CN1198895C - 共挤出粘合剂、用于多层结构的用途及由此获得的结构 - Google Patents

共挤出粘合剂、用于多层结构的用途及由此获得的结构 Download PDF

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CN1198895C
CN1198895C CNB001089005A CN00108900A CN1198895C CN 1198895 C CN1198895 C CN 1198895C CN B001089005 A CNB001089005 A CN B001089005A CN 00108900 A CN00108900 A CN 00108900A CN 1198895 C CN1198895 C CN 1198895C
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C·莱洛伊
X·马里卡尔
J·帕斯卡尔
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Arkema France SA
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Abstract

本发明涉及共挤出粘合剂，其中包括5-30份聚合物(A)和95-70份密度在0.930和0.950之间的聚乙烯(B)，(A)本身含有密度在0.935和0.980之间的聚乙烯(A1)和选自弹性体、非常低密度聚乙烯和乙烯共聚物的聚合物(A2)的混合物，为不饱和羧酸共接枝。该粘合剂特别适用于制备汽油箱。

Description

共挤出粘合剂、用于多层结构的用途及由此获得的结构
本发明涉及共挤出粘合剂、其用于多层结构的用途及由此获得的结构。
更具体地说，本发明的共挤出粘合剂包括：
——5-30份聚合物(A)，其本身含有密度在0.935和0.980之间的聚乙烯(A1)和选自弹性体、非常低密度聚乙烯和乙烯共聚物的聚合物(A2)的混合物，上述(A1)+(A2)混合物被不饱和羧酸所共接枝；
——95-70份密度在0.930和0.950之间的聚乙烯(B)；
——上述(A)和(B)的混合物，使得：
.其密度在0.930和0.950之间，
.接枝的不饱和羧酸的量在30和10000ppm之间，
.根据ASTM D 1238在190℃-21.6千克条件下测定的MFI(熔体流动指数)在5和100之间。
本发明还涉及一种多层结构，包括一层包含上面定义的共挤出粘合剂的层和一层直接与其附着的含氮或含氧的极性树脂(E)的层，例如一层聚酰胺树脂、一层脂肪族聚酮、一层皂化的乙烯-乙酸乙烯酯共聚物(EVOH)或者一层聚酯树脂，或者还有一层金属。
本发明还涉及一种结构，该结构包括上述结构，并且在粘合剂一侧直接与其附着一层聚烯烃(F)或者一层选自(E)层树脂的树脂，或者还有一层金属。
本发明还涉及一种结构，分别地，包括一层聚烯烃(F)、一层如前述定义的粘合剂、一层聚酰胺树脂或者一层皂化的乙烯-乙酸乙烯酯共聚物(EVOH)、一层如前述定义的粘合剂和一层聚烯烃(F)。
这些结构适用于制备软包装或硬包装，例如袋子、瓶子或者容器。这些包装物可以通过共挤出、层压成型或共挤出-吹塑成型方法制得。
本发明特别适用于制备共挤出成型的软管或管子和用于制备汽车汽油箱。
汽油箱通常由5层组成，分别是：
——高密度聚乙烯(PEHD)；
——粘合剂；
——聚酰胺(PA)或者具有乙烯单元和乙烯醇单元的共聚物(EVOH)；
——粘合剂；
——PEHD。
常常在一层粘合剂和一层PEHD之间加入第六层。该第六层是由箱模压过程中产生的生产废料或者极少量的、由没有用途的箱所组成。上述废料和这些没有用途的箱被压碎成颗粒。然后将反复磨碎的磨碎物在工厂中再熔融并且直接挤出，用于箱的共挤出成型。反复磨碎的磨碎物还可以在再使用之前通过挤出机例如双螺杆挤出机熔融，并且再次造粒。
按照一种方案，还可以将上述循环用产物与上述汽油箱的最外两层的PEHD共混。也可例如将循环用产物的颗粒和新的这两层的PEHD颗粒相混合。也可以使用这些循环操作的任何组合。
循环用材料的量可以至多占所述汽油箱的总重量的50％。
因此，所述第六层包含了所有多层结构的材料，即PEHD、粘合剂、PA或EVOH。
现有技术已经描述过多层汽油箱。欧洲专利文献EP834415描述了下面的结构：聚乙烯/粘合剂/EVOH/粘合剂/聚乙烯。
上述粘合剂是MFI为0.1-3，并且密度在0.920和0.930之间的被马来酸酐接枝的聚乙烯，并且它含有2-40重量％在90℃中不溶于正癸烷的物质。已说明接枝的聚乙烯在140℃中溶解于正癸烷，冷却到90℃，产生沉淀；然后过滤，不溶物在90℃过滤收集，其含量以沉淀的重量百分比计。
如果该含量在2-40％之间，则粘合剂对汽油具有良好的抗耐性。
上述文献中没有实施例描述这样一种聚合物。然而，说明书详细说明了粘合剂实际上是2-30份具有0.930和0.980之间的密度的接枝聚乙烯和70-98份具有0.910和0.940之间的密度，优选0.915和0.935之间的密度的未接枝聚乙烯的混合物。
申请人根据这样的教导，尝试制备粘合剂和相应的结构。其中发现粘合剂是不可重复生产的，也就是说以其密度选择产物是不够充分的指标。申请人还发现这些标准不足于使粘合剂耐受汽油。
现在详述本发明。
关于聚合物(A1)，它是聚乙烯均聚物或乙烯与选自下面的共聚用单体的共聚物：
——α-烯烃，优选具有3-30个碳原子的那些烯烃。
作为可能的共聚用单体的具有3-30个碳原子的α-烯烃包括：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以其中两者或多者的共混物形式使用。
——不饱和羧酸的酯，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包括：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。
 ——饱和羧酸的乙烯酯，例如乙酸乙烯酯或丙酸乙烯酯。
上述(A1)最好是密度在0.940和0.965之间的高密度聚乙烯(HDPE)。
(A1)的MFI在2.16千克条件下为0.1和3之间。
上述共聚物(A2)可以是例如乙烯/丙烯弹性体(EPR)或者乙烯/丙烯/二烯弹性体(EPDM)。
(A2)还可以是非常低密度聚乙烯(VLDPE)，为乙烯均聚物或者是乙烯/α-烯烃共聚物。
(A2)还可以是乙烯与选自下面的至少一种产物的共聚物：(I)不饱和羧酸、它们的盐和它们的酯，(ii)饱和羧酸的乙烯酯，(iii)不饱和二羧酸、它们的盐、它们的酯、它们的半酯和它们的酸酐。
(A2)还可以是金属茂聚乙烯。
(A1)和(A2)的量，最好是相对于40-5份的(A2)，有60-95份的(A1)。
(A1)和(A2)的混合物用不饱和羧酸接枝，也就是说(A1)和(A2)被共同接枝。使用这些酸的官能衍生物也在本发明的范围内。
不饱和羧酸的实例那些是具有2-20个碳原子的酸类，例如丙烯酸、甲基丙烯酸、马来酸、富马酸和衣糠酸。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、酰亚胺衍生物和金属盐(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，特别是其酸酐，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、衣糠酸、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-2，3-二羧酸和x-甲基双环[2.2.1]庚-5-烯-2，3-二羧酸、马来酸酐、衣糠酸酐、柠康酸酐、烯丙基琥珀酸酐、环己-4-烯-1，2-二羧酸酸酐、4-亚甲基环己-4-烯-1，2-二羧酸酸酐、双环[2.2.1]庚-5-烯-2，3-二羧酸酐和x-甲基双环[2.2.1]庚-5-烯-2，2-二羧酸酸酐。
其它接枝单体的例子包括不饱和羧酸的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、丙烯酸缩水甘油酯、甲基丙烯酸缩水甘油酯、马来酸单乙酯、马来酸二乙酯、富马酸单甲酯、富马酸二甲酯、衣糠酸单甲酯和衣糠酸二乙酯；不饱和羧酸的酰胺衍生物，例如丙烯基酰胺、甲基丙烯基酰胺、马来酸单酰胺、马来酸二酰胺、马来酸N-单乙基酰胺、马来酸N，N-二乙基酰胺、马来酸N-单丁基酰胺、马来酸N，N-二丁基酰胺、富马酸单酰胺、富马酸二酰胺、富马酸N-单乙基酰胺、富马酸N，N-二乙基酰胺、富马酸N-单丁基酰胺和富马酸N，N-二丁基酰胺；不饱和羧酸的酰亚胺衍生物，例如马来酰亚胺、N-丁基马来酰亚胺、N-苯基马来酰亚胺；和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。其中优选马来酸酐。
可以使用多种已知方法将接枝单体接枝到(A1)和(A2)的混合物上。该混合物可以以10ppm和5％之间的水平含有通常用于聚烯烃加工的添加剂，例如以取代的酚分子等为基础的抗氧化剂、紫外保护剂、加工助剂，例如脂肪酰胺、硬脂酸和硬脂酸的盐、已知防止挤出缺陷的氟化聚合物、以胺类为基础的防雾剂、防粘剂，例如二氧化硅或滑石，带有染料的母炼胶混合物、成核剂等等。
例如，这可以通过在有或没有溶剂存在和用或没用自由基引发剂的条件下，在大约150℃至大约300℃的高温下加热聚合物(A1)和(A2)进行反应。该反应中可以使用的合适的溶剂是苯、甲苯、二甲苯、氯苯、枯烯等。可以使用的合适的自由基引发剂包括叔丁基氢过氧化物、氢过氧化枯烯、氢过氧化二异丙基苯、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(叔丁基过氧异丙基)苯、过氧化乙酰、过氧化苯甲酰、过氧化异丁酰、双-(3，5，5-三甲基己酰基)-过氧化物和甲基乙基酮过氧化物。
据上述方法获得的接枝改性的(A1)和(A2)混合物中，接枝单体的量可以以合适的方法选择，但是以接枝的(A1)和(A2)的重量计，优选是0.01-10％，并以600ppm至6％为宜。
通过IRTF分光分析琥珀官能团来测定被接枝单体的量。
(A)，也就是说已经共同接枝的(A1)和(A2)的MFI是5-100/21.6千克。关于聚乙烯(B)，它是乙烯均聚物或共聚物。
(B)的密度最好是在0.930和0.940之间。
(B)的MFI：5-100/21.6千克。
根据本发明的优选方案，其中的粘合剂包含95-80份的(B)和5-20份的(A)。
上述混合物(A)+(B)的密度最好是在0.930和0.940之间。
本发明的多层结构是由包含上述粘合剂的一层和一层含氧或者含氮的极性树脂层(E)，或者一层金属所组成。
除了粘合剂外的层中，优选的极性树脂可以是聚酰胺树脂、脂肪族聚酮、皂化的乙烯-乙酸乙烯酯共聚物和聚酯。
更具体地说，它们包含主链中具有酰胺基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；通过皂化具有大约15-大约60摩尔％乙烯含量的乙烯/乙酸乙烯酯共聚物而得到的、具有大约90-100摩尔％皂化程度的皂化的乙烯/乙酸乙烯酯共聚物；聚酯，例如聚对苯二甲酸乙二醇酯、对苯二甲酸丁二醇酯、聚环烷酸乙酯；这些树脂的混合物，或者还有芳香族聚酯，例如液晶聚合物。
上述金属层可以是金属，如铝、铁、铜、锡、镍或者含有至少一种这样的金属作为主要成分的合金，的薄片、膜或箔。膜的厚度或者箔的厚度可以适当地选择，大约为0.01至大约0.2毫米。实际上在将本发明粘合剂层压到其上之前通常将金属层表面脱脂。上述的含氧或者含氮极性树脂层(E)还可以含有常规量的已知的添加剂。
本发明还涉及各自包括一层聚烯烃(F)、一层本发明的粘合剂和一层含氮或者含氧极性树脂(E)或者一层金属的一种结构。根据另一个具体实施方案，本发明涉及各自包括一层PEHD、一层本发明粘合剂、一层EVOH(或者一层EVOH合金)或者一层聚酰胺(或者以聚酰胺为基础)、一层本发明粘合剂和一层PEHD的一种结构。它最好是具有0.1-200升容积的刚性空心体形式。它的总厚度在0.2和20毫米之间，其中EVOH或聚酰胺占该厚度的0.5-15％，各粘合剂层分别占0.2-10％，其余的厚度是两层PEHD。
PEHD的MFI最好是在190℃/21.6千克条件下测定为3-17克/10分钟。
EVOH的MFI最好是在190℃/2.16千克条件下测定为1-10克/10分钟。
PEHD外层最好可以被两层取代，外面一层是由任选有色的新制备的PEHD制成，而另一层是由来自这些空心体挤出-吹塑成型的废料和切削料的循环用产物制成。加到循环用材料层厚度的PEHD外层的厚度基本上与单一PEHD外层情况下的厚度是相同。
这些结构适用于制备汽油箱或者用于灌注汽油箱的管子。
本发明结构的各层可以含有添加剂，例如填料、稳定剂、滑移剂、抗静电剂和阻燃剂。
本发明的结构可以通过热塑领域中公知的共挤出和挤出-吹塑方法来制备。
实施例
实施例描述通过下面条件经过挤出-吹塑制备的瓶的5-层结构。
瓶的结构：
-3种组分，5层；
-PEHD/粘合剂/EVOH或PA/粘合剂/PEHD；
-厚度：1.2/0.1/0.15(EVOH)-0.25(PA)/0.1/1.2毫米；
-PEHD：密度＝0.945-0.950和MFI＝5-6克/10分钟(190℃/21.6千克)；
-EVOH：乙烯含量＝29％，MFI＝1.7克/10分钟(190℃/2.16千克)；
-聚酰胺：共聚酰胺6/6，6，例如购自BASF公司的ULTRAMID C4FN。
瓶的类型：
具有两个平面，0.7升容量，高度＝270毫米和重量＝170克的圆筒(＝70毫米)。挤出-吹塑条件
温度曲线(℃)：              顶部
PEHD    200 210 220 230 230 230
粘合剂  210 220 220 220 220 230
EVOH    180 190 200 210 220 230
工具  塑模的直径＝20毫米
      心轴的直径＝12毫米
       间隙＝4毫米
吹塑拉申比：大约3。
层之间抗剥离强度的测定
-从瓶的平面部分切下15×150毫米试验用片样并且在23℃和50％R.H.条件下处理至少24小时；
-在粘合剂和EVOH之间或者粘合剂和聚酰胺之间的接触面的一面开始切割；
-在50毫米/分钟直角机头速度下进行“T”剥离试验。通过排除起始峰的剥离力的平顶值给出以N/cm表示的剥离强度。其中“AM”指马来酸酐，并且共同接枝了的混合物(A)的重量百分比表示了在A+B混合物中的A的比例。
                                        表1
                  配方   实施例1    实施例2    实施例3
聚合物A1 密度(g/cm3)   0.958     0.940     0.950
MF1(g/10分钟；2.16kg)   0.9     1     1
重量百分比   80     75     90
聚合物A2 共聚用单体   丙烯     1-辛烯     丙烯
密度(g/cm3)   0.880     0.870     0.880
MF1(g/10分钟；2.16kg)   0.2     5     0.2
重量百分比   20     25     10
被接枝了的A共混物 AM的含量(ppm)   4000     10000     6000
重量百分比   20     25     10
聚合物B 密度(g/cm3)   0.934     0.938     0.936
MF1(g/10分钟；2.16kg)   14     20     18
共混物A+B 密度(g/cm3)   0.936     0.934     0.937
MF1(g/10分钟；2.16kg)   15     18     18
AM的含量(ppm)   800     2500     600
抗剥离性 对于PA 6/66(N/cm)对于EVOH   7050     8055     7555

Claims (8)

1.共挤出粘合剂，包括：
——5-30份聚合物(A)，其本身含有密度在0.935和0.980之间的聚乙烯(A1)和选自弹性体、非常低密度聚乙烯和乙烯共聚物的聚合物(A2)的混合物，(A1)+(A2)混合物被不饱和羧酸或其官能衍生物所共接枝；
——95-70份密度在0.930和0.950之间的聚乙烯(B)；
——上述(A)和(B)的混合物，使得：
.其密度在0.930和0.950之间，
.接枝的不饱和羧酸的量在30和10000ppm之间，
.根据ASTM D 1238在190℃-21.6千克条件下测定的MFI(熔体流动指数)是在5和100之间。
2.根据权利要求1的粘合剂，其中(A)+(B)的密度是在0.930和0.940之间。
3.多层结构，包括一层包含有前面权利要求中任一项的粘合剂的层，和一层直接与其附着的含氮或含氧的极性树脂层(E)，或者还有一层金属。
4.权利要求3的多层结构，其中所述含氮或含氧的极性树脂层(E)是聚酰胺树脂层、脂肪族聚酮层、皂化的乙烯-乙酸乙烯酯共聚物(EVOH)层或者聚酯树脂层。
5.权利要求3的结构，其中一层聚烯烃层(F)或者一层选自(E)层的树脂的树脂层或者一层金属层直接附着在粘合剂面上。
6.据权利要求5的结构，各自包括一层高密度聚乙烯、一层权利要求1或2的粘合剂、一层EVOH或者一层EVOH合金，或者一层聚酰胺或者以聚酰胺为基础的层、一层权利要求1或2的粘合剂和一层高密度聚乙烯。
7.具有权利要求3-6中任一项的结构的刚性空心体。
8.具有权利要求6的结构的汽油箱。
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