CN1092224C - 抗静电组合物 - Google Patents
抗静电组合物 Download PDFInfo
- Publication number
- CN1092224C CN1092224C CN97118459A CN97118459A CN1092224C CN 1092224 C CN1092224 C CN 1092224C CN 97118459 A CN97118459 A CN 97118459A CN 97118459 A CN97118459 A CN 97118459A CN 1092224 C CN1092224 C CN 1092224C
- Authority
- CN
- China
- Prior art keywords
- multipolymer
- composition
- acid
- polymkeric substance
- butyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 238000002156 mixing Methods 0.000 claims abstract description 36
- 150000003839 salts Chemical class 0.000 claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 29
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- 150000002148 esters Chemical class 0.000 claims description 44
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 39
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- 239000011159 matrix material Substances 0.000 claims description 24
- 229920000620 organic polymer Polymers 0.000 claims description 23
- 239000002861 polymer material Substances 0.000 claims description 20
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 19
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- 239000004800 polyvinyl chloride Substances 0.000 claims description 17
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 17
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0075—Antistatics
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/10—Metal compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/095—Carboxylic acids containing halogens
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
- C08K5/42—Sulfonic acids; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
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Abstract
本发明涉及一种包含热塑性或弹性聚合物基质(A)和紧邻纤维形式的抗静电混合物(B)的组合物,所述混合物包含一种为纤维状或混合时形成纤维的有机聚合材料(b1);一种能离子导电的聚合物或共聚物(b2);和一种无机或低分子量有机质子酸的盐(b3)。本发明还涉及抗静电混合物(B)本身,涉及其使聚合物抗静电的用途,以及一种制备抗静电的热塑性或弹性聚合物基质的方法。
Description
本发明涉及一种包含热塑性或弹性聚合物基质(A)和紧邻纤维形式的抗静电混合物(B)的组合物,所述混合物包含一种为纤维状或混合时形成纤维且不溶于热塑性或弹性聚合物基质(A)中的有机聚合材料(b1);一种具有用于配合或溶剂化无机或低分子量有机质子酸的盐(b3)的嵌段且与为纤维状或混合时形成纤维的有机聚合物(b1)的相容性比与聚合有机基质(A)的相容性要好的能离子导电的聚合物或共聚物(b2);和一种已在聚合物或共聚物(b2)中配合或溶剂化的无机或低分子量有机质子酸的盐(b3)。本发明还涉及抗静电混合物(B)本身,涉及其使聚合物抗静电的用途,以及一种制备抗静电的热塑性或弹性聚合物基质的方法。
已知聚合物易遭受强的静电荷且这些电荷一旦被施加上仅能缓慢释放,因为聚合物的导电性低。快速放电不仅因美观原因而且在许多情况下因安全原因而需要。使用中的不利效果可列举如下:聚合物表面的沾污,对接触聚合物的人的电击,膜状料粘附对生产的破坏,电子元件的损坏,聚合物粉末的成块,以及电荷太高引起的火花,随之而来的着火,这经常引起严重的***。
已知通过添加改进表面导电性的添加剂来限制静态充电,但这类物质的缺点是当大气湿度低时在实践中无效。因此更好的是使用大气湿度低时有效的添加剂,这通常可通过增加单位体积导电率而达到。然而用于增加单位体积导电率的已知物质如炭黑或金属粉末改变聚合物的机械性能且不能用于透明聚合物。此外,对生态上可接受的添加剂的需求正日益增加。
关于抗静电添加剂和静态充电机理的详情例如可在“塑料添加剂手册”,R.Gchter和H.Müller编,Hanser Verlag,第三版,1990,第749-775页中找到。
为了使材料永久抗静电,DE-A-4324062已建议用半导体无色材料如氧化锡涂覆表面积大的材料如纤维。然后将涂覆的材料与聚合物颗粒掺混并加工。然而涂料的制备复杂,因为半导体混合物必须通过用盐的水溶液浸渍纤维状载体,随后干燥并热调节沉积的盐而制备。施于纤维上的化学品和加热工可能损坏纤维,这导致导电率比从半导体的导电率所期望的要低。另一缺点是纤维因机械应力而弯曲,脆性半导体涂层可能受损,因而也削弱导电率。
另一可能性描述于DE-A-4316607中,该专利建议将市售的金属化合成纤维加入润滑剂、粘合剂或涂料中,从而增加其导电率。然而金属化纤维较为昂贵且生产复杂,并且显著降低掺有它们的聚合物的透明性。此外,不能完全避免对导电层以及甚至对纤维的机械损伤(断裂)。
在EP-A-0613919中,建议将某些聚醚酯酰胺用作热塑性聚合物的抗静电添加剂。在具体的实施方案中,还可加入碱金属或碱土金属卤化物。还建议加入在热塑性基质和聚醚酯酰胺之间提供相容性的聚合物,为的是改善粘合和机械性能。在这里所建议的赋予聚合物抗静电性的方法中,聚合物的相容性和良好的混溶性似乎是重要的性能。
鉴于以上对赋予聚合物抗静电性的已知方法的限制,仍然需要一种在低大气湿度下有效的用于增加单位体积导电率的抗静电活性、生态上适用的添加剂体系,该体系的生产简单,易于掺入聚合物中或与其混合,长时间保留所达到的聚合物单位体积导电率,且可在所有市售聚合物中以少量使用而没有任何明显的局限。
现已发现一种形成纤维的或纤维状的有机聚合材料与另一种能离子导电的聚合物或共聚物一起可掺入热塑性或弹性基质中,从而使该聚合物或共聚物基本上以吸附方式连于纤维上或溶于其中并与其一起在热塑性或弹性基质中形成网络,在该网络中纤维不可溶。一部分能离子导电的聚合物或共聚物具有能够配合或溶剂化无机或有机质子酸的盐的极性基团。
纤维状或形成纤维的有机聚合材料必须选择得使其不溶于热塑性或弹性基质中,但能形成紧邻纤维的网状结构。
为了使导电性良好,有利的是有机材料的纤维在掺入聚合物中时互相邻近或在尽可能多的位置上相互交叉。这样形成了电荷能通过其流走的导电通道。
因纤维和能离子导电的聚合物或共聚物为高分子量化合物,因而它们实际上没有渗出的危险,结果导致抗静电性能尤其耐久。
聚合物的稳定性如热稳定性和耐光性及耐水解性在大多数情况下实际上不受影响。
当加入量小时,仅轻微改变光学性能,且透明材料基本保持透明,这对许多应用领域极具重要性。
本发明涉及一种包含热塑性或弹性聚合物基质(A)和紧邻纤维形式的抗静电混合物(B)的组合物,所述混合物包含一种为纤维状或混合时形成纤维且不溶于热塑性或弹性聚合物基质(A)中的有机聚合材料(b1);一种具有用于配合或溶剂化无机或低分子量有机质子酸的盐(b3)的嵌段且与为纤维状或混合时形成纤维的有机聚合物(b1)的相容性比与聚合有机基质(A)的相容性要好的能离子导电的聚合物或共聚物(b2);和一种已在聚合物或共聚物(b2)中配合或溶剂化的无机或低分子量有机质子酸的盐(b3)。
热塑性或弹性聚合物的实例列举如下。
1.单烯烃和二烯烃的聚合物,例如聚丙烯、聚异丁烯、聚丁烯-1、聚-4-甲基戊烯-1、聚异戊二烯或聚丁二烯,以及环烯烃如环戊烯或降冰片烯的聚合物,聚乙烯(可非必要地交联)如高密度聚乙烯(HDPE)、低密度聚乙烯(LDPE)、线型低密度聚乙烯(LLDPE)、支化低密度聚乙烯(BLDPE)。
聚烯烃,即前一自然段中列举的单烯烃的聚合物(特别是聚乙烯和聚丙烯)可通过不同的方法,特别是通过下列方法制备:
a)游离基聚合(通常在高压和高温下);
b)借助催化剂,该催化剂通常含有一种或多种IVb、Vb、VIb或VIII族的金属。这些金属通常具有一个或多个可进行p-或s-配位的配体,如氧化物、卤化物、醇化物、酯、醚、胺、烷基、链烯基和/或芳基。这些金属配合物可为游离形式或固定于载体上,如固定于活化氯化镁、氯化钛(III)、氧化铝或氧化硅上。这些催化剂可溶于或不溶于聚合介质中。这些催化剂本身可在聚合中呈活性或可使用另一些活化剂,如金属烷基化物、金属氢化物、金属烷基卤化物、金属烷基氧化物或金属烷基噁烷(oxane),所述金属为Ia、IIa和/或IIIa族的元素。活化剂可用另外的酯、醚、胺或甲硅烷基醚基团改性。这些催化剂体系通常称为Phillips、Standard Oil Indiana、Ziegler(-Natta)、TNZ(DuPont)、金属茂或单点催化剂(SSC)。
2. 1)中提及的聚合物的混合物,如聚丙烯与聚异丁烯、聚丙烯与聚乙烯(例如PP/HDPE、PP/LDPE)的混合物和不同类型聚乙烯(例如LDPE/HDPE)的混合物。
3.单烯烃和二烯烃相互之间或与其它乙烯基单体的共聚物,如乙烯/丙烯共聚物、线型低密度聚乙烯(LLDPE)和其与低密度聚乙烯(LDPE)的混合物、丙烯/丁烯-1共聚物、丙烯/异丁烯共聚物、乙烯/丁烯-1共聚物、乙烯/己烯共聚物、乙烯/甲基戊烯共聚物、乙烯/庚烯共聚物、乙烯/辛烯共聚物、丙烯/丁二烯共聚物、异丁烯/异戊二烯共聚物、乙烯/丙烯酸烷基酯共聚物、乙烯/甲基丙烯酸烷基酯共聚物、乙烯/乙酸乙烯酯共聚物和其与一氧化碳的共聚物或乙烯/丙烯酸共聚物和其盐(离聚物),以及乙烯与丙烯和二烯烃如己二烯、双环戊二烯或亚乙基降冰片烯的三元共聚物;及这些共聚物相互之间或与1)中提及的聚合物的混合物,如聚丙烯/乙烯-丙烯共聚物、LDPE/乙烯-乙酸乙烯酯共聚物、LDPE/乙烯-丙烯酸共聚物、LLDPE/乙烯-乙酸乙烯酯共聚物、LLDPE/乙烯-丙烯酸共聚物和交替或无规聚亚烷基/一氧化碳共聚物和其与其它聚合物如聚酰胺的混合物。
4.烃类树脂(例如C5-C9),包括其氢化改性物(如增粘剂树脂)以及聚亚烷基与淀粉的混合物。
5.聚苯乙烯、聚(对甲基苯乙烯)、聚(α-甲基苯乙烯)。
6.苯乙烯或α-甲基苯乙烯与二烯烃或丙烯酸衍生物的共聚物,如苯乙烯/丁二烯、苯乙烯/丙烯腈、苯乙烯/甲基丙烯酸烷基酯、苯乙烯/丁二烯/丙烯酸烷基酯、苯乙烯/丁二烯/甲基丙烯酸烷基酯、苯乙烯/马来酸酐、苯乙烯/丙烯腈/丙烯酸甲酯;苯乙烯共聚物与另一种聚合物如聚丙烯酸酯、二烯聚合物或乙烯/丙烯/二烯烃三元共聚物的高冲击强度混合物;苯乙烯的嵌段共聚物如苯乙烯/丁二烯/苯乙烯、苯乙烯/异戊二烯/苯乙烯、苯乙烯/乙烯/丁烯/苯乙烯或苯乙烯/乙烯/丙烯/苯乙烯。
7.苯乙烯或α-甲基苯乙烯的接枝共聚物,如苯乙烯接枝到聚丁二烯上;苯乙烯接枝到聚丁二烯-苯乙烯或聚丁二烯-丙烯腈共聚物上;苯乙烯和丙烯腈(或甲基丙烯腈)接枝到聚丁二烯上;苯乙烯、丙烯腈和甲基丙烯酸甲酯接枝到聚丁二烯上;苯乙烯和马来酸酐接枝到聚丁二烯上;苯乙烯、丙烯腈和马来酸酐或马来酰亚胺接枝到聚丁二烯上;苯乙烯和马来酰亚胺接枝到聚丁二烯上;苯乙烯和丙烯酸烷基酯或甲基丙烯酸烷基酯接枝到聚丁二烯上;苯乙烯和丙烯腈接枝到乙烯/丙烯/二烯烃三元共聚物上;苯乙烯和丙烯腈接枝到聚丙烯酸烷基酯或聚甲基丙烯酸烷基酯上;苯乙烯和丙烯腈接枝到丙烯酸酯/丁二烯共聚物上,及其与6)中列举的共聚物的混合物,如与称为ABS、MBS、ASA或AES聚合物的混合物。
8.含卤素的聚合物如聚氯丁二烯、氯代生橡胶、氯化或氯磺化聚乙烯、乙烯与氯化乙烯的共聚物、表氯醇均聚物和共聚物,特别是含卤素的乙烯基化合物的聚合物,如聚氯乙烯、聚偏二氯乙烯、聚氟乙烯、聚偏二氟乙烯,及其共聚物如氯乙烯/偏二氯乙烯、氯乙烯/乙酸乙烯酯或偏二氯乙烯/乙酸乙烯酯其聚物。
9.衍生自α,β-不饱和酸和其衍生物的聚合物,如聚丙烯酸酯和聚甲基丙烯酸酯;或用丙烯酸丁酯进行冲击改性的聚甲基丙烯酸甲酯、聚丙烯酰胺和聚丙烯腈。
10. 9)中所述单体相互之间或与其它不饱和单体的共聚物,如丙烯腈/丁二烯共聚物、丙烯腈/丙烯酸烷基酯共聚物、丙烯腈/丙烯酸烷氧基烷基酯共聚物、丙烯腈/乙烯基卤化物共聚物或丙烯腈/甲基丙烯酸烷基酯/丁二烯三元共聚物。
11.衍生自不饱和醇和胺或其酰基衍生物或缩醛的聚合物,如聚乙烯醇、聚乙酸乙烯酯、聚硬脂酸乙烯酯、聚苯甲酸乙烯酯、聚马来酸乙烯酯、聚乙烯醇缩丁醛、聚邻苯二甲酸烯丙酯、聚烯丙基密胺;以及它们与上述1)中所列烯烃的共聚物。
12.环醚的均聚物和共聚物,如聚(亚烷基)二醇、聚环氧乙烷、聚环氧丙烷或其与二缩水甘油醚的共聚物。
13.聚缩醛,如聚氧亚甲基和那些含有例如环氧乙烷作为共聚单体的聚氧亚甲基;用热塑性聚氨酯、丙烯酸酯或MBS改性的聚缩醛。
14.聚苯醚和硫醚,及其与苯乙烯聚合物或聚酰胺的混合物。
15.衍生自具有端羟基的聚醚,聚酯和聚丁二烯(一方面)和脂族或芳族多异氰酸酯(另一方面)的聚氯酯及其起始产物。
16.衍生自二胺和二羧酸和/或衍生自氨基羧酸或相应的内酰胺的聚酰胺和共聚酰胺,如聚酰胺4、聚酰胺6、聚酰胺6/6、6/10、6/9、6/12、4/6、12/12、聚酰胺11、聚酰胺12、衍生自间二甲苯、二胺和己二酸的芳族聚酰胺;由己二胺和间苯二甲酸或/和对苯二甲酸和在有或无弹性体作为改性剂下制备的聚酰胺,如聚-2,4,4-三甲基六亚甲基对苯二甲酰胺或聚间亚苯基间苯二甲酰胺。上述聚酰胺与聚烯烃、烯烃共聚物、离聚物或化学键合或接枝弹性体的嵌段共聚物;或与聚醚,如聚乙二醇、聚丙二醇或聚四亚甲基二醇的嵌段共聚物。以及用EPDM或ABS改性的聚酰胺或共聚酰胺;和在加工期间缩聚的聚酰胺(RIM聚酰胺体系)。
17.聚脲、聚酰亚胺、聚酰胺-酰亚胺和聚苯并咪唑。
18.衍生自二羧酸和二醇和/或衍生自羟基羧酸或相应内酯的聚酯,如聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯、聚对苯二甲酸1,4-二羟甲基环己烷酯和聚羟基苯甲酸酯,以及衍生自具有端羟基的聚醚的嵌段聚醚酯;和用聚碳酸酯或MBS改性的聚酯。
19.聚碳酸酯和聚酯碳酸酯。
20.聚砜、聚醚砜和聚醚酮。
21.天然聚合物,如天然橡胶、或聚合物-纤维素的同系化学改性衍生物,如乙酸纤维素、丙烯纤维素和丁酸纤维素,和纤维素醚如甲基纤维素。
22.上述聚合物的混合物(掺混聚合物),如PP/EPDM、聚酰胺/EPDM或ABS、PVC/EVA、PVC/ABS、PVC/MBS、PC/ABS、PBTP/ABS、PC/ASA、PC/PBT、PVC/CPE、PVC/丙烯酸酯、POM/热塑性PUR、PC/热塑性PUR、POM/丙烯酸酯、POM/MBS、PPO/HIPS、PPO/PA6,6和共聚物、PA/HDPE、PA/PP、PA/PPO。
优选热塑性或弹性聚合物基质(A)为聚烯烃,聚苯乙烯,丙烯腈/丁二烯/苯乙烯共聚物(ABS),α,β-不饱和酸的聚合物,含卤素的聚合物,环醚的均聚物或共聚物,不饱和醇和胺的聚合物,聚缩醛,聚苯醚,聚氨酯,聚酰胺,聚酯,聚脲,聚碳酸酯,聚砜或天然橡胶。
热塑性或弹性聚合物基质(A)尤其为聚烯烃,聚苯乙烯,丙烯腈/丁二烯/苯乙烯(ABS)共聚物,α,β-不饱和酸的聚合物,含卤素的聚合物或环醚的均聚物或共聚物。
更特别的是热塑性或弹性聚合物基质(A)为聚氯乙烯(PVC),聚苯乙烯,各种改性形式的聚乙烯,或聚丙烯。
纤维状或形成纤维的有机聚合材料(b1)可为长纺丝纤维形式或短纤维形式,且可以这种形式使用。纤维也可以平面网络,纺织型式,无纺织物或毛毡形式使用。
纤维状或形成纤维的有机聚合材料(b1)优选为合成聚合物纤维形式。
合适的纤维状或形成纤维的有机聚合材料的实例为聚酰胺或共聚酰胺,聚酯,聚乙酸乙烯酯,聚乙烯醇,改性纤维素,聚丙烯酸酯,聚甲基丙烯酸酯,聚丙烯腈,改良丙烯酸纤维(modacryl,丙烯腈和氯乙烯的共聚物),聚烯烃,聚酐,聚酯酰胺,聚苯硫醚,多氟烃,聚氨酯和聚脲。
优选纤维包含能在表面上或在横截面上离子导电的聚合物或共聚物(b2),且它们在聚合物基质中相互紧邻,因为这样可使单位体积导电率以离子形式发生。
纤维状有机材料的长度通常为0.01-200mm,优选0.1-20mm。它可以是宏观纤维形式,但也可以存在具有微观空腔的小纤丝。
然而,也可以使用颗粒或粉末形式的纤维状或形成纤维的有机聚合材料。当与聚合基质例如在压延机,三辊磨,挤出机或捏合机中混合和加工时,纤维状或纤丝排序因形成纤维的有机聚合材料不溶于基质聚合物且由于加工或混合方法而基本上在一个尺寸上延伸而达到。若需要,可通过随后的额外拉伸工艺进一步改进结果。混合和加工热塑性或弹性聚合物的方法对本领域技术人员是已知的且例如在Kunststoff-Taschenbuch,第12版,Hanser Verlag,1979,第35-195页有说明。
纤维状聚合材料(或混合时形成纤维的聚合材料)(b1)优选为聚丙烯酸酯,聚甲基丙烯酸酯,聚丙烯腈,聚乙烯醇,聚乙酸乙烯酯,聚酰胺,聚氨酯或聚酯。
纤维状聚合材料(或混合时形成纤维的聚合材料)(b1)尤其为聚酯,聚酰胺(x)或聚酰胺(x,y),其中x和y各自独立地为4-14的数。
更优选聚酰胺4,6;聚酰胺6,6;聚酰胺6或共聚酰胺6/6,6。
许多纤维状或形成纤维的聚合物可从市场上购到。若使用已为纤维状的材料,则可选择各种纤维厚度的材料。纤维厚度通常以分特(g/10000m)衡量。纤维厚度通常为0.5-500分特,优选使用1-100分特的纤维厚度。
优选的聚合物或共聚物(b2)是低聚乙氧基化的(oligoethoxylated)丙烯酸酯或甲基丙烯酸酯,在芳环上低聚乙氧基化的苯乙烯,聚醚聚氨酯(polyether urethane),聚醚聚脲(polyether urea),聚醚酰胺,聚醚酯酰胺和聚醚酯。共聚物可以是无规共聚物或嵌段共聚物,优选嵌段共聚物(权利要求7)。
尤其优选聚醚酰胺和聚醚酯酰胺。
嵌段共聚物尤其是聚醚酯酰胺,其中聚醚链段包括分子量Mn为200-6000道尔顿的聚乙二醇单元,而聚酰胺链段包括分子量Mn为200-6000道尔顿的聚酰胺(x)或聚酰胺(x,y),x和y为4-14的数。
合适的聚醚酯酰胺例如在EP-A-613919中描述。
其他同样合适的聚醚酯酰胺和其制备描述于DE-OS-2523991中。
本发明的聚合物或共聚物可从市场上购到或可例如按EP-A-613919或DE-OS-2523991中所述方法制备。
选择与纤维状或形成纤维的材料(b1)组合的聚合物或共聚物(b2)的重要前提是这二者相互之间的亲合力比对热塑性或弹性聚合基质的亲合力高。这可通过例如使它们各自部分具有相同的聚合物骨架而达到。实例包括这样一些情况,其中(b1)包括聚酰胺和(b2)包括聚醚酯酰胺,(b1)包括聚酯和(b2)包括聚醚酯酰胺或聚醚酯,(b1)包括丙烯腈和(b2)包括低聚乙氧基化的丙烯酸酯或甲基丙烯酸酯,以及热塑性或弹性聚合基质(A)例如为聚烯烃或PVC。
优选无机或低分子量有机盐(b3)为无机或低分子量有机质子酸的碱金属、碱土金属、锌或铵盐。
低分子量有机质子酸是例如具有1-4个碳原子的那些。实例为乙酸,三氟乙酸,甲磺酸和三氟甲磺酸。
尤其优选的是无机盐(b3)LiClO4,LiCF3SO3,NaClO4,LiBF4,NaBF4,KBF4,NaCF3SO3,KClO4,KPF6,KCF3SO3,KC4F9SO3,Ca(ClO4)2,Ca(PF6)2,Mg(ClO4)2,Mg(CF3SO3)2,Zn(ClO4)2,Zn(PF6)2和Ca(CF3SO3)2。
盐可以各种水合形式存在且可在有或无水合水存在下使用。
盐(b3)的存在量优选为0.05-10wt%,尤其是0.5-5wt%,以共聚物(b2)为基准计。
纤维状或混合时形成纤维的有机聚合材料(b1)与共聚物(b2)的质量比优选为20∶1-1∶10,尤其是10∶1-1∶3(权利要求13,14)。
组分(b1),(b2)和(b3)的抗静电活性混合物的总存在量优选为0.1-15wt%,尤其1-15wt%,更优选5-15wt%,以热塑性或弹性聚合物基质为基准计。
本发明的优选组合物包括PVC,聚乙烯或聚丙烯作为热塑性或弹性聚合物基质(A),聚酯或聚酰胺作为纤维状或形成纤维的有机聚合材料(b1),聚醚酯酰胺或聚醚酯作为能离子导电的共聚物(b2),以及NaClO4,KPF6或LiCF3SO3作为质子酸的无机盐(b3)。
热塑性或弹性聚合物基质以及纤维状聚合材料(或混合对形成纤维的聚合材料)可包括其他添加剂。这些其他添加剂尤其是抗氧剂,UV吸收剂和/或光稳定剂。热稳定涉及加工和使用(长期稳定性)。这些其他添加剂对本领域技术人员是已知的且绝大部分可从市场上购到。
若使用抗静电的含卤素聚合物如上面所述的那些,则它们还有利地包含至少一种无机锌、钡、镉、铝、钙、镁或稀土化合物,如氧化锌、氢氧化锌、氯化锌或硫化锌,或超碱性氧化锌/氢氧化锌加合物,或选自如下系列的有机锌、钡、镉、铝、钙、镁或稀土化合物:脂族饱和C2-C22羧酸盐,脂族不饱和C3-C22羧酸盐,被至少一个OH基团取代或其链至少被一个氧子间隔(氧杂酸)的脂族C2-C22羧酸盐,具有5-22个碳原子的环状或双环羧酸盐,未取代、被至少一个OH基团取代和/或被C1-C16烷基取代的苯基羧酸盐,未取代、被至少一个OH基团取代和/或被C1-C16烷基取代的萘基羧酸盐,苯基-C1-C16烷基羧酸盐,萘基-C1-C16烷基羧酸盐或未取代或C1-C12烷基取代的酚盐。
上述金属化合物可为各种化合物的混合物形式。优选所谓的增效金属皂混合物,例如金属Ca和Zn或Ba或Zn的增塑金属皂混合物。有机锌、钡、镉、铝、钙、镁或稀土化合物也可涂覆于水滑石,沸石或片钠铝石上;关于这一点参见DE-A-4 031 818。
合适的抗氧剂例如是:
1.烷基化的一元酚,如2,6-二叔丁基-4-甲基苯酚、2-丁基-4,6-二甲基苯酚、2,6-二叔丁基-4-乙基苯酚、2,6-二叔丁基-4-正丁基苯酚、2,6-二叔丁基-4-异丁基苯酚、2,6-二环戊基-4-甲基苯酚、2-(α-甲基环己基)-4,6-二甲基苯酚、2,6-二(十八烷基)-4-甲基苯酚、2,4,6-三环己基苯酚、2,6-二叔丁基-4-甲氧基甲基苯酚,2,6-二壬基-4-甲基苯酚、2,4-二甲基-6-(1’-甲基十一烷-1’-基)苯酚、2,4-二甲基-6-(1’-甲基十七烷-1’-基)苯酚、2,4-二甲基-6-(1’-甲基十三烷-1’-基)苯酚、辛基酚、壬基酚和其混合物。
2.烷硫基甲基苯酚,例如2,4-二辛硫基甲基-6-叔丁基苯酚、2,4-二辛硫基甲基-6-甲基苯酚、2,4-二辛硫基甲基-6-乙基苯酚、2,6-二-十二烷硫基甲基-4-壬基苯酚。
3.氢醌和烷基化的氢醌,例如2,6-二叔丁基-4-甲氧基苯酚、2,5-二叔丁基氢醌、2,5-二叔戊基氢醌、2,6-二苯基-4-十八烷氧基苯酚、2,6-二叔丁基氢醌、2,5-二叔丁基-4-羟基茴香醚、3,5-二叔丁基-4-羟基茴香醚、硬脂酸3,5-二叔丁基-4-羟基苯基酯、己二酸双(3,5-二叔丁基-4-羟基苯基)酯。
4.羟基化的二苯基硫醚,例如2,2’-硫代双(6-叔丁基-4-甲基苯酚)、2,2’-硫代双(4-辛基苯酚)、4,4’-硫代双(6-叔丁基-3-甲基苯酚)、4,4’-硫代双(6-叔丁基-2-甲基苯酚)、4,4’-硫代双(3,6-二仲戊基苯酚)、4,4’-双(2,6-二甲基-4-羟基苯基)二硫化物。
5.亚烷基双酚,例如2,2’-亚甲基双(6-叔丁基-4-甲基苯酚)、2,2’-亚甲基双(6-叔丁基-4-乙基苯酚)、2,2’-亚甲基双[4-甲基-6-(α-甲基环己基)-苯酚]、2,2’-亚甲基双(4-甲基-6-环己基苯酚)、2,2’-亚甲基双(6-壬基-4-甲基苯酚)、2,2’-亚甲基双(4,6-二叔丁基苯酚)、2,2’-亚乙基双(4,6-二叔丁基苯酚)、2,2’-亚乙基双(6-叔丁基-4-异丁基苯酚)、2,2’-亚甲基双[6-(α-甲基苄基)-4-壬基苯酚]、2,2’-亚甲基双[6-(α,α-二甲基苄基)-4-壬基苯酚]、4,4’-亚甲基双(2,6-二叔丁基苯酚)、4,4’-亚甲基双(6-叔丁基-2-甲基苯酚)、1,1-双(5-叔丁基-4-羟基-2-甲基苯基)丁烷、2,6-双(3-叔丁基-5-甲基-2-羟基苄基)-4-甲基苯酚、1,1,3-三(5-叔丁基-4-羟基-2-甲基苯基)丁烷、1,1-双(5-叔丁基-4-羟基-2-甲基苯基)-3-正十二烷基巯基丁烷、双[3,3-双(3’-叔丁基-4’-羟基苯基)丁酸]乙二醇酯、双(3-叔丁基-4-羟基-5-甲基-苯基)双环戊二烯、对苯二甲酸双[ 2-(3’-叔丁基-2’-羟基-5’-甲基苄基)-6-叔丁基-4-甲基苯基]酯、1,1-双(3,5-二甲基-2-羟苯基)丁烷、2,2-双(3,5-二叔丁基-4-羟苯基)丙烷、2,2-双(4-羟苯基)丙烷、2,2-双(5-叔丁基-4-羟基-2-甲基苯基)-4-正十二烷基巯基丁烷、1,1,5,5-四(5-叔丁基-4-羟基-2-甲基苯基)戊烷。
6.O-、N-和S-苄基化合物,例如3,5,3’,5’-四叔丁基-4,4’-二羟基二苄基醚、4-羟基-3,5-二甲基苄基巯基乙酸十八烷基酯、三(3,5-二叔丁基-4-羟苄基)胺、二硫代对苯二甲酸双(4-叔丁基-3-羟基-2,6-二甲基苄基)酯、双(3,5-二叔丁基-4-羟苄基)硫化物、3,5-二叔丁基-4-羟苄基巯基乙酸异辛基酯。
7.羟苄基化的丙二酸酯,例如2,2-双(3,5-二叔丁基-2-羟苄基)丙二酸二-十八烷基酯、2-(3-叔丁基-4-羟基-5-甲基苄基)丙二酸二-十八烷基酯、2,2-双(3,5-二叔丁基-2-羟苄基)丙二酸二-十二烷基巯乙基酯、2,2-双(3,5-二叔丁基-4-羟苄基)丙二酸二[4-(1,1,3,3-四甲基丁基)苯基]酯。
8.羟苄基芳族化合物,例如1,3,5-三(3,5-二叔丁基-4-羟苄基)-2,4,6-三甲基苯、1,4-双(3,5-二叔丁基-4-羟苄基)-2,3,5,6-四甲基苯、2,4,6-三(3,5-二叔丁基-4-羟苄基)苯酚。
9.三嗪化合物,例如2,4-双-辛基巯基-6-(3,5-二叔丁基-4-羟苯胺基)-1,3,5-三嗪、2-辛基巯基-4,6-双(3,5-二叔丁基-4-羟苯胺基)-1,3,5-三嗪、2-辛基巯基-4,6-双(3,5-二叔丁基-4-羟苯氧基)-1,3,5-三嗪、2,4,6-三(3,5-二叔丁基-4-羟苯氧基)-1,2,3-三嗪、1,3,5-三(3,5-二叔丁基-4-羟苄基)异氰脲酸酯、1,3,5-三(4-叔丁基-3-羟基-2,6-二甲基苄基)异氰脲酸酯、2,4,6-三(3,5-二叔丁基-4-羟苯乙基)-1,3,5-三嗪、1,3,5-三(3,5-二叔丁基-4-羟苯基丙酰基)-六氢-1,3,5-三嗪、1,3,5-三(3,5-二环己基-4-羟苄基)异氰脲酸酯。
10.膦酸酯,亚磷酸酯和亚膦酸酯(phosphonite),例如2,5-二叔丁基-4-羟苄基膦酸二甲酯、3,5-二叔丁基-4-羟苄基膦酸二乙酯、3,5-二叔丁基-4-羟苄基膦酸二-十八烷基酯、5-叔丁基-4-羟基-3-甲基苄基膦酸二-十八烷基酯、3,5-二叔丁基-4-羟苄基膦酸单乙酯的钙盐,亚磷酸三苯酯、亚磷酸二苯基烷基酯、亚磷酸苯基二烷基酯、亚磷酸三(壬基苯基)酯、亚磷酸三月桂酯、亚磷酸三-十八烷基酯、二亚磷酸二硬脂基季戊四醇酯、亚磷酸三(2,4-二叔丁基苯基)酯、二亚磷酸二异癸基季戊四醇酯、二亚磷酸双(2,4-二叔丁基苯基)季戊四醇酯、二亚磷酸双(2,6-二叔丁基-4-甲基苯基)季戊四醇酯、二亚磷酸二异癸氧基季戊四醇酯、二亚磷酸双(2,4-二叔丁基-6-甲基苯基)季戊四醇酯、二亚磷酸双(2,4,6-三(叔丁基苯基)季戊四醇酯、三亚磷酸三硬脂基山梨醇酯、4,4’-亚联苯基二亚膦酸四(2,4-二叔丁基苯基)酯、6-异辛氧基-2,4,8,10-四叔丁基-12H-二苯并[d,g]-1,3,2-二氧杂磷辛因、6-氟-2,4,8,10-四叔丁基-12-甲基-二苯并[d,g]-1,3,2-二氧杂磷辛因、亚磷酸双(2,4-二叔丁基-6-甲基苯基)甲基酯、亚磷酸双(2,4-二叔丁基-6-甲基苯基)乙基酯,(C9H19-C6H4)1.5-P-(O-C12-13H25-27)1.5。
11.酰氨基苯酚,例如4-羟基月桂酰苯胺、4-羟基硬脂酰苯胺、N-(3,5-二叔丁基-4-羟苯基)氨基甲酸辛酯。
12.β-(3,5-二叔丁基-4-羟苯基)丙酸与一元醇或多元醇的酯,所述醇的例子是:甲醇、乙醇、辛醇、十八烷醇、1,6-己二醇、1,9-壬二醇、乙二醇、1,2-丙二醇、新戊二醇、硫二甘醇、二甘醇、三甘醇、季戊四醇、三(羟乙基)异氰脲酸酯、N,N’-双(羟乙基)草酸二酰胺、3-硫杂十一烷醇、3-硫杂十五烷醇、三甲基己二醇、三羟甲基丙烷、4-羟甲基-1-磷杂-2,6,7-三氧杂双环[2.2.2]辛烷。
13.β-(5-叔丁基-4-羟基-3-甲苯基)丙酸与一元醇或多元醇的酯,所述醇的例子是:甲醇、乙醇、辛醇、十八烷醇、1,6-己二醇、1,9-壬二醇、乙二醇、1,2-丙二醇、新戊二醇、硫二甘醇、二甘醇、三甘醇、季戊四醇、三(羟乙基)异氰脲酸酯、N,N’-双(羟乙基)草酸二酰胺、3-硫杂十一烷醇、3-硫杂十五烷醇、三甲基己二醇、三羟甲基丙烷、4-羟甲基-1-磷杂-2,6,7-三氧杂双环[2.2.2]辛烷。
14.β-(3,5-二环己基-4-羟苯基)丙酸与一元醇或多元醇的酯,所述醇的例子是:甲醇、乙醇、辛醇、十八烷醇、1,6-己二醇、1,9-壬二醇、乙二醇、1, 2-丙二醇、新戊二醇、硫二甘醇、二甘醇、三甘醇、季戊四醇、三(羟乙基)异氰脲酸酯、N,N’-双(羟乙基)草酸二酰胺、3-硫杂十一烷醇、3-硫杂十五烷醇、三甲基己二醇、三羟甲基丙烷、4-羟甲基-1-磷杂-2,6,7-三氧杂双环[2.2.2]辛烷。
15. 3,5-二叔丁基-4-羟苯基乙酸与一元醇或多元醇的酯,所述醇的例子是:甲醇、乙醇、辛醇、十八烷醇、1,6-己二醇、1,9-壬二醇、乙二醇、1,2-丙二醇、新戊二醇、硫二甘醇、二甘醇、三甘醇、季戊四醇、三(羟乙基)异氰脲酸酯、N,N’-双(羟乙基)草酸二酰胺、3-硫杂十一烷醇、3-硫杂十五烷醇、三甲基己二醇、三羟甲基丙烷、4-羟甲基-1-磷杂-2,6,7-三氧杂双环[2.2.2]辛烷。
16.β-(3,5-二叔丁基-4-羟苯基)丙酸的酰胺,例如:N,N’-双(3,5-二叔丁基-4-羟苯基丙酰基)己二胺、N,N’-双(3,5-二叔丁基-4-羟苯基丙酰基)丙二胺、N,N’-双(3,5-二叔丁基-4-羟苯基丙酰基)肼。
17.硫代二乙酸和硫代二丙酸的酯
优选的是第5、10和14组的抗氧剂,尤其是2,2-双(4-羟苯基)丙烷,3,5-二叔丁基-4-羟苯基丙酸与十八烷醇或季戊四醇的酯或亚磷酸三(2,4-二叔丁基苯基)酯。
若需要,也可使用不同结构的抗氧剂混合物。
抗氧剂的用量可为例如0.01-10,有利的是0.1-10,尤其是0.1-5重量份/100重量份聚合物。
合适的UV吸收剂和光稳定剂例如是:
1. 2-(2’-羟苯基)苯并***,例如2-(2’-羟基-5’-甲基苯基)苯并***、2-(3’,5’-二叔丁基-2’-羟苯基)苯并***、2-(5’-叔丁基-2’-羟苯基)苯并***、2-(2’-羟基-5’-(1,1,3,3-四甲基丁基)苯基)苯并***、2-(3’,5’-二叔丁基-2’-羟苯基)-5-氯-苯并***、2-(3’-叔丁基-2’-羟基-5’-甲基苯基)-5-氯-苯并***、2-(3’-仲丁基-5’-叔丁基-2’-羟苯基)苯并***、2-(2’-羟基-4’-辛氧基苯基)苯并***、2-(3’,5’-二叔戊基-2’-羟苯基)苯并***、2-(3’,5’-双(α,α-二甲苄基)-2’-羟苯基)苯并***,2-(3’-叔丁基-2’-羟基-5’-(2-辛氧基羰基乙基)苯基)-5-氯-苯并***、2-(3’-叔丁基-5’-[2-(2-乙基己氧基)-羰基乙基]-2’-羟苯基)-5-氯-苯并***、2-(3’-叔丁基-2’-羟基-5’-(2-甲氧基羰基乙基)苯基)-5-氯-苯并***、2-(3’-叔丁基-2’-羟基-5’-(2-甲氧基羰基乙基)苯基)苯并***、2-(3’-叔丁基-2’-羟基-5’-(2-辛氧基羰基乙基)苯基)苯并***、2-(3’-叔丁基-5’-[2-(2-乙基己氧基)羰基乙基]-2’-羟苯基)苯并***、2-(3’-十二烷基-2’-羟基-5’-甲基苯基)苯并***和2-(3’-叔丁基-2’-羟基-5’-(2-异辛氧基羰基乙基)苯基苯并***的混合物,2,2’-亚甲基-双[4-(1,1,3,3-四甲基丁基)-6-苯并***-2-基苯酚];2-[3’-叔丁基-5’-(2-甲氧基羰基乙基)-2-羟苯基]苯并***与聚乙二醇300的酯基转移产物;[R-CH2CH2-COO(CH2)3]-,其中R=3’-叔丁基-4’-羟基-5’-2H-苯并***-2-基苯基。
2. 2-羟基二苯(甲)酮,例如4-羟基、4-甲氧基、4-辛氧基、4-癸氧基、4-十二烷氧基、4-苄氧基、4,2’,4’-三羟基和2’-羟基-4,4’-二甲氧基衍生物。
3.未取代或取代的苯甲酸的酯,例如水杨酸4-叔丁基苯基酯、水杨酸苯基酯、水杨酸辛基苯基酯、二苯甲酰间苯二酚、双(4-叔丁基苯甲酰)间苯二酚、苯甲酰间苯二酚、3,5-二叔丁基-4-羟基苯甲酸2,4-二叔丁基苯基酯、3,5-二叔丁基-4-羟基苯甲酸十六烷基酯、3,5-二叔丁基-4-羟基苯甲酸十八烷基酯、3,5-二叔丁基-4-羟基苯甲酸2-甲基-4,6-二叔丁基苯基酯。
4.丙烯酸酯,如α-氰基-β,β-二苯基丙烯酸乙酯、α-氰基-β,β-二苯基丙烯酸异辛酯、α-甲氧羰基肉桂酸甲酯、α-氰基-β-甲基-对甲氧基肉桂酸甲酯或α-氰基-β-甲基-对甲氧基肉桂酸丁酯、α-甲酯基-对甲氧基肉桂酸甲酯和N-(β-甲酯基-β-氰基乙烯基)-2-甲基二氢吲哚。
5.镍化合物,例如2,2’-硫代-双-[4-(1,1,3,3-四甲基丁基)苯酚]的镍配合物,如1∶1或1∶2配合物,该配合物有或无额外配体(如正丁胺、三乙醇胺或N-环己基二乙醇胺),二丁基二硫代氨基甲酸镍,4-羟基-3,5-二叔丁基苄基膦酸的单烷基酯如甲酯或乙酯的镍盐,酮肟如2-羟基-4-甲基苯基十一烷基酮肟的镍配合物,1-苯基-4-月桂酰基-5-羟基吡唑的镍配合物(有或无额外配体)。
6.位阻胺,如癸二酸双(2,2,6,6-四甲基哌啶基)酯、丁二酸双(2,2,6,6-四甲基哌啶基)酯、癸二酸双(1,2,2,6,6-五甲基哌啶基)酯、正丁基-3,5-二叔丁基-4-羟苄基丙二酸双(1,2,2,6,6-五甲基哌啶基)酯、1-羟乙基-2,2,6,6-四甲基-4-羟基哌啶与丁二酸的缩合物、N,N’-双(2,2,6,6-四甲基-4-哌啶基)己二胺与4-叔辛氨基-2,6-二氯-1,3,5-均三嗪的缩合物、三(2,2,6,6-四甲基-4-哌啶基)次氮基三乙酸酯、四(2,2,6,6-四甲基-4-哌啶基)1,2,3,4-丁烷四羧酸酯、1,1’-(1,2-亚乙基)双(3,3,5,5-四甲基哌嗪酮)、4-苯甲酰基-2,2,6,6-四甲基哌啶、4-硬脂氧基-2,2,6,6-四甲基哌啶、2-正丁基-2-(2-羟基-3,5-二叔丁基苄基)丙二酸双(1,2,2,6,6-五甲基哌啶基)酯、3-正辛基-7,7,9,9-四甲基-1,3,8-三氮杂螺[4.5]癸烷-2,4-二酮、癸二酸双(1-辛氧基-2,2,6,6-四甲基哌啶基)酯、丁二酸双(1-辛氧基-2,2,6,6-四甲基哌啶基)酯、N,N’-双(2,2,6,6-四甲基-4-哌啶基)己二胺与4-吗啉代-2,6-二氯-1,3,5-三嗪的缩合物、2-氯-4,6-二(4-正丁氨基-2,2,6,6-四甲基哌啶基)-1,3,5-三嗪与1,2-双(3-氨丙基氨基)乙烷的缩合物、2-氯-4,6-二(4-正丁氨基-1,2,2,6,6-五甲基哌啶基)-1,3,5-三嗪与1,2-双(3-氨丙基氨基)乙烷的缩合物、8-乙酰基-3-十二烷基-7,7,9,9-四甲基-1,3,8-三氮杂螺[4.5]癸烷-2,4-二酮、3-十二烷基-1-(2,2,6,6-四甲基-4-哌啶基)吡咯烷-2,5-二酮、3-十二烷基-1-(1,2,2,6,6-五甲基-4-哌啶基)吡咯烷-2,5-二酮和Chimassorb 966。
7.草酸二酰胺,例如4,4’-二辛氧基N,N’-草酰二苯胺,2,2’-二辛氧基-5,5’-二叔丁基N,N’-草酰二苯胺、2,2’-二(十二烷氧基)-5,5’-二叔丁基N,N’-草酰二苯胺、2-乙氧基-2’-乙基N,N’-草酰二苯胺、N,N’-双(3-二甲氨基丙基)草酰胺、2-乙氧基-5-叔丁基-2’-乙基N,N’-草酰二苯胺和其与2-乙氧基-2’-乙基-5,4’-二叔丁基N,N’-草酰二苯胺的混合物、邻-与对-甲氧基二取代的N,N’-草酰二苯胺的混合物和邻-与对-乙氧基二取代的N,N’-草酰二苯胺的混合物。
8. 2-(2-羟苯基)-1,3,5-三嗪,例如2,4,6-三(2-羟基-4-辛氧基苯基)-1,3,5-三嗪、2-(2-羟基-4-辛氧基苯基)-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪、2-(2,4-二羟苯基)-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪、2,4-双(2-羟基-4-丙氧基苯基)-6-(2,4-二甲基苯基)-1,3,5-三嗪、2-(2-羟基-4-辛氧基苯基)-4,6-双(4-甲基苯基)-1,3,5-三嗪、2-(2-羟基-4-十二烷氧基苯基)-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪、2-[2-羟基-4-(2-羟基-3-丁氧基丙氧基)苯基]-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪、2-[2-羟基-4-(2-羟基-3-辛氧基丙氧基)苯基]-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪。
合适的破坏过氧化物的化合物例如是:β-硫代二丙酸的酯,例如月桂酯、硬脂基酯、肉豆蔻基酯或十三烷基酯,巯基苯并咪唑,2-巯基苯并咪唑的锌盐,二丁基二硫代氨基甲酸锌,二-十八烷基二硫化物,季戊四醇-四(β-十二烷巯基)丙酸酯和乙二醇二巯基乙酸酯。
本发明还涉及一种抗静电混合物(B),包含(b1)一种为纤维状或混合时形成纤维且不溶于热塑性或弹性聚合物基质(A)中的有机聚合材料;(b2)一种具有用于配合成溶剂化无机或低分子量有机质子酸的盐(b3)的嵌段且与纤维状或形成纤维的有机聚合物的相容性比与聚合有机基质(A)的相容性要好的能离子导电的聚合物或共聚物;和(b3)一种已在聚合物或共聚物(b2)中配合或溶剂化的无机或低分子量有机质子酸的盐。
上面所给的定义和优选定义适用于纤维状或混合时形成纤维的有机聚合材料(b1),能离子导电的聚合物或共聚物(b2),以及无机或低分子量有机质子酸的盐(b3)。该混合物也可包含上述其它组分。
除了本发明的抗静电混合物外,也可存在其他已知抗静电活性化合物。这类抗静电剂大量已知且在例如Kunststoffe 67(1997)3,第154-159页中有描述。
例如抗静电剂可以是聚氧化烯化合物。实例为聚丙二醇月桂酯,聚丙二醇油基醚,聚丙二醇甲基二乙基氯化铵,聚乙二醇单甲醚,聚乙二醇二甲醚,聚乙二醇月桂酯,聚乙二醇油基酯,聚乙二醇油基醚,聚乙二醇脱水山梨醇单月桂酯,聚乙二醇硬脂基酯,聚乙二醇聚丙二醇月桂醚,聚乙二醇月桂醚羧酸,聚乙二醇二丙烯酸酯、单丙烯酸酯和三丙烯酸酯以及聚乙二醇二甲基丙烯酸酯、单甲基丙烯酸酯和三甲基丙烯酸酯。
若使用烯属不饱和化合物,则它可以在纤维上聚合或交联。
本发明还涉及一种制备抗静电热塑性或弹性聚合物基质(A)的方法,该方法包括将抗静电混合物(B)以原样或以其单个组分形式以任何顺序以及如果需要还有其他添加剂与一种热塑性或弹性聚合物(A)混合,所述混合物(B)包含:(b1)一种纤维状或在混合条件下形成纤维且不溶于热塑性或弹性聚合物基质(A)中的有机聚合材料,(b2)一种具有用于配合或溶剂化无机或低分子量有机质子酸的盐(b3)的嵌段且与为纤维状或形成纤维的有机聚合材料(b1)的相容性比与热塑性或弹性聚合有机基质(A)的相容性要好的能离子导电的聚合物或共聚物,和(b3)一种已在聚合物或共聚物(b2)中配合或溶剂化的无机或低分子量有机质子酸的盐,其中存在或形成的纤维相互紧邻。
制备可以本身已知的方式通过使用本身已知的装置如压延机、混合机、捏合机、挤出机等将所述组分以及如果需要还有其它添加剂与聚合物混合而进行。添加剂可单独加入或以相互之间的混合物加入。也可使用所谓的母料。
可由本发明得到的抗静电热塑性聚合物可以已知方式制成所需形式。这些方法包括例如研磨、压延、挤出、注塑、熔结、压缩/熔结或纺丝,还有挤坯吹塑,或按增塑溶胶(plastisol)方法加工。抗静电热塑性聚合物也可加工成发泡材料。
本发明还涉及本发明抗静电混合物赋予热塑性或弹性聚合物抗静电性的用途。
本发明聚合物组合物尤其适于电线包覆和电缆绝缘。然而也可生产装饰膜、发泡材料、农用毡、管材,密封型材和办公用膜。本发明聚合物组合物也可用作生产中空制品(瓶)、包装膜(深撑压膜)、吹制膜、防冲垫膜(汽车)、管道、发泡材料、重荷型材(窗框)、照明壁用型材、建筑型材、挡板、配件、办公用膜和仪器壳体(计算机、家用电器)的模塑组合物。
下列实施例说明本发明。
实施例1.抗静电硬PVC的制备
将60g根据DIN 53774的硬PVC,Wacker Chemie的Vinnol,2.1g其中已加有3wt%NaClO4·H2O的聚醚酯酰胺(Sanyo Chemicals的Pelestat7490)和4.0g聚酰胺6,6短纤维(长1.5mm,2.2分特)使用刮铲混合。混合物在双辊压延机上于190℃下加工(辊压时间5分钟,速度26/33转/分,辊隙0.5mm),得到辊压片材。然后在加热的高压压机(加热温度195℃,加热时间5分钟)中由辊压片材生产压制板(厚0.5mm)。通过水冷却方式冷却压制板5分钟。生产后立即测量压制板,其体积电阻RD(按DIN534 82测量,使用20cm2的防护圈电极,间隙5mm,在500伏下保持5分钟后测量)为4.5×1010Ω,在空气(50%相对湿度)中储存14天后,RD降至2.0×109Ω。生产后的表面电阻RO(使用相同的防护圈电极测量)为6.0×1010Ω,在空气(50%相对湿度)中储存14天后为5.0×109Ω。
实施例2.抗静电软PVC的制备
使用刮铲混合50g软PVC,100份EVIPOLSH7020,48份邻苯二甲酸二辛酯,2份环氧化大豆油(Reoplast39),2份BZ561,0.15g其中已加入3wt%NaClO4·H2O的聚醚酯酰胺(Sanyo Chemicals的Pelestat7490)和4.5g聚酰胺6,6短纤维(长1.5mm,2.2分特)。在双辊压延机上于180℃下加工该混合物(辊压时间5分钟,速度22/26转/分,辊隙0.5mm),得到辊压片材。在生产之后立即测量辊压片材,其体积电阻RD(按DIN53482测量,使用20cm2的防护圈电极,间隙5mm,在500伏下保持5分钟后测量)为3×1010Ω,在空气(50%相对湿度)中储存14天后降至3×109Ω。表面电阻RO(使用相同的防护圈电极测量)在生产后为3×1011Ω,在空气(50%相对湿度)中储存14天后为2×1010Ω。
实施例3.抗静电聚丙烯的生产
将194g聚丙烯(MoplenFLF20,已稳定化),2.88g聚醚酯酰胺(Pelestat6321粉末,Sanyo Chemicals),3.00g聚酰胺6短纤维(1.8mm,11.0分特)和0.12g NaClO4·H2O在混合器中混合3分钟,然后使用单螺杆挤出机(BRABENDER 25D)在230℃下挤出,然后造粒。在200℃和300巴下生产的压制板在用水冷却并储存2天(60%相对湿度)后的体积电阻RD(按DIN53482测量,使用20cm2的防护圈电极,间隙5mm,在500伏下保持5分钟后测量)为5.5×109Ω和表面电阻RO(使用相同的防护圈电极测量)为4.×1010Ω。
实施例4.涂覆纤维形式的抗静电混合物的制备
将3.33g聚醚酯酰胺(Sanyo Chemicals的Pelestat7490)溶于160g甲醇中,往其中加入13.33g聚酰胺6纤维(长1.8mm,11分特)和由3.20g聚乙二醇600二甲基丙烯酸酯和0.13gNaClO4·H2O组成的溶液。在约10毫巴的真空下于40℃蒸发甲醇。然后在40℃和0.7毫巴下干燥涂覆纤维5小时。
实施例5.赋予聚丙烯抗静电性
将聚丙烯与实施例4所述涂覆纤维形式的抗静电混合物以各种比例相互混合。在单螺杆挤出机(Brabender 25D)中挤出该混合物。挤出机模头中组合物温度约为236℃。将挤出的聚丙烯造粒并在200℃压缩形成板。厚度各为0.57mm的这些板的外层电阻RO(DIN 53482)用簧片电极在22℃和50%相对湿度下测量。混合比和测量结果示于表1。
表1
实施例 | 聚丙烯[份] | 涂覆纤维[份] | RO[欧姆] |
对照 | 100 | 0 | 4×1015 |
5a | 98 | 2 | 4.1×1012 |
5b | 97 | 3 | 1.5×1011 |
5c | 96 | 4 | 3.5×1010 |
5d | 95 | 5 | 6.4×109 |
实施例6.聚合物共混物形式的抗静电混合物的制备
将50g聚酰胺6,6粉末,49g聚醚酯酰胺(Sanyo Chemicals的Pelestat7490)和1.0g NaClO4·H2O混在一起。在单螺杆挤出机(Brabender 25D)中挤出该混合物。在挤出机模头中组合物温度约为239℃。造粒该聚合物共混物,然后在70℃干燥30分钟。该颗粒由纤维状、结晶状和无定形区域组成。
实施例7.赋予硬PVC抗静电性
将55.2g硬PVC和4.8g实施例6所述聚合物共混物形式的抗静电混合物混在一起。在双辊轧制机上混合该混合物5分钟,辊温为197℃(前)和193℃(后)。所得辊压片材在195℃下压缩成板。0.6mm厚板的外层电阻RO在22℃和50%相对湿度下使用簧片电极测量,其值为1×1011欧姆。
实施例8.抗静HD聚乙烯的制备
使用刮铲混合55.8g HD-PE HostalenGF7660(Hoechst),0.6g其中已加入5wt%NaClO4·H2O的聚醚酯酰胺(ELf-AtochemS.A.的PebaxMH1657)和3.6g聚酰胺6,6短纤维(长0.6mm,0.9分特)。在双辊压延机上于175℃下加工该混合物(辊压时间5分钟,速度22/26转/分,辊隙0.5mm),生产出辊压片材。然后在加热的高压压机(加热温度180℃,加热时间5分钟)中由辊压片材生产0.5mm厚的压制板。在加压下在第二个水冷却的压机中冷却压制板(5分钟)。生产一天后该板在20%相对湿度下的体积电阻RD(按DIN 53482由防护圈电极测量,20cm2,间隙5mm,在500伏下保持5分钟后测量)为1×1010欧姆,在约40%相对湿度的空气中储存1周后降至3×109欧姆。表面电阻RO(使用相同的防护圈电极测量)为1.2×1011欧姆(20%相对湿度)和5×1010欧姆(约40%相对湿度,1周后)。该板呈白色不透明状。
实施例9.抗静电HD聚乙烯的生产
使用到铲混合55.2g HD-PE HostalenGF 7660(Hoechst),1.2g其中已加入5wt%NaClO4·H2O的聚醚酯酰胺(Elf-Atochem S.A.的PebaxMH 1657)和3.6g芳族聚酰胺纤维型FAR700/75(Schwarzwlder Textilwerke,D-7771 Schenkenzell)。在双辊压延机上于160℃下加工该混合物(辊压时间5分钟,速度28/36转/分,辊隙0.5mm),生产出辊压片材。在加热的高压压机(加热温度180℃,加热时间5分钟)中由该辊压片材生产出0.5mm厚的压制板。在加压下在第二个水冷却的压机中冷却压制板(5分钟)。生产后立即测量,该板的体积电阻RD在20%相对湿度下为2.5×109欧姆(按DIN 53482由防护圈电极测量,20cm2,间隙5mm,在500伏下保持5分钟后测量),在约50%相对湿度下储存一周后降到1.3×109欧姆。表面电阻RO为2.3×1010欧姆(在20%相对湿度下)且在空气(50%相对湿度)中储存一周后为1.0×1010欧姆。该板因黄色芳族聚酰胺纤维而呈黄色不透明状。
实施例10.抗静电HD聚乙烯的生产
使用刮铲混合55.8g HD-PE HostalenGF7660(Hoechst),0.6g其中已加入10wt%NaClO4·H2O的聚醚酯酰胺(SanyoChemicals的Pelestat6321)和3.6g聚酰胺6短纤维(长1.8mm,11分特)。在双辊压延机中于160℃下加工该混合物(辊压时间8分钟,速度22/26转/分,辊隙0.5mm),生产出辊压片材。在加热的高压压机(加热时间5分钟,于165℃下)中由该辊压片材生产出0.5mm厚的压制板。将该板在加压下在第二个水冷却压机中冷却(5分钟)。生产1天后,该板的体积电阻RD(按DIN53482由防护圈电极测量)为2×1012欧姆(20%相对湿度),在空气中储存4个月后为4×1010欧姆(48%相对湿度)。表面电阻RO在生产后为2.3×1013欧姆(20%相对湿度),在空气(48%相对湿度)中储存4个月后为2×1012欧姆。
实施例11.抗静电苯乙烯/丁二烯嵌段共聚物的生产
使用刮铲混合55.9g SB嵌段共聚物(StyroluxRE31,BASF),0.48g其中已加入5wt%Na ClO4·H2O的聚醚酯酰胺(PebaxMH1657,Elf-Atochem S.A.)和3.6g聚酰胺6,6短纤维(长0.6mm,0.9分特)。在双辊压延机上于190℃下加工该混合物(辊压时间5分钟,速度26/32转/分,辊隙0.5mm)。在加热的高压压机(加热时间5分钟,于195℃下)中由所得均相物质生产出0.5mm厚的压制板。将该板在加压下在第二个水冷却的压机中冷却(5分钟)。生产后立即测量,该板的体积电阻RD为2×1011欧姆,表面电阻RO为4×1011欧姆(20%相对湿度下)。在空气中储存1天后,体积电阻RD为3×1010欧姆,表面电阻RO为8×1010欧姆(48%相对湿度)。测量按DIN 53482使用防护圈电极(20cm2,间隙5mm,在500伏下保持5分钟后)进行。
实施例12.抗静电PPE/PA共混物的生产
使用刮铲混合55.2gPPE/PA共混物(Hamamatsu-CHO,Japan)1.2g其中已加入5wt%NaClO4·H2O的聚醚酯酰胺(Elf-Atochem S.A.的PebaxMH1657)和3.6g聚酰胺66短纤维(长0.6mm,0.9分特)。在双辊压延机上于230℃下加工该混合物(辊压时间5分钟,速度22/26转/分,辊隙0.5mm)。在加热的高压压机(加热时间5分钟,于235℃下)中从所得物质生产出0.5mm厚的压制板。该板在加压下在第二个水冷却的压机中冷却(5分钟)。该板的体积电阻RD在生产1天后在20%相对湿度下为1.6×1012欧姆,在空气(50%相对湿度)中储存一周后为6×1011欧姆。表面电阻RO为7×1012欧姆(20%相对湿度)和4×1012欧姆(50%相对湿度)。测量按DIN 53482使用防护圈电极进行。
实施例13.抗静电硬PVC的生产
使用刮铲混合60g硬PVC(稳定的EvipolSH7020,EVCEuropean Vinyls Corporation AG),1.4g其中已加入10%NaClO4·H2O的聚醚酯酰胺(Sanyo Chemicals的Pelestat7490)和4.0g芳族聚酰胺纤维型F AR 700/40(Schwarzwlder Textilwerke D-7771 Schenkenzell)。在双辊压延机上加工该混合物,生产出辊压片材(辊压时间5分钟,于190℃下,速度22/26转/分,辊隙0.5mm)。使用加热的高压压机(加热时间5分钟,于195℃下)从该辊压片材生产0.5mm厚的压制板。在加压下使用第二个水冷却的压机冷却该板(5分钟)。生产后立即测量,该压制板的体积电阻RD为1.3×1012欧姆,表面电阻RO为2×1012欧姆(55%相对湿度)。在空气中储存一周后,RD为2×1011欧姆,RO为4×1011欧姆(约55%相对湿度)。根据DIN 53482使用防护圈电极进行测量。该板因使用黄色芳族聚酰胺纤维而呈黄色。
实施例14.抗静电ABS的生产
使用刮铲混合54g ABS CycolacTCA(GEP),3g其中已加入10wt%LiCF3SO3的聚醚酯酰胺(日本Sanyo Chemicals的Pelestat7490)和3g聚酰胺6,6短纤维(长2mm,1.7分特)并在双辊压廷机上加工,生产出辊压片材(辊压时间5分钟,170℃,速度22/26转/分,辊隙0.5mm)。在加热的高压压机(在175℃下加热时间为5分钟)中由辊压片材生产0.5mm厚的压制板。在加压下于第2个水冷却的压机中冷却该板(5分钟)。在生产后直接使用防护圈电极按DIN 53482在20%相对湿度下测定导电率:体积电阻RD为3.2×1010欧姆,表面电阻RO为7.4×1010欧姆。在空气(约55%相对湿度)中储存一周后,RD为3.1×109欧姆,RO为1.3×1010欧姆。
实施例15.抗静电ABS的生产
用刮铲混合54g ABS CycolacTCA(GEP),2.4g其中已加入5wt%NaClO4·H2O的聚醚酯酰胺(Elf-Atochem S.A.的PebaxMH 1657)和3.6g芳族聚酰胺纤维型F AR700/075(Schwarzwlder Textilwerke,D7771 Schenkenzell)并加工以生产出辊压片材(辊压时间5分钟,175℃,速度28/36转/分,辊隙0.5mm)。使用加热的高压压机(在185℃加热时间为5分钟)由辊压片材生产0.5mm厚的压制板。使用第2个水冷却的压机在加压下冷却该板5分钟。生产后直接使用防护圈电极按DIN53482在20%相对湿度下测量导电率:体积电阻RD为4×1010欧姆,表面电阻RO为3×1011欧姆。在空气(50%相对湿度)中储存一周后,RD为2.6×1010欧姆,RO为2.7×1010欧姆。该板因黄色芳族聚酰胺纤维而呈黄色。
实施例16.抗静电LLD-聚乙烯的生产
使用刮铲混合54.6g LLD-PE Dowlex2045E(DowChemicals),1.8g其中已加入5wt% NaClO4·H2O的聚醚酯酰胺(Elf-Atochem S.A.的PebaxMH 1657)和3.6g聚酰胺6,6短纤维(长0.6mm,0.9分特)并在双辊压延机上加工,生产出辊压片材(在180℃辊压时间为5分钟,速度22/26转/分,辊隙0.5mm)。在加热的高压压机(加热时间5分钟,190℃)中由该辊压片材生产0.5mm厚的压制板。使用第2个水冷却的压机在加压下冷却该板(5分钟)。在20%相对湿度下储存3天后,压制板的体积电阻RD为2×109欧姆,表面电阻RO为1.3×1010欧姆。在50%相对湿度的空气中储存1周后,RD为7×108欧姆,RO为4×109欧姆。测量通过使用防护圈电极按DIN 53482进行。
实施例17.抗静电聚丙烯的生产
在混合器中将192g聚丙烯(Profax6501,稳定化),3.84g聚醚酯酰胺(日本Sanyo Chemicals的Pelestat6321),4.00g聚酰胺6短纤维(1.8mm,11.0分特)和0.16g NaClO4·H2O混合2分钟,然后使用单螺杆挤出机(BRABENDER 25D)在285℃挤出,随后造粒。在260℃和300巴下生产的压制板在水冷却和储存8天(58%相对湿度,23℃)后的体积电阻RD(使用防护圈电极按DIN 53482测量,20cm2,间隙5mm,在500伏下保持5分钟后)为1.9×1010Ω,表面电阻RO(使用相同的防护圈电极测量)为1.7×1012Ω。
实施例18.抗静电聚丙烯的生产
在混合器中将190g聚丙烯(Profax6501,稳定化),4.80g聚醚酯酰胺(PebaxMH1657粉末,EIf Atochem,France),5.00g聚酰胺66粉末(UltramidAS 2500S)和0.2gNaClO4·H2O混合3分钟,然后使用单螺杆挤出机(BRABENDER 25D)在245℃下挤出,随后造粒。在200℃和300巴下生产的压制板在水冷却和储存2天(51%相对湿度,23℃)后的体积电阻RD(使用防护圈电极按DIN 53482测量,20cm2,间隙5mm,在500伏下保持5分钟后)为1.1×1010Ω,表面电阻RO(使用相同的防护圈电极测量)为7.7×1010Ω。
实施例19.抗静电聚苯乙烯的生产
在混合器中将191.8g聚苯乙烯(聚苯乙烯168N,BASF),3.84g聚醚酯酰胺(Pelestat6321粉末,Sanyo Chemicals,日本),4.00g聚酰胺6粉末(长1.8mm,11分特),0.16gNaClO4·H2O和0.20g Irganox900FF(Ciba SpecialtyChemicals)混合3分钟,然后使用单螺杆挤出机(BRABENDER25D)在210℃下挤出,随后造粒。在200℃和300巴下生产的压制板在水冷却和储存2天(40%相对湿度,23℃)后的体积电阻RD(使用防护圈电极按DIN 53482测量,20cm2,间隙5mm,在500伏下保持5分钟后)为8.7×1011Ω,表面电阻RO(使用相同的防护圈电极测量)为3.2×1011Ω。
实施例20.抗静电聚苯乙烯的生产
在混合器中将189.8g聚苯乙烯(聚苯乙烯168N,BASF),4.80g聚醚酯酰胺(Pelestat6321,日本Sanyo Chemicals),5.00g聚酰胺66粉末(UltramidAS 2500S),0.20gNaClO4·H2O和0.20g Irganox900FF(Ciba SpecialtyChemicals)混合3分钟,然后使用单螺杆挤出机(BRABENDER25D)在235℃下挤出,随后造粒。在230℃和300巴下生产的压制板在水冷却和储存2天(48%相对湿度,23℃)后的体积电阻RD(使用防护圈电极按DIN 53482测量,20cm2,间隙5mm,在500伏下保持5分钟后)为93.2×1010Ω,表面电阻RO(使用相同防护圈电极测量)为9.2×1010Ω。
Claims (13)
1.一种包含热塑性或弹性聚合物基质(A)和紧邻纤维形式的抗静电混合物(B)的组合物,所述混合物包含
(b1)一种为纤维状或混合时形成纤维且不溶于热塑性或弹性聚合物基质(A)中的有机聚合材料,该材料选自聚丙烯酸酯、聚甲基丙烯酸酯、聚丙烯腈、聚乙烯醇、聚乙烯乙酸酯、聚酰胺、聚氨酯或聚酯;
(b2)一种具有用于配合或溶剂化无机质子酸的盐的嵌段且能传导离子电荷的聚合物或共聚物,所述聚合物或共聚物选自聚醚脲、聚醚酰胺、聚醚酯酰胺或聚醚酯;和
(b3)一种已在聚合物或共聚物(b2)中配合或溶剂化的盐,该盐选自LiClO4,LiCF3SO3,NaClO4,LiBF4,NaBF4,KBF4,NaCF3SO3,KClO4,KPF6,KCF3SO3,KC4F9SO3,Ca(ClO4)2,Ca(PF6)2,Mg(ClO4)2,Mg(CF3SO3)2,Zn(ClO4)2,Zn(PF6)2或Ca(CF3SO3)2。
2.根据权利要求1的组合物,其中组分(A)是聚烯烃,聚苯乙烯,丙烯腈/丁二烯/苯乙烯共聚物,聚氯乙烯或苯乙烯和丁二烯的共聚物,聚苯醚,聚酰胺。
3.根据权利要求2的组合物,其中组分(A)是聚烯烃,聚苯乙烯,丙烯腈/丁二烯/苯乙烯共聚物,聚氯乙烯或苯乙烯和丁二烯的共聚物。
4.根据权利要求3的组合物,其中组分(A)是聚氯乙烯,聚乙烯,聚苯乙烯或聚丙烯。
5.根据权利要求1的组合物,其中纤维状或混合时形成纤维的聚合材料(b1)为聚酯,聚酰胺x或聚酰胺x,y,其中x和y各自独立地为4-14的数。
6.根据权利要求1的组合物,其中聚合物或共聚物(b2)为嵌段共聚物聚醚酯酰胺,其中聚醚链段包括分子量Mn为200-6000道尔顿的聚乙二醇单元,聚酰胺链段包括分子量Mn为200-6000道尔顿的聚酰胺x或聚酰胺x,y,其中x和y为4-14的数。
7.根据权利要求1的组合物,其中无机盐(b3)的存在量基于共聚物(b2)为0.05-10wt%。
8.根据权利要求7的组合物,其中无机盐(b3)的存在量基于共聚物(b2)为0.5-5wt%。
9.根据权利要求1的组合物,其中纤维状或混合时形成纤维的有机聚合材料(b1)与共聚物(b2)的质量比为20∶1-1∶10。
10.根据权利要求9的组合物,其中纤维状或混合时形成纤维的有机聚合材料(b1)与共聚物(b2)的质量比为10∶1-1∶3。
11.根据权利要求1的组合物,其中组分(b1)、(b2)和(b3)的抗静电活性混合物的总存在量基于热塑性或弹性聚合物基质为0.1-15wt%。
12.根据权利要求1的组合物,其中热塑性或弹性聚合物基质(A)为聚氯乙烯,聚乙烯或聚丙烯,纤维状或形成纤维的有机聚合材料(b1)为聚酯或聚酰胺,能离子导电的共聚物(b2)为聚醚酯酰胺或聚醚酯,质子酸的无机盐(b3)为NaClO4,KPF6或LiCF3SO3。
13.一种抗静电混合物,包含
(b1)一种为纤维状或混合时形成纤维且不溶于热塑性或弹性聚合物基质(A)中的有机聚合材料,该材料选自聚丙烯酸酯、聚甲基丙烯酸酯、聚丙烯腈、聚乙烯醇、聚乙烯乙酸酯、聚酰胺、聚氨酯或聚酯;
(b2)一种具有用于配合或溶剂化无机质子酸的盐的嵌段且能传导离子电荷的聚合物或共聚物,所述聚合物或共聚物选自聚醚脲、聚醚酰胺、聚醚酯酰胺或聚醚酯;和
(b3)一种已在聚合物或共聚物(b2)中配合或溶剂化的盐,该盐选自LiClO4,LiCF3SO3,NaClO4,LiBF4,NaBF4,KBF4,NaCF3SO3,KClO4,KPF6,KCF3SO3,KC4F9SO3,Ca(ClO4)2,Ca(PF6)2,Mg(ClO4)2,Mg(CF3SO3)2,Zn(ClO4)2,Zn(PF6)2或Ca(CF3SO3)2。
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- 1997-09-12 CA CA002215461A patent/CA2215461C/en not_active Expired - Lifetime
- 1997-09-13 KR KR1019970047964A patent/KR100525183B1/ko not_active IP Right Cessation
- 1997-09-15 TW TW086113377A patent/TW460520B/zh not_active IP Right Cessation
- 1997-09-15 CN CN97118459A patent/CN1092224C/zh not_active Expired - Lifetime
- 1997-09-15 ZA ZA9708287A patent/ZA978287B/xx unknown
- 1997-09-15 NO NO974246A patent/NO309868B1/no not_active IP Right Cessation
- 1997-09-15 CZ CZ19972903A patent/CZ294418B6/cs not_active IP Right Cessation
- 1997-09-16 JP JP26939397A patent/JP3196072B2/ja not_active Expired - Lifetime
- 1997-09-16 BR BR9704720A patent/BR9704720A/pt not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
KR19980024827A (ko) | 1998-07-06 |
EP0829520A1 (de) | 1998-03-18 |
ID18264A (id) | 1998-03-19 |
NO974246L (no) | 1998-03-17 |
AU3746997A (en) | 1998-03-19 |
NO974246D0 (no) | 1997-09-15 |
JPH10120924A (ja) | 1998-05-12 |
AU723382B2 (en) | 2000-08-24 |
RU2188220C2 (ru) | 2002-08-27 |
DE59712007D1 (de) | 2004-11-18 |
CZ290397A3 (cs) | 1998-03-18 |
CA2215461A1 (en) | 1998-03-16 |
JP3196072B2 (ja) | 2001-08-06 |
NO309868B1 (no) | 2001-04-09 |
CZ294418B6 (cs) | 2004-12-15 |
SK284540B6 (sk) | 2005-06-02 |
EP0829520B1 (de) | 2004-10-13 |
CA2215461C (en) | 2006-11-07 |
ZA978287B (en) | 1998-03-16 |
SK124697A3 (en) | 1998-04-08 |
TW460520B (en) | 2001-10-21 |
KR100525183B1 (ko) | 2006-01-27 |
ES2229326T3 (es) | 2005-04-16 |
ATE279479T1 (de) | 2004-10-15 |
BR9704720A (pt) | 1998-12-15 |
CN1183448A (zh) | 1998-06-03 |
MX9706948A (es) | 1998-08-30 |
US5965206A (en) | 1999-10-12 |
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