CN1345355A - 包含聚碳酸酯和接枝橡胶的具有改进低温韧性的组合物 - Google Patents
包含聚碳酸酯和接枝橡胶的具有改进低温韧性的组合物 Download PDFInfo
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- CN1345355A CN1345355A CN00805506A CN00805506A CN1345355A CN 1345355 A CN1345355 A CN 1345355A CN 00805506 A CN00805506 A CN 00805506A CN 00805506 A CN00805506 A CN 00805506A CN 1345355 A CN1345355 A CN 1345355A
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Abstract
公开了一种热塑性模塑组合物,适用于制备具有改进性能的模塑制品,最特别的是其低温下的高韧性和高冲击强度。该组合物包括芳族聚碳酸酯和至少两种接枝橡胶的混合物的树脂共混物。接枝橡胶的混合物包括重均粒度小于0.3微米的“小型”组分和重均粒度等于或大于0.3微米的“大型”组分。
Description
发明领域
本发明涉及一种热塑性模塑组合物,并且特别涉及含聚碳酸酯和接枝橡胶的组合物。
发明概述
本发明公开了一种适于用作制备具有改进性能的模塑制品的热塑性模塑组合物,最特别的是具有高韧性和低温冲击强度。该组合物包含芳族聚碳酸酯与至少两种接枝橡胶的混合物的树脂共混物。接枝橡胶的混合物包含具有重均粒度小于0.3微米的“小型”组分(“small-mode”)和具有重均粒度等于或大于0.3微米的“大型”组分(“large-mode”)。
发明技术背景
已知热塑性模塑组合物含有接枝橡胶如ABS以及聚碳酸酯树脂。以这种组合物为基础的商品,特别是Bayer公司出售的Bayblend组合物,长期以来得到了广泛的市场认可。值得注意的是美国专利3,954,905和4,560,725已经公开了相关的组合物。包括ABS组分的组合物也是周知的,ABS的橡胶颗粒具有双峰粒度分布。所述技术包括美国专利3,509,237,该专利公开了一种组合物,该组合物含有第一类和第二类接枝共聚物,该组合物具有橡胶基体和一种单亚乙烯基芳烃与一种不饱和腈的共聚物覆盖物。第一类和第二类接枝共聚物的数均粒径范围分别为0.8-2.0微米和0.01-0.25微米。第一类接枝物被认为是悬浮聚合的产物,以及第二类接枝物是通过乳液聚合制备的。值得注意的是美国专利4,677,162中已公开的组合物,它含有聚碳酸酯、接枝共聚物和冲击改性剂。而接枝共聚物要求粒子平均粒径大于0.75微米,在应用实施例中要求的冲击改性剂包括一种具有与本发明相关化学组成和粒子大小的第二类接枝共聚物。
发明详述
本发明组合物包括含量约60-80%的聚碳酸酯树脂和含量为20-40%至少两种接枝橡胶的混合物的树脂共混物。在优选的实施方案中,共混物包含65-75%的聚碳酸酯以及25-35%的混合物,在所有的实例中,百分数均是相对于共混物重量的重量百分数。接枝橡胶混合物包含具有重均粒度小于0.3微米、优选约0.15-0.28微米的“小型”组分(ABS-s),以及“大型”组分(ABS-1),其中该组分的重均粒度至少为0.3微米,优选约0.35-0.65微米。混合物中ABS-s与ABS-1的重量比例范围为3/27-7.5/22.5,优选3/27-5/25。在优选的实施方案中,ABS-s是众所周知的乳液聚合法的产物,以及ABS-1是已知的本体法、更优选连续本体聚合法的产物。
本发明范围内使用的芳族聚碳酸酯树脂包括均聚聚碳酸酯和共聚聚碳酸酯及其混合物。合适的聚碳酸酯其重均分子量为10,000-200,000,优选20,000-80,000,以及按ASTMD-1238方法,在300℃下测得它们的熔体流动速率,为约1-约65g/10min,优选约2-24g/10min。可以如下制备这些树脂,例如,用碳酸衍生物如碳酰氯和由缩聚法得到的二羟基化合物通过已知的两相界面法制备(参见德国Offenlegungsschriften 2,063,050、2,063,052、1,570,703、2,211,956、2,211,957和2,248,817,法国专利1,561,518,以及H.Schnell专论“《聚碳酸酯的化学与物理》(Chemistry and Physicsof Polycarbonates)”,Interscience出版社,纽约,1964年,在此引入这些作为参考)。
在本发明内容中,适用于制备本发明人的聚碳酸酯的二羟基化合物,具有结构化学式(1)或(2)。 其中:A表示1-8个碳原子的亚烷基(alkylene)、2-8个碳原子的亚烷基(alkylidene)、5-15个碳原子的亚环烷基(cycloalkylene)、5-15个碳原子的亚环烷基(cycloalkylidene)、羰基基团、氧原子、硫原子、-SO-、或者-SO2-或者符合下式的基团:e和g二者均表示数字0-1,Z表示F、Cl、Br或者C1-4烷基且如果在一个芳基基团中多个Z基团是取代基,则它们彼此可以相同或者不同;d表示0-4的整数;以及f表示0-3的整数。
本发明实际应用中所用的二羟基化合物是:氢醌、间苯二酚、双(羟苯基)烷烃类、双(羟苯基)醚类、双(羟苯基)酮类、双(羟苯基)亚砜类、双(羟苯基)硫醚类、双(羟苯基)砜类和α,α-双(羟苯基)二异丙苯类,以及它们的核烷基化化合物。这些以及其它适用的芳族二羟基化合物描述在例如,美国专利5,126,428、5,104,723、5,041,521、5,034,457、3,028,356、2,999,835、3,148,172、2,991,273、3,271,367以及2,999,846中,在此引入这些作为参考。
其它适用的双酚类例子包括:2,2-双(4-羟苯基)丙烷(双酚A)、2,4-双(4-羟苯基)-2-甲基丁烷、1,1-双(4-羟苯基)环己烷、α,α′-双(4-羟苯基)对二异丙苯、2,2-双(3-甲基-4-羟苯基)丙烷、2,2-双(3-氯代-4-羟苯基)丙烷、双(3,5-二甲基-4-羟苯基)甲烷、2,2-双(3,5-二甲基-4-羟苯基)丙烷、双(3,5-二甲基-4-羟苯基)硫醚、双(3,5-二甲基-4-羟苯基)亚砜、双(3,5-二甲基-4-羟苯基)砜、二羟基苯酮、2,4-双(3,5-二甲基-4-羟苯基)环己烷、α,α′-双(3,5-二甲基-4-羟苯基)对二异丙基苯以及4,4’-磺酰基联苯酚。
特别优选的芳族双酚的实例是2,2-双(4-羟苯基)丙烷、2,2-双(3,5-二甲基-4-羟苯基)丙烷和1,1-双(4-羟苯基)环己烷。
最优选的双酚是2,2-双(4-羟苯基)丙烷(双酚A)。
本发明的聚碳酸酯可以要求其结构单元衍生自一种或者多种合适的双酚类。
本发明实施中适合的树脂中包括了酚酞基聚碳酸酯、共聚碳酸酯类以及三聚碳酸酯类,如美国专利3,036,036和4,210,741中所描述,在此引用两个专利作为参考。
本发明中的聚碳酸酯也可以通过向其中缩聚少量如0.05-2.0mol%(相对于双酚而言)的多羟基化合物而被支化。
已经在很多专利中描述过这类聚碳酸酯,例如,德国Offenlegungsschriften 1,570,533、2,116,974和2,113,374;英国专利885,442和1,079,821;以及美国专利3,544,514。下述是可以用于该目的的多羟基化合物的一些实例:间苯三酚、4,6-二甲基-2,4,6-三(4-羟苯基)庚烷、1,3,5-三(4-羟苯基)苯、1,1,1-三(4-羟苯基)乙烷、三(4-羟苯基)苯基甲烷、2,2-双(4,4-(4,4’-二羟基二苯基))环己基丙烷、2,4-双(4-羟基-1-异propylidine)酚、2,6-双(2’-二羟基5’-甲基苄基)-4-甲基酚、2,4-二羟基苯甲酸、2-(4-羟苯基)2-(2,4-二羟苯基)丙烷和1,4-双(4,4’-二羟基三苯基甲基)苯。其它一些多官能团化合物是:2,4-二羟基苯甲酸、1,3,5-苯三酸、氰尿酰氯和3,3-双(4-羟苯基)2-氧代-2,3-二氢吲哚。
除了上面已经提及的缩聚法以外,用于制备本发明聚碳酸酯类的其它方法有均相缩聚法和酯基转移法。合适的方法公开在美国专利3,028,365、2,999,846、3,153,008和2,991,273中,在此引用作为参考。
制备聚碳酸酯的优选方法是界面缩聚法。
可以用其它类合成方法制备本发明聚碳酸酯,如美国专利3,912,688公开的方法,在此引用作为参考。
商业可购买到合适的聚碳酸酯树脂,例如Makrolon 2400、Makrolon2600、Makrolon2800和Makrolon3100,所有这些都是双酚基均聚聚碳酸酯树脂,只是各自分子量不同而有区别,它们的特征在于:按照ASTM D-1238测定它们的熔体流动指数(MFR)分别是约16.5-24、13-16、7.5-13.0和3.5-6.5g/10min。这些产品都是宾夕法尼亚州匹兹堡的Bayer公司的产品。
适合本发明实际应用的聚碳酸酯树脂是已知的,且它们的结构和制备方法已经公开在例如美国专利3,030,331、3,169,121、3,395,119、3,729,447、4,255,556、4,260,731、4,369,303和4,714,746中,在此引入作为参考。
包含在本发明组合物中的混合物含有其重均粒度小于0.3微米、优选0.15-0.28微米的“小型”组分(ABS-s),以及其重均粒度至少为0.3微米、优选0.35-0.65微米的“大型”组分(ABS-1)。混合物中ABS-s与ABS-1的重量比范围为3/27-7.5/22.5,优选3/27-5/25。
在速混物(instant mixture)中两种接枝橡胶组分的接枝相包含单亚乙烯基芳烃和不饱和腈。这类单体包括至少50.0wt%、优选至少75wt%的接枝相。最希望的是,这类单体包括至少90wt%的接枝相。可以包括少量、优选小于10%的其它共单体。在制备接枝相中可使用的单亚乙烯基芳烃实例包括苯乙烯,α-烷基单亚乙烯基单芳族化合物如α-甲基苯乙烯、α-乙基苯乙烯、α-甲基-乙烯基甲苯、α-甲基二烷基苯乙烯等,环上被取代的烷基苯乙烯类如乙烯基甲苯、邻-乙基苯乙烯、对-乙基苯乙烯、2,4-二甲基苯乙烯等,环上被取代的卤代苯乙烯例如邻-氯代苯乙烯、对-氯代苯乙烯、邻-溴代苯乙烯、2,4-二氯代苯乙烯等,环上被烷基取代、环上被卤代的苯乙烯类如2-氯代-4-甲基苯乙烯、2,6-二氯代-4-甲基苯乙烯等,乙烯基萘、乙烯基蒽等。烷基取代基通常含有1-4个碳原子且可以包括异丙基和异丁基。如果需要,可以采用这种单亚乙烯基芳族单体的混合物。
用于制备接枝相的不饱和腈类的实例,包括丙烯腈、甲基丙烯腈和乙基丙烯腈,这些腈类可以单独使用或者与其它腈类混合使用。
在接枝相中可以共聚少量的其它单体的实例包括:共轭1,3-二烯例如丁二烯、异戊二烯等,α-或β-不饱和一元酸及其衍生物例如丙烯酸、丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、丙烯酸-2-乙基己酯、甲基丙烯酸及其相应的酯类,丙烯酰胺、甲基丙烯酰胺,乙烯基卤代物如氯乙烯、乙烯基溴等,1,1-氯乙烯、1,1-溴乙烯等,乙烯基酯类如乙酸乙烯酯、丙酸乙烯酯等,马来酸二烷基酯类或富马酸二烷基酯类如马来酸二甲酯、马来酸二乙酯、马来酸二丁酯、相对应的富马酸酯类等。
形成接枝相的可聚合单体混合物含有至少20wt%的单亚乙烯基芳族单体,且优选至少50wt%的单亚乙烯基芳族单体。它们也可以包含至少5wt%的不饱和腈和优选至少10wt%的不饱和腈。从非常有利于商业实用价值的角度看,单体配方中含有20-95wt%、且优选60-85wt%的亚乙烯基芳烃,和80-5wt%、且优选40-15wt%不饱和腈。
在两种接枝橡胶组分中的橡胶基体是二烯橡胶,所述橡胶基体在聚合过程中以及在其存在下接枝相被接枝到其上。它们是由一种或多种共轭1,3-二烯类如丁二烯、异戊二烯、戊间二烯、氯丁二烯等制备的。这类橡胶包括共轭1,3-二烯与多至等重量的-种或多种可共聚的单烯属不饱和单体的均聚物和共聚体,其中单烯属不饱和单体例如单亚乙烯基芳烃(例如苯乙烯;芳烷基-苯乙烯如邻-、间-和对-甲基苯乙烯,2,4-二甲基苯乙烯,芳-乙基苯乙烯、对叔丁基苯乙烯等;α-烷基苯乙烯如α-甲基苯乙烯、α-乙基苯乙烯、α-甲基-对乙基苯乙烯等;乙烯基萘等),芳卤代单亚乙烯基芳烃类(例如邻-、间-和对-氯代苯乙烯,2,4-二溴代苯乙烯,2-甲基-4-氯代苯乙烯等),丙烯腈,甲基丙烯腈,丙烯酸烷基酯类(例如丙烯酸甲酯、丙烯酸丁酯、丙烯酸-2-乙基己酯等),相对应的甲基丙烯酸烷基酯,丙烯酰胺类(例如丙烯酰胺、甲基丙烯酰胺、N-丁基丙烯酰胺等),不饱和酮类(例如乙烯基甲基酮、甲基异丙基酮等),α-烯烃类(例如乙烯、丙烯等),吡啶,乙烯基酯类(例如醋酸乙烯酯、硬脂酸乙烯酯等),乙烯基和亚乙烯基卤化物(例如乙烯基和亚乙烯基的氯化物和溴化物等)等等。
相对于形成橡胶的单体重量而言,可以通过向可聚合的混合物中加入最高用量达到约2%的常规交联剂而使橡胶基体发生交联,交联剂为例如二乙烯基苯、马来酸二烯丙基酯、富马酸二烯丙基酯、己二酸二烯丙基酯、丙烯酸烯丙基酯、甲基丙烯酸烯丙基酯、多元醇的二丙烯酸酯类和二甲基丙烯酸酯类,如二甲基丙烯酸乙二醇酯。
优选的橡胶类是基本由75wt%-100wt%丁二烯和/或异戊二烯及最高含量达25wt%的下述单体组成的那些橡胶,这些单体选自单亚乙烯基芳烃(例如苯乙烯)和不饱和腈(例如丙烯腈),或它们的混合物,特别有利的基体是丁二烯均聚物或90-95wt%的丁二烯以及5-10wt%的丙烯腈或苯乙烯的共聚物。
优选地,本发明的ABS-s组分是用已知的乳液聚合法制备的。相对于ABS-s组分的重量而言,它的橡胶基体的量可达到约50-60%,且接枝相的特征在于聚合的单亚乙烯基芳烃和聚合的不饱和腈的重量比为70-80/30-20,优选75-78/25-22。
在乳液聚合法中,通过使用合适的乳化剂将单体和橡胶基体在水中进行乳化,合适的乳化剂例如有脂肪酸皂类、高分子量烷基或烷芳基硫酸盐和磺酸盐的碱金属或铵皂类、长链脂肪族胺类的无机酸盐类等。已证明特别有利的乳化剂是油酸钠、棕榈酸钠、硬脂酸钠以及其它的钠皂类。通常地,提供的乳化剂用量是每100重量份数的单体中加入乳化剂用量约1-15重量份数。提供的水用量是每份单体中加入水约1-4份,如果需要更大地稀释液时甚至可进一步加大这个比例。
如果需要,在橡胶基体的乳液聚合中形成的水胶乳可提供水介质,在有或者没有另外加入的乳化剂的情况下,加入单体到其中。但是,橡胶可以溶解在单体和乳化的混合物中,或者可以单独制备其胶乳。
一般将各种水溶性自由基聚合引发剂用于橡胶单体乳液聚合中,其包括常用的过氧化物和perazo催化剂,并且所得的胶乳可以用作水介质,与共聚物单体进行掺和。在这种方法中,用于橡胶聚合的催化剂可以全部或部分用作用于接枝聚合的催化剂。然而,可以在接枝聚合时加入另外的催化剂。适用的过氧化物催化剂的典型实例有:碱金属的过氧化物、过硫酸盐、过硼酸盐、过乙酸盐和过碳酸盐类,以及过氧化氢。如果需要,可以将催化剂活化形成氧化还原体系。此外,如果包括一种油溶性催化剂例如上文指明的适用于本体乳液聚合法中的那些催化剂将是有利的。然而,仍可以采用其它产生自由基的催化剂如光化辐射作用。
需要时可包括链转移剂和其它聚合改性剂,且通常加入较高级烷基硫醇是有利的,例如叔十二烷基硫醇,既可以作为助催化剂也可以作为调节剂。此外,可以加入抗氧剂和稳定剂如烷基化的酚类。
然后在20-100℃、搅拌并用惰性气体保护下,聚合乳液混合物。采用的压力是每平方英寸1-100磅,以及可以在反应周期的某一阶段递增地或者连续地加入单体和/或另外的催化剂。聚合反应持续进行到基本全部即90%以上的单体反应完成为止。然后将剩余单体和其它挥发性组分从胶乳中蒸馏出来,随后脱水并进行干燥。
本发明组合物中的ASB-1组分优选用已知的本体法制备,更优选连续本体聚合法制备。在这种接枝共聚物中的橡胶优选是丁二烯或者丁二烯/苯乙烯共聚物(重量比90/10)以及相对于接枝共聚物的重量而言橡胶含量约为14-20%。接枝相的特征在于已聚合的单亚乙烯基芳烃与已聚合的不饱和腈的重量比是73-80/27-20,优选75-78/25-22。
在连续本体聚合法中,先将橡胶基体溶于单体和溶液中,再将引发剂和其它一些任选的组分如溶剂连续加入到搅拌或者不搅拌的反应器中,得到含基本全部均一组成的聚合混合物的连续聚合反应区域。可以采用多个串联反应器,以达到要求的转化率,在每个反应器中以连续方式进行聚合反应。当聚合反应进行到所要求的转化率水平后,将剩余单体从聚合物中汽提出来。无论采用的是一个聚合反应器还是一系列聚合反应器,脱挥发分的过程都是相同的,通常是在分离装置如刮板式薄膜脱挥发分装置或沉降单纱脱挥发分装置(fallingstrand devolatilizer)中进行。
采用本体聚合法连续生产接枝橡胶的常用现有技术方法见述于美国专利3,243,481、3,337,750、3,511,895以及4,417,030,后者的内容在此引用作为参考。
聚合反应可以通过任何自由基发生引发剂引发,该引发剂可以促进接枝并可在设计的反应温度下被活化。适用的引发剂包括常规的单体可溶解的过氧化物和perazo化合物。典型的引发剂有:叔丁基过氧化新癸酸酯、叔丁基过氧化-2-乙基己酸酯、1-叔丁基偶氮-1-氰基环己烷、过氧化二叔丁基、过氧化苯甲酰基、过氧化月桂酰、过氧化油基、过氧化甲苯酰、二过邻苯二甲酸二叔丁基酯、过乙酸叔丁基酯、过苯甲酸叔丁基酯、过氧化二枯基、叔丁基过氧化异丙基碳酸酯、2,5-二甲基-2,5-二(叔丁基过氧基)己烷、2,5-二甲基-2,5-二(叔丁基过氧基)己炔-3、过氧化氢叔丁基、bumene过氧化氢、对甲烷过氧化氢、环戊烷、过氧化氢、过氧化氢二异丙基苯、对叔丁基枯烯过氧化氢、penant过氧化氢、2,5-二甲基己烷化-2,5-二过氧化氢,以及过碳酸盐化合物如叔丁基-2-乙基己基单过氧碳酸盐等,及它们的混合物。
根据单体及所需要的聚合周期,通常加入的引发剂量为可聚合物质重量的0.001-1.0wt%,且优选约0.005-0.5wt%。
经常需要加入分子量调节剂如硫醇、卤化物和萜,加入量相当少,占可聚合物质重量的约0.001-1.0wt%。此外,还可视需要而加入小量的抗氧剂或稳定剂如常规烷基化酚类。另一方面,这些物质可以在聚合过程中也可以在聚合后加入。配制剂中也可以包含其他添加剂如增塑剂、润滑剂、着色剂和适用的或者可分散在其中的非反应性预制聚合物物质。
溶剂或稀释剂可用于稀释反应混合物以达到以下稀释程度:搅拌反应器中搅拌所需要的功率不过量。部分或者全部的这些稀释剂或者作为添加的组分可与橡胶在单体中的溶液一起加入,或者将所用橡胶先溶解在适用溶剂中后再与稀释剂一起加入。稀释剂也可以独立地加入到一个或多个反应器中。
稀释剂可以是含6-10个碳原子的液体芳烃,例如苯、甲苯、二甲苯、乙基苯、对异丙基苯甲烷、枯烯或它们的混合物。其他有机溶剂如饱和脂肪烃例如己烷、环己烷、环戊烷或者含5-7个碳原子的其它脂肪烃,也可以使用酮类如丁酮、甲基环戊烷、甲基·异丁基酮、环己烷或甲基·丙基酮。优选丁酮。
单独制备未接枝基体共聚物的优选连续本体法见美国专利3,813,369所公开内容,在此引入作为参考。总之,单体被连续地加入到已混合好的包含液相和气相的聚合反应区中。液相含有作为溶剂的单体组合物,由单体组合物形成的共聚物被溶解在其中。液相上面的气相包括单体组合物。液体和气体连续地从反应区中取出,并以约等于单体聚合和排出的速度进行补料。取出的气相可以通过回流冷凝作用被冷凝,作为加入到反应区的单体组合物中一部分返回到反应区中。取出的聚合物和单体的混合物通过上述类型的一个或多个脱挥发分装置,将聚合物分离出来。然后将热熔体用常规设备造粒,而分离出来的单体被冷凝和返回到反应区。链转移剂和液体溶剂、引发剂、和上面所述与连续本体接枝聚合法相关的其他添加剂可以与单体组合物一起或者单独地连续加入到反应区中。
橡胶接枝共聚物即橡胶基体及其接枝共聚物上层物(superstrate)的平均粒度,是根据每种橡胶接枝共聚物组分中几种粒径的粒子得到的平均值,粒度是用光学沉降仪测定的,具体方法按照Graves.M.J等的British Chemical Engineering(英国化学工程)(1964年)、卷9第742-744页中所发表的“离心光学沉降仪亚筛粉末粒径分析”法。替换地,可以使用电子显微镜法。
本发明组合物可以用本技术领域专业人员所熟知的传统方法和下述步骤进行制备和加工。
实施例
制备说明本发明的组合物且其性能已被测定,下表概述了测定的结果。在制备组合物中,使用了下述组分:
聚碳酸酯:以双酚A为基础的均聚聚碳酸酯,根据ASTMD-1238,测定熔体流动速率约11g/10min。
ABS-1(a):接枝共聚物,含16%丁二烯/苯乙烯(90/10wt%)橡胶,并且具有S/AN比等于77/23,重均粒度0.64微米。
ABS-1(b):接枝共聚物,含16%丁二烯/苯乙烯(90/10wt%)橡胶,并且具有S/AN比等于77/23,重均粒度0.35微米。
ABS-s:接枝共聚物,含53%丁二烯橡胶,具有SAN比等于73/27,重均粒度0.28微米。
SAN:共聚物相,苯乙烯/丙烯腈比=72.5/27.5。
维卡温度由ASTM1525测定,伊佐德冲击强度根据ASTMD256测定,多轴冲击强度根据ASTMD3763(测试速度6.7m/s选择的冲击物质在冲击过程中能使速度损失最小)测定,韧性:下表中给出的实例的韧性破坏的定义依据是“通用汽车工程标准”GMP.ABS+PC.002。使用多轴冲击试验时,如果在测试样品打孔时,裂纹辐射到距离冲击点中心不超过10mm,则测试样品认为呈现韧性破坏。报告的韧性破坏表示以这种方式韧性破坏的样品百分数,以15个测试样品为基础计。
组合物中也包括了常规数量的脱模剂和抗氧剂,本发明内容中它们不是关键的。本发明中组合物(实施例1、2、3和4中所示)与对应的组合物实施例5进行了比较,虽然实施例5含有相应量的橡胶,具有等同的或更好的维卡性能和伊佐德冲击强度,但其特点是在低温下比本发明组合物更脆。
1 | 2 | 3 | 4 | 5(比较) | |
聚碳酸酯 | 70 | 70 | 70 | 70 | 70 |
ABS-1(a) | 30 | 27 | |||
ABS-1(b) | 30 | 27 | |||
ABS-s | 3 | 3 | 13 | ||
SAN | 17 | ||||
橡胶总量 | 4.8 | 5.91 | 4.8 | 5.91 | 6.89 |
性能 | |||||
维卡温度(℃)1Kg@120℃/hr | 144 | 144.9 | 144.2 | 144.3 | 145 |
冲击强度。伊佐德(ft-1b/in) | |||||
1/8″23℃ | 11.7 | 10.9 | 10.9 | 11 | 11.5 |
1/8″-30℃ | 5.3 | 7.1 | 5.7 | 7.8 | 9 |
多轴冲击强度,在-30℃(J) | |||||
(E最大) | 50 | 56 | 52 | 51 | 46 |
(E破坏) | 55 | 60 | 56 | 56 | 48 |
脆性/韧性 | 9/6 | 1/14 | 10/5 | 2/13 | 10/0 |
韧性破坏,% | 40 | 93 | 33 | 87 | 0 |
虽然为达到说明的目的,前面已经详细地描述了本发明,但是应该理解为完全是为了该目的,除去受本发明的权利要求的限定以外,在不背离本发明宗旨和范围的条件下,本领域专业人员可能作些改变,这些也是本发明范围。
Claims (14)
1.一种热塑性模塑组合物,其包含下述组分组成的共混物:
(i)60-80%聚碳酸酯树脂和
(ii)20-40%的至少两种接枝橡胶的混合物,
所述百分数基于共混物的重量,
其中,混合物包含:包含重均粒度小于0.3微米的接枝橡胶的小型组分,以及包含重均粒度至少为0.3微米的接枝橡胶的大型组分;该混合物另外的特征在于:存在于共混物中的所述小型组分和大型组分之间的重量比范围为3/27-7.5/22.5。
2.权利要求1的热塑性模塑组合物,其中所述共混物含65-75%的聚碳酸酯和25-35%的所述混合物。
3.权利要求1的热塑性模塑组合物,其中所述范围是3/27-5/25。
4.权利要求1的热塑性模塑组合物,其中所述小型组分是乳液聚合的产物。
5.权利要求1的热塑性模塑组合物,其中所述大型组分是本体聚合的产物。
6.权利要求1的热塑性模塑组合物,其中所述大型组分是连续本体聚合的产物。
7.权利要求1的热塑性模塑组合物,其中小型组分的重均粒度是0.15-0.28微米。
8.权利要求1的热塑性模塑组合物,其中所述大型组分的重均粒度是0.35-0.65微米。
9.权利要求1的热塑性模塑组合物,其中所述小型组分包含橡胶的量相对于该小型组分重量是50-60%。
10.权利要求9的热塑性模塑组合物,其中所述小型组分包含接枝相,聚合的单亚乙烯基芳烃和聚合的不饱和腈之间的重量比为70-80/30-20。
11.权利要求9的热塑性模塑组合物,其中所述小型组分包括接枝相,聚合的单亚乙烯基芳烃和聚合的不饱和腈之间的重量比为75-78/25-22。
12.权利要求1的热塑性模塑组合物,其中所述大型组分包含橡胶的量相对于该大型组分重量是14-20%。
13.权利要求12的热塑性模塑组合物,其中所述大型组分包括接枝相,聚合的单亚乙烯基芳烃和聚合的不饱和腈之间的重量比为70-80/30-20。
14.权利要求12的热塑性模塑组合物,其中所述大型组分包括接枝相,聚合的单亚乙烯基芳烃和聚合的不饱和腈之间的重量比为75-78/25-22。
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US27621599A | 1999-03-25 | 1999-03-25 | |
US09/276,215 | 1999-03-25 | ||
US09/276215 | 1999-03-25 |
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CN1345355A true CN1345355A (zh) | 2002-04-17 |
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EP (1) | EP1185585B1 (zh) |
JP (1) | JP4587568B2 (zh) |
KR (1) | KR20010108382A (zh) |
CN (1) | CN1160411C (zh) |
AR (1) | AR023137A1 (zh) |
AT (1) | ATE334171T1 (zh) |
AU (1) | AU4326100A (zh) |
BR (1) | BR0009208B1 (zh) |
CA (1) | CA2365270A1 (zh) |
DE (1) | DE60029587T2 (zh) |
ES (1) | ES2267523T3 (zh) |
HK (1) | HK1045706A1 (zh) |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1325562C (zh) * | 2002-07-09 | 2007-07-11 | 拜尔材料科学有限责任公司 | 高韧性热塑性聚碳酸酯组合物 |
CN100386378C (zh) * | 2005-06-10 | 2008-05-07 | 上海华谊本体聚合技术开发有限公司 | 一种高抗冲高耐热共混abs树脂的制备方法 |
CN100387650C (zh) * | 2002-05-28 | 2008-05-14 | 兰爱克谢斯德国有限责任公司 | 生产具有改进冲击强度特性的abs组合物的方法 |
CN102746631A (zh) * | 2011-04-20 | 2012-10-24 | 中国石油化工股份有限公司 | 耐低温冲击的聚碳酸酯/abs树脂塑料合金 |
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DE10060410A1 (de) * | 2000-12-05 | 2002-06-06 | Bayer Ag | Thermoplastische Formmassen |
JP5758649B2 (ja) * | 2011-02-22 | 2015-08-05 | 三菱エンジニアリングプラスチックス株式会社 | ポリカーボネート樹脂組成物及び成形体 |
EP2647669A1 (de) * | 2012-04-05 | 2013-10-09 | Bayer MaterialScience AG | Schlagzähmodifizierte Polycarbonat-Zusammensetzungen zur vereinfachten Herstellung von tieftemperaturzähen Bauteilen mit hochglänzenden und matten Bauteilabschnitten |
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US4677162A (en) * | 1983-04-15 | 1987-06-30 | Mobay Corporation | Polycarbonate blends having low gloss |
DE3339001A1 (de) * | 1983-07-06 | 1985-01-17 | Bayer Ag, 5090 Leverkusen | Thermoplastische polyester-formmassen mit hoher zaehigkeit |
DE3615607A1 (de) * | 1986-05-09 | 1987-11-12 | Basf Ag | Thermoplastische formmasse auf basis von polycarbonat, asa und vinylaromaten/an enthaltenden copolymerisaten |
DE3735754A1 (de) * | 1987-10-22 | 1989-05-03 | Basf Ag | Thermoplastische formmasse, verfahren zu ihrer herstellung und deren verwendung |
DE3939046A1 (de) * | 1989-11-25 | 1991-05-29 | Basf Ag | Thermoplastische formmassen mit hoher kaeltezaehigkeit |
DE4221935A1 (de) * | 1992-07-03 | 1994-01-05 | Bayer Ag | Thermoplastische Formmassen |
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2000
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN100387650C (zh) * | 2002-05-28 | 2008-05-14 | 兰爱克谢斯德国有限责任公司 | 生产具有改进冲击强度特性的abs组合物的方法 |
CN1325562C (zh) * | 2002-07-09 | 2007-07-11 | 拜尔材料科学有限责任公司 | 高韧性热塑性聚碳酸酯组合物 |
CN100386378C (zh) * | 2005-06-10 | 2008-05-07 | 上海华谊本体聚合技术开发有限公司 | 一种高抗冲高耐热共混abs树脂的制备方法 |
CN102746631A (zh) * | 2011-04-20 | 2012-10-24 | 中国石油化工股份有限公司 | 耐低温冲击的聚碳酸酯/abs树脂塑料合金 |
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ES2267523T3 (es) | 2007-03-16 |
EP1185585A1 (en) | 2002-03-13 |
DE60029587T2 (de) | 2007-08-09 |
AR023137A1 (es) | 2002-09-04 |
KR20010108382A (ko) | 2001-12-07 |
JP2002540241A (ja) | 2002-11-26 |
TWI230727B (en) | 2005-04-11 |
HK1045706A1 (zh) | 2002-12-06 |
BR0009208B1 (pt) | 2010-08-24 |
DE60029587D1 (de) | 2006-09-07 |
CN1160411C (zh) | 2004-08-04 |
ATE334171T1 (de) | 2006-08-15 |
EP1185585B1 (en) | 2006-07-26 |
WO2000056816A1 (en) | 2000-09-28 |
BR0009208A (pt) | 2001-12-26 |
MXPA01009576A (es) | 2002-03-14 |
AU4326100A (en) | 2000-10-09 |
CA2365270A1 (en) | 2000-09-28 |
JP4587568B2 (ja) | 2010-11-24 |
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