CN108290982B - 丙烯共聚物 - Google Patents

丙烯共聚物 Download PDF

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CN108290982B
CN108290982B CN201680068706.9A CN201680068706A CN108290982B CN 108290982 B CN108290982 B CN 108290982B CN 201680068706 A CN201680068706 A CN 201680068706A CN 108290982 B CN108290982 B CN 108290982B
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propylene
hexene
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C·卡瓦列里
P·马萨里
M·格拉茨兹
G·佩尔加蒂
R·潘塔莱昂尼
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Basell Poliolefine Italia SRL
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Abstract

一种含有5.5至9.0重量％的1‑己烯衍生单元的丙烯1‑己烯共聚物，其具有：a)在0至5mW范围内的DSC曲线中的两个峰的高度差；b)在141.0℃至151.0℃范围内的由DSC测得的较高熔化温度；c)在3.5至8.0g/10min范围内的熔体流动速率(MFR，根据ASTM D1238测量，230℃/2.16kg)。

Description

丙烯共聚物
技术领域
本发明涉及丙烯与1-己烯的共聚物，特别适用于制备膜，特别是具有低密封起始温度的双轴取向聚丙烯膜(BOPP)和流延膜。
背景技术
丙烯和1-己烯的共聚物在本领域中是已知的，例如WO 2006/002778涉及一种具有0.2至5重量％的1-己烯衍生单元的丙烯和1-己烯的共聚物。该共聚物具有单峰型的分子量分布并用于管道***。
WO 2009/077287涉及一种丙烯与己烯-1的共聚物，其含有5至9重量％的源自己烯-1的重复单元，所述共聚物具有125℃至140℃的熔化温度和0.1至3g/10min的熔体流动速率(ASTM D1238，230℃/2.16kg)。
WO 2015/062787涉及一种丙烯与1-己烯的多峰共聚物，其具有0.6重量％至3.0重量％的1-己烯衍生单元的含量并特别适用于工业板材的生产。
申请人发现通过使用多峰丙烯1-己烯共聚物可以生产具有高雾度值和低密封起始温度(SIT)的BOPP和流延膜。
发明内容
因此，本发明提供了一种含有5.5至9.0重量％的1-己烯衍生单元的丙烯1-己烯共聚物，其具有：
a)在0至5mW范围内的DSC曲线中的两个峰的高度差；
b)在141.0℃至151.0℃范围内的由DSC测得的较高熔化温度；
c)在3.5至8.0g/10min范围内的熔体流动速率(MFR，根据ASTM D1238测量，230℃/2.16kg，即在230℃，2.16kg的载荷下)。
具体实施方式
本发明提供一种含有5.5至9.0重量％，优选地6.0至8.5重量％，更优选地6.5至8.0重量％的1-己烯衍生单元的丙烯1-己烯共聚物，其具有：
a)在0至5mW范围内的DSC曲线中的两个峰的高度差；优选地0至3mW；
b)在141.0℃至151.0℃范围内的由DSC测得的较高熔化温度；优选地142.0℃至149.0℃；更优选地142.5℃至145.0℃；
c)在3.5至8.0g/10min范围内的熔体流动速率(MFR，根据ASTM D1238测量，230℃/2.16kg，即在230℃，2.16kg的载荷下)；优选地3.8至7.5g/10min；更优选地4.0至6.0g/10min。
优选地，两个峰的熔化温度的差值在5℃至30℃的范围内；更优选地7℃至15℃；甚至更优选地8℃至12℃。
本发明的丙烯1-己烯共聚物仅含有丙烯和1-己烯衍生单元。
DSC曲线(温度/熔化热(mW))中的峰值被定义为在温度A下与温度A的±1℃范围内的熔化热的值(mW)相比具有最高熔化热值的DSC曲线(温度/熔化热(mW))上的点。
所述量的1-己烯单元是指共聚物的总重量。
熔化温度值根据ISO 11357-3通过差示扫描量热法(DSC)以20℃/分钟的加热速率测定。
此外，本发明的共聚物优选地在25℃下在二甲苯中的溶解度等于或低于25重量％，优选地等于或低于20重量％；高于12重量％。
本发明的丙烯1-己烯共聚物具有低雾度和低密封起始温度(SIT)，使得该材料可以有利地用于制造膜，特别是流延膜或BOPP膜。
本发明的丙烯1-己烯共聚物可以通过在负载在二卤化镁上的立体特异性齐格勒-纳塔催化剂存在下进行的聚合方法来获得。通过适当给料分子量调节剂(优选地氢气)。
可以连续或分批的聚合方法按照已知技术进行，并且在气相中操作，或者在存在或不存在惰性稀释剂的液相中操作，或通过混合液-气技术操作。优选地在两个反应器中在气相中进行聚合。
聚合反应时间，压力和温度并不严格，但如果温度为20至100℃，则最好。压力可以是大气压或更高。
如前所述，分子量的调节通过使用已知的调节剂进行，特别是氢。
所述立体特异性聚合催化剂包含以下物质之间的反应产物：
1)含有钛化合物和负载在二卤化镁(优选地氯化物)上的电子给体化合物(内部给体)的固体组分；
2)烷基铝化合物(助催化剂)；以及，任选地，
3)电子给体化合物(外部给体)。
所述催化剂优选地能够制造全同立构指数高于90％的丙烯均聚物(以室温下不溶于二甲苯的部分的重量测定)。
固体催化剂组分(1)含有通常选自醚、酮、内酯、含有N、P和/或S原子的化合物以及单和二羧酸酯的化合物作为电子给体。
具有上述特征的催化剂在专利文献中是众所周知的；特别有利的是美国专利4,399,054和欧洲专利45977中描述的催化剂。
所述电子给体化合物中特别适合的是邻苯二甲酸酯和琥珀酸酯。
合适的琥珀酸酯由式(I)表示：
Figure BDA0001671547210000031
其中基团R1和R2彼此相同或不同，为任选地含有杂原子的C1-C20直链或支链烷基、烯基、环烷基、芳基、芳烷基或烷芳基；基团R3至R6彼此相同或不同，为氢或任选地含有杂原子的C1-C20直链或支链烷基、烯基、环烷基、芳基、芳烷基或烷芳基，以及连接在同一碳原子上的基团R3至R6可以连接在一起以形成环。
R1和R2优选地为C1-C8烷基、环烷基、芳基、芳烷基和烷芳基。特别优选的是其中R1和R2选自伯烷基，特别是支链伯烷基的化合物。合适的R1和R2基团的实例是甲基、乙基、正丙基、正丁基、异丁基、新戊基、2-乙基己基。特别优选的是乙基、异丁基和新戊基。
由式(I)描述的优选化合物群组中的一个是其中R3至R5为氢且R6为具有3至10个碳原子的支链烷基、环烷基、芳基、芳烷基和烷芳基的那个化合物。那些式(I)化合物中另一组优选的化合物是其中R3至R6中至少两个基团不同于氢且选自C1-C20直链或支链烷基、烯基、环烷基、芳基、芳烷基或烷芳基，任选地含有杂原子的那个化合物。特别优选的是其中不同于氢的两个基团连接到相同碳原子的化合物。此外，其中至少两个不同于氢的基团(即R3和R5或R4和R6)连接到不同的碳原子的化合物是特别优选的。
其他电子给体特别适合的是1,3-二醚，如公开的欧洲专利申请EP-A-361 493和728769中所述。
对于助催化剂(2)，优选使用三烷基铝化合物，例如三乙基铝，三异丁基铝和三正丁基铝。
可以用作外部电子给体的电子给体化合物(3)(加入烷基铝化合物中)包括芳族酸酯(如烷基苯甲酸酯)、杂环化合物(如2,2,6,6-四甲基哌啶和2,6-二异丙基哌啶)，特别是含有至少一个Si-OR键(其中R是烃基)的硅化合物。所述硅化合物的实例是式Ra 1Rb 2Si(OR3)c的那些，其中a和b是0至2的整数，c是1至3的整数并且(a+b+c)的总和是4；R1，R2和R3是任选地含有杂原子的具有1-18个碳原子的烷基、环烷基或芳基。
特别优选的是叔己基三甲氧基硅烷(2,3-二甲基-2-三甲氧基甲硅烷基-丁烷)。
先前所述的1,3-二醚也适合用作外部给体。在内部给体是所述1,3-二醚中一种的情况下，可以省略外部给体。
催化剂可以与少量烯烃预接触(预聚合)，将催化剂保持在烃溶剂中的悬浮液中，并在室温至60℃的温度下聚合，由此产生0.5至3倍催化剂重量的聚合物量。
本发明的共聚物还可以包含通常用于烯烃聚合物的添加剂，例如成核剂和澄清剂以及加工助剂。
本发明的丙烯1-己烯共聚物可以有利地用于制备膜。优选地，流延膜或BOPP膜单层或多层，其中至少一层包含本发明的丙烯1-己烯共聚物。
给出以下实例来说明本发明而不是限制目的
实例
通过下面报道的方法测定与实例的聚合物材料和膜有关的数据。
熔化温度(ISO11357-3)
通过差示扫描量热法(DSC)测定。将重6±1mg的样品以20℃/min的速率加热至200±1℃，并在氮气流中在200±1℃下保持2分钟，然后以20℃/min的速率冷却至40±2℃，由此在该温度下保持2分钟以使样品结晶。然后，再次将样品以20℃/min的升温速率熔融至200℃1。记录熔化扫描，获得热分析图(℃相对于mW)，并由此读取对应于峰的温度。。将与在第二次熔融期间记录的最强熔化峰相对应的温度作为熔化温度。
熔体流动速率(MFR)
根据ASTM D1238，在230℃下，以2.16kg的载荷进行测定。
在25℃在二甲苯中的溶解度
将2.5g聚合物和250ml二甲苯引入配备有致冷器和磁力搅拌器的玻璃烧瓶中。温度在30分钟内升高至溶剂的沸点。然后将因此获得的澄清溶液回流并再搅拌30分钟。然后将封闭的烧瓶在冰水浴中保持30分钟，并在25℃的恒温水浴中保持30分钟。将因此形成的固体在快速滤纸上过滤。将100ml过滤的液体倒入预先称重的铝容器中，在氮气流下在加热板上加热，通过蒸发除去溶剂。然后将容器在真空下保持在80℃的烘箱中直至获得恒重。然后计算在室温下可溶于二甲苯的聚合物的重量百分比。
特性粘度(IV)
在四氢萘中在135℃下测定
通过NMR测定1-己烯含量
13C NMR光谱通过在150.91MHz下以傅立叶变换模式在120℃下操作的AV-600光谱仪得到。在28.83下的丙烯CH的峰值用作内标。使用以下参数获得13C NMR光谱：
谱宽(SW) 60ppm
谱中心(O1) 30ppm
解耦序列 WALTZ65_64pl
脉冲程序 ZGPG
冲长度(P1) 90°脉
总点数(TD) 32K
弛豫延迟 15秒
瞬态数量 1500
使用以下关系由diad以摩尔百分比计计算1-己烯的总量：
[P]＝PP+0.5PH
[H]＝HH+0.5PH
根据下表计算丙烯/1-己烯共聚物的13C NMR光谱的分配：
Figure BDA0001671547210000061
Figure BDA0001671547210000071
密封起始温度(SIT)
制备膜样品
通过在单螺杆Collin挤出机(螺杆长度/直径比为1:25)中在7m/min的膜拉伸速度和210-250℃的熔化温度下将每种测试组合物挤出来制备一些50μm厚度的膜。将每个所得膜叠加在具有97重量％的二甲苯不溶部分和2g/10min的MFR L的丙烯均聚物的1000μm厚的膜上。在Carver压机中，在200℃，9000kg的载荷下将叠加的膜彼此粘合，保持5分钟。利用TOM Long膜拉伸机在150℃下将得到的层压件纵向和横向(即双轴)拉伸6倍，由此获得20μm厚的膜(18μm均聚物+2μm测试)。从膜上切下2×5cm样品。
确定SIT。
对于每个测试，将两个上述样品叠加排列，相邻层是特定测试组合物的层。使用型号HSG-ETK745的Brugger Feinmechanik密封器沿着2cm的一侧密封叠加的样品。在0.1N/mm2的压力下，密封时间为5秒。对于每个密封，密封温度从低于测试组合物的熔化温度的约10℃开始升高2℃。将密封的样品冷却，然后将它们未密封的端部连接到Instron机器，在其中它们以50mm/min的牵引速度进行测试。
SIT是在所述测试条件下施加至少2牛顿的载荷时密封不破裂的最小密封温度。。
雾度的测定
已经使用了如上所述用于SIT测定制备的50μm膜样品。使用连接到Hazemeter型UX-10的Gardner光度装置或具有带滤光片“C”的G.E.1209光源的等同仪器测量雾度值。具有已知雾度的参考样品用于校准仪器。
丙烯与1-己烯的共聚物的制备
共聚物如下制备。
聚合中使用的固体催化剂组分是负载在氯化镁上的高度立体特异性齐格勒-纳塔催化剂组分，其含有约2.2重量％的钛和邻苯二甲酸二异丁酯作为内部给体，通过类似于用于制备催化剂组分A的WO 03/054035中所述的方法制备。
催化剂体系和预聚合处理
在将其引入聚合反应器之前，使上述固体催化剂组分在15℃下与三乙基铝(TEAL)和叔己基三甲氧基硅烷(2,3-二甲基-2-三甲氧基甲硅烷基-丁烷)以等于约7的TEAL/叔己基三甲氧基硅烷重量比并以使得TEAL/固体催化剂组分重量比等于约6的量接触约6分钟。
然后将催化剂体系在20℃下在液态丙烯中的悬浮液中保持约20分钟使其进行预聚合，然后将其引入聚合反应器中。
聚合实例1
聚合反应在两个气相聚合反应器中，通过以连续和恒定流以气态进料预聚合的催化剂体系、氢气(用作分子量调节剂)、丙烯和1-己烯进行。
表1中报道了主要聚合条件
表1
第一反应器 第二反应器
温度： ℃ 75 75
压力 巴-g 16 16
停留时间 min 46 46
C6/C6+C3 mol/mol 0.010 0.022
H2/C3 mol/mol 0.016 0.017
C3＝丙烯；C6＝1-己烯H2＝氢
将离开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，然后干燥。
表2中报道了实例1中获得的共聚物的性质。
表2
Figure BDA0001671547210000091
Figure BDA0001671547210000101
nm＝未测量
比较实例2是WO2009/077287的实例的共聚物，其中已经测量了50μm流延膜上的雾度。
根据表1，即使1-己烯衍生单元含量和二甲苯可溶物大致相同，实例1的共聚物相对于比较实例2的共聚物具有更好的雾度。

Claims (9)

1.一种包含丙烯1-己烯共聚物的膜，所述丙烯1-己烯共聚物含有5.5至9.0重量％的1-己烯衍生单元，所述丙烯1-己烯共聚物具有：
a）在0至5 mW范围内的DSC曲线中的两个峰的高度差；
b）在141.0℃至151.0℃范围内的由DSC测得的较高熔化温度；
c）在3.5至8.0 g/10 min范围内的根据ASTM D1238，230℃/2.16 kg测量的熔体流动速率。
2.根据权利要求1所述的膜，其中所述丙烯1-己烯共聚物包含6.0至8.5重量％的1-己烯衍生单元。
3.根据权利要求2所述的膜，其中所述丙烯1-己烯共聚物含有6.5至8.0重量％的1-己烯衍生单元。
4.根据权利要求1所述的膜，其中两个峰的熔化温度的差在5℃至30℃的范围内。
5.根据权利要求1所述的膜，其中由DSC测得的所述较高熔化温度在142.0℃至149.0℃范围内。
6.根据权利要求1所述的膜，其中所述丙烯1-己烯共聚物在25℃下在二甲苯中的溶解度等于或低于25重量％，高于12重量％。
7.根据权利要求6所述的膜，其中所述丙烯1-己烯共聚物在25℃下在二甲苯中的溶解度等于或低于20重量％，高于12重量％。
8.根据权利要求1所述的膜，其中所述熔体流动速率在3.8至7.5 g/10 min范围内。
9.根据权利要求8所述的膜，其中所述熔体流动速率在4.0至6.0 g/10 min范围内。
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