CN1296496A - 催化剂组合物和制备线性、全同立构聚合物的方法 - Google Patents

催化剂组合物和制备线性、全同立构聚合物的方法 Download PDF

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CN1296496A
CN1296496A CN99804918A CN99804918A CN1296496A CN 1296496 A CN1296496 A CN 1296496A CN 99804918 A CN99804918 A CN 99804918A CN 99804918 A CN99804918 A CN 99804918A CN 1296496 A CN1296496 A CN 1296496A
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Abstract

本发明涉及用于制备线性全同立构聚合物的催化剂组合物,其中所述催化剂组合物含有金属配合物和活化剂;本发明还涉及制备线性、全同立构聚合物的方法,该聚合物具有其中立构规整度在25—60%[mmmm]五单元浓度范围内变化并排除了全同立构和无规立构嵌段的随意或相当规则的序列的一种结构,在该方法中C2－C20烯烃与催化剂组合物反应。

Description

催化剂组合物和制备线性、全同立构聚合物的方法
本发明涉及一种新的催化剂组合物和制备线性、全同立构聚合物的方法，其中由于聚合物链中体视误差的统计分布，线性聚合物的全同立构规整度的范围是25-60％的[mmmm]五单元浓度。
长时间以来，全同立构聚合物已经用作具有相对良好的抗变形性能的制品(如家用电器的衬板)的塑料。总之，有丙烯作为单体的这类全同立构聚合物具有高结晶性，因此较硬、很少有或根本没有抗冲击性，这样它们仅对于需要上述特性的应用领域才具有实际意义。
最近，人们进行了各种尝试，旨在制备也具有弹性的聚丙烯。欧洲专利公开0707016A1指定了催化剂组合物和制备聚烯烃的方法。在欧洲专利公开0707016A1中指出的催化剂实质上是由具有经由碳、硅或锗桥接的茚环和芴环的金属茂化合物组成的。对于金属茂化合物，在这一情况下，很显然重要的是在茚环体系中至少由R4表示的残基不是氢。当残基R4是氢时，将不会获得上述欧洲专利公开说明书中指出的效果(P6，从L57到P7，L3)。然而，在欧洲专利公开0707016A1中指出的并用金属茂制备的聚合物，尤其用上述金属茂制得的聚丙烯，能够从实施例和附图中了解到，但就弹性而言不令人满意。
撇开所有这些事实，本发明的目的是寻找一种新的催化剂组合物和提出一种从可获得的烯属不饱和化合物制备聚合物的方法，该聚合物不仅显示热塑性，而且与此同时还显示出热塑性-弹性特性，因此适用于许多应用领域。
就催化剂组合物而言，该目的可通过权利要求1的特征来实现；就制备聚合物的方法而言，它通过权利要求5的特征实现。
本发明涉及一种含有金属配合物和活化剂的新催化剂组合物。
金属配合物是金属茂化合物。因此，元素周期表的第四副族ⅣB的金属化合物一般就可使用，该化合物以定义的金属配合物形式存在并且活化剂与该化合物混合。一般而言，该金属以带正电荷方式存在于该配合物中。
至于金属，钛、锆、铪、钒、铌和钽有特定的实际意义，该金属原子优选有卤素或C1-C8烷基、芳基或苄基作为残基X。
金属茂由通式Ⅰ定义。
Figure 9980491800061
其中残基R1-R7是线性或支化C1-C10烷基；5-7元环烷基，它进而可携带一个或几个C1-C6烷基残基作为取代基；C6-C18芳基、芳烷基或烷芳基；在这种情况下R1、R2；R3、R4；和R6、R7可部分或同时结合到与其稠合的5-7元环烷基或芳基环中。
对于根据通式Ⅰ的金属茂化合物，重要的是，在通式Ⅰ中与残基R7相邻的碳原子和与残基R6相邻的碳原子，对于茚环体系，仅仅是氢。因此可以确保，对于茚环体系，线性体系能够由残基R6和R7形成，该体系将被证明当制备本发明的全同立构弹性体时是特别理想的。与欧洲专利公开0707016A1的金属茂配合物相比较，对于其它残基仅是氢原子而没有碳原子能够在前面提及的位置见到，而这是上述欧洲专利公开说明书所规定的。
在这方面，合适的桥接用结构单元E是1.2-乙基，1.3-丙基，1.4-丁基，碳，硅或锗。对于E是碳、硅或锗的情况，桥接用结构单元E因此可另外携带残基R9和R10，该残基则是C1-C8烷基、C4-C7元环烷基或芳基，R9和R10也能够与E相连形成4-7元环烷基或芳基。
本发明的特别优选的实施例在于使用由通式Ⅶ表示的金属茂配合物。
Figure 9980491800071
其中所有的残基具有上述的含义。然而，与通式Ⅰ的金属茂配合物相比较，现在对茚环体系有硬性规定：与其稠合的另一个环必须存在，此环通过两个E2基团来桥接。
因此E2表示CH2、氧或硫和n是1或2。
正如专利权利要求1中所定义的，根据本发明还必须另外使用至少一种不同于上述的金属茂化合物的活化剂。因此本发明一般包括了在现有技术中对于金属茂化合物已知的所有活化剂。此类活化剂已在欧洲专利公开0707016A1中进行了说明。然而，作为活化剂，特别优选使用具有通式Ⅱ-Ⅵ的至少一种化合物。因此，该活化剂可以是如下所示的通式Ⅱ或Ⅲ的开链或环状铝氧烷化合物：
其中R8是C1-C4烷基和n是5-30之间的数。
对于根据本发明的催化剂组合物，上述指定的通式Ⅱ和Ⅲ化合物能够单独使用或与由通式Ⅳ-Ⅵ表示的其它活化剂相结合使用。
在通式Ⅳ-Ⅵ中，在这方面R9表示C1-C4烷基或芳基。
因此当根据通式Ⅰ的金属茂配合物和根据通式Ⅱ-Ⅵ的活化剂以使得来自铝氧烷的铝或来自阳离子活化剂的硼与来自金属茂配合物的过渡金属之间的原子比在1∶1-106∶1范围内的用量使用时，已经证明是特别理想的。
本发明进一步涉及从烯属不饱和化合物制备线性、热塑性-弹性聚合物的方法，它具有单体单元的全同立构排列和沿各链的独立的体视误差的统计分布，在25-60％[mmmm]五单元浓度范围内变化的立构规整度。因此排除了全同立构和无规立构嵌段的规则序列。在很多情况下，人们发现[rmrm]五单元完全消失或以最高占全部五单元面积的2.5％的比例存在。而且，在大多数场合下比较清楚的是，[rrrr]和[rrrm]五单元总是多于[rmrm]五单元。本发明的方法的特征在于按前面所述使用专门选择的催化剂组合物。
1-100巴、优选3-20巴和尤其优选5-15巴的压力已经被证明是制备线性、热塑性、弹性的烯烃聚合物的合适反应参数。可用的温度是在-50℃-200℃范围内，优选在100-150℃范围内和更优选在20-50℃范围内。
聚合反应能够在气相中、在悬浮液中和在超临界单体中和尤其在聚合反应条件下呈惰性的溶剂中进行。尤其溶液聚合已经证明明显优于目前的其它制备方法。用于此目的的合适惰性溶剂是在分子中不含有任何反应活性基团的溶剂，即象苯、甲苯、二甲苯、乙基苯之类的芳族烃溶剂或链烷烃类如丙烷、正丁烷、异丁烷、戊烷、己烷、庚烷或它们的混合物。
根据本发明制备的聚合物是烯属不饱和化合物的线性、热塑性、弹性聚合物，它具有单体单元的全同立构排列和沿各链的独立的体视误差的统计分布，以及聚合物的平均分子量Mw是在100，000-800，000g/mol范围内和Tg在-50℃到+30范围内。
对于根据本发明制得的聚合物，必不可少的是体视误差位于聚合物链本身中和获得特定的五单元浓度。在这方面已经发现，对于根据本发明制得的聚合物，一般存在着最高占全部五单元面积的2.5％比例的[rmrm]五单元。在很多情况下，还发现[rmrm]五单元完全消失。
而且，在大多数场合下比较清楚的是，[rrrr]和[rrrm]五单元总是多于[rmrm]五单元。聚合物中五单元浓度的测定，严格地说，在现有技术中是已知的并在例如J.A.Ewen，“Catalytic Polymerisation ofOlefins”，Eds.T.Keii，K.Soga编；Kodanska Elsevier Pub.；东京，1986，P271以及后面的页数中有说明。现在给出的根据本发明的五单元浓度测定也是通过以上提及的一篇相关文献中说明的方法来进行的。
除了以上提及的特定五单元浓度外，该线性、全同立构聚合物的分子量在100，000-800，000范围内，优选在110，000-500，000范围内和特别优选在120，000-300，000g/mol范围内。聚合物的平均分子量Mw(重均值)是通过凝胶渗透色谱(GPC)方法在135℃下以微聚苯乙烯型交联共聚物作为柱填充材料和1，2，4-三氯苯作为溶剂，针对极接近分布的聚丙烯标准物来测定的。聚合物的分子量分布Mw/Mn(重均值/数均值)同样通过凝胶渗透色谱法测量并且一般测得值是1.2-3.5。
除所有这些之外，该聚合物显示玻璃化转变温度Tg在-50℃至+30℃范围内、Tg优选在-20℃至+10℃范围内。玻璃化转变温度是通过DSC方法测定的。
根据本发明制备的线性、全同立构聚合物最终具有一种或多种C2-C20烯烃的结构。在这种情况下，该烯烃优选是C3-C20烷-1-烯。该C3-C20烷-1-烯的例子是：丙烯，1-丁烯，2-丁烯，1-戊烯，1-己烯，1-辛烯，1-壬烯，1-癸烯，1-十二碳烯，1-十六碳烯，1-十八碳烯，1-二十碳烯。
除了已提及的烯烃外，C5-C20环烯烃属于特别合适的类型。它的例子是环戊烯，环己烯，降冰片二烯和它的衍生物。
对于线性、全同立构聚合物，聚丙烯是尤其优选的。其它合适的聚合物是丙烯和C4-C20烯烃或环烯烃的共聚物。也有可能制备出三元共聚物，当它们具备丙烯、C2-C20烯烃和环烯烃的结构时，具有专利权利要求1中定义的特征。
根据本发明制得的聚合物例如可在20-80℃下溶于甲苯中；它们在用标准万能试验机ZWICK1445测量的拉伸强度测试中显示出明显的弹性，如实施例中所说明的，并且通常由差示扫描量热法(DSC)测得的结晶熔化温度在-50℃到150℃范围内。尤其应该强调的是，也在这种情况下，该聚合物在它们的弹性-热塑性上明显不同于现有技术，即不同于在本说明书的介绍部分提及的欧洲专利公开0707016A1。既然如此，根据本发明制得的聚合物特别适合于制造具有相对优良的抗变形性能的制品，如家用电器的衬板。而且，有必要提及的是该聚合物可用于抗冲击性改性的聚合物混合物中。由于它们的弹性特性，该聚合物尤其适合于弹性片材，模塑体和垫圈。
下面根据几个催化剂制备实施例和根据聚合实施例来详细解释本发明。因此，给出了：
图1对根据本发明制得的两种聚合物的拉伸强度测量，与欧洲专利公开0707016A1的两种聚合物进行对比，
图2根据本发明的金属茂配合物的X射线结构分析，
图3根据本发明制得的聚合物的核磁共振(NMR)谱，和
图4根据本发明制得的另一种聚合物的核磁共振(NMR)谱。
图1现在说明了欧洲专利公开0707016A1的两个所选实施例的拉伸强度测量值，与根据本发明制得的两种聚合物比较。对于图1中的说法“参见图4”和“参见图5”，在这种情况下是指欧洲专利公开0707016A1的相应实施例。从它们的拉伸强度曲线与根据本发明制得的聚合物(PP36和PP45)的拉伸强度曲线对比可以看出，根据本发明的聚合物显示出一个明显的橡胶-弹性体平台。与此相反，根据欧洲专利公开0707016A1的聚合物显示出流动性(图4)或该聚合物在施加较大外力时会破裂(图5)。正是这一对比清楚地说明了根据本发明制得的聚合物的令人惊奇的特性和显示出明显的橡胶-弹性。
催化剂制备
5.6-环戊二烯并2-甲基-2，3-二氢-1-茚酮的获得
40.4mL的甲基丙烯酰氯(387.9mmol)与62.06g的无水氯化铝(20mol％过量)一起被引入到250mL已冷却至-78℃的CH2Cl2中，然后缓慢地与50.0mL的1，2-二氢化茚(45.84g，387.9mmol)混合。在1，2-二氢化茚添加进去后，颜色从嫩黄变至橙红色。该混合物小心地用稀盐酸水溶液淬灭，用K2CO3水溶液和水洗涤，然后用Na2SO4干燥。
产量：70.07g(376.2mmol)的油状产物，97.0％的理论NMR值(200mcps，CDCl3 7.24ppm)：δ 1.25ppm d(J=6.9cps)3H甲基，δ2.10ppm m(J=3.7至7.6cps)2H环的脂族质子，δ2.62ppm m 2H 2，3-二氢-1-茚酮环的脂族质子，δ2.86ppm m(J=11 to 14 cps)4H环的脂族质子，δ3.25ppm m(J=7.0cps)1H 2，3-二氢-1-茚酮体系的脂族质子，δ7.21和7.51ppm s 2H芳族MS(GC-MS)m/z 186(M+100％)，(186，251mol-1)。5.6-环戊二烯并2-甲基-2，3-二氢-1-茚醇的获得
70.07g(376.2mmol)的2-甲基-5.6-环戊基-2，3-二氢-1-茚酮用5g的LiAlH4在200mL Et2O中进行还原反应，方法是将酮缓慢地(2小时)滴加到LiAlH4的冰冷悬浮液中。搅拌进行一整夜和用水淬灭反应，溶液的颜色从石灰绿变成嫩黄。现在添加15mL浓盐酸，乳液被搅拌1小时。分离醚相，用200mL的K2CO3溶液中和，用水洗涤三次。
其后，用Na2SO4进行干燥，和完全除去溶剂。获得了非对映异构体2，3-二氢-1-茚醇的晶体混合物。NMR(200mcps，CDCl3)：δ1.13ppm d 3H甲基，δ1.76ppm宽1H OH基团，δ2.05ppm m 2H环的脂族质子，δ2.15至2.71ppm m 2H 2，3-二氢-1-茚醇环的脂族质子，δ2.87ppm m 4H环的脂族质子，δ3.08ppm 1H 2，3-二氢-1-茚醇体系的脂族质子，δ4.17和4.93ppm d 2H对于2，3-二氢-1-茚醇环上的OH官能团，δ7.08和7.23ppm d 2H芳族。
产量：69.62g，，369.8mmol，98.3％的理论MS(GC-MS)m/z188(M+100％)，(188.267g mol-1)5.6-环戊二烯并-2-甲基茚的获得
将69.62g(369.8mmol)的2-甲基-5.6-环戊基茚-1-醇的非对映体混合物溶于500mL苯中；然后添加3-5g的p-TosOH，该乳液在回流条件下在水分离器中煮沸三刻钟。分离有机相，用200mL的K2CO3溶液中和，用水洗涤三次。其后，用Na2SO4进行干燥，和完全除去溶剂。
从正戊烷中结晶出无色的产物；产量：57.67g，338.7mmol，对应于91.6％的理论MS(GC-MS)m/z 170(M+100％)，(170.225g mol- 1)。NMR(200mcps，CDCl3 7.24ppm)：δ 2.23ppm m/s 5H茚体系的亚甲基和2-甲基，δ3.01ppm t 4H亚甲基，δ3.32ppm s 2H亚甲基酸，δ6.51ppm s 1H烯属茚体系，δ7.20和7.34ppm s 2H芳族，13-NMR(200mcps，CDCl3)：δ16.8ppm甲基，δ25.8ppm环5的亚甲基，δ32.66和32.72ppm环的亚甲基，δ42.2ppm茚体系的亚甲基，δ127.1ppm茚体系的叔碳原子，δ115.5和119.5(各自有H)ppm芳族碳原子，同样的它但没有氢则是139.6，141.7，142.1，144.4和145.0ppm incl 4°茚体系的烯属碳原子(cf.CH关联和HH-COSY).1-(9-芴基)-2(1-(5.6-环戊二烯并-2-甲基)茚基)乙烷的获得
3.89g的2-甲基-5.6-环戊基茚-1(22.85mmol)用14.3mL的n-Buli在150mL二噁烷中去除质子，然后与25.13mmol的2-(9′-芴基)乙基三氟甲烷磺酸酯在100mL二噁烷中的溶液混合。搅拌进行一整夜，经过半小时加热至60℃，该溶液用大约3mL H2O淬灭。除去二噁烷，产物用200mL Et2O萃取三次。无需进行色谱处理，获得6.49gms(17.9mmol，78.3％的理论值)的无色、结晶性产物。
NMR(200mcps，CDCl3，7.24ppm)：δ1.89ppm s 3H甲基，δ1.41ppm至1.72ppm m 4H桥的脂族质子，δ2.10ppm pseudo-t 2H环的脂族质子，δ2.90ppm pseudo-t 4H环的脂族质子，δ3.87 ppmt1H芴体系的脂族质子，δ6.40ppm s 1H茚质子，δ6.98和7.07ppm茚体系的芳族质子，δ7.31至7.77ppm m 8H芴的芳族。MS(FD)m/z362.5(M+100％)。
1-(9-芴基)-2-(1-(5.6-环戊二烯并-2-甲基)茚基)乙烷二茂锆二氯化物的获得
1.711g的1-[1′-(2′-甲基)5′，6′-环戊基茚基-2-(9″-芴基)]乙烷(4.72mmol)溶于100mL甲苯中，与10mL二噁烷混合，然后在低温下用5.9mL的n-BuLi去除质子。搅拌进行大约1小时，然后将该悬浮液再次冷却到-78℃。现在添加1.10g的ZrCl4。该悬浮液在室温下再搅拌14小时，在这一情况下，形成了细的红色粉末，在从甲苯中分离所形成的LiCl之后它能够发生结晶。
产量2.148g(4.11mmol，87.1％的理论值)。NMR(500mcps，C2D2Cl4 80℃)；δ2.00ppm m 2H亚甲基环戊烷环(J6.8至7.5cps)，δ2.15ppm s 3H甲基，δ2.79至2.94ppm m 4H与芳族体系邻近的亚甲基环戊烷环(J=7.5至9.7cps)，δ4.05ppm m(J=3.5至13.2cps)2H桥的脂族质子(对于芴)，δ3.83和4.57ppm m(J=4.2至10.0cps)1H桥(非对映异构)的脂族质子(在一时)，δ6.05ppm s1H茚质子，δ7.03至7.85ppm m 10H芳族。
MS(E1)m/z 5，22，6同位素模式对应
EA-CH-燃烧分析：计算值64.35％C 4.63％H
实测值：64.08/63.89％ 4.53/4.63％聚合实施例
所有的聚合反应都是在表1中指定的条件下在300mL甲苯中进行。
利用Bruker AMX500装置来测量NMR数据并根据文献中数据来进行评价。
表1

Claims (8)

1．用于制备线性全同立构聚合物的催化剂组合物，该催化剂组合物含有活化剂和通式Ⅰ所示的金属配合物：
其中各取代基具有以下意义：
R1-R7代表线性或支化C1-C10烷基；5-7元环烷基，其中环烷基可携带一个或几个C1-C6烷基残基作为取代基；C6-C18芳基或芳烷基或烷芳基；在这种情况下，R1/R2、R3/R4、R6/R7能够部分或同时结合到与其稠合的5-7元环烷基或芳基环中；
R9、R10代表C1-C8烷基，4-7元环烷基，芳基，在这种情况下R9、R10能够与E结合形成4-7元环烷基或芳基；
R11代表C1-C8烷基，芳基，C1-C8氧烷基，C1-C8三烷基硅氧基；
M代表钛，锆，铪，钒，铌，钽；
X代表卤素或C1-C8烷基，芳基，苄基；
E代表碳，硅，锗或1，2-乙基，1，3-丙基，1，4-丁基。
2．根据权利要求1的催化剂和活化剂的组合物，其特征在于所述活化剂是通式Ⅱ或Ⅲ所示的开链或环状铝氧烷化合物
Figure 9980491800022
R8表示C1-C4烷基和n表示5和30之间的数，和/或通式Ⅳ-Ⅵ的阳离子活化剂
Figure 9980491800031
R9表示C1-C4烷基或芳基。
3．根据权利要求1或2的催化剂组合物，其特征在于通式Ⅰ所示的金属配合物是具有通式Ⅶ的化合物
其中残基R1-R11具有在通式Ⅰ中指定的意义和E2=CH2、O或S，和n=1或2。
4．根据权利要求1-3中至少一项的催化剂组合物，其特征在于通式Ⅰ所示的金属茂配合物和通式Ⅱ-Ⅵ所示的活化剂是以使得来自铝氧烷的铝和/或来自阳离子活化剂的硼与来自金属茂配合物的过渡金属之间的原子比在1∶1-106∶1范围内的用量来使用。
5．制备线性、全同立构聚合物的方法，所述聚合物的立构规整度在25-60％[mmmm]五单元浓度范围内变化，并排除了全同立构和无规立构嵌段的随意或相当规则的序列，在该方法中C2-C20烯烃与权利要求1-4中定义的催化剂组合物反应。
6．根据权利要求5的方法，其特征在于所述聚合反应是在气相中、在悬浮液中或在超临界单体中，尤其是在聚合反应条件下呈惰性的溶剂中进行。
7．根据权利要求5或6的方法，其特征在于作为惰性溶剂，使用不含任何反应活性分子的溶剂，如苯、甲苯、二甲苯、乙基苯或链烷烃类如丙烷、正丁烷、异丁烷、戊烷、己烷、庚烷或它们的混合物。
8．根据权利要求5-7中至少一项的方法，其特征在于聚合反应是在1-100巴，优选3-20巴和尤其优选5-15巴的压力下，和在-50℃到200℃之间、优选在10-150℃之间和尤其优选在20-40℃之间的温度下进行。
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