CN101007931A - 具有内聚破坏的基于接枝聚乙烯和高抗冲或结晶聚苯乙烯的连接物 - Google Patents

具有内聚破坏的基于接枝聚乙烯和高抗冲或结晶聚苯乙烯的连接物 Download PDF

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CN101007931A
CN101007931A CNA200710001791XA CN200710001791A CN101007931A CN 101007931 A CN101007931 A CN 101007931A CN A200710001791X A CNA200710001791X A CN A200710001791XA CN 200710001791 A CN200710001791 A CN 200710001791A CN 101007931 A CN101007931 A CN 101007931A
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connector
grafted
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阿诺·格鲍利特
法布里克·乔皮奈兹
阿兰·布伊劳克斯
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Arkema France SA
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Abstract

本发明涉及一种连接物,其含有接枝聚乙烯(简写为PE)、接枝或非接枝高抗冲或结晶聚苯乙烯(简写为PS)和任选非接枝PE的共混物。接枝PE优选由两种不同的共接枝PE组成。该连接物用于制备可用于土木工程(CEW)领域的多层结构,更具体地用于制备可用于铝板、多层管领域,以及包装领域的多层结构。

Description

具有内聚破坏的基于接枝聚乙烯和高抗冲或结晶聚苯乙烯的连接物
本发明涉及一种连接物(tie),其含有接枝聚乙烯(简写为PE)、接枝或非接枝的高抗冲或结晶聚苯乙烯(简写为PS)和任选非接枝PE的共混物。该接枝PE优选由两种不同的共接枝PE组成。该连接物用于制备可用于土木工程(CEW)领域的多层结构,更具体地用于制备可用于铝板、多层管领域,以及包装领域的多层结构。
专利文献US-6855432涉及一种组合物,其基本上由下列物质组成:
a)20-60重量份聚乙烯;
b)10-30重量份用马来酸酐接枝的聚乙烯;
c)10-25重量份高抗冲聚苯乙烯(简写为HIPS);和
d)10-25重量份三元乙丙橡胶(简写为EPDM)。
该连接物被用于将金属基底层连接至聚合物层的多层结构中。
专利文献EP1400566涉及一种共挤出连接物,其包括:
a)10-35wt%的聚合物(A),其本身由PE共混物组成(80-20wt%由茂金属催化而得到的PE(A1)和20-80wt%非茂金属LLDPE聚乙烯PE(A2),并且(A1)和(A2)共混物用接枝单体进行了共接枝);
b)40-60wt%的SBS嵌段共聚物;
c)20-35wt%的由茂金属催化而得到的LLDPE或PE。
该技术问题是由这样一种多层结构的连接物来解决的,该连接物在水中老化后随着时间的流逝仍能保持稳定并且显示出具有内聚破坏(cohesive failure)的高剥离强度。本发明使解决该技术问题成为可能。
本发明连接物不含弹性体,其包括:
●相对于连接物总重量为10-79wt%,优选15-70wt%,更优选10-60wt%的PE(A)或至少两种聚乙烯PE(A1)和PE(A2)的共混物,所述共混物依次包括相对于PE(A1)+PE(A2)重量为95-5wt%的PE(A1)和5-95wt%的PE(A2),其中PE(A1)和PE(A2)不同,并且PE(A)是接枝的,或者共混物PE(A1)+PE(A2)是接枝或共接枝的;
●相对于连接物总重量为21-50wt%的接枝或非接枝的高抗冲PS(B)或接枝或非接枝的结晶PS(B),其优选为21-30%,并更优选为25-30%;
●0-70%的非接枝PE(C),并优选为0-60%;
已知PE(A)或PE(A1)+PE(A2)的共混物以及任选的PS(B)每一个都分别进行接枝或者在同一接枝步骤中一起进行共接枝,并且PE(A)和PE(C)不同。
因此,本发明的主题是这样一种连接物,其不含弹性体,并包括(以所述连接物的总重量的百分数计):
●10-79%的PE(A),该PE(A)是密度在0.870和0.910g/cm3之间的VLDPE,或者为10-79%的至少两种聚乙烯PE(A1)和PE(A2)的共混物,其中:
○PE(A2)是密度在0.870和0.910g/cm3之间的VLDPE,且不同于PE(A1),
○PE(A)是接枝的,或者PE(A1)和(A2)共混物是接枝或共接枝的,
○PE(A)、PE(A1)或PE(A2)选自PE均聚物和共聚物,其中在共聚物情况下至少有51%的乙烯,和作为共聚单体的α-烯烃,该α-烯烃选自丙烯、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(eicocene)、1-二十二烯(dococene)、1-二十四烯(tetracocene)、1-二十六烯(hexacocene)、1-二十八烯(octacocene)、1-三十烯(triacontene)及其混合物,
●21-50%的接枝或非接枝的高抗冲PS(B)或接枝或非接枝的结晶PS(B),
●0-70%由Ziegler-Natta催化得到的非接枝PE(C)。
根据一个实施方式,该连接物特征在于其包括:
●15-70%的PE(A)或至少两种聚乙烯PE(A1)和PE(A2)的混合物,
●21-30%的接枝或非接枝的结晶或高抗冲PS(B),
●0-60%由Ziegler-Natta催化得到的非接枝PE(C)。
根据一个实施方式,该连接物特征在于PE(A1)选自LLDPE、LDPE和PEm。
根据一个实施方式,该连接物特征在于PE(C)是密度在0.910和0.935g/cm3之间的LLDPE。
根据一个实施方式,该连接物特征在于该接枝聚合物用马来酸酐作为接枝单体进行接枝。
根据一个实施方式,该连接物特征在于接枝单体的量是接枝聚合物的0.01-10wt%。
本发明的另一个主题是该连接物在包括铝层/连接物层/PE层的多层结构中的用途。
根据一个实施方式,该用途其特征在于该PE层是LDPE层。
根据一个实施方式,该用途其特征在于该PE层含有阻燃填料。
Figure A20071000179100061
PE(A)是极低密度聚乙烯(VLDPE)或含有至少一种VLDPE的共混物,这种情况下PE(A)是至少两种聚乙烯PE(A1)和PE(A2)的共混物,并且所述共混物中PE(A2)是VLDPE,PE(A1)不同于VLDPE。该VLDPE密度在0.870和0.910g/cm3之间。
关于聚乙烯(A)或至少两种聚乙烯PE(A1)和PE(A2)的共混物,术语“聚乙烯”是指均聚物或共聚物,条件是乙烯共聚物含有至少51%并优选75%(摩尔)的乙烯。
作为共聚单体,可提及α-烯烃,优选为具有3-30个碳原子的那些;作为α-烯烃的例子,可以提及丙烯、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两种或多种的混合物使用。
下述化合物被排除在聚乙烯(A)或至少两种聚乙烯PE(A1)和PE(A2)的共混物之外:
-不饱和羧酸的酯,例如(甲基)丙烯酸烷基酯,其中烷基可能含有至多24个碳原子;丙烯酸烷基酯或甲基丙烯酸烷基酯的例子具体地说是甲基丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯、丙烯酸异丁酯或丙烯酸2-乙基己基酯,
-饱和羧酸的乙烯基酯,例如乙酸乙烯酯或丙酸乙烯酯,
-二烯,例如1,4-己二烯。
聚乙烯(A)或至少两种聚乙烯PE(A1)和PE(A2)的共混物的MFI(190℃,2.16kg下的粘度指数)优选在0.1-1000g/10min之间。
作为聚乙烯PE(A1)的例子,可以提及:
-低密度聚乙烯(LDPE);
-线型低密度聚乙烯(LLDPE);
-通过茂金属催化得到的聚乙烯(PEm),也就是通过使乙烯和α-烯烃如丙烯、丁烯、己烯或辛烯在单点催化剂存在下共聚而得到的聚合物,所述单点催化剂通常由一个锆或钛原子和两个与金属相连的环烷基分子组成。更具体的是,茂金属催化剂通常由两个与该金属相连的环戊二烯环组成。这些催化剂往往和作为助催化剂或活化剂的铝氧烷(aluminoxane),优选为甲基铝氧烷(MAO)一起使用。铪也可以用作与环戊二烯连接的金属。其它茂金属可以包括IVA、VA和VIA族的过渡金属。也可以使用选自镧系的金属。
(A)优选为PE(A1)和PE(A2)的共混物,并且PE(A1)和PE(A2)不同。
它是密度在0.910和0.935g/cm3之间的PE(A1)和密度在0.870和0.910g/cm3之间的PE(A2)的共混物。优选PE(A1)是LLDPE并且PE(A2)是VLDPE。
Figure A20071000179100071
非接枝聚乙烯(C)被认为表示通过Ziegler-Natta催化而得到的均聚或共聚的聚乙烯。通过茂金属催化而得到的PE除外。
作为共聚单体,可以提及:
-α-烯烃,优选为具有3-30个碳原子的那些;作为α-烯烃的例子,可以提及丙烯、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两种或多种的混合物使用,
-不饱和羧酸的酯,例如(甲基)丙烯酸烷基酯,其中烷基可能含有至多24个碳原子;丙烯酸烷基酯或甲基丙烯酸烷基酯的例子具体地是甲基丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯、丙烯酸异丁酯或丙烯酸2-乙基己基酯,并且乙烯/(甲基)丙烯酸烷基酯共聚物可能含有至多60wt%的(甲基)丙烯酸烷基酯,并优选为2-40%,
-饱和羧酸的乙烯基酯,例如乙酸乙烯酯或丙酸乙烯酯,
-二烯,例如1,4-己二烯。
该聚乙烯可以含有几种上述共聚单体。
有利的是,乙烯共聚物含有至少51%并优选为75%(摩尔)的乙烯。其密度可以在0.86和0.98g/cm3之间。其MFI(190℃,2.16kg下的粘度指数)优选在0.1-1000g/10min之间。
作为聚乙烯的例子,可以提及:
-低密度聚乙烯(LDPE);
-线型低密度聚乙烯(LLDPE);
-极低密度聚乙烯(VLDPE)。
其优选为LLDPE。
Figure A20071000179100072
关于聚苯乙烯(B),它是高抗冲聚苯乙烯,简写为HIPS,或者是结晶聚苯乙烯。苯乙烯弹性体除外。HIPS具有约0.5-12g/10min的熔体流动指数,其有利地在1和6g/10min之间,并优选在2和4g/10min之间,该指数按照ASTM D-1238在条件G(200℃,5000g)下测定,并且该HIPS具有1.04-1.05的密度。
它们是例如由DoW以标号Styron457和484(高抗冲PS)或以标号Styron634和637(结晶PS)销售的PS,或者由Total Petrochemical以标号8350、7240、4241和3450(高抗冲PS)或以标号1160、1340和1450N(结晶PS)销售的PS。
使用预先接枝的高抗冲PS或预先接枝的结晶PS不脱离本发明的范围。并且还可以考虑PE(A1)+PE(A1)+PS(B)的“一锅”共接枝,换句话说在一个步骤中的同时接枝操作。
Figure A20071000179100081
接枝单体是不饱和羧酸。使用该酸的官能性衍生物不脱离本发明的范围。
不饱和羧酸的例子是具有2-20个碳原子的那些,例如丙烯酸、甲基丙烯酸、马来酸、富马酸和衣康酸。这些酸的官能性衍生物包括,例如该不饱和羧酸的酸酐、酯衍生物、酰胺衍生物、酰亚胺衍生物和金属盐(如碱金属盐)。
具有4-10个碳原子的不饱和二羧酸及其官能性衍生物,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、二环[2.2.1]庚-5-烯-2,3-二羧酸和x-甲基二环[2.2.1]庚-5-烯-2,3-二羧酸,以及马来酸酐、衣康酸酐、柠康酸酐、烯丙基琥珀酸酐、环己-4-烯-1,2-二羧酸酐、4-亚甲基环己-4-烯-1,2-二羧酸酐、二环[2.2.1]庚-5-烯-2,3-二羧酸酐和x-甲基二环[2.2.1]庚-5-烯-2,2-二羧酸酐。
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、衣康酸单甲酯和衣康酸二乙酯;不饱和羧酸的酰胺衍生物,例如丙烯酰胺、甲基丙烯酰胺、马来单酰胺、马来二酰胺、马来N-单乙酰胺、马来N,N-二乙酰胺、马来N-单丁酰胺、马来N,N-二丁酰胺、富马单酰胺、富马二酰胺、富马N-单乙酰胺、富马N,N-二乙酰胺、富马N-单丁酰胺、富马N,N-二丁酰胺;不饱和羧酸的酰亚胺衍生物,例如马来酰亚胺、N-丁基马来酰亚胺和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。
优选马来酸酐(简写为MAH)。
可使用各种已知方法使接枝单体接枝。
接枝反应在单或双螺杆挤出机中进行,该挤出机用进料斗中的聚烯烃(例如粒状聚烯烃)进行进料。在挤出机的第一区域中,通过加热以熔化聚烯烃,在第二区域中,将反应物加入至聚烯烃的熔融体中。
接枝反应例如可以通过在约150℃-约300℃的高温下加热要接枝的聚合物而进行,并且其中可存在或不存在溶剂、具有或不具有自由基引发剂。能够用于该反应的合适溶剂特别是苯、甲苯、二甲苯、氯苯或异丙基苯。
优选的是,反应物的进料区域足够长并具有足够低的温度以确保反应物的良好分散以及自由基引发剂热分解的可能性最小。
接枝反应在能够确保自由基引发剂完全分解的温度下在挤出机的第三区域中适当地进行。在挤出机头中熔融体离开之前,设置排放区域,排放(例如在真空下排放)由引发剂分解所得到的产物和未反应的接枝单体。
在冷空气中冷却后,在挤出机的出口处回收接枝的聚烯烃,其例如为粒状带子(granulated laces)的形式。
(接枝)/(接枝聚全物)的重量比通常在0.1和5之间,优选在0.15和2.5之间。
自由基引发剂可以选自过氧化物、过酸、过酯或过缩醛。它们通常以相对于要接枝的聚烯烃为0.01wt%-0.5wt%的比例使用。可使用的合适自由基引发剂包括叔丁基氢过氧化物、异丙基苯过氧化氢、二异丙苯过氧化氢、过氧化二(叔丁基)、过氧化叔丁基异丙苯、过氧化二异丙苯(DICUP)、1,3-二(叔丁基过氧化异丙基)苯、过氧化乙酰、过氧化苯甲酰、过氧化异丁酰、二(3,5,5-三甲基己酰)过氧化物、过氧化甲乙酮、2,5-二甲基-2,5-二(过氧叔丁基)己烷(DHBP)和α,α’-二(过氧化叔丁基)二异丙苯(Y1490)。
在例如通过计量泵将自由基引发剂加入熔融态聚烯烃之前,优选将其溶于液态的接枝单体中。
通过FTIR光谱学对琥珀酸官能团的定量测定来测量已接枝的单体的量。
以上述方法得到的由接枝进行改性的聚合物中,接枝单体的量可以进行适当选择,并优选为0.01-10wt%,更优选为0.5-2wt%,相对于接枝聚合物的重量。
接枝的热塑性聚合物的熔体流动指数(MFI)在0.1和15g/10min之间(在190℃,2.16kg下测量),并优选在0.4和5g/10min之间。熔点在80和130℃之间。
现在给出本发明的实施例。实施例和对比例的组成在表1中给出。
表1
连接物 对比例1 实施例2 实施例3 对比例4
聚合物(A)的特性 PE类型 VLDPE LLDPE VLDPE LLDPE VLDPE LLDPE VLDPE LLDPE
密度(g/cm3) 0.87 0.92 0.87 0.92 0.87 0.92 0.87 0.92
共聚单体 1-辛烯 1-丁烯 1-辛烯 1-丁烯 1-辛烯 1-丁烯 1-辛烯 1-丁烯
组成(%)** 30% 70% 30% 70% 30% 70% 30% 70%
接枝度(%)*** 0.90% 0.90% 0.90% 0.90%
接枝单体 MAH MAH MAH MAH
MFI(g/10min),190℃-2.16kg 0.7 0.7 0.7 0.7
A的比例(%)**** 15% 15% 15% 15%
聚合物(B)的特性 PS类型 高抗冲PS 结晶PS 高抗冲PS
密度(g/cm3) 1.04 1.05 1.04
MFI(g/10min),200℃-2.16kg 4.5 4 4.5
B的比例(%)**** 30% 30% 20%
聚合物(C)的特性 PE类型 LLDPE LLDPE LLDPE LLDPE
密度(g/cm3) 0.91 0.91 0.91 0.91
共聚单体 C4 C4 C4 C4
MFI(g/10min),190℃-2.16kg 3 3 3 3
C的比例(%)**** 85% 55% 55% 65%
**相对于聚合物(A)的总重量所表示的wt%
***相对于接枝聚合物总重量的接枝单体的wt%
****相对于连接物总重量所表示的%
表1(续)
连摇物 实施例5 对比例6 实施例7*
聚合物(A)的特性 PE类型 VLDPE LLDPE LLDPE VLDPE LLDPE
密度(g/cm3) 0.87 0.92 0.92 0.87 0.92
共聚单体 1-辛烯 1-丁烯 1-丁烯 1-辛烯 1-丁烯
组成(%)** 30% 70% 100% 7% 93%
接枝度(%)*** 0.90% 0.90% 0.90%
接枝单体 MAH MAH MAH
MFI(g/10min),190℃-2.16kg 0.7 0.7 0.7
A的比例(%)**** 15% 15% 70%
聚合物(B)的特性 PS类型 高抗冲PS 高抗冲PS 高抗冲PS
密度(g/cm3) 1.04 1.04 1.04
MFI(g/10min),200℃-2.16kg 4.5 4.5 4.5
B的比例(%)**** 25% 30% 30%
聚合物(C)的特性 PE类型 LLDPE LLDPE
密度(g/cm3) 0.91 0.91
共聚单体 C4 C4
MFI(g/10min),190℃-2.16kg 3 3
C的比例(%)**** 60% 55%
*聚合物(A)和聚合物(B)是共接枝的
**相对于聚合物(A)的总重量所表示的wt%
***相对于接枝聚合物总重量的接枝单体的wt%
****相对于连接物总重量所表示的%
Figure A20071000179100131
制备具有Alu(350μm)/连接物(35μm)/PE(30μm)/连接物(35μm)/Alu(350μm)型结构的样品1-7,并且对于连接物来说,其具有对应样品1-7的(对比)实施例1-7的组成(参见上表1)。
制备样品1-7的过程如下:
1)在Collin共挤出机中挤出由35μm连接物和15μm低密度聚乙烯(简写为LDPE)组成的双层薄膜。
2)在3MPa和170℃下挤压Alu(350μm)/连接物(35μm)/PE(30μm)/连接物(35μm)/Alu(350μm)结构5分钟,然后用空气冷却。该时间为t0。
3)在180°角下用50mm/min的拉扯速度(pull rate)测量剥离强度。
4)破坏类型的评价,其中用AF定义粘合破坏(adhesive failure),用CF定义内聚破坏(cohesive failure)。
5)结果附于表2中。
表2
样品1 样品2 样品3 样品4 样品5 样品6 样品7
剥离强度(N/cm) 30  70  68  70  65  40  72
破坏类型 AF  CF  CF  AF  CF  AF  CF
Figure A20071000179100132
然后在如上所定义的t0时进行剥离强度测量,并在如下所示的不同条件下进行。其测量结果在下表3中进行比较。
表3
              剥离强度(N/cm)
样品1(对比例1) 样品2(实施例2) 样品5(实施例5) 样品7(实施例7)
t0 30  70  65  72
t0+11天 24  76  66  72
在沸水中t0+8小时 15  74  67  74
在23℃水中t0+500小时 17  70  66  75
由此发现包含本发明连接物的组成在水中老化后其剥离强度仍保持在令人满意的程度。
该配方使我们在剥离的内聚(cohesive)方面获得了与铝的高粘合性并且随着时间的流逝以及在水中老化之后仍保持剥离强度。

Claims (12)

1.一种不含弹性体的连接物,其包括(以所述连接物的总重量的百分数计):
●10-79%的PE(A),该PE(A)是密度在0.870和0.910g/cm3之间的VLDPE,或者10-79%的至少两种聚乙烯PE(A1)和PE(A2)的共混物,其中:
○PE(A2)是密度在0.870和0.910g/cm3之间的VLDPE,且不同于PE(A1),
○PE(A)是接枝的,或者PE(A1)和(A2)共混物是接枝的或共接枝的,
○PE(A)、PE(A1)或PE(A2)选自PE均聚物和共聚物,其中在共聚物情况下至少有51%的乙烯,和作为共聚单体的α-烯烃,该α-烯烃选自丙烯、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、1-三十烯及其混合物,
●21-50%的接枝或非接枝的高抗冲PS(B)或接枝或非接枝的结晶PS(B),
●0-70%的由Ziegler-Natta催化得到的非接枝PE(C)。
2.根据权利要求1的连接物,特征在于其包括:
●15-70%的PE(A)或至少两种聚乙烯PE(A1)和PE(A2)的共混物,
●21-30%的接枝或非接枝的结晶或高抗冲PS(B),
●0-60%的由Ziegler-Natta催化得到的非接枝PE(C)。
3.根据前述权利要求之一的连接物,其特征在于PE(A1)选自LLDPE、LDPE和PEm。
4.根据权利要求3的连接物,其特征在于PE(A1)是LLDPE。
5.根据权利要求2-4之一的连接物,其特征在于PE(C)选自LDPE、LLDPE和VLDPE。
6.根据权利要求5的连接物,其特征在于PE(C)是LLDPE。
7.根据前述权利要求之一的连接物,其特征在于该接枝聚合物是用选自具有2-20个碳原子的不饱和羧酸及其衍生物、以及具有4-10个碳原子的不饱和二羧酸及其衍生物的接枝单体进行接枝。
8.根据权利要求7的连接物,其特征在于该接枝单体是马来酸酐。
9.根据权利要求7和8之一的连接物,其特征在于接枝单体的量是接枝聚合物重量的0.01-10%。
10.根据前述权利要求之一的连接物在包括铝层/连接物层/PE层的多层结构中的用途。
11.根据权利要求10的用途,其特征在于该PE层是LDPE层。
12.根据权利要求10和11之一的用途,其特征在于该PE层含有阻燃填料。
CNA200710001791XA 2006-01-16 2007-01-16 具有内聚破坏的基于接枝聚乙烯和高抗冲或结晶聚苯乙烯的连接物 Pending CN101007931A (zh)

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FR06/00364 2006-01-16
FR0600364A FR2896249A1 (fr) 2006-01-16 2006-01-16 Liant a base de polyethylene greffe et de polystyrene choc ou cristal a rupture cohesive
US60/777,059 2006-02-27

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US20080163978A1 (en) * 2007-01-09 2008-07-10 Botros Maged G Process for producing multi-layer structures having improved metal adhesion
US8197947B2 (en) * 2009-12-01 2012-06-12 Equistar Chemicals, Lp Adhesive compositions
CN102585729A (zh) * 2011-12-15 2012-07-18 广州市合诚化学有限公司 一种低熔点粘接树脂及其制备方法与应用
CN110330593A (zh) * 2019-06-03 2019-10-15 中韩(武汉)石油化工有限公司 一种以钛系催化剂制备的聚烯烃制造高支化度聚烯烃树脂的方法

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JPS6114272A (ja) * 1984-06-29 1986-01-22 Ube Ind Ltd 接着性ポリエチレン組成物及びその金属積層体
US4861676A (en) * 1988-08-29 1989-08-29 E. I. Du Pont De Nemours And Company Improved coextrudable adhesive and products therefrom
US5225482A (en) * 1989-08-07 1993-07-06 Mitsui Petrochemical Industries Co., Ltd. Adhesive resin composition, laminate comprising this composition as adhesive layer, and process for preparation thereof
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FR2806734A1 (fr) * 2000-03-24 2001-09-28 Atofina Liant de coextrusion a base de polyethylene metallocene cogreffe
FR2845094B1 (fr) * 2002-09-27 2006-05-05 Atofina Liant de coextrusion pour polyester a base de polyethylene metallocene et lldpe cogreffes et de polyethylene metallocene

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