post-treatment to obtain antistatic properties, and the post-treatment synthetic Antistatic properties are not durable and it is easy to lose antistatic properties after repeated washings.

目前实现耐久抗静电人造纤维的方法主要有以下两种方法： a、授权公告号为 CN1103384C, 名称为《有色聚丙烯超细旦抗静电纤维的制造方法》的中国发明专利，公开了一种将导电碳黑和金属衍生物添加到基础树脂中制备抗静电纤维的方法，其核心是利用导电炭黑和金属衍生物连成网络的导电机理，制成导电碳纤维和金属氧化物抗静电纤维，有皮芯结构、异型海岛结构等； b、将碳纳米管材料添加到合成纤维中制备的碳纳米管抗静电纤维，碳纳米管抗静电纤维有皮芯结构、异型海岛结构或者是单一结构等。上述两种人造纤维共同的缺点是：一、由于在基础树脂中填充了无机材料，可纺性能由此大大降低, 并且在纺丝过程中，无机材料易堵塞纺丝组件（喷嘴），纺丝难度加大，成本增加。二、采用导电碳黑或碳纳米管的抗静电纤维颜色单一，只有黑色或灰色两种，应用受到限制；采用导电金属氧化物的抗静电纤维，虽然可以^:成彩色，但是成本偏高，纺丝难度大。三、织成的服装在穿着过程中，有可能出现掉碳粉或导电粉的问题，无法满足严格的无尘室要求，不能满足电子工业、石油化工等需要防尘、防静电、防爆服装的工业部门对防尘的要求。此外，由于颜色和成本以及纤维强度的制约，现有的抗静电纤维也难以在普通化纤面料上大量应用，目前只能局限在羊毛面料、地毯等有限领域的小规模应用。 At present, the methods for realizing durable antistatic rayon have the following two methods: a. The authorization publication number is CN1103384C, and the Chinese invention patent entitled "Manufacturing Method of Colored Polypropylene Superfine Antistatic Fiber" discloses a kind of A method for preparing an antistatic fiber by adding conductive carbon black and a metal derivative to a base resin, the core of which is to form a conductive carbon fiber and a metal oxide antistatic fiber by using a conductive mechanism in which a conductive carbon black and a metal derivative are connected into a network. The core structure, the special-shaped island structure, etc.; b. The carbon nanotube antistatic fiber prepared by adding the carbon nanotube material to the synthetic fiber, the carbon nanotube antistatic fiber has a sheath core structure, a hetero-island structure or a single structure. The disadvantages of the above two kinds of rayon fibers are as follows: 1. Since the inorganic resin is filled in the base resin, the spinnability is greatly reduced, and in the spinning process, the inorganic material easily blocks the spinning assembly (nozzle), and is spun. The difficulty is increased and the cost is increased. Second, the antistatic fiber using conductive carbon black or carbon nanotubes has a single color, only black or gray, and the application is limited; the antistatic fiber using conductive metal oxide, although it can be colored, but the cost is high, Spinning is difficult. Third, the woven garments may have the problem of toner or conductive powder in the process of wearing, unable to meet the strict clean room requirements, and can not meet the needs of dust, anti-static and explosion-proof clothing for the electronics industry and petrochemical industry. The dust requirements of the industrial sector. In addition, due to color and cost and fiber strength constraints, existing antistatic fibers are also difficult to apply in a large number of common chemical fiber fabrics, and currently can only be limited to small-scale applications in limited fields such as wool fabrics and carpets.

发明内容本发明提供一种导电高分子树脂以及由该树脂制得的一种皮芯复合结构可染色抗静电纤雉，目的是解决现有的抗静电纤维的抗静电性能不持久、' H 难度大的问题。 Summary of the invention The invention provides a conductive polymer resin and a sheath-core composite structure prepared from the resin, which can dye antistatic fiber reinforced fiber, and aims to solve the problem that the antistatic property of the existing antistatic fiber is not durable, and the H is difficult. problem.

为达到上述目的，本发明采用的技术方案是：一种导电高分子树脂，主要由下列质量百分含量的原料组成： In order to achieve the above object, the technical solution adopted by the present invention is: A conductive polymer resin mainly composed of the following mass percentages of raw materials:

. 聚醚酯酰胺 10 % ~ 60 %； Polyether ester amide 10% ~ 60%;

基础树脂 30 % ~ 80 %； Base resin 30% ~ 80%;

盐大于 0, 小于或等于 10 % ; Salt is greater than 0, less than or equal to 10%;

其中,所述基础树脂至少选择以下材料中的一种：聚对苯二曱酸丁二醇酯、聚对苯二曱酸乙二醇酯、聚对苯二曱酸丙二醇酯、聚酰胺、聚丙婦、聚醚酯、聚乙埽和聚丙烯腈； Wherein, the base resin selects at least one of the following materials: polybutylene terephthalate, polyethylene terephthalate, propylene terephthalate, polyamide, polypropylene Women, polyether esters, polyethyl hydrazine and polyacrylonitrile;

所述盐至少选择以下材料中的一种：双（三氟曱基磺酰基）酰亚胺锂 ( Li(CF₃S0₂)₂N )、 1,1,1-三氟 -C-[(三氟曱基）磺酰基）曱磺酰胺]锂盐 ( Li(CF₃S0₂)₂C )、高氯酸锂（LiC10₄ )、三氟曱磺酸锂（ LiCF₃S0₃ )、四氟硼酸锂（ LiBF₄ )、四氟硼酸钠 ( NaBF₄ )、三氟曱磺酸钠（ NaCF₃S0₃ )、双 (三氟曱基磺酰基)酰亚胺锂（Na(CF₃S0₂)₂N )、 1,1,1-三氟 -C- [(三氟曱基)磺酰基)曱磺酰胺]钠盐（ Na(CF₃S0₂)₂C )、高氯酸钠（NaC10₄ )、四氟硼酸鉀（KBF₄ )、高氯酸钾（KC10₄ )、六氟硼酸钾（KPF₆ )、全氟丁基磺酸钾（KC₄F₉S0₃ )、高氯酸钙（Ca(C10₄)₂ )、六氟硼酸钙（Ca(PF₆)₂ )、三氟曱磺酸钙（ Ca(CF₃S0₃)₂ )、高氯酸锌（ Zn(C10₄)₂ )、高氯酸镁（Mg(C10₄)₂ )、三氟曱磺酸镁（ Mg(CF₃S0₃)₂ )。 The salt is selected from at least one of the following materials: lithium bis(trifluoromethylsulfonyl)imide (Li(CF ₃ S0 ₂ ) ₂ N ), 1,1,1-trifluoro-C-[( Trifluoromethylsulfonyl) sulfonamide amide] lithium salt (Li(CF ₃ S0 ₂ ) ₂ C ), lithium perchlorate (LiC10 ₄ ), lithium trifluoromethanesulfonate (LiCF ₃ S0 ₃ ), tetrafluoro Lithium borate (LiBF ₄ ), sodium tetrafluoroborate (NaBF ₄ ), sodium trifluorosulfonate (NaCF ₃ S0 ₃ ), lithium bis(trifluorodecylsulfonyl)imide (Na(CF ₃ S0 ₂ )) ₂ N ), 1,1,1-trifluoro-C-[(trifluoromethylsulfonyl) sulfonamide] sodium salt (Na(CF ₃ S0 ₂ ) ₂ C ), sodium perchlorate (NaC10 ₄ ), potassium tetrafluoroborate (KBF ₄ ), potassium perchlorate (KC10 ₄ ), potassium hexafluoroborate (KPF ₆ ), potassium perfluorobutyl sulfonate (KC ₄ F ₉ S0 ₃ ), calcium perchlorate (Ca ( C10 ₄ ) ₂ ), calcium hexafluoroborate (Ca(PF ₆ ) ₂ ), calcium trifluoroantimonate (Ca(CF ₃ S0 ₃ ) ₂ ), zinc perchlorate (Zn(C10 ₄ ) ₂ ), high Magnesium chlorate (Mg(C10 ₄ ) ₂ ), magnesium trifluoroantimon sulfonate (Mg(CF ₃ S0 ₃ ) ₂ ).

为达到上述目的，本发明采用的技术方案是：一种皮芯复合结构可染色抗静电纤维，由下列质量百分含量的皮层和芯层构成： In order to achieve the above object, the technical solution adopted by the present invention is: A sheath-core composite structure dyeable antistatic fiber, which is composed of the following mass percentage of skin layer and core layer:

皮层 5 ~ 50 %； Cortex 5 ~ 50%;

芯层 50 - 95 %； Core layer 50 - 95%;

其中，皮层为权利要求 1中所述的导电高分子树脂；所述芯层至少选择以下材料中的一种：聚对苯二曱酸丁二醇酯、聚对苯二曱酸乙二醇酯、聚对苯二曱酸丙二醇酯、聚酰胺、聚丙烯、聚醚酯、聚乙烯和聚丙烯腈。 Wherein, the skin layer is the conductive polymer resin described in claim 1; and the core layer is selected from at least one of the following materials: polybutylene terephthalate, polyethylene terephthalate , poly(trimethylene terephthalate), polyamide, polypropylene, polyetherester, polyethylene and polyacrylonitrile.

上述技术方案中的有关内容解释如下： The relevant content in the above technical solutions is explained as follows:

1、上述方案中，所述聚醚酯酰胺是醚、酯和酰胺的多嵌段共聚物，是一种热塑性弹性体。热塑性弹性体是既具有弹性体的性能：回弹性和吸收能量，又有热塑材料的易加工性。一种高分子材料要有以上两种特性，至少具有两种不同类型的长链段组成，这两种不同的链段在固态时可以分相，一种链段应具有较低的玻璃化转变温度和低熔点，一般称作软链段，在室温下软链段形成类似液体的相, 从而提供高分子弹性，另一组分称为硬链段，能产生分子间的締合或结晶而形成一个可逆的网状结构，由这种締合所形成的物理交联提供材料尺寸稳定性和较少冷流（***、郭凡修，聚醚酯和聚醚酯酰胺多嵌段共聚物的电子显微镜研究 [J], 电子显微学报， 1983.2， 1_4)。 1. In the above scheme, the polyether ester amide is a multi-block copolymer of an ether, an ester and an amide, and is a thermoplastic elastomer. Thermoplastic elastomers are properties that have both elastomeric properties: resilience and energy absorption, as well as ease of processing of thermoplastic materials. A polymer material has the above two characteristics, and has at least two different types of long-chain segments. The two different segments can be phase-separated in the solid state, and one segment should have a lower glass transition. Temperature and low melting point, generally referred to as soft segments, forming soft segments at room temperature a liquid-like phase that provides polymer elasticity, and another component, called a hard segment, that produces intermolecular association or crystallization to form a reversible network structure, a physical crosslink formed by such association Provide material dimensional stability and less cold flow (Zhu Lilan, Guo Fanxiu, polyether ester and polyether ester amide multi-block copolymer electron microscopy [J], Journal of Chinese Electron Microscopy, 1983.2, 1_4).

2、上述方案中，所述的导电高分子树脂， .主要由下列质量百分含量的原料组成： 2. In the above scheme, the conductive polymer resin is mainly composed of the following mass percentages of raw materials:

聚醚酯酰胺 30% 50%; Polyether ester amide 30% 50%;

基础树脂 45% 65 %； Base resin 45% 65 %;

0.1% -7%。 0.1% -7%.

3、上述方案中由下列质量百分含量的皮层和芯层构成: 3. In the above scheme, the following mass percentages of the skin layer and the core layer are formed:

皮层 15~50%； Cortex 15~50%;

芯层 50~85%。 The core layer is 50~85%.

4、上述方案中由下列质量百分含量的皮层和芯层构成： 4. In the above scheme, the following mass percentages of the skin layer and the core layer are formed:

皮层 35 ~ 45 %； Cortex 35 ~ 45%;

芯层 55 - 65 % Core layer 55 - 65 %

5、上述方案中所述聚醚酯酰胺具有硬链段聚酰胺段，以及软链段聚醚和聚酯結构，聚酰胺段是 PA6， PA11, PA12的低聚物。 5. The polyetheresteramide of the above scheme has a hard segment polyamide segment, and a soft segment polyether and polyester structure, and the polyamide segment is an oligomer of PA6, PA11, PA12.

由于上述技术方案运用，本发明与现有技术相比具有下列优点和效果： Due to the above technical solutions, the present invention has the following advantages and effects compared with the prior art:

1、本发明制造的皮芯复合结构可染色抗静电纤维, 强度高，容易染色，抗静电效果好，抗静电性能永久有效。本发明和各种人造纤维混纺容易，可制得各种手感优良的抗静电织物，大大扩大化纤织物的应用范围。 1. The sheath-core composite structure produced by the invention can dye antistatic fibers, has high strength, is easy to dye, has good antistatic effect, and has antistatic property for permanent and effective. The invention is easy to blend with various rayon fibers, can produce various antistatic fabrics with excellent hand feeling, and greatly expands the application range of the chemical fiber fabric.

2、本发明区别于以往抗静电纤维的一个显著特征是：采用有机导电高分子树脂，并掺杂盐，将盐溶解于聚醚酯酰胺中，形成配位络合，实现纯塑料聚合物导电，这完全不同于以往抗静电纤维依靠无机粉体导电的机理。 2. A distinguishing feature of the present invention which is different from the conventional antistatic fiber is that: an organic conductive polymer resin is used, and a salt is doped, and the salt is dissolved in the polyether ester amide to form a coordination complex to realize conduction of the pure plastic polymer. This is completely different from the mechanism by which antistatic fibers rely on inorganic powders to conduct electricity.

3、本发明的纤维基本是由纯的高分子树脂组成，因此成纤性^好，强度高，外观和手感上与普通化纤基本一样，抗静电效果几乎不受环境温湿度影响，并且易于织造和染色，在服装、无纺布、填充棉、地毯、人造头发、毛线衣等领域都非常适用。皮芯复合结构抗静电纤维的表面电阻率约 10⁶~ ΙΟ^Ω/ τ^ 附图说明 3. The fiber of the invention is basically composed of pure polymer resin, so the fiber forming property is good, the strength is high, the appearance and the hand feeling are basically the same as the ordinary chemical fiber, the antistatic effect is hardly affected by the environment temperature and humidity, and the weaving is easy. And dyeing, very suitable in the fields of clothing, non-woven fabrics, filled cotton, carpets, artificial hair, sweaters, etc. The surface resistivity of the anti-static fiber of the core-sheath composite structure is about 10 ⁶ ~ ΙΟ ^ Ω / τ ^

附图 1为皮芯复合结构可染色抗静电纤维中的圆形结构示意图； 1 is a schematic view showing a circular structure in a skin-core composite structure dyeable antistatic fiber;

附图 2为皮芯复合结构可染色抗静电纤维中的多芯形结构示意图 2 is a schematic view of a multi-core structure in a skin-core composite structure dyeable antistatic fiber;

附图 3为皮芯复合结构可染色抗静电纤维中的海岛形结构示意图 Figure 3 is a schematic view of a sea-island structure in a skin-core composite structure dyeable antistatic fiber.

附图 4为皮芯复合结构可染色抗静电纤维中的半月形结构示意图附图 5为皮芯复合结构可染色抗静电纤维的扫描电镜图。 Figure 4 is a schematic view of a half-moon structure in a skin-core composite structure dyeable antistatic fiber. Figure 5 is a scanning electron micrograph of a skin-core composite structure dyeable antistatic fiber.

具体实施方式 detailed description

下面结合附图及实施例对本发明作进一步描述: The present invention is further described below in conjunction with the accompanying drawings and embodiments:

实施例一：一种导电高分子树脂以及由该树脂制得的一种皮芯复合结构可染色抗静电纤维 Embodiment 1: A conductive polymer resin and a sheath-core composite structure made of the resin can dye antistatic fibers

一种导电高分子树脂，由下列质量百分含量的原料组成： A conductive polymer resin consisting of the following mass percentages of raw materials:

聚醚酯酰胺 15 % ; Polyether ester amide 15 % ;

基础树脂 76 % ; Basic resin 76 % ;

盐 2 % ; 2 % salt ;

紫外线吸收剂氯代苯并***（ UV-326 ) 3 % ; UV absorber chlorobenzotriazole ( UV-326 ) 3 % ;

钙锌复合热稳定剂 4 %。 Calcium-zinc composite heat stabilizer 4%.

基础树脂选取聚对苯二曱酸丁二醇酯（ PBT ), 其粘度 VI值为 0.8, 盐选择双（三氟曱基磺酰基）酰亚胺锂，将双（三氟曱基磺酰基）酰亚胺锂 ( Li(CF₃S0₂)₂N )溶解于聚醚酯酰胺，形成配位络合。 The base resin is selected from polybutylene terephthalate (PBT), and its viscosity VI value is 0.8. The salt is selected from lithium bis(trifluoromethylsulfonyl)imide, and bis(trifluoromethylsulfonyl) Lithium imide (Li(CF ₃ S0 ₂ ) ₂ N ) is dissolved in the polyether ester amide to form a coordination complex.

将皮层和芯层分别按照下列质量百分含量的配比制备成四种皮芯复合结构可染色抗静电纤维： The skin layer and the core layer were respectively prepared into four kinds of sheath-core composite structures for dyeing antistatic fibers according to the following mass percentage ratios:

皮层分别选取 20 %、 30 %、 40 %和 50 %； The cortex is selected as 20%, 30%, 40% and 50% respectively;

芯层对应选取 80 %、 70 % ; 60 %和 50 % ; The core layer is 80 % , 70 % , 60 % and 50 % ;

其中，皮层为导电高分子树脂；芯层选择聚对苯二甲酸丁二醇酯（PBT )。皮芯复合结构可染色抗静电纤维的制备方法如下：， Wherein, the skin layer is a conductive polymer resin; and the core layer is selected from polybutylene terephthalate (PBT). The preparation method of the skin-core composite structure dyeable antistatic fiber is as follows:

步骤①、以 PBT基础树脂为芯层原料，经第一螺杆挤出机熔融后，经计量泵计量后输送到复合纺丝箱体中，进一步分配到复合组件，成为皮芯结构纤维的芯层。 Step 1. The PBT base resin is used as the core material, and after being melted by the first screw extruder, it is metered by the metering pump and then transported to the composite spinning box, and further distributed to the composite component to become the core layer of the sheath core structure fiber. .

步骤②、以有机导电高分子树脂为皮层原料，经第二螺杆挤出机熔融后，经计量泵计量后输送到复合纺丝箱体中，进一步分配到复合组件，成为皮芯结构纤维的皮层。 Step 2: using an organic conductive polymer resin as a skin material, melting through a second screw extruder, measuring by a metering pump, transporting it to a composite spinning box, and further distributing the composite component to a skin layer of the sheath core structure fiber .

步骤③、将复合组件中的双组份熔体挤出，熔融丝线经过冷却、预牵伸处理、定型，得到皮芯复^^结构的抗静电纤维。基础树脂 PBT和有机导电高分子树脂先干燥，可以用真空干燥或者热风干燥，使其含水量降至 0. 03 %以下，再进入各自的熔融螺杆。皮层纺丝温度设定为 250°C，芯层纺丝温度设定为 270 °C。制成的纤维如附图 1所示，皮层 2完全包住芯层 1。扫描电镜图如附图 2 所示。 Step 3. The two components in the composite assembly are melt extruded, and the molten wire is subjected to cooling, pre-draw processing, and shaping to obtain an antistatic fiber having a sheath-core structure. The base resin PBT and the organic conductive polymer resin are dried first, and may be dried by vacuum drying or hot air to reduce the water content to less than 0.03%, and then enter the respective molten screws. The skin spinning temperature was set to 250 ° C and the core spinning temperature was set to 270 ° C. The resulting fiber is as shown in Fig. 1, and the skin layer 2 completely encases the core layer 1. The scanning electron microscope image is shown in Figure 2.

皮芯复合结构抗静电纤维加工成牽伸丝的方法可选自常规低速纺丝 -拉伸法、高速纺-拉伸法等加工工艺。 The method for processing the anti-static fiber of the sheath-core composite structure into the drawn yarn may be selected from the conventional low-speed spinning-drawing Stretching, high-speed spinning-stretching and other processing techniques.

改变皮芯结构不同的质量比，得到抗静电纤维，测量结果如下表: The anti-static fibers were obtained by changing the mass ratio of the core-sheath structure. The measurement results are as follows:

本发明制得的以 PBT作为芯层的抗静电纤维成型良好，具有优异的抗静电特性，拉伸强度，以及可染色。 . The antistatic fiber obtained by the present invention using PBT as a core layer is well formed, has excellent antistatic properties, tensile strength, and dyeability. .

实施例二：一种导电高分子树脂以及由该树脂制得的一种皮芯复合结构可染色抗静电纤维 Embodiment 2: A conductive polymer resin and a sheath-core composite structure made of the resin can dye the antistatic fiber

聚醚酯酰胺 57%; Polyether ester amide 57%;

基础树脂 36%; 金属粉 4%。 Base resin 36%; metal powder 4%.

基础树脂选取聚对苯二曱酸丁二醇酯（PBT), 其粘度 VI值为 0.8，盐选择三氟曱磺酸钙 ( Ca(CF₃S0₃)₂ )和高氯酸辞（Zn(C10₄)₂), 两者之间的质量比例为 1： 1, 将三氟曱磺酸钙（Ca(CF₃S0₃)₂)和高氯酸锌（Zn(C10₄)2)溶解于聚醚酯酰胺，形成配位络合。 The base resin is selected from polybutylene terephthalate (PBT), and its viscosity VI value is 0.8. The salt is selected from calcium trifluorosulfonate (Ca(CF ₃ S0 ₃ ) ₂ ) and perchloric acid (Zn ( C10 ₄ ) ₂ ), the mass ratio between the two is 1: 1, dissolving calcium trifluoromethanesulfonate (Ca(CF ₃ S0 ₃ ) ₂ ) and zinc perchlorate (Zn(C10 ₄ ) 2 ) The polyether ester amide forms a coordination complex.

将皮层和芯层分别按照下列质量百分舍量的配比制备成四种皮芯复合结构可染色抗静电纤维： The skin layer and the core layer were prepared into four kinds of sheath-core composite structures for dyeing antistatic fibers according to the following mass ratios:

皮层分别选取 20%、 30%、 40%和 50%; The cortex is selected 20%, 30%, 40% and 50% respectively;

芯层对应选择 80%、 70% ; 60%和 50%; The core layer corresponds to 80%, 70%; 60% and 50%;

其中，皮层为导电高分子树脂；芯层选择聚对苯二曱酸乙二醇酯（PET )。皮'芯复合结构可染色抗静电纤维制备方法：同实施例一，皮层纺丝温度设定为 255°C，芯层纺丝温度设定为 285 °C。制成的纤维如附图 2所示，皮层 2 完全包住多个芯层 1。 Wherein, the skin layer is a conductive polymer resin; and the core layer is selected from polyethylene terephthalate (PET). The preparation method of the dyed core composite structure dyeable antistatic fiber: In the same manner as in the first embodiment, the skin spinning temperature was set to 255 ° C, and the core spinning temperature was set to 285 ° C. The resulting fiber is as shown in Fig. 2, and the skin layer 2 completely encases the plurality of core layers 1.

改变皮芯结构不同的质量比，抗静电纤维，测量结果如下表: Change the different mass ratio of the core structure, antistatic fiber, the measurement results are as follows:

本发明制得的以 PET为芯层的抗静电纤维成型良好，具有优异的抗静电特性，拉伸强度, 以及可染色。 The antistatic fiber with PET core layer prepared by the invention has good shape and excellent antistatic property. Properties, tensile strength, and dyeability.

实施例三：一种导电高分子树脂以及由该树脂制得的一种皮芯复合结构可染色抗静电纤维 Embodiment 3: A conductive polymer resin and a sheath-core composite structure made of the resin can dye antistatic fibers

聚醚酯酰胺 55%; Polyether ester amide 55%;

基础树脂 44%; Basic resin 44%;

盐 1 %； Salt 1%;

基础树脂选取聚酰胺 ( PA6 )和聚丙烯（ PP )、两者之间的质量比例为 2： 1,其粘度 VI值为 0.8,盐选择高氯酸锂（LiC10₄)、三氟曱磺酸锂（LiCF₃S0₃)、四氟硼酸俚 ( LiBF₄ )、双 (三氟曱基磺酰基)酰亚胺锂（ Na(CF₃S0₂)₂N ), 1,1,1- 三氟 -C- [(三氟曱基）磺酰基）曱磺酰胺]钠盐（Na(CF₃S0₂)₂C)、高氯酸钠 (NaC10₄)，六者之间的质量比例为 1 : 1 : 2 : 1.5： 3： 0.5，将盐的混合物溶解于聚醚酯酰胺，形成配位络合。 The base resin is selected from polyamide (PA6) and polypropylene (PP). The mass ratio between the two is 2:1, and the viscosity VI is 0.8. The salt is selected from lithium perchlorate (LiC10 ₄ ), trifluoromethanesulfonic acid. Lithium (LiCF ₃ S0 ₃ ), lanthanum tetrafluoroborate (LiBF ₄ ), lithium bis(trifluoromethylsulfonyl)imide (Na(CF ₃ S0 ₂ ) ₂ N ), 1,1,1-trifluoro -C- [(Trifluoromethyl)sulfonyl) sulfonamide] sodium salt (Na(CF ₃ S0 ₂ ) ₂ C), sodium perchlorate (NaC10 ₄ ), the mass ratio between the six is 1: 1 : 2 : 1.5: 3: 0.5, a mixture of salts is dissolved in a polyether ester amide to form a coordination complex.

芯层对应选择 80%、 70%; 60%和 50%; The core layer corresponds to 80%, 70%; 60% and 50%;

其中，皮层为导电高分子树脂；芯层选择聚酰胺（PA6)。 Wherein, the skin layer is a conductive polymer resin; and the core layer is selected from a polyamide (PA6).

皮芯复合结构可染色抗静电纤维制备方法：同实施例一，皮层纺丝温度设定为 260°C，芯层纺丝温度设定为 275 °C。制成的纤维如附图 3所示, 芯层 1 形如半岛形镶嵌在皮层 2上。 The preparation method of the anti-static fiber for the sheath-core composite structure: In the same manner as in the first embodiment, the skin spinning temperature is set to 260 ° C, and the core spinning temperature is set to 275 ° C. The resulting fiber is as shown in Fig. 3, and the core layer 1 is shaped like a peninsula embedded in the skin layer 2.

本发明制得的以 PA6 为芯层的抗静电纤维成型良好，具有优异的抗静电特性，拉伸强度，以及可染色。 - 实施例四：一种导电高分子树脂以及由该树脂制得的一种皮芯复合结构可染色抗静电纤维 The antistatic fiber with PA6 as the core layer prepared by the invention has good shape, excellent antistatic property, tensile strength, and dyeability. - Embodiment 4: A conductive polymer resin and a sheath-core composite structure made of the resin can dye the antistatic fiber

聚醚酯酰胺 49%; Polyether ester amide 49%;

基础树脂 41%; ACR-201 (曱基丙烯酸酯与丙烯酸酯共聚物） 1 %。 Basic resin 41%; ACR-201 (methacryl acrylate and acrylate copolymer) 1%.

基础树脂选取聚丙烯（PP),其熔融指数为 50。盐选择高氯酸钠（NaC10₄)、四氟硼酸钾（KBF₄)、高氯酸钟（KC10₄)、六氟硼酸鉀（KPF₆), 四者之间的质量比例为 5： 1： 2： 1.5： 0.5, 将盐的混合物溶解于聚醚酯酰胺，形成配位络合。 The base resin was selected from polypropylene (PP) having a melt index of 50. The salt is selected from sodium perchlorate (NaC10 ₄ ), potassium tetrafluoroborate (KBF ₄ ), perchloric acid clock (KC10 ₄ ), and potassium hexafluoroborate (KPF ₆ ). The mass ratio between the four is 5: 1: 2: 1.5: 0.5, a mixture of salts is dissolved in a polyether ester amide to form a coordination complex.

其中，皮层为导电高分子树脂；芯层选择聚对苯二曱酸乙二醇酯（PET) 和聚丙烯（PP)，两者之间的质量比例为 1： 3。 The skin layer is a conductive polymer resin; the core layer is selected from polyethylene terephthalate (PET) and polypropylene (PP), and the mass ratio between the two is 1:3.

皮芯复合结构可染色抗静电纤维制备方法: 同实施例一，皮层纺丝温度设定为 265°C, 芯层纺丝温度设定为 280°C。制成的纤维如附图 4所示, 芯层 1 形如半月形镶嵌在皮层 2上。 The preparation method of the anti-static fiber for the sheath-core composite structure: In the same manner as in the first embodiment, the skin spinning temperature is set to 265 ° C, and the core spinning temperature is set to 280 ° C. The resulting fiber is as shown in Fig. 4, and the core layer 1 is formed in the shape of a half moon on the skin layer 2.

本发明制得的以聚丙烯（PP) 为芯层的抗静电纤维成型良好，具有优异的抗静电特性，拉伸强度，以及可染色。 The antistatic fiber made of polypropylene (PP) as a core layer of the present invention is well formed, has excellent antistatic properties, tensile strength, and dyeability.

实施例五：一种导电高分子树脂以及由该树脂制得的一种皮芯复合结构可染色抗静电纤维 Embodiment 5: A conductive polymer resin and a sheath-core composite structure made of the resin can dye the antistatic fiber

聚醚酯酰胺 25%; Polyether ester amide 25%;

基础树脂 63 %； Basic resin 63%;

盐 . . 6%; Salt . . 6%;

抗氧化剂 1010 (四季戊四醇酯） 4%; Antioxidant 1010 (four seasons pentaerythritol ester) 4%;

着色剂（钛白粉） 2%。 Colorant (titanium dioxide) 2%.

基础树脂选取聚对苯二曱酸丙二醇酯（PTT), 粘度值为 0.8。盐选择高氯酸锂（ LiC10₄ )、四氟硼酸锂 ( LiBF₄ )、三氟曱磺酸钠（ NaCF₃S0₃ ), 三者之间的质量比例为 1 : 1 : 2，将盐的混合物溶解于聚醚酯酰胺，形成配位络合。然后，将皮层和芯层分别按照下列质量百分含量的配比制备成四种皮芯复合结构可染色抗静电纤维： The base resin was selected from poly(trimethylene terephthalate) (PTT) and had a viscosity of 0.8. The salt is selected from lithium perchlorate (LiC10 ₄ ), lithium tetrafluoroborate (LiBF ₄ ), sodium trifluorosulfonate (NaCF ₃ S0 ₃ ), and the mass ratio between the three is 1: 1: 2, the salt will be The mixture is dissolved in a polyether ester amide to form a coordination complex. Then, the skin layer and the core layer are respectively prepared into four kinds of sheath-core composite structure dyeable antistatic fibers according to the following mass percentage ratios:

芯层对应选择 80 %、 70 %； 60 %和 50 %； The core layer corresponds to 80%, 70%; 60% and 50%;

其中，皮层为导电高分子树脂；芯层选择聚对苯二曱酸丙二醇酯（PTT)。皮芯复合结构可染色抗静电纤维制备方法：同实施例一,皮层纺丝温度设定为 250°C, 芯层纺丝温度设定为 270°C。 Wherein, the skin layer is a conductive polymer resin; and the core layer is selected from polypropylene terephthalate (PTT). The core-sheath composite structure dyeable antistatic fiber preparation method: In the same manner as in the first embodiment, the skin spinning temperature is set to 250 ° C, and the core spinning temperature is set to 270 ° C.

改变皮芯结构不同的质量比，得到抗静电纤维，测量结果如下表： The anti-static fibers were obtained by changing the mass ratio of the core-sheath structure. The measurement results are as follows:

本发明制得的以聚对苯二曱酸丙二醇酯（PTT)为芯层的抗静电纤维成型良好，具有优异的抗静电特性，拉伸强度，以及可染色。 The antistatic fiber obtained by the present invention having a polybutylene terephthalate (PTT) as a core layer is well formed, has excellent antistatic properties, tensile strength, and dyeability.

实施例六：一种导电高分子树脂以及由该树脂制得的一种皮芯复合结构可染色抗静电纤维 Embodiment 6: a conductive polymer resin and a sheath-core composite structure made of the resin, which can dye antistatic fibers

聚醚酯酰胺 37%; Polyether ester amide 37%;

^出树脂 ' 59%; ^Resin '59%;

盐 4%; Salt 4%;

其中，所述基础树脂选择：聚对苯二曱酸丁二醇酯（polybutylene terephthalate， PBT )、聚对苯二曱酸乙二醇酯（ polyethylene terephthalate , PET )、聚对苯二曱酸丙二醇酯（ polytrimethylene terephthalate, PTT )，三者'之间的质量比例为 3 : 2 : 5。 Wherein, the base resin is selected from: polybutylene terephthalate (PBT), polyethylene terephthalate (PET), poly(trimethylene terephthalate) (polytrimethylene terephthalate, PTT), the mass ratio between the three is 3: 2: 5.

所述盐选择三氟曱磺酸钠（NaCF₃S0₃)、 1,1,1-三氟 -C- [(三氟甲基)磺酰基）曱磺酰胺]钠盐（Na(CF₃S0₂)₂C)、高氯酸钠（NaC10₄)、四氟硼酸钾（KBF₄)、高氯酸钾（KC10₄)、全氟丁基磺酸 4甲（KC₄F₉S0₃)、高氯酸钙（Ca(C10₄)₂)、六氟硼酸 4弓（Ca(PF₆)₂ )、高氯酸镁（Mg(C10₄)₂),九种盐之间的质量比例为 7： - 2 ： 5： 1 ： 1 ： 2 ： 1.5： 3： 6。 The salt is selected from sodium trifluorosulfonate (NaCF ₃ S0 ₃ ), 1,1,1-trifluoro-C-[(trifluoromethyl)sulfonyl) sulfonamide] sodium salt (Na(CF ₃ S0) ₂ ) ₂ C), sodium perchlorate (NaC10 ₄ ), potassium tetrafluoroborate (KBF ₄ ), potassium perchlorate (KC10 ₄ ), perfluorobutylsulfonic acid 4 (KC ₄ F ₉ S0 ₃ ), high chlorine Calcium acid (Ca(C10 ₄ ) ₂ ), hexafluoroborate 4 bow (Ca(PF ₆ ) ₂ ), magnesium perchlorate (Mg(C10 ₄ ) ₂ ), the mass ratio between the nine salts is 7: - 2 : 5: 1 : 1 : 2 : 1.5: 3: 6.

一种皮芯复合结构可染色抗静电纤维，由下列质量百分含量的皮层和芯层构成： A sheath-core composite structure capable of dyeing antistatic fibers consisting of the following mass percent skin and core layers:

皮层 30%; Cortex 30%;

芯层 70%; 其中，皮层为导电高分子树脂；所述芯层选择聚对苯二曱酸丁二醇酯、聚对苯二曱酸乙二醇酯和聚对苯二曱酸丙二醇酯，三者之间的质量比例为 3 : 1 : 7。 . Core layer 70%; Wherein, the skin layer is a conductive polymer resin; the core layer is selected from the group consisting of polybutylene terephthalate, polyethylene terephthalate and polypropylene terephthalate. The mass ratio is 3:1: 7. .

实施例七:一种导电高分子树脂以及由该树脂制得的一种皮芯复合结构可染色抗静电纤维 Embodiment 7: a conductive polymer resin and a sheath-core composite structure made of the resin, which can dye antistatic fibers

聚醚酯酰胺 32%; Polyether ester amide 32%;

基础树脂 67.7%; Basic resin 67.7%;

盐 0.3 %； Salt 0.3%;

其中，所述基础树脂选择：聚丙烯、聚乙烯和聚丙烯腈，三者之间的质量比例为 ·2： 2.5： 1.5。用聚乙二醇与己二酸反应合成聚醚酯，再用聚醚酯与己内酰胺反应得到聚醚酯酰胺。 Wherein, the base resin is selected from the group consisting of polypropylene, polyethylene and polyacrylonitrile, and the mass ratio between the three is 2: 2.5: 1.5. The polyether ester is synthesized by reacting polyethylene glycol with adipic acid, and the polyether ester is reacted with caprolactam to obtain a polyether ester amide.

所述盐选择高氯酸钙（Ca(C10₄)₂)、六氟硼酸 4弓（Ca(PF₆)₂)、三氟曱磺酸钙（ Ca(CF₃S0₃)₂ )、三氟曱磺酸镁（Mg(CF₃S0₃)₂)，四种盐之间的质量比例为 7： 2： 1· 5： 4。 The salt is selected from calcium perchlorate (Ca(C10 ₄ ) ₂ ), hexafluoroborate 4 (Ca(PF ₆ ) ₂ ), calcium trifluoromethanesulfonate (Ca(CF ₃ S0 ₃ ) ₂ ), trifluoro Magnesium sulfonate (Mg(CF ₃ S0 ₃ ) ₂ ), the mass ratio between the four salts is 7: 2: 1· 5: 4.

一种皮芯复合结构可染色抗静电纤维，由下列质量百分含量的皮层和芯层构成: A sheath-core composite structure capable of dyeing antistatic fibers consisting of the following mass percent skin and core layers:

皮层 40%; , Cortex 40%;

芯层 60%; Core layer 60%;

其中，皮层为导电高分子树脂；所述芯层选择以下材料中的一种：聚丙埽、聚乙烯和聚丙烯腈，三者之间的质量比例为 1.5： 2： 5。釆用聚己内酰胺（PA6) 和聚乙二醇（PEG)嵌段共聚反应制备聚醚酯酰胺（PEEA)。 Wherein, the skin layer is a conductive polymer resin; the core layer is selected from one of the following materials: polypropylene, polyethylene and polyacrylonitrile, and the mass ratio between the three is 1.5:2:5. Polyether ester amide (PEEA) was prepared by block copolymerization of polycaprolactam (PA6) and polyethylene glycol (PEG).

上述实施例只为说明本发明的技术构思及特点，其目的在于让熟悉此项技术的人士能够了解本发明的内容并据以实施，并不能以此限制本发明的保护范围。凡根据本发明精神实质所作的等效变化或修饰，都应涵盖在本发明的保护范围之内。 The above embodiments are merely illustrative of the technical concept and the features of the present invention, and the purpose of the present invention is to enable those skilled in the art to understand the present invention and to implement the present invention. Equivalent variations or modifications made in accordance with the spirit of the invention are intended to be included within the scope of the invention.

Claims

权禾 iJ 要求书 Quanhe iJ request

1、一种导电高分子树脂，其特征在于: 主要由下列质量百分含量的原料组成二 1. A conductive polymer resin, characterized in that: mainly composed of the following mass percentages of raw materials

聚醚酯酰胺 10% ~60%； Polyether ester amide 10% ~ 60%;

基础树脂 30% ~80%； Basic resin 30% ~ 80%;

盐大于 0，小于或等于 10%; Salt is greater than 0, less than or equal to 10%;

其中，所述基础树脂至少选择以下材料中的一种：聚对苯二曱酸丁二醇酯、聚对苯二曱酸乙二醇酯、聚对苯二曱酸丙二醇酯、聚酰胺、聚丙烯、聚醚酯、聚乙烯和聚丙烯腈; Wherein, the base resin selects at least one of the following materials: polybutylene terephthalate, polyethylene terephthalate, propylene terephthalate, polyamide, poly Propylene, polyetherester, polyethylene and polyacrylonitrile;

所述盐至少选择以下材料中的一种：双（三氟曱基磺酰基）酰亚胺锂、 1,1,1- 三氟 -C- [ (三氟曱基）磺酰基）曱磺酰胺]锂盐、高氯酸锂、三氟曱磺酸锂、四氟硼酸锂、四氟硼酸钠、三氟曱磺酸钠、双（三氟曱基磺酰基）酰亚胺锂、 1,1,1- 三氟 -C- [ (三氟曱基)磺酰基）曱磺酰胺]钠盐、高氯酸钠、四氟硼酸钾、高氯酸钾、六氟硼酸钾、全氟丁基磺酸钾、高氯酸钙、六氟硼酸钙、三氟曱磺酸钙、高氯酸锌、高氯酸镁和三氟曱磺酸镁。 The salt is selected from at least one of the following materials: lithium bis(trifluorodecylsulfonyl)imide, 1,1,1-trifluoro-C-[(trifluoromethylsulfonyl)sulfonamide Lithium salt, lithium perchlorate, lithium trifluorosulfonate, lithium tetrafluoroborate, sodium tetrafluoroborate, sodium trifluorosulfonate, lithium bis(trifluorodecylsulfonyl)imide, 1,1 , 1-trifluoro-C-[(trifluoromethylsulfonyl)sulfonamide] sodium salt, sodium perchlorate, potassium tetrafluoroborate, potassium perchlorate, potassium hexafluoroborate, potassium perfluorobutanesulfonate , calcium perchlorate, calcium hexafluoroborate, calcium trifluoroantimonate, zinc perchlorate, magnesium perchlorate and magnesium triflate.

2、根据权利要求 1所述的导电高分子树脂，其特征在于：主要由下列质量百分含量的原料组成： The conductive polymer resin according to claim 1, which is mainly composed of the following raw materials of a mass percentage:

聚醚酯酰胺 30% ~50%； Polyether ester amide 30% ~ 50%;

基础树脂 45 % ~ 65 %； Base resin 45 % ~ 65 %;

盐 0.1% ~7 %。 Salt 0.1% ~ 7%.

3、一种皮芯复合结构可染色抗静电纤维，其特征在于：由下列质量百分含量的皮层和芯层构成： 3. A sheath-core composite structure for dyeing an antistatic fiber, characterized by: a skin layer and a core layer having the following mass percentages:

皮层 5~50%； Cortex 5~50%;

芯层 . 50~95%； Core layer. 50~95%;

其中，皮层为权利要求 1中所述的导电高分子树脂；所述芯层至少逸择以下材料中的一种：聚对苯二曱酸丁二醇酯、聚对苯二曱酸乙二醇酯、聚对苯二曱酸丙二醇酯、聚酰胺、聚丙浠、聚醚酯、聚乙烯和聚丙埤腈。 Wherein, the skin layer is the conductive polymer resin described in claim 1; the core layer is at least one of the following materials: polybutylene terephthalate, polyethylene terephthalate Ester, poly(trimethylene terephthalate), polyamide, polypropylene, polyetherester, polyethylene and polyacrylonitrile.

4、根据权利要求 3所述的皮芯复合结构可染色抗静电纤维，其特征在于：由下列质量百分含量的皮层和芯层构成： The sheath-core composite structure dyeable antistatic fiber according to claim 3, which is characterized by: a skin layer and a core layer having the following mass percentages:

皮层 15~50%； Cortex 15~50%;

芯层 50~85%。 The core layer is 50~85%.

5、根据权利要求 3所述的皮芯复合结构可染色抗静电纤维，其特征在于：由下列质量百分含量的皮层和芯层构成：皮层 . 35~45%； The sheath-core composite structure dyeable antistatic fiber according to claim 3, which is characterized by: a skin layer and a core layer having the following mass percentages: Cortex. 35~45%;

芯层 · 55~65 % ₀ Core layer · 55~65 % ₀

6、根据权利要求 3所述的皮芯复合结构可染色抗静电纤维，其特征在于: 所述导电高分子树脂主要由下列质量百分含量的原料组成： The sheath-core composite structure dyeable antistatic fiber according to claim 3, wherein the conductive polymer resin is mainly composed of the following mass percentages of raw materials:

聚醚酯酰胺 30% ~50%； Polyether ester amide 30% ~ 50%;

基础树脂 45% ~65%； Base resin 45% ~ 65%;

盐 0.1% ~7%。 Salt 0.1% ~ 7%.