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CN1257243C - 以共接枝的金属茂聚乙烯为主要成分的共挤出粘合剂 - Google Patents

以共接枝的金属茂聚乙烯为主要成分的共挤出粘合剂 Download PDF

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CN1257243C
CN1257243C CNB011190302A CN01119030A CN1257243C CN 1257243 C CN1257243 C CN 1257243C CN B011190302 A CNB011190302 A CN B011190302A CN 01119030 A CN01119030 A CN 01119030A CN 1257243 C CN1257243 C CN 1257243C
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P·罗伯特
C·莱罗伊
J·帕斯卡尔
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Abstract

本发明涉及一种共挤出粘合剂，它包括：5-35份共聚物(A)，其本身由80-20份密度为0.865-0.915的金属茂聚乙烯(A1)和20-80份非金属茂聚乙烯LLDPE(A2)的混合物组成，(A1)和(A2)混合物通过不饱和羧酸共接枝，和95-65份选自均聚或共聚的聚乙烯和弹性体的聚乙烯(B)，(A)和(B)混合物为：接枝的不饱和羧酸含量是30至105ppm，MFI，即熔融态流动指数(标准ASTM D1238，于190℃下，负载2.16kg)是0.1-10克/10分钟。本发明还涉及一种多层结构。

Description

以共接枝的金属茂聚乙烯为主要成分的共挤出粘合剂
本发明涉及以共接枝的金属茂聚乙烯为主要成分的共挤出粘合剂，还涉及它们用于制备多层结构以及所得到的结构。
现有技术EP802207已经描述过以共接技的金属茂聚乙烯和聚丙烯为主要成分的粘合剂。在该现有技术中，共接枝一种含有至少一种聚乙烯和至少一种聚丙烯的混合物，以便通过在接枝自由基引发剂作用下聚丙烯粘度降低来补偿聚乙烯粘度的增加。这与本发明没有关系，本发明是共接枝两种聚乙烯混合物。
现有技术WO 97/27259描述了由下面成分组成的一种粘合剂：(a)HDPE、LLDPE、VLDPE或LDPE类型聚乙烯(b)5-35％接枝金属茂聚乙烯和(c)0-35％弹性体，金属茂聚乙烯没有被共接枝。
这些粘合剂没有足够的热稳定性，特别是包含这些粘合剂的多层包装物不能很好地承受热处理和温度应力，例如像巴氏灭菌和热焊接。
本发明的粘合剂的优点在于它们能够很好地耐受这些热处理和各种不同类型的温度应力。本发明粘合剂的另一个优点涉及它们的制备。这些粘合剂往往通过在熔融态接枝和在熔融态混合来制备，并且在挤出机或任何其它相当设备的出口处以颗粒形式回收，申请人发现这种颗粒化作用比上述现有技术的粘合剂要容易得多。
本发明涉及一种共挤出粘合剂，它含有
-5-35份共聚物(A)，其本身由80-20份密度在0.865和0.915之间的金属茂聚乙烯(A1)和20-80份非金属茂聚乙烯LLDPE(A2)的混合物组成(A1)和(A2)的混合物通过不饱和羧酸，即接枝单体共接枝，和
-95-65份的选自均聚或共聚的聚乙烯和弹性体的聚乙烯(B)；
(A)和(B)的混合物是这样：
.接技的不饱和羧酸含晅量是30至105ppm，
.MFI，即熔融态流动指数(标准ASTMD 1238：于190℃，在负载2.16kg下)是0.1-10g/10分钟。
根据该粘合剂的一个实施方案，聚乙烯(A2)的密度在0.900和0.950之间。
根据该粘合剂的一个实施方案，接枝单体的比例是以共接枝A1和A2混合物的重量计为600至5000ppm。
根据该粘合剂的一个实施方案，聚乙烯(B)是密度在0.910至0.935之间的LLDPE。
本发明还涉及一种由80-20份密度在0.865和0.915之间的金属茂聚乙烯(A1)和20-80份非金属茂聚乙烯LLDPE(A2)的混合物组成的共挤出粘合剂，该(A1)和(A2)混合物是通过不饱和羧酸共接枝的；
该(A1)和(A2)的混合物是这样的：
-接枝的不饱和羧酸含量是30至105ppm；
-MFI，即熔融态流动指数(标准ASTMD1238：于190℃，在负载2.16kg下)是0.1-10g/10分钟。
本发明还有一个的目是一种多层结构，该结构包括一层含有前述权利要求中任一项权利要求所述的粘合剂的层，和直接与其相连的层(E)，所述层(E)是-含氮或含氧的极性树脂，例如聚酰胺树脂，脂肪族聚酮树脂，乙烯和乙酸乙烯酯皂化共聚物树脂(EVOH)或聚酯树脂；或者
-金属。
根据该结构的一种实施方案，直接与粘合剂一侧连接的是一层聚烯烃(F)，或者一层选自层(E)树脂的树脂层，或者一金属层。
本发明还有一个的目是由如上所述结构制成的刚性中空体。
本发明还涉及一种结构，该结构分别包括一层聚烯烃(F)，一层如上定义的粘合剂，一层聚酰胺树脂或乙烯和乙酸乙烯酯皂化共聚物树脂(EVVOH)，一层如上定义的粘合剂和一层聚烯烃(F)。
这些结构用于制备柔性或刚性包装物，例如袋，瓶或容器。这些包装物可以采用共挤出，层压或吹塑共挤出方法制备。
本发明还用于共挤出的管和用于机动车辆的多层燃料箱。
现在详细描述本发明。
关于(A1)，术语“金属茂聚乙烯”是指通过在单位点(monosite)作用催化剂的存在下，由乙烯与α-烯烃共聚合获得的聚合物，其中所述α-烯烃例如是丙烯，丁烯，己烯或辛烯，所述催化剂一般由一个金属原子和两个连接该金属的环烷基分子组成，所述金属例如可以是锆或钛。更具体地说，所述金属茂催化剂一般由两个与所述金属连接的环戊二烯环组成。这些催化剂常常与作为助催化剂或活化剂的铝氧烷(aluminoxane)，优选地甲基铝氧烷(MAO)一起使用。铪也可以用作固定环戊二烯的金属。其它金属茂可以包括IVA，VA和VIA族的过渡金属。也可以使用镧系的金属。
这些金属茂聚乙烯也可以用它们的 Mw/ Mn＜3并且优选地＜2来表征，其中Mw和 Mn分别指重均分子量和数均分子量。术语金属茂聚乙烯还指MFR(熔体流动比或流体指数比)小于6.53和 Mw/ Mn比大于MFR而小于4.63的聚合物。MFR指MFI10(在10kg负载下的MFI)与MFI2(在2.16kg负载下的MFI)的比值。其它金属茂聚乙烯用MFR等于或大于6.13并且 Mw/ Mn比小于或等于MFR而小于4.63加以限定。
有利地，(A1)的密度是0.870和0.900之间。
关于聚乙烯(A2)，正是乙烯和LLDPE(线性低密度聚乙烯)型α-烯烃的共聚物不是金属茂的来源。所述α-烯烃最好具有3-30个碳原子。
作为任选的共聚用单体具有3-30个碳原子的α-烯烃实例包括丙烯，1-丁烯，1-戊烯，3-甲基-1-丁烯，1-己烯，4-甲基-1-戊烯，3-甲基-1-戊烯，1-辛烯，1-癸烯，1-十二烯，1-十四烯，1-十六烯，1-十八烯，1-二十烯，1-二十二烯，1-二十四烯，1-二十六烯，1-二十八烯和1-三十烯。这些α-烯烃可以单独使用或者以两种或两种以上的混合物使用。
(A2)的密度有利地在0.900和0.950之间。(A2)的MFI在0.1和8g/10分钟(于190℃，在负载2.16kg下)之间。
(A1)和(A2)混合物用不饱和羧酸接枝，也就是说共接枝(A1)和(A2)。使用该酸的官能衍生物也在本发明的范围内。
不饱和羧酸的实例是具有2-20个碳原子的那些不饱和羧酸，例如丙烯酸，甲基丙烯酸，马来酸，富马酸和衣康酸。这些酸的官能衍生物包括例如不饱和羧酸的酸酐，酯衍生物，酰胺衍生物，亚酰胺衍生物和金属盐(例如碱金属盐)。
具有4-10个碳原子的不饱和二羧酸及其官能衍生物，特别是它们的酸酐，是特别优选的接枝单体。
这些接枝单体包括，例如马来酸、富马酸、衣康酸、柠康酸、烯丙基琥珀酸、环己-4-烯-1，2-二羧酸、4-甲基环己-4-烯-1，2-二羧酸、双环(2，2，1)庚-5-烯-2，3-二羧酸，x-甲基双环(2，2，1)-庚-5-烯-2，3-二羧酸，和马来酸、衣康酸、柠康酸烯丙基琥珀酸、环己-4-烯-1，2-二羧酸、4-亚甲基环己-4-烯-1，2-二羧酸、双环(2，2，1)庚-5-烯-2，3-二羧酸和x-甲基双环(2，2，1)庚-5-烯-2，3-二羧酸的酸酐。
其它接枝单体的实例包括不饱和酸的C1-C8烷基酯或缩水甘油酯衍生物，例如丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸丁酯、甲基丙烯酸丁酯、丙烯酸甘油酯、甲基丙烯酸甘油酯、马来酸一乙酯、马来酸二乙酯、富马酸一甲酯、富马酸二甲酯、衣康酸一甲酯、衣康酸二乙酯；不饱和酸的酰胺衍生物，例如丙烯酰胺、甲基丙烯酰胺、马来酸一酰胺、马来酸二酰胺、马来酸N-一乙基酰胺、马来酸N，N-二乙基酰胺、马来酸N-一丁基酰胺、马来酸N，N-二丁基酰胺、富马酸一酰胺、富马酸二酰胺、富马酸N-一乙基酰胺、富马酸N，N-二乙基酰胺、富马酸N-一丁基酰胺和富马酸N，N-二丁基酰胺；不饱和酸的酰亚胺衍生物，例如马来酰亚胺、N-丁基马来酰亚胺和N-苯基马来酰亚胺；不饱和羧酸的金属盐，例如丙烯酸钠、甲基丙烯酸钠、丙烯酸钾和甲基丙烯酸钾。马来酸酐是优选的。
可以使用各种已知的方法将接枝单体接枝到(A1)和(A2)的混合物上。所述混合物可以含有含量为10ppm至5％的加工聚烯烃时通常使用的添加剂，例如以取代酚分子为主要成分的抗氧化剂、防UV剂、加工助剂、例如脂肪酰胺、硬脂酸及其盐，已知作为避免出现挤出缺损助剂的氟化聚合物、以胺为主要成分的防雾剂，防粘连结剂，例如二氧化硅或滑石，带有染料基料混合物，特别是成核剂。
例如，可以通过在有或没有溶剂存在下，有或没有自由基引发剂时，将聚合物(A1)和(A2)加热到约150℃至约300℃的高温下进行该反应。该反应中可以使用的合适溶剂特别是苯、甲苯、二甲苯、氯苯、异丙基苯。可以使用的合适自由基引发剂包括叔丁基-氢过氧化物、氢过氧化-枯烯、二异丙基-苯过氧化物、二叔丁基-过氧化物、叔丁基-枯基-过氧化物、二枯基-过氧化物、1，3-双(叔丁基过氧化-异丙基)-苯、乙酰基-过氧化物、苯甲酰基-过氧化物、异丁酰基-过氧化物、双-3，5，5-三甲基-己酰基-过氧化物和甲基-乙基-酮-过氧化物。
在以上述方式得到的通过接枝改性的(A1)和(A2)混合物中，以合适的方式选择接枝单体的量，但是接枝单体的量优选地是以接枝的(A1)和(A2)重量比计为0.01至10％，更好地是600ppm至5000ppm。
通过IRTF光谱测定琥珀官能团来确定接枝单体的量。(A)，也就是说共接枝的(A1)和(A2)的MFI，有利地是0.1-10克/10分钟之间。
关于聚乙烯(B)，涉及均聚物聚乙烯或乙烯与选自α-烯烃、不饱和羧酸酯或钥和羧酸乙烯酯单体的共聚物。这些α-烯烃如上定义。不饱和羧酸酯是例如(甲基)丙烯酸烷基酯，其中烷基具有1-24个碳原子。可以使用的丙烯酸烷基酯或甲基丙烯酸烷基酯的例子特别是，甲基丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯、丙烯酸异丁酯和丙烯酸2-乙基己酯。饱和羧酸乙烯酯是，例如，乙酸乙烯酯或丙酸乙烯酯。(B)可以是HDPE、LDPE、LLDPE或VLDPE聚乙烯或金属茂PE。
(B)还可以是一种具有弹性体特性的聚合物，也就是说其可以是(i)ASTMD412意义上的弹性体，其指室温下可以拉伸至其长度的两倍，并且持续5分钟，然后释放后恢复到小于其初始长度10％的材料，或者(ii)并不是正好具有上述特征，但是可以拉伸并且可以恢复至大约其初始长度的聚合物。作为例子，可以提到：
-EPR(乙烯-丙烯橡胶，也称之为EPM)和EPDM(乙烯-丙烯-二烯三元共聚物)；
-苯乙烯弹性体，例如SBR(苯乙烯-丁二烯-橡胶)、苯乙烯/丁二烯/苯乙烯嵌段共聚物(SBS)、苯乙烯/乙烯/丁二烯/苯乙烯嵌段共聚物(SEBS)和苯乙烯/异戊二烯/苯乙烯嵌段共聚物(SIS)。
有利地，(B)是密度为0.910-0.935的LLDPE聚乙烯或者密度为0.935-0.950的PEHD。
最好，(A)和(B)的比例分别是每90-70份(B)有10-30份(A)。
根据第二个实施方案，本发明涉及一种用来稀释在聚乙烯或弹性体(B)中的仅由共接枝(A1)和(A2)混合物组成的组合物。事实上，本申请人发现，通过颗粒与(B)的化合或混合，根据不同的用途可以使用(A)调节最后粘合剂(即(A)和(B)混合物)的浓度。
本发明的粘合剂用于多层结构，例如膜、片、管和中空体例如燃料箱。
本发明的多层结构包括一层含有上述粘合剂的层和一层含氧或含氮的极性树脂(E)，或一层金属层。
在无粘合剂的那层中优选的极性树脂例子是聚酰胺树脂、脂肪族聚酮、乙烯/乙酸乙烯酯皂化共聚物和聚酯。
更具体地说，它们包括主链中具有酰胺基团结构单元的长链合成聚酰胺，例如PA-6、PA-6，6、PA-6，10、PA-11、PA-6/6，6和PA-12；皂化度约90-100摩尔％乙烯和乙酸乙烯酯皂化共聚物，该共聚物是通过皂化乙烯含量约15-60摩尔％的乙烯/乙酸乙烯酯共聚物得到的；聚酯，例如聚对苯二甲酸乙二酯、聚对苯二甲酸丁二酯和聚萘酸乙二酯，这些树脂的混合物，或者芳香族聚酯，例如液晶聚合物。
所述金属层例如可以是一种金属，例如铝、铁、铜、锡和镍或者含有这些金属中的至少一种作为主要成分的合金的片、膜或箔。膜或箔的厚度可以适当地选择，并且是例如是约0.01至约0.2mm。通常实施时，在将本发明的粘合剂层压到其上时先将金属层表面去脂。含氧或含氮极性树脂层(E)同样可以含有通常量的已知添加剂。
本发明还涉及一种结构，该结构分别包括一层聚烯烃(F)，一层本发明的粘合剂和一层含氮或含氧极性树脂(E)或者一层金属。
本发明结构的各层可以含有添加剂，例如填充剂、稳定剂、增滑剂、抗静电剂和阻燃剂。
本发明的结构可以采用热塑技术领域公知的共挤出和吹塑挤出方法来制备。
下表1和2汇集了粘合剂的组成，百分比是重量百分比。
比较表1中的剥离力值，可以看到，根据本发明的实施例4在23℃时比对比实施例2和3具有更好的粘合性能，并且在50-90℃范围的温度下，粘合性能与对比实施例1-3的粘合性能相同或比对比实施例1-3的粘合性能更好。
比较表2中的剥离力值，可以看到，根据本发明的实施例8在23℃和25℃时比对比实施例6和7具有更好的粘合性能，并且在70-90℃范围的温度下，粘合性能比对比实施例5-7的粘合性能更好。
可以得出结论，两种类型PE(金属茂和非金属茂)混合物的共接枝可以通过增效作用提高粘合剂的粘合性能。
                                                                 表1
  对比实施例1   对比实施例2  对比实施例3   实施例4
  聚合物(A)   只是接枝的A1   只是接枝的A2  (接枝的A1)+(接枝的A2)   接枝的(A1+A2)
  PE类型   金属茂   LLDPE  (金属茂)+(LLDPE)   (金属茂)+(LLDPE)
  密度   0.870   0.920  (0.870)+(0.920)   (0.870)+(0.920)
  共聚用单体   1-辛烯   1-丁烯  (1-辛烯+1-丁烯)   (1-辛烯+1-丁烯)
  组成   100％A1   100％A2  (50％A1)+(50％A2)   (50％A1)+(50％A2)
  接枝程度   0.6％   0.7％  0.65％   0.7％
  MFI(g/10min)190℃-2.16kg   2.0   0.5  1.1   1.2
  (A)的比例   15％   15％  15％   15％
  聚乙烯(B)   PE类型   LLDPE   LLDPE  LLDPE   LLDPE
  共聚用单体   1-丁烯   1-丁烯  1-丁烯   1-丁烯
  密度   0.910   0.910  0.910   0.910
  (B)的比例   85％   85％  85％   85％
  剥离强度(N/15mm)   T＝23℃   12.0   8.5  9.2   11.5
  T＝50℃   8.3   4.8  5.6   8.3
  T＝70℃   6.2   3.0  3.8   6.9
  T＝80℃   4.2   2.2  2.9   6.0
  T＝90℃   0   0.8  0.8   4.1
*在温度T、剥离速度为200毫米/钟条件下，在共挤出薄膜中粘合剂层和EVOH层之间进行的剥离试验，所述膜包括5层(PE/粘合剂/EVOH/粘合剂/PE)，其中PE密度为0.935，并且EVOH含有38％乙烯，厚度以微米计分别为80/10/10/10/80。
                                                                        表2
  对比实施例5   对比实施例6   对比实施例7   实施例8
  聚合物(A)   只是接枝的A1   只是接枝的A2  (接枝的A1)+(接枝的A2)   接枝的(A1+A2)
 PE类型   金属茂   LLDPE   (金属茂)+(LLDPE)   (金属茂)+(LLDPE)
 密度   0.890   0.930   (0.890)+(0.930)   (0.890)+(0.930)
 共聚用单体   1-辛烯   1-丁烯   (1-辛烯+1-丁烯)   (1-辛烯+1-丁烯)
 组成   100％A1   100％A2   (50％A1)+(50％A2)   (50％A1)+(50％A2)
 接枝程度   0.8％   0.7％   0.75％   0.7％
 MFI(g/10min)190℃-2.16kg   1.0   0.7   0.8   0.9
 (A)的比例   15％   15％   15％   15％
  聚乙烯(B)  PE类型   LLDPE   LLDPE   LLDPE   LLDPE
 共聚用单体   1-丁烯   1-丁烯   1-丁烯   1-丁烯
 密度   0.920   0.920   0.920   0.920
 (B)的比例   85％   85％   85％   85％
  剥离强度(N/15mm)  T＝23℃   13.1   3.5   5.8   13.0
 T＝50℃   9.4   3.2   4.6   9.2
 T＝70℃   7.0   2.9   3.4   7.6
 T＝80℃   5.0   2.4   2.6   6.2
 T＝90℃   1.2   1.3   1.2   4.3
*在T温度、剥离速度为200毫米/分钟的条件下，在共挤出薄膜中的粘合剂层和EVOH层之间进行的剥离试验，所述膜包括5层(PE/粘合剂/EVOH/粘合剂/PE)，其中PE密度为0.935，并且EVOH含有38％乙烯，厚度以微米计分别为80/10/10/10/80。

Claims (9)

1.共挤出粘合剂，该粘合剂含有：
-5-35份共聚物(A)，其本身由80-20份密度为0.865-0.915的金属茂聚乙烯(A1)和20-80份非金属茂聚乙烯LLDPE(A2)的混合物组成，(A1)和(A2)混合物通过不饱和羧酸或所述酸的官能衍生物，即接枝单体共接枝，和
-95-65份选自均聚或共聚的聚乙烯和弹性体的聚乙烯(B)；
(A)和(B)混合物是这样：
-接枝的不饱和羧酸含量是30至105ppm，
-MFI，即在ASTM D1238标准：于190℃，负载2.16kg下的熔融态流动指数为0.1-10克/10分钟。
2.根据权利要求1所述的粘合剂，其中聚乙烯(A2)密度是0.900-0.950。
3.根据权利要求1或2所述的粘合剂，其中接枝单体的比例是以共接枝(A1)和(A2)混合物重量计为600-5000ppm。
4.根据权利要求1或2所述的粘合剂，其中聚乙烯(B)是密度为0.910-0.935的LLDPE。
5.根据权利要求1或2所述的粘合剂，其中所述酸的官能衍生物是马来酸酐。
6.由80-20份密度为0.865-0.915的金属茂聚乙烯(A1)和20-80份非金属茂聚乙烯LLDPE(A2)的混合物组成的共挤出粘合剂，(A1)和(A2)混合物用不饱和羧酸共接枝；
(A1)和(A2)的混合物是这样的：
-接枝的不饱和羧酸含量是30至105ppm，
-MFI，即在ASTMD1238标准：于190℃，在负载2.16kg下的熔融态流动指数是0.1-10克/10分钟。
7.多层结构，该结构包括一层有上述权利要求中任一权利要求所述粘合剂的层，和直接与所述有粘合剂的层相连的一层(E)，所述(E)层是：
-含氮或含氧的极生树脂，选自聚酰胺树脂，脂肪族聚酮树脂，乙烯/乙酸乙烯酯皂化共聚物树脂或聚酯树脂，或
-金属。
8.根据权利要求7所述的结构，其中在粘合剂一侧直接粘合有一层聚烯烃(F)，或者一层选自(E)层树脂层或者一层金属层。
9.由根据权利要求7和8中任一权利要求所述结构制备的刚性中空体。
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ATE261480T1 (de) 2004-03-15
CA2342084A1 (fr) 2001-09-24
AR028287A1 (es) 2003-04-30
FR2806734A1 (fr) 2001-09-28
US20010053821A1 (en) 2001-12-20
PT1136536E (pt) 2005-01-31
CA2342084C (fr) 2009-08-25
KR20010100832A (ko) 2001-11-14
KR100587759B1 (ko) 2006-06-09
TWI245790B (en) 2005-12-21
EP1136536A1 (fr) 2001-09-26
CN1318609A (zh) 2001-10-24
JP2001329127A (ja) 2001-11-27
DE60102254D1 (de) 2004-04-15
JP5307311B2 (ja) 2013-10-02
US6528587B2 (en) 2003-03-04
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