CN100445330C - 聚烯烃母料和适于注射模塑的组合物 - Google Patents
聚烯烃母料和适于注射模塑的组合物 Download PDFInfo
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- CN100445330C CN100445330C CNB2004800091630A CN200480009163A CN100445330C CN 100445330 C CN100445330 C CN 100445330C CN B2004800091630 A CNB2004800091630 A CN B2004800091630A CN 200480009163 A CN200480009163 A CN 200480009163A CN 100445330 C CN100445330 C CN 100445330C
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- propylene
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Classifications
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L23/10—Homopolymers or copolymers of propene
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Ethene-propene or ethene-propene-diene copolymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/02—Heterophasic composition
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
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Abstract
一种母料组合物包含(重量百分数):A)50-90%的结晶聚丙烯组分,该聚丙烯组分包含:AI)25%-75%的部分,熔体流动速率MFRI为0.1-10g/10min;和AII)75%-25%的部分,熔体流动速率值MFRII等于或低于100g/10min;其中MFRI/MFRII的比率为5-60;和B)10%-50%的乙烯和至少一种C3-C10α-烯烃的共聚物组分,该共聚物含有15-50%的乙烯;所述母料组合物的在室温(约25℃)可溶于二甲苯的部分的特性粘度值等于或高于3.5dl/g,该母料组合物被加入聚烯烃材料中以获得适合于注射模塑的成品组合物。
Description
本发明涉及可用于制造适于注射模塑为相对大的制品的聚烯烃组合物的聚烯烃母料(masterbatch)。更加特别地,所述聚烯烃组合物可被注射模塑为大的制品,其中所述制品具有改进的表面性质特别是就虎纹带(tiger striping)和凝胶的降低而言。
聚丙烯和热塑性聚烯烃因为它们突出的成本/性能特点而在商业上得到广泛应用。例如,这些聚合物由于它们良好的耐候性而被用于模塑色应用中。
聚丙烯和热塑性聚烯烃通常被注射模塑为需要的制品。相对大的制品,例如汽车保险杠和仪表盘,带来了特别的挑战性问题例如冷流、虎纹带和凝胶。当注入模具的熔融聚合物在该模具被聚合物完全充满之前就开始冷却和固化的时候就会出现“冷流”。“虎纹带”是指注射模塑制品表面上颜色和光泽的差异,这种差异是在聚合物被注入到模具中并形成期望的形状的时候由于熔融聚合物不稳定的模具填充性质造成的。“凝胶”是指在最终成型制品表面出现的小点,是由于一种或多种聚合组分相对差的分散造成的。此类凝胶以及虎纹带具有恶化最终成型制品表面外观的效果。
使用母料组合物的一个有利之处是,母料可以加入很多并且不同种类的聚烯烃中以便获得通过注射模塑制造大制品例如汽车保险杠的成品聚烯烃组合物。因此一直都需求这样一种母料组合物,该种母料组合物能够通过和各种聚烯烃材料共混而制造具有物理性能和表面性能良好平衡的成品组合物。
在美国专利No.5519090中教导了可以通过一起共混具有不同熔体流动指数的两种聚丙烯和丙烯/乙烯共聚物而获得良好的熔体流动性和良好的力学性能特别是高刚性。
根据WO 02/28958,熔体流动性、力学性能和特别是关于虎纹带减少的表面性能的特别良好的平衡,可通过向聚烯烃基质中加入包含如下成分的母料组合物(重量百分数)而获得:
A)20%-90%的结晶聚丙烯组分,该组分包含25%-75%的熔体流动速率MFRI为0.5-10g/10min的AI组分和75%-25%的熔体流动速率MFRII满足MFRII/MFRI为30-2000的AII组分;并且组分AI和AII相互独立地选自丙烯均聚物、含最多8%乙烯的丙烯无规共聚物和含最多8%至少一种C4-C10α-烯烃的丙烯无规共聚物;和
B)10%-80%的乙烯和至少一种C3-C10α-烯烃的共聚物组分,该共聚物含有10-70%的乙烯和任选的少量二烯,所述共聚物在室温可溶于二甲苯,并且特性粘度[η]为4-9dl/g。
现在已经发现,通过恰当地选择聚丙烯组分的熔体流动速率值以及和组合物相关的其它特征和各个组分的比例,可以获得具有特别有用的一系列物理和力学性质并且特别适合于制造成品聚烯烃组合物的母料组合物,其中所述成品聚烯烃组合物由于减少了虎纹带和没有凝胶因而具有优良的表面外观。
因此本发明涉及母料组合物,其包含(重量份):
A)50-90%,优选55-80%的结晶聚丙烯组分,该聚丙烯组分包含:
AI)25%-75%,优选30%-70%的部分,熔体流动速率MFRI为0.1-10g/10min,优选0.1-5g/10min,更优选0.1-3g/10min;和
AII)25%-75%,优选30%-70%的部分,熔体流动速率值MFRII等于或低于100g/10min,尤其是5-100g/10min,优选10-100g/10min,更优选10-68g/10min;
其中MFRII/MFRI的比率(即(AII)的MFR值与(AI)的MFR值得比值)为5-60,优选10-55,并且所述(AI)和(AII)部分相互独立地选自丙烯均聚物,含最多3%乙烯的丙烯无规共聚物和含最多6%至少一种C4-C10α-烯烃的丙烯无规共聚物;和
B)10%-50%,优选20-45%的乙烯和至少一种C3-C10α-烯烃的共聚物组分,该共聚物含有15-50%,优选20-48%,更优选25-38%的乙烯和任选的少量二烯;
所述母料组合物的在室温(约25℃)可溶于二甲苯的部分的特性粘度值[η]等于或高于3.5dl/g,特别是3.5-9dl/g,优选4-8dl/g。
根据ASTM-D 1238条件L(230℃,2.16kg载荷)测量MFR值。
母料组合物的熔体流动速率优选为0.1-10g/10min,更优选0.1-5g/10min。
可存在于(AI)和/或(AII)中的说明性C4-C10α-烯烃包括1-丁烯,1-戊烯,1-己烯,4-甲基-1-戊烯和1-辛烯,特别优选1-丁烯。
优选(AI)和(AII)都是丙烯均聚物。
在共聚物组分(B)中存在的C3-C10α-烯烃中,丙烯是优选的。
本发明母料组合物的其它优选特征是:
-(A)的P.I.(多分散性指数)为4-7;
-(AI)和(AII)的Mw/Mn值都高于4,优选高于4.5,特别是高于5(在135℃在三氯苯中用凝胶渗透色谱法测定);
-整个组合物中在室温可溶于二甲苯的部分的数量低于35重量%。
本发明的母料组合物可以通过接续聚合制备,该接续聚合包括至少三个接续步骤,其中组分(A)和(B)在不同的接续步骤中制备,所述接续步骤除了第一步骤之外每一步骤都在前一步骤制备的聚合物和使用的催化剂的存在下进行。只在第一步骤中加入催化剂,但是催化剂的活性却能够在后续的所有步骤中保持活性。
特别是组分(A)需要两个接续步骤,一个用于制备(AI)部分,另一个用于制备(AII)部分。
优选组分(A)在组分(B)之前制备。
(AI)和(AII)部分的制备顺序不是关键所在。
聚合,可以是连续的或是间歇的,根据已知技术进行,可以在存在或不存在惰性稀释剂的情况下在液相中进行,或在气相中进行,或通过液-气混合技术进行。优选聚合在气相中进行。
与聚合步骤相关的反应时间、压力和温度不是关键所在,但是最好温度是50-100℃。压力可以是大气压或更高。
分子量的调节通过使用已知的调节剂进行,特别是氢气。
本发明的母料组合物也可以通过在至少两个互相连接的聚合区进行的气相聚合方法制备。所述类型的方法描述于欧洲专利申请782587。
详细而言,上述方法包括在催化剂存在下在聚合条件下将一种或多种单体加入所述聚合区域并从所述聚合区域收集聚合物产物。在所述方法中,增长的聚合物颗粒在快速流体化条件下向上流动通过所述聚合区其中的一个(第一)(上升区(riser)),离开所述的上升区并进入另一个(第二)聚合区(下降区(downcomer)),在重力的作用下聚合物以致密的形式向下流动通过该第二聚合区,离开所述下降区并再次进入上升区,从而在上升区和下降区之间建立了聚合物的循环。
在下降区中固体密度达到了较高的值,该值接近聚合物的堆积密度。因此沿流动方向可获得正压,从而可以不借助于特别机械手段的帮助而将聚合物重新引入上升区。按这种方式,建立了一种“环管(loop)”循环,该循环由两个聚合区之间的压力平衡以及由引入系统的压头损失确定。
通常,在上升区的快速流体化条件通过向所述上升区引入包含相关单体的气体混合物来建立。优选通过使用任意适当的气体分配器手段在低于将聚合物引入所述上升区的点的位置将气体混合物引入。在操作条件下输运气体进入上升区的速度高于输运速度,优选为2-15m/s。
通常,离开上升区的聚合物和气体混合物被输送到固体/气体分离区。固体/气体分离可以采用常规的分离手段进行。从分离区聚合物进入下降区。离开分离区的气体混合物被压缩、冷却并被传输,如果适当还要加入补偿单体和/或分子量调节剂,到上升区。传输可以通过用于气体混合物的再循环线进行。
在两个聚合区之间聚合物循环的控制可以通过测量离开下降区的聚合物的数量实施,其中聚合物数量的测量使用适于控制固体流动的手段例如机械阀进行。
操作参数例如温度是那些在气相烯烃聚合方法中常用的参数,例如50-120℃。
上述方法可以在0.5-10Mpa,优选1.5-6Mpa的操作压力下进行。
有利地,在聚合区中维持一种或多种惰性气体,其数量是这样:所述惰性气体的分压的总和优选为气体总压力的5-80%。所述惰性气体例如可以是氮气或丙烷。
各种催化剂在所述上升区任意的点被引入所述上升区。但是,也可以在下降区任意的点引入催化剂。催化剂可以是任意的物理形态,因此固体或液体形态的催化剂都可以使用。
所述聚合优选在有规立构Ziegler-Natta催化剂的存在下进行。所述催化剂的必需组分是包含具有至少一个钛-卤素键的钛化合物的固体催化剂组分和电子-给体化合物,两者都承载于活性形式的卤化镁上。另一种必需的组分(助催化剂)是有机铝化合物,例如烷基铝化合物。
任选加入外电子给体(external donnor)。
通常用于本发明方法中的催化剂能够制造全同立构指数大于90%,优选大于95%的聚丙烯。具有上述特性的催化剂在专利文献中是公知的;特别有利地是描述于美国专利4399054和欧洲专利45977中的催化剂。
用于所述催化剂的固体催化剂组分包括作为电子-给体(内电子给体)的选自以下物质的化合物:醚,酮,内酯,含N、P和/或S原子的化合物,和单-和二羧酸的酯。
特别适合的电子-给体化合物是苯二甲酸酯,例如邻苯二甲酸二异丁酯、邻苯二甲酸二辛酯、邻苯二甲酸二苯酯和邻苯二甲酸苄基丁基酯。
其它特别适合的电子-给体是下式所示的1,3-二醚:
其中RI和RII相同或不同,是C1-C18烷基,C3-C18环烷基或C7-C18芳基;RIII和RIV相同或不同,是C1-C4烷基;或是其中在2位上的碳原子属于由5、6或7个碳原子组成并含有两个或三个不饱和度的环状或多环结构的1,3-二醚。
此类醚描述于公开的欧洲专利申请361493和728769之中。
所述二醚的代表性例子是2-甲基-2-异丙基-1,3-二甲氧基丙烷,2,2-二异丁基-1,3-二甲氧基丙烷,2-异丙基-2-环戊基-1,3-二甲氧基丙烷,2-异丙基-2-异戊基-1,3-二甲氧基丙烷,9,9-二(甲氧基甲基)芴。
上述催化剂组分的制备通过多种方法进行。
例如,将其中n通常是1-3和ROH是乙醇、丁醇和异丁醇的MgCl2·nROH加合物(特别是球形颗粒的形式)与含有电子-给体化合物的过量TiCl4反应。反应温度通常为80-120℃。然后分离固体并在电子-给体化合物存在或不存在的情况下再次与TiCl4反应,此后分离固体并用等分的烃洗涤直到所有的氯离子都消失。
在固体催化剂组分中,钛化合物,以钛Ti表示,通常的存在量为0.5-10重量%。仍然固定在固体催化剂组分上的电子-给体化合物的数量相对于二卤化镁通常为5-20摩尔%。
可用于制造上述固体催化剂组分的钛化合物是钛的卤化物和钛的卤素醇化物。四氯化钛是优选的化合物。
上述反应导致活性形式卤化镁的形成。文献中已知从不是卤化物的镁化合物例如羧酸镁开始导致活性形式卤化镁形成的其它反应。
用作助催化剂的Al-烷基化合物包括Al-三烷基化合物例如Al-三乙基、Al-三异丁基、Al-三正丁基,和含有通过O或N原子、或SO4或SO3基团相互连接的两个或更多个Al原子的线型或环状Al-烷基化合物。
Al-烷基化合物通常的使用量是使Al/Ti比达到1-1000。
可以用作外给体的电子-给体化合物包括芳香族酸酯例如苯甲酸烷基酯,特别是含有至少一个Si-OR键的硅化合物,其中R是烃基。
硅化合物的例子是(叔丁基)2Si(OCH3)2,(环己基)(甲基)Si(OCH3)2,(苯基)2Si(OCH3)2和(环戊基)2Si(OCH3)2。也可以有利地使用具有上述结构式的1,3-二醚。如果内给体是这些二醚中的一种,那么外给体可以省去不用。
可用于本发明方法中的其它催化剂是茂金属类催化剂,如USP5324800和EP-A-0129368中所述;特别有利地是桥接二茚基茂金属,例如如USP5145819和EP-A-0485823中所述。另一类适合的催化剂是所谓的受限结构催化剂(constrained geometry catalyst),如EP-A-0416815(Dow)、EP-A-0420436(Exxon)、EP-A-0671404、EP-A-0643066和WO91/04257中所述。这些茂金属化合物可特别用于生产组分(B)。
催化剂可以和少量烯烃预接触(预聚合)。
本发明的母料组合物还可以含有本领域通常使用的添加剂,例如抗氧化剂,光稳定剂,热稳定剂,着色剂和填料。
如前所述,本发明的母料组合物有利地可以与额外的聚烯烃混合,特别是丙烯聚合物例如丙烯均聚物、无规共聚物和热塑性弹性体聚烯烃组合物。因而,本发明的第二实施方案涉及含有上述母料组合物适于注射模塑的热塑性聚烯烃组合物。优选地,所述的热塑性聚烯烃组合物含有至多30重量%,典型地为5-20重量%的本发明的母料组合物。
向其中加入母料的聚烯烃(即除了母料中存在的聚烯烃以外的聚烯烃)的实际例子是下面所述的聚合物:
1)结晶丙烯均聚物,特别是全同立构的或主要为全同立构的均聚物;
2)与乙烯和/或C4-C10α-烯烃的结晶丙烯共聚物,其中相对于共聚物的重量共聚单体的总含量为0.05-20重量%,并且其中优选的α-烯烃是1-丁烯,1-己烯,4-甲基-1-戊烯和1-辛烯;
3)结晶乙烯均聚物和与丙烯和/或C4-C10α-烯烃的共聚物,例如HDPE;
4)乙烯与丙烯和/或C4-C10α-烯烃的弹性体共聚物,任选含有少量的二烯例如丁二烯、1,4-己二烯、1,5-己二烯和亚乙基(ethylidene)-1-降冰片烯,其中二烯的含量通常为1-10重量%;
5)热塑性弹性体组合物,含有一种或多种丙烯均聚物和/或第2)项的共聚物和含有第4)项的一种或多种共聚物的弹性体部分,通常根据已知的方法通过在熔融状态混合各个组分或通过接续聚合制造,并通常含有5-80重量%数量的所述弹性体部分。
所述聚烯烃组合物可以通过使用已知的技术和设备将母料组合物和额外的聚烯烃混合在一起,挤出混合物和对得到的组合物造粒而制备。
所述聚烯烃组合物还可以含有常规的添加剂例如无机填料,着色剂和稳定剂。可以用于组合物中的无机填料包括滑石、CaCO3、二氧化硅,例如硅灰石(CaSiO3),粘土,硅藻土,二氧化钛和沸石。典型的无机填料为颗粒状,平均直径为0.1-5微米。
本发明还提供由所述聚烯烃组合物制造的最终制品例如保险杠和仪表盘。
本发明的实践和有利之处在下面的实施例中进行公开。这些实施例只是用于说明目的,并不是以任何方式对本发明允许的范围进行任何限制。
采用下面的分析方法表征聚合物组合物。
熔体流动速率:ASTM-D 1238,条件L。
[η]特性粘度:在135℃在四氢萘(tetradydronaphtalene)中测定。
乙烯含量:I.R.光谱。
挠曲模量:ISO 178
屈服强度:ISO 527
断裂伸长率和屈服伸长率:ISO 527
缺口悬臂梁式冲击测试:ISO 180/1A
多分散性指数(P.I.)
该性能与受测聚合物的分子量分布严格相关。特别是其与熔融状态下聚合物的抗蠕变性成反比。所述抗蠕变性在低模量值(500Pa)称为模量分离,在200℃通过使用在从0.1rad/sec增加到100rad/sec的振动频率下操作的平行板流变仪测量,所述流变仪由RHEOMETRICS(USA)销售,型号为RMS-800。从模量分离值,可以从下式得到P.I.:
P.I.=54.6*(模量分离)-1.76
其中模量分离定义为:
模量分离=G’=500Pa的频率/G”=500Pa的频率
其中G’是储能模量,G”是损耗模量。
二甲苯可溶部分和不溶部分
将2.5g聚合物和250cm3的二甲苯加入装配有冷冻机和磁力搅拌器的玻璃烧瓶中。在30分钟内将温度升至溶剂的沸点。接着将所得到的透明溶液在搅拌下保持回流30分钟。然后封闭的烧瓶在冰水浴中放置30分钟,接着在25℃的恒温水溶中也放置30分钟。在快速滤纸上过滤如此形成的固体。将100cm3过滤液倒入预先称量过的铝容器中,该容器在氮气流下在加热板上加热以通过蒸发除去溶剂。然后将该容器置于80℃的真空烘箱中直到恒重。然后计算在室温溶于二甲苯的聚合物的重量百分数。
在室温不溶于二甲苯的聚合物的重量百分数被认为是聚合物的全同立构指数。该值基本上对应于通过用沸腾正庚烷萃取测定的全同立构指数,该值定义为聚丙烯的全同立构指数。
流延薄膜评估
使用成膜设备Plasticisers MKII从实施例的组合物制造100μm厚的流延薄膜。
挤出机螺杆的直径和长度分别为19和400nm。
模口宽度为80mm,模口间隙为0.2mm。
挤出机和模口的温度为270℃。
当在薄膜样品种发现的凝胶的平均直径小于1.5mm的时候,组合物被分类为“良好”,而当检测到凝胶平均直径等于或大于所述值,组合物被分类为“差”。
共混物中的虎纹带
为了评估虎纹带,在密炼机中制备具有实施例组成(在下文中如表2所示)的下述共混物。
用于虎纹带评估的共混物
聚合物材料(wt%) | MFR L | |||||
HECO | 2 | 12 | 12 | 12 | 12.5 | 12.5 |
EPR | 1.5 | 6 | 6 | 6 | 6 | 6 |
HOMO1 | 2000 | 22.5 | 22.5 | 22.5 | 22 | 22 |
HOMO2 | 400 | - | - | - | - | - |
EPDM | 0.6 | 11 | 11 | 11 | 11 | 11 |
实施例1的组合物 | 10 | - | - | - | - | |
实施例2的组合物 | - | 10 | - | - | - | |
实施例3的组合物 | - | - | 10 | - | - | |
实施侧4的组合物 | - | - | - | 10 | - | |
对比实施例1的组合物 | - | - | - | - | 10 | |
Neotalc Natural | 17.5 | 17.5 | 17.5 | 17.5 | 17.5 |
注释(所有的百分数都是重量百分数):
HECO=Ziegler-Natta催化剂制备的多相共聚物,由44%MFR L为90g/10min的丙烯均聚物和56%总MFR L为2.5g/10min乙烯为49%的丙烯/乙烯二元聚合物构成;
EPR=Ziegler-Natta催化剂制备的乙烯/丙烯橡胶,含有60%乙烯,总MFR L为1.5g/10min;
HOMO1=Ziegler-Natta催化剂制备的丙烯均聚物,MFR L为2000g/10min;
HOMO2=Ziegler-Natta催化剂制备的丙烯均聚物,MFR L为400g/10min;
EPDM=V-基催化剂制备的乙烯/丙烯/二烯橡胶,含有66%乙烯和4.5%亚乙基-降冰片烯-1,MFR L为0.6g/10min;
Neotalc Natural=天然滑石。
用于虎纹带评估的板(长度250mm,宽度150mm,厚度3mm)使用注射压机Negri Bossi(225吨闭合力)模塑,模塑条件如下:
-螺杆转速:100rpm
-熔融温度:215-220℃
-模具温度:55℃
-注入时间:11秒
-保压压力:20-30巴
-保压时间:5秒
-冷却时间:40秒。
在如此获得的板上通过测量注入点和第一条虎纹带之间的距离来进行评估。显而易见,上述距离越长,所述被检测材料减少虎纹带的能力越好。
实施例1-4和对比实施例1
用于聚合的固体催化剂组分是承载于氯化镁之上的高度立体有择的Ziegler-Natta催化剂组分,含有约2.5重量%的钛和作为内给体的邻苯二甲酸二异丁酯,通过与欧洲公开专利申请674991的实施例中描述的方法相似的方法制备。
催化剂体系和预聚合处理
在引入聚合反应器之前,上述固体催化剂组分在-5℃与三乙基铝(TEAL)和二环戊基二甲氧基硅烷(DCPMS)反应5分钟,其中TEAL/DCPMS的重量比等于约15并且数量为TEAL/Ti的摩尔比等于65。
然后在引入第一聚合反应器之前,通过将其保持悬浮于20℃的液态丙烯中大约20分钟而将催化剂体系进行预聚合。
聚合
通过在连续并且恒定的料流中向第一气相聚合反应器中引入预聚合的催化剂体系、氢气(用作分子量调节剂)和气态丙烯,制造了聚丙烯均聚物((AII)部分)。
聚合条件列在表1中。
在第一反应器中制造的聚丙烯均聚物在连续料流中被排出,并在吹扫尽未反应的单体之后在连续料流中与氢气和气态丙烯的定量恒定流一起被引入第二气相反应器。
在第二反应器中制造了一种丙烯均聚物((AI)部分)。聚合条件、反应物的摩尔比和得到的共聚物的组成都列在表1中。
来自第二反应器的聚合物在连续料流中被排出,并在吹扫尽未反应的单体之后在连续料流中与氢气和气态乙烯的定量恒定流一起被引入第三气相反应器。
在第三反应器中制造了一种丙烯/乙烯共聚物((B)组分)。聚合条件、反应物的摩尔比和得到的共聚物的组成都列在表1中。
对离开第三反应器的聚合物颗粒进行蒸汽处理以除去反应性单体和挥发性物质,然后进行干燥。
然后上述聚合物颗粒被引入转鼓中,在那里它们与0.05重量%的石蜡油ROL/OB 30(密度根据ASTM D 1298测量在20℃为0.842kg/l,根据ASTM D 97测量流点为-10℃),0.15重量%B215(由约34%1010和66%168制成)和0.05重量%硬脂酸钙混合。
所述的Irganox 1010是2,2-二[3-[5-二(1,1-二甲基乙基)+-4-羟基苯基]-1-氧代丙氧基]甲基]-1,3-丙烷二基-3,5-二(1,1-二甲基乙基)-4-羟基苯-丙酸酯,而Irgafos 168是三(2,4-二叔丁基苯基)亚磷酸酯。
然后聚合物颗粒被引入双螺杆挤出机Berstorff ZE25(螺杆的长度/直径比:33)中在下列条件下在氮气气氛下挤出:
旋转速度:250rpm;
挤出机产量:6-20kg/hour;
熔融温度:200-250℃。
关于该聚合物组合物的性质,通过对如此挤出的聚合物进行测量而获得并列在表2中。
表1
注释:C3-=丙烯;C2-=乙烯;split=在相关反应器中制造的聚合物的数量。
表2
实施例编号 | 1 | 2 | 3 | 4 | 1C | |
MFR L | 9/10’ | 0.52 | 0.58 | 0.49 | 0.76 | 0.93 |
二甲苯中可溶 | wt% | 32.8 | 30.1 | 29.9 | 29.3 | 28.2 |
C2-含量 | wt% | 14.4 | 10.1 | 10.3 | 10.3 | 13.4 |
X.S.I.V.挤出前 | dl/g | 6.34 | 7.02 | 7.24 | 6.58 | 6.59 |
X.S.I.V.挤出后 | dl/g | 5.22 | 5.60 | 5.73 | 6.12 | 6.31 |
挠曲模量 | MPa | 768 | 814 | 739 | 795 | 930 |
屈服强度 | MPa | 16.4 | 19.2 | 18.3 | 18.0 | 18.7 |
屈服伸长率 | % | 12.0 | 13.2 | 15.3 | 14.7 | 10.6 |
断裂强度 | MPa | 25.0 | 33.0 | >26.0 | 30.0 | 29.0 |
断裂伸长率 | % | 530 | 550 | >660 | 516 | 490 |
23℃的悬臂梁式冲击强度 | KJ/m<sup>2</sup> | N.B. | N.B. | N.B. | N.B. | N.B. |
-30℃的悬臂梁式冲击强度 | KJ/m<sup>2</sup> | N.B. | 12.6 | 14.0 | 13.5 | 15.0 |
流延薄膜评估 | 良好 | 良好 | 良好 | 良好 | 差 | |
虎纹带起始点(在共混物中) | mm | 130 | 141 | 162 | 185 | 120 |
注释:X.S.I.V=在二甲苯中可溶部分的特性粘度;N.B.=无断裂。
Claims (7)
1.母料组合物,包含,其表示为重量百分数:
A)50-90%的结晶聚丙烯组分,该聚丙烯组分包含:
AI)25%-75%的部分,熔体流动速率MFRI为0.1-5g/10min;
和
AII)25%-75%的部分,熔体流动速率值MFRII为5-100g/10min;
其中MFRII/MFRI的比率为10-55,并且所述AI和AII部分相互独立地选自丙烯均聚物,含最多3%乙烯的丙烯无规共聚物和含最多6%至少一种C4-C10α-烯烃的丙烯无规共聚物;
和
B)10%-50%的乙烯和至少一种C3-C10α-烯烃的共聚物组分,该共聚物含有15-50%的乙烯和任选的少量二烯;
所述母料组合物在室温可溶于二甲苯的部分的特性粘度值[η]等于或高于3.5dl/g。
2.权利要求1的母料组合物,MFR值为0.1-10g/10min。
3.含权利要求1的母料组合物的热塑性聚烯烃组合物。
4.权利要求3的热塑性聚烯烃组合物,其中相对于热塑性组合物的总重量,母料组合物的含量为5-20重量%。
5.权利要求3的热塑性聚烯烃组合物,其中除了包含于母料组合物中的那些以外的烯烃聚合物选自:
1)结晶丙烯均聚物;
2)丙烯与乙烯和/或C4-C10α-烯烃的结晶共聚物,其中相对于共聚物的重量,共聚单体乙烯和/或C4-C10α-烯烃的总含量为0.05-20重量%;
3)结晶乙烯均聚物和乙烯与丙烯和/或C4-C10α-烯烃的共聚物;
4)乙烯与丙烯和/或C4-C10α-烯烃的弹性体共聚物,任选含有少量的二烯;
5)热塑性弹性体组合物,含有一种或多种丙烯均聚物和/或第2)项的共聚物和含有第4)项的一种或多种共聚物的弹性体部分,含有5-80重量%数量的所述弹性体部分;
6)第1)-第5)项的两种或更多种聚合物或组合物的共混物。
6.通过包含至少三个接续步骤的接续聚合制备权利要求1的母料组合物的方法,其中组分(A)和(B)在不同的接续步骤中制造,所述接续步骤除了第一步骤之外每一步骤都在前一步骤制备的聚合物和使用的催化剂的存在下进行。
7.包含权利要求1的母料组合物的保险杠和仪表盘。
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EP1608701B1 (en) | 2007-02-21 |
AU2004226244B2 (en) | 2009-03-05 |
US20060194924A1 (en) | 2006-08-31 |
AU2004226244A1 (en) | 2004-10-14 |
KR101085374B1 (ko) | 2011-11-21 |
PL1608701T3 (pl) | 2007-08-31 |
US8008400B2 (en) | 2011-08-30 |
JP2006522169A (ja) | 2006-09-28 |
RU2005133721A (ru) | 2006-03-10 |
CN1768107A (zh) | 2006-05-03 |
MY136027A (en) | 2008-07-31 |
DE602004004884T2 (de) | 2007-11-15 |
AR043814A1 (es) | 2005-08-17 |
JP4990614B2 (ja) | 2012-08-01 |
RU2341543C2 (ru) | 2008-12-20 |
CA2520270A1 (en) | 2004-10-14 |
ZA200507822B (en) | 2006-12-27 |
KR20050110036A (ko) | 2005-11-22 |
MXPA05010631A (es) | 2005-12-12 |
ES2280954T3 (es) | 2007-09-16 |
BRPI0409514A (pt) | 2006-04-18 |
WO2004087805A1 (en) | 2004-10-14 |
DE602004004884D1 (de) | 2007-04-05 |
ATE354616T1 (de) | 2007-03-15 |
EP1608701A1 (en) | 2005-12-28 |
TW200427761A (en) | 2004-12-16 |
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