CN1069324C - 乙烯和丙烯的弹性共聚物及其制备方法 - Google Patents

乙烯和丙烯的弹性共聚物及其制备方法 Download PDF

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CN1069324C
CN1069324C CN94106002A CN94106002A CN1069324C CN 1069324 C CN1069324 C CN 1069324C CN 94106002 A CN94106002 A CN 94106002A CN 94106002 A CN94106002 A CN 94106002A CN 1069324 C CN1069324 C CN 1069324C
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M·加林贝蒂
E·阿尔比扎蒂
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Abstract

乙烯与丙烯并任选地与少量二烯或多烯形成的新的共聚物，所述共聚物在未硫化状态具有好的弹性性能，其特征在于部分丙烯以短程全同序列结构存在。在乙烯/丙烯之比为特定值时得到永久变形值(200%)小于15，并且特征粘度大于3。

Description

乙烯和丙烯的弹性共聚物及其制备方法
本发明涉及乙烯与丙烯并任选地与少量二烯或多烯的新的共聚物，所述共聚物在未硫化状态具有好的弹性性能。
EP和EPDM橡胶，乙烯与丙烯和少量二烯或多烯的弹性共聚物分别是本领域已知的产品。
这些共聚物通常是在由钒化合物(例如乙酰丙酮化物)和卤化烷基铝得到的齐格勒一纳塔催化剂存在下，使乙烯和丙烯并任选地与二烯或多烯的混合物聚合而制得的。
为了获得工业应用上感兴趣的弹性性能，必须对如此获得的共聚物进行硫化处理(用过氧化物或硫)。在其未硫化状态，它们不具有感兴趣的弹性性能。
热塑性聚烯烃橡胶(TPO)是已知的，它们能在保持热塑性聚合物可加工性的同时具有弹性性能。这些橡胶是在交联剂存在下，由结晶聚合物特别是全同立构聚丙烯与EP或EPDM橡胶的混合物进行高温动态硫化制得的。
具有某种程度的弹性-塑性性能的共聚物是已知的，它们是通过用载于二氯化镁之上的基于钛化合物的催化剂使丙烯与少量乙烯的混合物聚合制得的(USP4298721)。这些共聚物的特征在于聚丙烯型，并任选地聚乙烯型结晶含量高；这些共聚物的弹性性能是不能令人满意的(200％永久变形值太高)。
通过用Ti、Zr或Hf金属茂和铝氧烷化合物的均相催化剂使单体混合物聚合而得到的乙烯与丙烯和/或α-烯烃并任选地与少量二烯或多烯的弹性共聚物的制备方法是已知的。
欧洲专利申请EP-A-347128描述了制备乙烯与α-烯烃的弹性共聚物的方法，其中所使用的催化剂是由桥接的二环戊二烯基-Zr、-Ti或Hf化合物与聚甲基铝氧烷反应得到的，所述桥接化合物例如是亚乙基-双(茚基)二氯化锆或亚乙基-双(四氢茚基)-二氯化锆或二甲基亚甲硅烷基-双(四氢茚基)-二氯化锆。
聚合反应在液态单体中，在温度为0°～80℃，优选20°～60℃之间进行。
欧洲专利申请EP-A-347129描述了制备乙烯与包含少量非共轭二烯的α-烯烃的弹性共聚物的方法，它类似于欧洲专利申请EP-A-347128所公开的方法。
在上面两个引述的欧洲专利申请或实施例中所公开的聚合物没有一种在非硫化状态显示理想的弹性-塑性性能。200℃永久变形值高于30％，拉伸强度低于4-5MPa。
迄今未知乙烯与丙烯并任选地包含源自二烯或多烯的共聚物在未硫化状态具有感兴趣的弹性性能，特别是200％永久变形值(25℃，1分钟)小于15％。永久变形按随后报告的方法测定。
我们意外地发现，使用特别的催化剂在溶剂中进行聚合，可以合成具有上述弹性性能的乙烯-丙烯共聚物。
所述共聚物乙烯含量在55-70％(重量)之间，优选在58-65％(重量)之间，丙烯含量在30-45％(重量)之间，优选在35-42％(重量)之间，二烯或多烯含量在0-10％(重量)之间。
该共聚物的特征在于
-25℃戊烷中溶解度高于95％；
-几乎没有结晶(熔化焓低于15J/g)；
-三单元组形式的丙烯单元含量占丙烯的3～10％；至少70％的所述三单元组为全同立构结构。
二烯或多烯单元的含量通常在0-10％(重量)之间，优选0.5-5％(重量)。
分子量分布非常窄，特别是Mw/Mn比例相当低，通常低于4，优选低于3。
本发明共聚物的特征还在于乙烯和丙烯单元在大分子链中适当的分布(产物的共聚单体反应竞聚率在0.4-0.6之间)。
共聚物的比浓对数粘度高于3dl/g，优选高于3.5dl/g。
为了得到未硫化状态的好的弹性性能，乙烯的含量和特性粘度是非常重要的参数；就三单元组形式的丙烯含量和反应竞聚率的乘积而言结构相同而乙烯含量和特性粘度超出说明书所述值的共聚物，在未硫化状态不显示感兴趣的弹性性能，特别是其在200％的永久变形值不少于15％。
通过溶液法得到的本发明共聚物其特征还在于好的组成均一性，这可以由溶剂分馏得到证实。当在液态丙烯中操作时，不能得到如此水平的组成均一性。
可通过生产热塑性材料的常规方法(压塑、挤出、注塑等)将共聚物转化成成形制品，而得到的制品具有可以与硫化橡胶相比拟的弹性性能。
本发明的共聚物可通过以下方法制备：用手性催化剂使乙烯和丙烯的混合物并任选地在二烯或多烯存在下聚合，所述手性催化剂由锆金属茂衍生物(例如亚乙基-双(四氢茚基)-二氯化锆或二甲基亚甲硅烷基-双(四氢茚基)-二氯化锆)和烷基铝在惰性烃溶剂中操作，并在水存在下得到的，Al/H2O摩尔比高于1∶1，低于100∶1，优选在1∶1和50∶1之间。
Al/Zr摩尔比在约100-10000之间，优选500-5000之间，更优选选500-2000之间。
烷基铝化合物的非限制性实例是：Al(iBu)3，AlH(iBu)2，Al(iHex)3，Al(C6H5)3，Al(CH2C6H5)3，Al(CH2CMe3)3，Al(CH2SiCMe3)3，AlMe2iBu，AlMe(iBu)2(iBu-异丁基，iHex-异己基，Me-甲基)。
用在聚合反应中的烃类溶剂可以是芳香族的，例如甲苯，或脂族的，例如戊烷、己烷、环己烷、庚烷。
聚合温度通常在0-100℃之间，优选20-60℃之间。
本发明共聚物的分子量可以控制，例如，使用分子量调节剂，其中优选氢。
二烯或多烯优选是选自非共轭线型二烯类，例如1，4-己二烯或内部桥连环二烯类，例如5-亚乙基-2-降冰片烯。
聚合物的热性能是通过示差扫描量热法，对聚合物样品进行分析，示差扫描量热法按下列步骤进行：第一扫描正程从T1＝-20℃至T2＝180℃，加热速度20℃/分钟。
键合乙烯含量是通过红外分析测定的。
丙烯三单元组的含量是对于次甲基Tββ由13C-NMR测定的，见“G.J.Ray，P.E.Johnson，J.R.Knox，Macromolecules，10，4，773(1977)”。报告的数值指丙烯含量。
全同立构三单元组含量通过13C-NMR应用下式测定的，
ISO％＝(A[Tββ]mm)/(A[Tββ]mm+A[Tββ]mr+A[Tββ]rr)，其中A是相当于叔碳原子(Tββ)峰的下面的面积；mm、mr和rr分别为全同、杂同和间同立构三单元组。
反应竞聚率乘积r1·r2(r1为乙烯的反应竞聚率、r2为丙烯的反应竞聚率)由下列式子计算；
r1·r2＝1+f·(x+1)-(f+1)·(x+1)1/2，其中：
f＝(乙烯摩尔数/丙烯摩尔数)共聚物；
x＝两个或更多个丙烯连续单元的百分率与孤立的丙烯百分率之比。
永久变形的值是在200℃温度下，在200kg/cm3压力下，由在Carver型压机中压模的尺寸为120×120×1.18mm的板获得的样品测定的。维持同样压力，将模塑制品冷却至室温。用于永久变形试验的样品是由如此得到的板制得的，其长度L0＝50mm，宽2mm，末端较宽以连接在拉伸仪器上。
将样品拉伸至长100mm，保持拉伸1分钟然后放松，1分钟后测量最终长度。按下式计算永久变形值：
              TS200％＝[(L-L0)/L0]100
表2中给出的值是由试验3中获得的数据通过计算得到的。
在戊烷中的溶解度按如下方法测量，将2g聚合物放在250ml正戊烷中；将混合物加热至沸腾温度，同时搅拌20分钟，将其在搅拌下冷却至25℃。30分钟后将得到的混合物滤过一个折叠(pleated)过滤器；真空干燥后，测定不溶性聚合物部分。
特性粘度是在135℃，在1，2，3，4-四氢化萘中测定的。
用GPC测定分子量分布Mw/Mn。
下列实施例用于说明本发明，无限制目的。
                       实施例
                  催化体系的制备
根据H.H.Britzinger等，J.Organomet.Chem.，288，第63页(1985)所述方法制备亚乙基-双(四氢茚基)-二氯化锆(EBTHIZrCl2)。
                    通用聚合方法
在室温下向4升钢制高压釜中加入2升己烷，并加入丙烯、乙烯并任选地加入氢(按表1中给出的量)。将温度升至50℃，加入10cm3锆化合物、Al(iBu)3和水的甲苯溶液(按表1中给出的量)。在反应过程中，以60/40(重量)比例连续加入乙烯/丙烯混合物以维持恒定的高压釜压力。60分钟后加入600cm3CO停止反应，将包含聚合物的溶液卸料到含3升丙酮的5升接受器中。将制得的固体聚合物在70℃烘箱中干燥。
                      实施例1-5
通过遵循上述通用方法，在表1中给出的操作条件下进行一些聚合试验。
在表2中，给出了得到的聚合物的特征。
                                                              表1
 实施例(n*)        Zr(mmol.10-3)    Al/Zr(mol)   Al/H2O(mol)                                      聚合
   C2/液(％wt)     C2/气(mol％)     C2/液(％wt)    C2/气(mol％)    H2/气(mol％)     活性kgpol/gEY
    1       1.86     690    1.6     2.33     39.0     19.6     56.0      --     204.7
    2       1.88    1000     2     2.0     34.0     21.7     61.3      --     175.4
    3       1.88     890    1.6     2.0     34.0     21.7     61.3    0.016     251.5
      1.86     890    1.8     1.68     28.0     24.2     67.5      --     181.3
    5比较实施例       1.88     890    1.8     2.0     34.0     21.7     61.3     0.031     233.9
                                                                   表2
实施例(n*) ％C2(wt.)    特性粘度(dl/g) Mw/Mn DSC扫描             NMR分析       溶解度(％wt.)    永久变形(％)
   M.P.(℃)    Hf    三单元组(％)     ％全同立构    r1.r2     溶  不溶
      1    66.9    5.74     1.9    39.4   11.5    3.76    100    0.512    100   --     15
      2    63.4    5.39     2.1     --    --    100   --      4
      3    60.6    3.82     2.0     --    --    8.19    100    0.464    100   --     10
      4    55.5    3.56     2.2     --    --    9.80    100    0.453    100   --     10
      5比较实施例    60.7    2.89     2.0     --    --    6.87    100    0.456    100   --     25

Claims (8)

1.乙烯与丙烯并任选地与少量源自二烯或多烯的单元的共聚物，它包含55-70重量％乙烯、30-45重量％丙烯和0-10重量％二烯或多烯，所述共聚物具有下列性质：
-结晶含量，以测定熔化焓表示，低于15J/g；
-25℃戊烷中溶解度高于95％；
-三单元组形式丙烯单元含量占丙烯的3-10％；至少70％所述三单元组为全同立构结构。
-单体反应竞聚率乘积r1·r2在0.4-0.6之间，其中r1是乙烯的反应竞聚率，r2是丙烯的反应竞聚率；
-特性粘度高于3dl/g。
2.权利要求1的共聚物，其中乙烯含量在58-65重量％之间，丙烯含量在35-42重量％之间，所述二烯或多烯含量不超过5摩尔％。
3.权利要求1的乙烯和丙烯共聚物，其特性粘度高于3.5dl/g。
4.权利要求3的共聚物，包含不超过5重量％的源自1，4-己二烯或5-亚乙基-2-降冰片烯的单元。
5.权利要求1的共聚物，其特征在于永久变形小于15％，其中永久变形的测试条件是：在20℃下，将样品拉伸1分钟至初始长度的200％，1分钟后进行测量。
6.乙烯与丙烯并任选地与少量二烯或多烯的共聚物的制备方法，所述共聚物包含55-70重量％乙烯，30-45重量％丙烯和0-10重量％二烯或多烯，具有下列性质：
-结晶含量，以测定熔化焓表示，低于15J/g；
-25℃戊烷中溶解度高于95％；
-三单元组形式丙烯单元含量占丙烯的3-10％；至少70％所述三单元组为全同立构结构；
-单体反应竞聚率乘积r1·r2在0.4-0.6之间，其中r1是乙烯的反应竞聚率，r2是丙烯的反应竞聚率；
-特性粘度高于3dl/g。其中乙烯、丙烯并任选地与多烯或二烯在惰性烃溶液中，在水存在下与手性催化剂接触，所述手性催化剂包括，锆金属茂衍生物和烷基铝化合物，其中Al/H2O摩尔比高于1∶1，但低于100∶1。
7.权利要求6的方法，其中金属茂选自亚乙基-双(四氢茚基)-二氯化锆或二甲基亚甲硅烷基-双(四氢茚基)-二氯化锆；烷基铝化合物选自Al(iBu)3，AlH(iBu)2，Al(iHex)3，Al(C6H5)3，Al(CH2C6H5)3，Al(CH2CMe3)3，Al(CH2SiCMe3)3，AlMe2iBu，AlMe(iBu)2，其中iBu表示异丁基，iHex表示异己基，Me表示甲基；Al/H2O摩尔比在1∶1至50∶1之间。
8.由上述权利要求1-5的共聚物制得的生产制品。
CN94106002A 1993-06-30 1994-05-11 乙烯和丙烯的弹性共聚物及其制备方法 Expired - Fee Related CN1069324C (zh)

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