CN100378154C - 填充剂组合物 - Google Patents
填充剂组合物 Download PDFInfo
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- CN100378154C CN100378154C CNB038091100A CN03809110A CN100378154C CN 100378154 C CN100378154 C CN 100378154C CN B038091100 A CNB038091100 A CN B038091100A CN 03809110 A CN03809110 A CN 03809110A CN 100378154 C CN100378154 C CN 100378154C
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Abstract
一种组合物，其包含塑料材料、无机颗粒固体(例如三水合铝)和式A-(X-Y-CO)m(O-B-CO)nOH 的偶联改性剂，其中A是含有带有1到2个相邻羰基基团的封端乙烯键的基团；X是直接键、 O 或 N ；Y是C1-18亚烷基或C2-18亚烯基；B是C2-6亚烷基；m是1到4且n是0到5，其条件是当A含有2个与乙烯键相邻的羰基基团时，X是氮。其具体例子是B-羧基乙基丙烯酸酯和5-羧基戊基顺丁烯二酰亚胺。
Description
本发明涉及到一种组合物，该组合物包含聚合物材料或弹性体、无机颗粒固体和偶联剂。所述偶联剂包含封端羧酸基团和封端乙烯类不饱和基团。
将无机填充剂添加到热塑性聚合物、热固性聚合物、弹性体和橡胶等聚合物材料中是已知的。尽管此类含有填充剂的聚合物材料制成的成型物的刚性、硬度和抗蠕变性通常呈现出改进，制品的韧性和展延性同时显著地趋向于降低。对于填充热塑性聚合物尤其如此，此时成型物变得太脆、抗冲击性太低、拉伸太差，以至无任何的实际用途。
为克服上述缺陷以改善无机颗粒固体与聚合物材料的相容性，已经发表了多种方法。这些方法包括混入颗粒固体的表面改性剂，所述表面改性剂可以涂在颗粒固体上做为单独的预处理物，或者在加工期间适当的阶段，加入到聚合物材料及颗粒固体的混合物中。
表面改性剂通常被分为两类，即偶联改性剂和非偶联改性剂。在非偶联表面改性剂中，改性剂与颗粒固体表面发生相互作用，但不与聚合基质发生相互作用。在偶联表面改性剂中，改性剂在颗粒固体与聚合基质表面两者之间具有强烈相互作用。酸性官能改性剂在两类中都存在，并包括脂肪酸类和聚合物酸类。脂肪酸类通常是非偶联改性剂，其中羧基基团强烈地与无机颗粒固体表面结合，而脂肪基团与聚合基质发生相互作用。聚合物酸类一般被认为是偶联表面改性剂，其中羧基基团与无机颗粒固体表面之间强烈地发生作用，而聚合链与聚合基质之间强烈地发生相互作用。相互作用的程度主要地取决于表面改性剂的官能度和聚合物材料的类型。含有自由烯基团的聚合酸类的例子在US 4,385,138、US 3,519,593和GB1,223,286中公开。含有不饱和烯键的简单羧酸也已经作为偶联改性剂得到了考察。由此，丙烯酸本身作为聚丙烯中的碳酸钙填充剂的偶联改性剂已经公开于European Polymer Jounal，36，2000，137-148中。可是，加工中其挥发性是一个明显的缺陷，JP 64-33163也公开了使用羟基C2-6-烷基丙烯酸的丁二酸半酯的表面处理，然而，含有烯烃键的这类酸全都是不能令人完全满意的。
现已发现，顺丁烯二酰亚胺和(甲基)丙烯酸的某些衍生物作为无机颗粒固体的表面改性剂与那些本领域中已知的相比呈现出优越性。因此，根据本发明提供了一种组合物，该组合物包含塑料材料、无机颗粒固体以及式1的偶联改性剂：
A-(X-Y-CO)m(O-B-CO)nOH 1
式中：
A是带有具有一个或两个相邻羰基的烯类封端基团的基团；
X是直接键、O或N；
Y是C1-18亚烷基或C2-18亚烯基；
B是C2-6亚烷基；
m是从1到4；
n是0到5；
丙烯酸除外，且当A含有2个与烯类团相邻的羰基时，X是N。
当A含有仅一个羰基并且X是O时，A-X-基团优选C1-6-烷基丙烯酸(如甲基丙烯酸，特别是丙烯酸)的残基。当A含有2个邻近烯类双键的羰基并且X是N时，A-X-基团更优选顺丁烯二酰亚胺的残基。
Y可以是直链的或者是支化的，但优选直链的。也优选Y是亚烷基，并且Y含的碳原子数不少于2个。
B可以被一个或多个C1-6烷基取代，烷基可以是直链的，也可以是支化的。(O-B-CO)n基团可以是一到多个不同的羟基羧酸或其内酯的残基，优选B含有5到6个碳原子，适宜的羟基羧酸或内酯的例子是5-羟基戊酸、6-羟基己酸、δ-戊内酯、ε-己内酯和烷基取代ε-己内酯如4-甲基、3-甲基、7-甲基、5-甲基、5-叔丁基、4，4，6-三甲基和4，6，6-三甲基ε-己内酯。当(O-B-CO)n基团是二个或多个不同的羟基羧酸或内酯的残基时，优选其从δ-戊内酯和ε-己内酯衍生。当(O-B-CO)n衍生自二个或多个不同的羟基羧酸或其内酯时，主要成分还优选6-羟基己酸或ε-己内酯。
除A-X-是C1-6烷基丙烯酸的残基之外，更优选n是0。
在一类优选的化合物中，m是从1到4，特别是当n是0时尤其如此，并且在另一类优选的化合物中，mi是1，n是0，A-X-是顺丁烯二酰亚胺酐的残基。
商品级的丙烯酸通常含有结构为CH2＝CH-CO(OCH2CH2CO)xOH的聚合物材料，其中x是从2到4。应该明白，上文涉及到的丙烯酸衍生物包括此类聚合物。
式1的化合物的具体例子是丙烯酸β-羧基乙基酯、6-羧基己基顺丁烯二酰亚胺和10-羧基癸基顺丁烯二酰亚胺。
聚合物材料可以是无机颗粒固体与之一起使用的任何聚合物基质，并且包括橡胶、树脂和塑料材料。此类聚合物材料的例子是天然橡胶，合成橡胶如苯乙烯-丁二烯橡胶、乙烯-丙烯三元共聚物橡胶、聚氨酯橡胶，聚烯烃如聚乙烯、聚丙烯和聚异丁烯；聚丙烯腈；聚丁二烯；丁二烯和丙烯腈的共聚物；聚苯乙烯；聚(苯乙烯丙烯腈)；苯乙烯与丁二烯和丙烯腈的共聚物；乙烯与丙烯或1-丁烯或醋酸乙烯酯或顺丁烯二酸酐的共聚物；聚碳酸酯树脂；苯氧基树脂；聚氯乙烯；氯乙烯与醋酸乙烯酯或其他乙烯基酯的共聚物；聚醋酸乙烯酯；聚醋酸乙基乙烯酯；直链聚酯；聚乙烯醇缩醛；聚偏二氯乙烯，偏二氯乙烯与氯乙烯及丙烯酸的共聚物；聚(甲基丙烯酸甲酯)，超聚酰胺如尼龙6，6和6，10；聚酰亚胺；聚砜；烷基树脂如苯二甲酸二烷基酯聚合物；环氧树脂；酚树脂；硅树脂；聚酯树脂，包括烷基树脂；聚(醋酸乙烯酯-氯乙烯)；聚偏二氯乙烯；热塑性聚氨酯；热塑性聚羟基醚；热塑性聚酯和聚(氯乙烯-顺丁烯二酸酐)。聚合物材料优选热塑性聚合物，如聚乙烯、聚丙烯、乙烯丙烯橡胶或聚醋酸乙基乙烯酯。
无机颗粒固体可以是任何与聚合物材料一起使用的固体物料，特别包括做为填充剂使用的固体。这些固体可以是粒状的固体或者是粉状的、特别是吹粉形式的固体。例子包括碳酸钙、硫酸钙、硫酸钡、碳酸钡、氧化镁、氢氧化镁、二氧化钛、氧化铁、钙及镁的硅酸盐、硅酸铝、高岭土、云母、滑石、金属纤维及粉末、锌、铝、氢氧化铝、玻璃纤维、耐火纤维、炭黑包括增强的和非增强的炭黑、氧化铝、石英、木粉、粉状的纸/纤维、石棉、crysatille、直闪石、青石棉、硅灰石、硅镁土等等。
使用氢氧化铝和碳酸钙为无机颗粒固体和醋酸乙基乙烯酯或聚丙烯为聚合物材料，得到了有用的效果。
当n是0时，式1的化合物可用现有技术的任意方法制造。因此，当A是顺丁烯二酰亚胺的残基时，偶联改性剂可以用顺丁烯二酸酐与氨基羧酸在适当的溶剂里反应制造。适宜的溶剂是C1-18-低级烷基羧酸，特别是醋酸。氨基羧酸含有含多至18个碳原子的、可以是支化的或优选直链的亚烷基或亚烯基链。例子是6-氨基己酸、11-氨基十一烷酸和β-丙氨酸。反应通常在约50℃以上、优选约90℃以上的温度下进行。在低级烷基羧酸的沸点进行反应是便利的。EP 847,991叙述了顺丁烯二酰亚胺亚烷基羧酸的制备方法。
当A是(甲基)丙烯酸的残基、X是N或O且n是0时，偶联改性剂可以通过将(甲基)丙烯酸与含有带有多至18个碳原子的亚烷基链或亚烯基链的氨基羧酸或羟基羧酸反应得到。反应可以任选地在惰性溶剂存在下进行，并且通常在50℃到120℃下进行。一个例子是丙烯酸β-羧基乙酯。
当n是1到5时，偶联改性剂可以通过将式1的化合物(其中n为0)与羟基羧酸或其内酯在惰性气氛及50℃到250℃的温度下获得。内酯的例子是δ-戊内酯和ε-己内酯，包括其混合物。惰性气氛可由周期表中的任意惰性气体提供，但优选氮。反应优选在100℃以上的温度下进行，特别是在150℃以上的温度下进行。为了使偶联改性剂的炭化最小化，温度优选不高于200℃，特别是不高于180℃。也优选在酯化反应催化剂(例如烷醇的金属盐如丁醇锆)存在下进行反应。
式1的某些偶联改性剂是新的，因此，本发明的另一方面提供了式1的化合物，其中，A、X、Y、B和m定义在上文中，而n是从1到5。
可以在组合物制备的任何方便的阶段将偶联改性剂涂覆在颗粒固体的表面。因此，颗粒固体可以用偶联改性剂预涂，或者可以在组合物制备期间把偶联改性剂加入到颗粒固体和聚合物材料的混合物中。
当颗粒固体用偶联改性剂预涂时，可以在无水条件下将两种成分一起混合对其进行制备。这种混合可以伴随研磨加工以减少颗粒固体的颗粒度。另一种方法是，偶联改性剂可以施于液体载体或含水的乳状液中的颗粒固体上，所述液体载体可以是极性的或非极性的有机溶剂。颗粒固体与含有偶联改性剂的载体之间的接触可以本领域中已知的方法进行，例如通过浸渍或喷雾。可以通过任何适当的方法(例如过滤)从有机溶剂里分离涂覆过的颗粒固体，如果需要，可以通过用适当的有机溶剂洗涤除去过量的偶联改性剂。另外一种方法是通过蒸发有机溶剂得到涂覆过的固体颗粒。适宜的有机溶剂的例子是甲醇、乙醇、丙醇、乙醚、丙酮、甲乙酮、乙酸乙酯、苯、甲苯、二甲苯、己烷、戊烷、十氢化萘、萘满、氯仿、二氯甲烷及氯仿。
本发明的另一方面提供了一种组合物，该组合物包括颗粒固体和式1的偶联改性剂。
颗粒固体与偶联改性剂的混合一般在20℃到偶联改性剂的分解温度之间进行，可以在正常大气压下混合，但较高或较低的压力也是可以的，倘如果这样做有助于偶联改性剂在颗粒固体表面上的分布的话。
当颗粒固体和偶联改性剂在无水条件下混合时，颗粒固体的表面涂覆优选在空气或氧的存在下进行，因为这样减少了偶联改性剂的聚合的机会。
当颗粒固体被载体里的偶联改性剂所涂覆时，优选其包括阻聚剂，如对苯二酚、甲基对苯二酚、p-苯醌、萘醌或叔丁基儿茶酚或受阻酚如2，6-二叔丁基苯酚。受阻酚可以在商标Irganox(Ciba Geigy)下购得。基于偶联改性剂的重量，阻聚剂的量优选不大于10％，更优选小于5％，特别是不大于0.2％。也优选基于偶联改性剂的重量，阻聚剂不少于0.05％，特别是不少于0.2％。
施于颗粒固体表面上的偶联改性剂的量主要依赖于固体的性质和它的表面积。偶联改性剂的优选的量足以提供在固体颗粒上至少覆盖一个单分子层的偶联改性剂。一般地，基于颗粒固体重量，偶联改性剂的量不大于20％，更优选不大于6％，特别是不大于2％。也优选基于颗粒固体重量，偶联改性剂优选的量不少于0.01％，更优选不少于0.2％，特别是不少于0.3％。
涂覆有偶联改性剂的颗粒固体在被与热塑性聚合物材料一起使用时已被发现特别有效，上述聚合物材料的例子是聚烯烃如高密度聚乙烯、中或低密度聚乙烯、结晶聚丙烯、结晶乙烯丙烯嵌段共聚物、聚丁烯、聚-4-甲基-1-戊烯；聚氯乙烯、聚偏二氯乙烯，聚苯乙烯、聚(甲基)丙烯酸甲酯、聚酰胺、聚缩醛、直链聚酯、聚氨酯、ABS聚合物包括其混合物，以及它们与弹性体的共混物。
对于热塑性聚合物，优选将聚合物、颗粒固体和偶联改性剂在有自由基发生剂(如二枯基过氧化物、2，5-二甲基-2，5-二(叔丁基过氧化)己烷、偶氮二异丁腈、二丁基氧化锡和二叔丁基过氧化异丙基苯)熔融混合，当聚合物材料已经含有自由基发生剂，可能没有再进一步加入自由基发生剂的必要。发明人认为，自由基发生剂导致偶联改性剂的烯键与其本身和/或聚合物材料聚合。
另外，自由基发生剂也可以已经存在于聚合物材料中。
自由基发生剂的量可以在宽范围内变化，但优选基于偶联改性剂的量在1到100重量％之间。优选自由基发生剂的量基于偶联改性剂的量不大于70％，特别是不大于50％。
当含有颗粒固体和偶联改性剂的聚合物材料被用于涂覆固体表面时，当组合物也含有适当的光引发剂时，也可以通过其他的方法引发聚合，例如电子束或光化辐射。
取决于颗粒固体的性质及所希望的组合物的用途，含有塑料材料、颗粒固体和偶联改性剂的组合物里的颗粒固体的量可以在宽范围内变化。基于组合物的量，颗粒固体的典型用量为从20到80％，特别是从20到60％。
虽然通常优选用偶联改性剂涂覆颗粒固体，有时预制备偶联改性剂和聚合物材料的混合物，然后用此类混合物来涂覆颗粒固体更方便。特别当偶联改性剂的量在最后组合物中相对较少时更是如此。
因此，本发明的另一方面提供了包含偶联改性剂和聚合物材料的组合物。基于聚合物材料的量，优选偶联改性剂的量是从1到30重量％。混合可以在任何适宜的、对偶联改性剂和聚合物材料的物理状态适当的设备中进行。已混合的偶联材料和聚合物材料的混合物可含有阻聚剂或者聚合催化剂，这取决于优选偶联改性剂聚合之前或聚合之后加入已混合的混合物到颗粒固体中。
包含偶联改性剂和聚合物材料的组合物可以通过类似以上用于偶联改性剂和颗粒固体的方式制备。这种组合物可以被用作“母料”，并在形成制品时加入其他的聚合物材料中。与其他的聚合物材料混合的“母料”的量可以在宽范围内改变，这取决于聚合物材料和颗粒固体的性质，但基于最终组合物的总重，优选从0.5到50％。基于组合物的总重，优选“母料”量不少于10％，特别是不少于20％。虽然用于制备“母料”的聚合物可以不同于加进的聚合物，但优选使用一样的聚合物。当聚合物材料是聚丙烯、聚乙烯、聚乙烯/聚丙烯二烯、醋酸乙基乙烯酯、聚氯丁二烯、氯化聚乙烯、氯磺化聚乙烯、聚氯乙烯，特别是天然橡胶和合成橡胶如丁二烯基弹性体(如丁二烯-苯乙烯、丁二烯-丙烯腈橡胶)、聚丁二烯、聚异戊二烯和天然橡胶时，“母料”的使用是特别有用。
组合物可以含有其他添加剂，这些添加剂通常作为稳定剂、UV吸收剂、增塑剂、润滑剂、交联剂、交联加速剂、颜料、阻燃剂、抗静电剂、增稠剂、发泡剂、脱模剂加入到组合物中。
当偶联改性剂是液体时，以把改性剂吸收在多孔的固体上为有利，因为这样有助于偶联改性剂在塑料材料、母料或作为填充剂的涂层中的均匀分布。多孔固体的例子是吹粉，如钙或铝的硅酸盐、硅藻土和膨润土。偶联改性剂可与多孔固体本身混合或者在有机液体、水中或以乳状液的形式加入多孔固体。基于多孔固体的重量，偶联改性剂的量优选20到80％。含有偶联改性剂的多孔固体可以以与偶联改性剂加入方式一样的方式加入塑料材料中或填充剂中。包含偶联改性剂和多孔固体的组合物也可以含有其他最终的组合物通常包括的添加剂。
本发明以如下的实施例来说明，其中所涉及的“份”出明确指出并非如此外以重量计。
偶联改性剂的制备
改性剂1：5羧基戊基顺丁烯二酰亚胺改性剂
按照EP 847,991实施例4进行制备。
顺丁烯二酸酐(80.4份，820mM，来至Aldrich)和6-氨基己酸(60份，657mM，来至Aldrich)在20℃在400毫升冰醋酸里制成料浆，然后，反应物在回流(130℃)搅拌5小时，得到清澈的橙色溶液，溶液体积随着醋酸的部分蒸发减少。冷却到20℃之后，分离橙色固体产物，在600毫升水里重结晶，得到黄色固体(33.6份，mp＝71-72℃)。
以同样方式制备2-羧基乙基顺丁烯二酰亚胺和10-羧基癸基顺丁烯二酰亚胺。
实施例2到6
三水合铝(39份，Alcan SF7E，Alcan)与下表1的偶联改性剂充分混合，得到大约0.115摩尔当量/克。然后已涂覆的填充剂与乙烯醋酸酯树乙脂(26份，1020VN5，Elf Atochem)在Brabender Plasti-Corder混合器重通过在加入树脂之前首先把混合室加热到180℃混合。树脂熔化后，加入已涂覆填充剂，在180℃下充分混合10分钟，然后组合物冷却并令其静置24小时，然后在160℃热压10分钟，得到大约2mm厚的扁平薄片，薄片冷却到20℃，静置24小时之后，切割成具有大约4mm腰部的哑铃形样品。用Hounsfield H10张力计测量样品的拉伸强度和伸长率，张力计上装有1000牛顿荷载和H500L激光伸长计。6个重复样品的平均拉伸强度和伸长率载于表1。
表1
| 实施例 | 偶联改性剂 | 改性剂与填充剂之比摩尔当量/克 | 拉伸强度 | 伸长率％ |
| 1 | CEM | 0.115 | 11.46 | 137.8 |
| 2 | CPM | 0.114 | 12.28 | 130.6 |
| 3 | CDM | 0.113 | 12.51 | 181.2 |
| 4 | BCA | 0.115 | 13.72 | 161.7 |
| 5 | BCA<sup>＊</sup> | 0.115 | 15.44 | 159.1 |
CEM是2-羧基乙基顺丁烯二酰亚胺。
CPM是5-羧基戊基顺丁烯二酰亚胺。
COM是10-羧基癸基顺丁烯二酰亚胺。
BCA是Bimax的2-羧基乙基丙烯酸酯。
＊除组合物含有基于混合时加入的填充剂的重量0.06％重量的枯基过氧化物外，样品5是样号4的重复。
Claims (15)
1.一种组合物，其包含塑料材料、颗粒固体和式1的偶联改性剂，
A-(X-Y-CO)m(O-B-CO)nOH 1
其中：
A是含有带有1到2个相邻羰基基团的封端乙烯键的基团；
X是直接键、O或N；
Y是C1-18亚烷基或C2-18亚烯基；
B是C2-6亚烷基；
m是1到4；
n是0到5；
其条件是当A含有2个与乙烯键相邻的羰基基团时，X是氮。
2.权利要求1的组合物，其中，A-X-是丙烯酸的残基。
3.权利要求1的组合物，其中，A-X-是顺丁烯二酰亚胺的残基。
4.权利要求1的组合物，其中，(O-B-CO)n是δ-戊内酯或∈-己内酯的残基或其混合物，n是1到5。
5.权利要求1的组合物，其中，n是0。
6.权利要求1的组合物，其中，颗粒固体是无机填充剂。
7.权利要求6的组合物，其中，无机填充剂是三水合铝。
8.权利要求1的组合物，其中，塑料材料是热塑性的聚合物。
9.权利要求1的组合物，其中，基于颗粒固体的量，偶联改性剂的量不少于0.01％且不大于10％。
10.权利要求1的组合物，其中，基于组合物的量，颗粒固体的量是20％到80％。
11.权利要求1的组合物，其进一步包含聚合引发剂。
12.一种组合物，其包含颗粒固体和式1的偶联改性剂，
A-(X-Y-CO)m(O-B-CO)nOH 1
其中：
A是含有带有1个或多个相邻羰基基团的封端乙烯键的基团；
X是直接键、O或N；
Y是C1-18亚烷基或C2-18亚烯基；
B是C2-6亚烷基；
m是1到4；
n是0到5；
其条件是当A含有2个与乙烯键相邻的羰基基团时，X是氮。
13.权利要求12的组合物，其进一步包含阻聚剂。
14.一种组合物，其包含聚合物材料和式1的偶联改性剂，
A-(X-Y-CO)m(O-B-CO)nOH 1
其中：
A是含有带有1个或多个相邻羰基基团的封端乙烯键的基团；
X是直接键、O或N；
Y是C1-18亚烷基或C2-18亚烯基；
B是C2-6亚烷基；
m是1到4；
n是0到5；
其条件是当A含有2个与乙烯键相邻的羰基基团时，X是氮。
15.式1的偶联改性剂：
A-(X-Y-CO)m(O-B-CO)nOH 1
其中：
A是含有带有1到2个相邻羰基基团的封端乙烯键的基团；
X是直接键、O或N；
Y是C1-18亚烷基或C2-18亚烯基；
B是C2-6亚烷基；
m是1到4；
n是从1到5；
其条件是当A含有2个与乙烯键相邻的羰基基团时，X是氮。
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GBGB0206755.1A GB0206755D0 (en) | 2002-03-22 | 2002-03-22 | Filler composites |
| GB0206755.1 | 2002-03-22 | ||
| GB0226925.6 | 2002-11-16 | ||
| GBGB0226925.6A GB0226925D0 (en) | 2002-03-22 | 2002-11-16 | Filler composites |
| PCT/GB2003/000718 WO2003080720A1 (en) | 2002-03-22 | 2003-02-19 | Filler composites |
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| CN1646617A CN1646617A (zh) | 2005-07-27 |
| CN100378154C true CN100378154C (zh) | 2008-04-02 |
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| US (1) | US7732514B2 (zh) |
| EP (1) | EP1487913B1 (zh) |
| JP (1) | JP4279686B2 (zh) |
| KR (1) | KR100910283B1 (zh) |
| CN (1) | CN100378154C (zh) |
| AU (1) | AU2003208421A1 (zh) |
| BR (1) | BR0308647A (zh) |
| CA (1) | CA2480098C (zh) |
| ES (1) | ES2389435T3 (zh) |
| GB (2) | GB0206755D0 (zh) |
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| US8530573B2 (en) * | 2006-05-10 | 2013-09-10 | Designer Molecules, Inc. | Modified calcium carbonate-filled adhesive compositions and methods for use thereof |
| ES2391042T3 (es) * | 2006-10-24 | 2012-11-20 | Lubrizol Limited | Agentes de acoplamiento poliméricos |
| EP2606074B1 (de) | 2010-08-18 | 2014-07-23 | BYK-Chemie GmbH | Härtbare polymermischung |
| DK2537883T3 (da) * | 2011-06-20 | 2014-05-26 | Imerys Minerals Ltd | Fremgangsmåder og sammensætninger i forbindelse med genanvendelse af polymeraffald |
| US11067204B2 (en) | 2014-09-09 | 2021-07-20 | Imertech Sas | Polymer compositions |
| GB201416456D0 (en) * | 2014-09-17 | 2014-10-29 | Imerys Minerals Ltd | Polymeric compositions |
| GB201608480D0 (en) * | 2016-05-13 | 2016-06-29 | Imerys Minerals Ltd | Resin composition and article |
| DE102017106505A1 (de) | 2017-03-27 | 2018-09-27 | NK Neuhäuser Kunststoff GmbH | Verträglichkeitsvermittler zur Verträglichmachung von Polyolefin-Gemischen, Verfahren zu dessen Herstellung, sowie Verfahren zur Herstellung von Formteilen aus Polyolefin-Gemischen |
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| US3519593A (en) | 1967-05-22 | 1970-07-07 | Amicon Corp | Polymer coated mineral filler and method of making and using same |
| GB1223286A (en) | 1967-08-28 | 1971-02-24 | Amicon Corp | Reinforced polymer filler |
| JPS51132256A (en) * | 1975-04-30 | 1976-11-17 | Japan Synthetic Rubber Co Ltd | Thermoplastic composition |
| US4320173A (en) * | 1980-05-19 | 1982-03-16 | Monsanto Company | Rubber compositions containing N-(carboxyalkyl)maleamic acid |
| US4385136A (en) | 1981-08-27 | 1983-05-24 | Union Carbide Corporation | Reinforcement promoters for filled thermoplastic polymers |
| DE258242T1 (de) * | 1985-04-25 | 1988-06-30 | The British Hydromechanics Research Association, Cranfield, Bedford, Gb | Schleifmittelstroemung. |
| US4687810A (en) * | 1986-01-02 | 1987-08-18 | Monsanto Company | Making rubber blends of diene rubber & EPR or EPDM |
| DD258242A1 (de) * | 1987-03-05 | 1988-07-13 | Akad Wissenschaften Ddr | Verfahren zur herstellung von thermoplast/fuellstoff-verbunden mit verbesserten mechanischen eigenschaften |
| JPS6433163A (en) | 1987-07-30 | 1989-02-03 | Nippon Soda Co | Surface treating agent |
| EP0847991A1 (en) | 1996-12-16 | 1998-06-17 | Dainippon Ink And Chemicals, Inc. | Method for the preparation of N-(carboxyalkyl) imides |
| JP3980721B2 (ja) * | 1997-10-23 | 2007-09-26 | 株式会社日本触媒 | 複合微粒子、その用途 |
| US20050288457A1 (en) * | 2002-10-22 | 2005-12-29 | Puwei Liu | Co-curable compositions |
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| The performance of selected unsaturated coatings forcalcium carbonate filler in polypropylene. Arunee Tabtiang,Richard Venables.EUROPEAN POLYMER JOURNAL,Vol.36 No.1. 2000 * |
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| JP2005520903A (ja) | 2005-07-14 |
| GB0226925D0 (en) | 2002-12-24 |
| EP1487913A1 (en) | 2004-12-22 |
| GB0206755D0 (en) | 2002-05-01 |
| CA2480098C (en) | 2012-05-01 |
| AU2003208421A1 (en) | 2003-10-08 |
| US20050165144A1 (en) | 2005-07-28 |
| ES2389435T3 (es) | 2012-10-26 |
| WO2003080720A1 (en) | 2003-10-02 |
| KR20050018646A (ko) | 2005-02-23 |
| TW200304463A (en) | 2003-10-01 |
| KR100910283B1 (ko) | 2009-08-03 |
| BR0308647A (pt) | 2005-01-25 |
| US7732514B2 (en) | 2010-06-08 |
| EP1487913B1 (en) | 2012-08-08 |
| CA2480098A1 (en) | 2003-10-02 |
| JP4279686B2 (ja) | 2009-06-17 |
| TWI300080B (en) | 2008-08-21 |
| CN1646617A (zh) | 2005-07-27 |
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