CN101061143A - 用四氢茚基-型催化剂体系制备的聚乙烯的固态性能 - Google Patents
用四氢茚基-型催化剂体系制备的聚乙烯的固态性能 Download PDFInfo
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Abstract
本发明公开了具有优异的尺寸稳定性、固态机械性能和阻隔性能的制品,该制品使用按照基于桥接的联茚基配位体的催化剂体系所制备的聚乙烯树脂来生产。
Description
本发明涉及的领域是使用基于四氢茚基催化剂组分的催化剂体系所制备的聚乙烯和它们的固态性能。
旋转模塑用来制造由简单到复杂的各种空心塑料制品。它能够用于对各种材料例如聚乙烯、聚丙烯、聚碳酸酯或者聚氯乙烯(PVC)进行模制。聚乙烯(PE)在旋转模塑市场所用的聚合物中的份额超过80%。这归结于聚乙烯在加工中对热降解的良好的耐受性,归结于其容易研磨、良好的流动性以及低温冲击性能。
用齐格勒-纳塔催化剂制备的聚乙烯一般用于旋转模塑中,但由金属茂制备的聚乙烯是所期望的,因为它们狭窄的分子量分布使其在加工中具有更好的冲击性能和更短的周期。
在市场上可获得的大多数金属茂制备的聚乙烯树脂(参见ANTEC,第1卷,2001)用基于双(正丁基-环戊二烯基)二氯化锆的催化剂体系来制备。它们具有差的尺寸稳定性,例如高收缩和翘曲。它们还具有在应力下的蠕变或永久变形。
Godinho等(在Polymers,Rubbers and Composites,vol 29,n°7,pp 316,2000中)公开了:对于半结晶聚合物(例如聚乙烯)来说,相当于精细微结构(finemicrostructure)的小球晶尺寸提供了改进的尺寸稳定性以及其他固态性能如改进的冲击强度。
本发明的目标是提供具有能够根据需要来调整的精细微结构的聚乙烯树脂。
本发明的目标还在于提供具有减少收缩的聚乙烯树脂。
本发明的另一个目标是在于提供具有减少翘曲的聚乙烯树脂。
本发明的另一个目标是在于提供具有高抗蠕变性的聚乙烯树脂。
本发明的再一个目标是在于提供具有高抗冲击性的聚乙烯树脂。
本发明的再一个目标是在于提供具有高度的抗应力开裂性能的聚乙烯树脂。
本发明的目标还在于提供具有优异阻隔性能的聚乙烯树脂。
因此,本发明公开了用于制备乙烯的均聚物或共聚物的方法,包括以下步骤:
a)将包括i)具有通式I的金属茂催化剂组分、ii)活化剂和iii)任选载体的催化剂体系注射入反应器中,其中,通式I为
R”(Ind)2MQ2 (I)
其中(Ind)是取代或未取代的茚基或氢化的茚基,R″是位于两个茚基之间以赋予立体刚性的结构桥,其包括:C1-C4亚烷基、二烷基锗或硅或硅氧烷、或烷基膦或胺基,该桥为取代或未取代的;Q是含1到20个碳原子的烃基基团或卤素,且M是周期表4族的过渡金属或钒;
b)将乙烯单体以至少6.5wt%的浓度注射入该反应器中;
c)注入一定量的氢以使得在进料中的H2/C2的比率低于85g/106g;
d)在聚合条件下将温度维持在低于90℃;
e)取出适于制备具有优异固态和阻隔性能的制品的聚乙烯树脂。
每个茚基或氢化的茚基化合物均可以在环戊二烯基环、环己烯基环和桥接上的一个或多个位置上按照相同或互相不同的方式来取代。
在茚基上的各取代基可以独立地选自具有式XRV的那些,其中X选自周期表的14族、氧和氮,且各R相同或不同并选自氢或含1到20个碳原子的烃基,且v+1是X的化合价。X优选是C。如果环戊二烯基环被取代,则其取代基基团不得太大以至于影响烯烃单体与金属M的配位。在环戊二烯基环上的取代基优选具有R例如氢或CH3。更优选,至少一个环戊二烯基环是未取代的和最优选两个环戊二烯基环都是未取代的。
在特别优选的实施方案中,两个茚基都是未取代的,并且它们最优选是未取代的氢化茚基。
用来聚合乙烯的活性催化剂体系包括上述的催化剂组分和具有电离作用的合适的活化剂。
合适的活化剂在本领域中是熟知的。
任选地,催化剂组分能够在载体上承载。
获得期望的聚乙烯树脂所需的聚合条件包括高浓度乙烯、很少或没有氢以及低的聚合温度。乙烯的浓度是至少6.5wt%,优选至少7wt%。对氢的量进行选择,使得在进料中的H2/C2至多是85g/106g,优选至多是60g/106g,更优选在进料中没有氢。聚合温度是低于90℃,优选地低于88℃,更优选从80到85℃。
由本发明的金属茂催化剂体系制备的PE树脂可以是具有从0.930到0.965g/cc的密度范围的乙烯的均聚物或共聚物。该密度在23℃的温度下按照标准测试ASTM 1505的方法来测量。熔体指数典型地是至少0.5,优选至少3,该熔体指数在190℃的温度下在2.16公斤的荷载下按照标准测试ASTM D1238的方法来测量。它们的特征为窄的分子量分布,典型地具有的多分散性指数(D)低于3。多分散性指数定义为重均分子量Mw与数均分子量Mn的比Mw/Mn。长链支化指数(LCBI)是高于(superior to)0的,表明存在长链支化。令人吃惊地发现:长链支化(LCB)引发自动成核过程。此成核过程的量(magnitude)随着长链支化的增加而增加,且LCB本身能够通过改变聚合条件来进行变化。此自动成核过程抑制或减少对聚乙烯树脂的外部成核剂的需要。
这些聚乙烯树脂能够采用在本领域中一般使用的所有方法(例如旋转模塑、注射模塑、吹塑或者挤出)来用来制备制品。它们在旋转模塑应用中是特别有利的。
根据本发明的最终制品具备若干吸引人的性能。
-它们具有非常精细的微结构,其特征在于平均球晶直径小于那些用齐格勒-纳塔(ZN)树脂制备的制品或使用由其他金属茂催化剂体系制备的树脂所制得的制品的平均球晶直径。根据本发明得到的乙烯共聚物的典型球晶尺寸低于20μm,优选低于18μm。
-它们具有优异的固态性能,例如
i)机械性能,
ii)阻隔性能,
iii)尺寸稳定性。
用根据本发明的树脂所制备的制品的阻隔性能低于1g/天,优选低于0.5g/天。
这些性能将以举例方式来说明。
附图说明
图1A到1J表明:在700ml旋转模塑瓶上所测量的微结构,该瓶分别用树脂R1到R10来制备。
图2显示:对于树脂R7、R8和R9而言,以cm为单位表示的实际变形为以星期为单位表示的时间的函数。在此图中,树脂R8的“星”表明破损。
图3显示:对于树脂R3、R4和R6而言,以cm为单位表示的实际变形为以星期为单位表示的时间的函数。
图4表明:在80℃的温度下,在分别用树脂R4和R6制备的旋转模塑部件上施加14到18MPa的应力的条件下所进行的牵引蠕变试验中,用mm为单位表示的真实的纵向变形为用秒为单位表示的时间的函数。
图5表明:在室温下,在分别用树脂R3和R6制备的旋转模塑部件上施加16MPa的应力的条件下所进行的牵引蠕变试验中,用mm为单位表示的真实的纵向变形为用秒为单位表示的时间的函数。
图6表明:长链支化指数LCBI为用μm为单位表示的球晶尺寸的函数。
图7表明:用μm为单位表示的球晶尺寸为用dg/分钟为单位表示的熔体指数MI2的函数。
图8表明:LCBI为以dg/分钟为单位表示的熔体指数MI2的函数。
图9a、9b和9c表明:在-40℃的温度下,对于4.5mm厚的、分别用树脂R6、R3和R4制备的旋转模塑制品的荷载位移曲线。荷载用牛顿表示且位移用mm来表示。
实施例
将几种聚乙烯树脂分别用以制备如下制品:
-使用专用模具模塑的700ml旋转模塑瓶;
-使用专用模具模塑的10L旋转模塑瓶;
-罐;
-使用专用模具模塑的直径32mm的管;
-模塑的样品;以及
-粉末样品
树脂R1是由Exxon Mobill Chemicals以名称LX0210销售的齐格勒-纳塔(ZN)PE树脂。
树脂R2是由Matrix以名称N307销售的ZN PE树脂。
树脂R3是由Dow Chemicals以名称NG2432销售的ZN PE树脂。
树脂R4是由Borealis以名称RM7402销售的金属茂制备的PE树脂。
树脂R5是由Borealis以名称RG7403销售的ZN PE树脂。
树脂R6是根据本发明用桥接的双(四氢茚基)-型催化剂体系制备的树脂。
树脂R7是由Borealis以名称RM8403销售的金属茂制备的PE。
树脂R8是由Dow Chemicals以名称NG2431销售的ZN PE树脂。
树脂R9是根据本发明用桥接的双(四氢茚基)-型催化剂体系制备的树脂。
树脂R10是根据本发明用桥接的双(四氢茚基)-型催化剂体系制备的树脂。
树脂R11是根据本发明用桥接的双(四氢茚基)-型催化剂体系制备的乙烯均聚物。
它们的性能总结在表I中。
表I
MI2dg/分钟 | 密度g/cc | Tm℃ | LCBI | 球晶尺寸μm | |
R1 | 4.15 | 0.941 | 127.5 | 0 | 27.55 |
R2 | 3.77 | 0.941 | 126.5 | 0 | 21.48 |
R3 | 3.64 | 0.940 | 127 | 0 | 20.18 |
R4 | 3.98 | 0.940 | 127.5 | 0 | 19.82 |
R5 | 3.83 | 0.944 | 127.5 | 0 | 20.81 |
R6 | 3.8 | 0.940 | 126 | 0.6 | 14.4 |
R7 | 6 | 0.934 | 0 | 37.6 | |
R8 | 7 | 0.935 | 0 | 30.7 | |
R9 | 8 | 0.934 | 0.3 | 16 | |
R10 | 0.9 | 0.934 | 1.6 | 8 | |
R11 | 7.39 | 0.960 | 137 | 0.14 | 22* |
*必须注意,球晶尺寸随着密度的增加而增加;并且对于密度是0.960g/cc的树脂R11而言,所观察到的球晶尺寸是极小的。
熔体流动指数MI2按照标准测试ASTM D 1238的方法在2.16kg荷载下和在190℃的温度下来测量。密度通过在23℃的温度下按照标准测试ASTMD 1505的方法来测量。
球晶尺寸由小角光散射(SALS)测量。当光柱穿过被安置在两个交叉的偏振器之间的半结晶聚合物的薄片时,聚合物的球晶散射光并且四叶图样被投射于位于第二个偏振器之后的屏幕上。图样的大小与球晶直径成反比并且可以用于球晶直径的测定。
如下进行刚度分析。
对于压缩模塑的样品,通过按照在具有相同密度的样品R3和R6上的标准测试ASTM D 790的方法来测量杨氏模量。树脂R6的高于现有技术树脂R3的杨氏模量,树脂R3的杨氏模量为575MPa,树脂R6的杨氏模量为615MPa。
对于树脂R3和R6,在粉末样品上进行扭转模式下的流变动态分析,和对于树脂R1、R3、R4、R5和R6,进行拉伸模式下的流变动态分析。在测试温度的所有范围内,根据本发明的树脂的弹性模量E’(拉伸模式)相比于所有现有技术的树脂的值而言具有更高的值。
动态机械分析测量在700ml的、由230℃的峰值内部空气温度(PIAT)所制备的旋转模塑瓶上进行。进行压缩试验来确定获得5mm位移所必须的力和某些树脂的最大力。本发明的树脂胜过所有其他树脂。
拉伸分析在旋转模塑罐上通过使用标准测试ISO R527/样品类型5的方法,在23℃的温度下和在100mm/分钟的拉伸速率下来进行。对于屈服应力、杨氏模量和断裂伸长来说,树脂R6的性能类似于或略优于现有技术树脂的那些性能。
抗冲击性通过在旋转模塑罐上进行落锤(falling weight)试验和通过在10升、6mm壁厚的旋转模塑瓶上进行落体试验(drop test)来测试。
根据本发明的树脂与现有技术树脂相比而言全部是脆性较低的。
落体试验在-18℃的温度下,在10升、壁厚6mm、由专用模具制备的旋转模塑瓶上来进行。瓶从增加的高度落下,直到失败发生为止。
现有技术树脂R1在高度1.5m失败。
现有技术树脂R4在高度2m失败。
现有技术树脂R5在高度6m失败。
根据本发明的树脂R6在-18℃的温度和在-40℃的温度下最高到高度6.5m都没有失败。
在700ml旋转模塑瓶上,还对所有树脂进行堆积试验,这些瓶用专用模具来制备,并且填充有润湿剂(在水中的5%的Huperol)和在35kg荷载下放置。在装载之前并在装载后的不同间隔时间,测量瓶的高度。结果示于表II中。
表II
树脂 | 瓶重(g) | 瓶高(mm) | ||||||
t=0 | t=24h | t=72h | t=1wk | t=2wk | t=5wk | t=8wk | ||
R2 | 78.95 | 212 | 208 | 198.5 | 破裂 | - | - | - |
R3 | 79.2 | 212.25 | 209.75 | 204.25 | 203.25 | 201 | 破裂 | - |
R4 | 78.825 | 212 | 209 | 203.75 | 204 | 204 | 破裂 | - |
R5 | 78.55 | 212 | 208.5 | 破裂 | - | - | - | - |
R6 | 78.65 | 211 | 208.5 | 201.5 | 199.75 | 200 | 201 | 破裂 |
在此表中,术语“破裂”意味着在测试期间,至少50%的被测试的样品破裂。
从表II可以显见:本发明的聚乙烯树脂在堆积试验中显示出优异的性能。
在40℃的温度下,在700ml、壁厚2.5mm、由树脂R7、R8和R9及专用模具制备的、填充有润湿剂(在水中的5%的Huperol)和在40kg荷载下放置的旋转模塑瓶上所进行的堆积试验显示于图2中,该图显示了用cm作单位的翘曲与用天作单位的时间的函数关系。
在40℃的温度下,在700ml、壁厚1.5mm、由树脂R3、R4和R6及专用模具制备的、填充有HNO3(55%)和在35kg荷载下放置的旋转模塑瓶上所进行的堆积试验显示于图3中,该图显示了用cm作单位的翘曲与用天作单位的时间的函数关系。
抗环境应力开裂性能(瓶ESCR)测试在700ml旋转模塑瓶上来进行,该瓶壁厚为1.5mm,采用专用模具制备并且填充有10%的Antarox溶液。在60℃的温度下,它们承受6牛顿/cm2的力。本发明的树脂胜过了所有其他树脂,如在表III中所示。
表III
树脂 | R1 | R3 | R4 | R5 | R6 |
ESCR(hr) | 26 | 40 | 48 | 19 | 54 |
还进行蠕变试验。在室温下,对管施予16Mpa的牵引蠕变,真实的纵向变形与时间的函数的结果示于图4(对于树脂R8和R9)和图5(对于树脂R3和R6)中。这些图显示了本发明树脂R9和R6的改进的性能。
压力测试在旋转模塑管上来进行,该管直径为32mm且壁厚为3mm。它们在80℃的温度下承受3.5Mpa压力。在50小时之后,现有技术树脂R3失败了,比较而言,根据本发明的树脂R6在400个小时之后才失败。
阻隔性能在旋转模塑的10升瓶上被研究,该瓶壁厚为6mm并且用专用模具来制备。在40℃的温度下,它们充满着燃料(CEC RF08-A-85,根据NormStandard ECE34-附录5)。在表IV中所显示的对燃料的渗透性(以g/天为单位)的结果清楚地显示了树脂R6和R11卓著的阻隔性能。
表IV
树脂 | R2 | R3 | R4 | R5 | R6 | R11 |
渗透性(g/天) | 2.6 | 1.17 | 0.771 | 2.1 | 0.457 | 0.097 |
能够看出:根据本发明的树脂明显地胜过所有现有技术的树脂,其渗透率低于0.5g/天。
另外,与现有技术树脂相当相反地,观察到在长链支化指数LCBI、球晶尺寸以及熔体指数之间的清楚的相互关系。此特征分别在图6到8中描述。图6显示了LCBI和球晶尺寸之间的线性相互关系。对于树脂R6、R9和R10而言,球晶尺寸随着LCBI的增加而线性地减少,然而对于现有技术树脂而言,其保持不变。图7显示了根据本发明的树脂的LCBI和熔体指数MI2之间的相互关系。熔体指数随着LCBI的减少而增加。在本发明的树脂中,LCB含量因而能通过变化熔体指数来变化。图8显示了熔体指数和球晶尺寸之间的线性相互关系。熔体指数随着球晶尺寸的增加而线性地被增加。
冲击试验分别在由本发明树脂R6制备的旋转模塑制品上以及由在本领域中通常被使用的树脂R3和R4制备的旋转模塑制品上来进行。测试将按照标准测试ISO 6603-2的方法分别在20℃、-20℃和-40℃的温度下和在厚度为4.5和6mm的样品上来进行。结果示于表V中。
表V
树脂 | 厚度(mm) | 温度(℃) | 峰值负荷(kN) | 峰值能量(J) | 总能量(J) |
R6 | 4.5 | 20 | 5.47 | 44.5 | 129.9 |
R3 | 5.5 | 46.7 | 104.9 | ||
R4 | 5.89 | 48.9 | 89.7 | ||
R6 | 6.0 | 8.6 | 102.5 | 252.8 | |
R3 | 6.62 | 55.9 | 118.6 | ||
R4 | 8.81 | 90.1 | 279.5 | ||
R6 | 4.5 | -20 | 7.32 | 63.2 | 188.6 |
R3 | 4.43 | 16.8 | 25.7 | ||
R4 | 5.94 | 31.8 | 74.0 | ||
R6 | 6.0 | 11.13 | 127.5 | 314.5 | |
R3 | 4.74 | 15.1 | 25.2 | ||
R4 | 11.2 | 113.1 | 295 | ||
R6 | 4.5 | -40 | 7.99 | 66.1 | 178.4 |
R3 | 2.38 | 4.3 | 11.7 | ||
R4 | 6.38 | 31.8 | 58.4 | ||
R6 | 6.0 | 12.11 | 125.2 | 334.3 | |
R3 | 4.04 | 7.7 | 14.8 | ||
R4 | 10.46 | 92.4 | 235.5 |
根据本发明的树脂R6在所有测试的温度胜过其他树脂。
对于分别用树脂R6、R3和R4制备的4.5mm旋转模塑样品,图9a、9b和9c表明了在-40℃的温度下的荷载位移曲线。
树脂R6在所有测试温度显示了真实的延展行为,与其他测试的树脂相反。
另外,落锤冲击试验也在-20℃的温度下,在10升的、壁厚为6mm且用树脂R11制备的旋转模塑瓶上来进行。所有瓶均具有完全的延展行为并且冲击结果总结在表VI中。
表VI
总能量J | 速度m/s | 最大能量J |
107.03 | 3.34 | 66.2 |
126.03 | 3.09 | 68.44 |
72.15 | 3.73 | 37.44 |
119.97 | 3.17 | 81.02 |
94.76 | 3.48 | 61.65 |
根据本发明制备的所有制品也具有卓著的光学性能。
总而言之,对于所有所进行的试验,根据本发明的聚乙烯树脂被证明至少是与所有现有技术树脂一样的好,且在多数情况下远远优于所有现有技术的树脂。
同样结论适用于通过使用旋转模塑之外的其他方法(例如挤出、注射模塑、涂凝模塑(slush moulding)或者热成型)所制备的制品。
Claims (9)
1.一种用于制备乙烯的均聚物或共聚物的方法,包括以下步骤:
a)将包括i)具有通式I的金属茂催化剂组分、ii)活化剂和iii)任选载体的催化剂体系注射入反应器中,其中,通式I为
R”(Ind)2MQ2 (I)
其中(Ind)是取代或未取代的茚基或氢化的茚基,R″是位于两个茚基之间以赋予立体刚性的结构桥,其包括:C1-C4亚烷基、二烷基锗或硅或硅氧烷、或烷基膦或胺基,该桥为取代或未取代的;Q是含1到20个碳原子的烃基基团或卤素,且M是周期表4族的过渡金属或钒;
b)将乙烯单体以至少6.5wt%的浓度注射入该反应器中;
c)注入一定量的氢以使得在进料中的H2/C2的比率低于85g/106g;
d)在聚合条件下将温度维持在低于90℃;
e)收取聚乙烯树脂。
2.根据权利要求1的方法,其中,在该金属茂组分中,两个茚基都是未取代的。
3.根据权利要求2的方法,其中两个未取代的茚基都是四氢茚基。
4.根据权利要求1到3中任一项的方法,其中在该聚合反应器中的乙烯浓度大于7wt%。
5.根据前述权利要求中任一项的方法,其中对在该聚合反应器中的氢的量进行选择以获得低于60g/106g的C2/H2比率。
6.根据前述权利要求中任一项的方法,其中聚合温度低于88℃。
7.根据前述权利要求中任一项的方法,其生产自动成核聚乙烯树脂。
8.根据前述权利要求中任一项的方法所制备的聚乙烯树脂在通过旋转模塑、注射模塑、挤出、热成型或者涂凝模塑来生产具有优异固态和阻隔性能的最终制品中的用途。
9.能够通过权利要求1到7中任一项的方法获得的渗透率低于1g/天的旋转模塑制品。
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US8822611B2 (en) | 2014-09-02 |
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