CN102317395B - 基于聚烯烃的粘合剂的制备 - Google Patents

基于聚烯烃的粘合剂的制备 Download PDF

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CN102317395B
CN102317395B CN200980154247.6A CN200980154247A CN102317395B CN 102317395 B CN102317395 B CN 102317395B CN 200980154247 A CN200980154247 A CN 200980154247A CN 102317395 B CN102317395 B CN 102317395B
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maleinization
polyolefine
density polyethylene
tackiness agent
hdpe
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C·D·李
M·G·巴特罗斯
C·S·霍兰
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Equistar Chemicals LP
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Abstract

公开了一种基于聚烯烃的粘合剂的制备方法。在所述方法中，依次将马来酸化聚烯烃与聚烯烃弹性体然后与线性低密度聚乙烯混合。根据本发明的方法制备的基于聚烯烃的粘合剂在多层聚烯烃薄膜中显示了改进的透明度和粘合性。

Description

基于聚烯烃的粘合剂的制备
技术领域
本发明涉及基于聚烯烃的粘合剂的制备。尤其是，本发明涉及一种在多层聚烯烃薄膜中具有改进的透明度和粘合性的基于聚烯烃的粘合剂的制备方法。
背景技术
基于聚烯烃的粘合剂对于粘接聚烯烃和极性材料例如尼龙、乙烯乙烯醇共聚物(EVOH)和金属是有用的。基于聚烯烃的粘合剂通常包含马来酸酐接枝聚烯烃。所述接枝通常是在马来酸酐的存在下，有或者没有自由基引发剂，通过减粘裂化(visbreaking)所述聚烯烃以在所述聚合物链上形成可以与马来酸酐反应的自由基来实施的。一般地用另外的聚烯烃树脂稀释所述接枝聚烯烃到需要的浓度并提供基于聚烯烃的粘合剂。参见美国专利4,487,885。
可以通过各种聚烯烃树脂稀释(let-down)所述接枝聚烯烃，所述聚烯烃树脂包括高密度聚乙烯(HDPE)、低密度聚乙烯(LDPE)、线性低密度聚乙烯(LLDPE)、聚丙烯和乙烯-醋酸乙烯酯共聚物。高性能的粘合剂也可以使用聚烯烃弹性体作为稀释树脂(let-down resin)。在已知的方法中，将所述弹性体与其它稀释树脂预混合，然后将所述混合物与所述接枝聚烯烃混合。或者，将所述接枝聚烯烃、弹性体和其它稀释树脂同时混合。
存在对生产基于聚烯烃的粘合剂的改进的方法的需求，所述基于聚烯烃的粘合剂在多层聚烯烃薄膜应用中提供更好的透明度和粘合性。
发明概述
本发明是制备基于聚烯烃的粘合剂的方法。所述粘合剂包含马来酸化聚烯烃、聚烯烃弹性体和线性低密度聚乙烯。所述方法包括依次将所述马来酸化聚烯烃与所述聚烯烃弹性体混合，然后与线性低密度聚乙烯混合。根据本发明的方法制备的粘合剂在多层聚烯烃薄膜中具有好的透明度和好的粘合性。
发明详述
本发明的方法包括，依次地，将马来酸化聚烯烃与聚烯烃弹性体混合，然后与线性低密度聚乙烯(LLDPE)混合。用于本发明的合适的马来酸化聚烯烃包括工业中已知的那些。例子包括马来酸化高密度聚乙烯(HDPE)、低密度聚乙烯(LDPE)、线性低密度聚乙烯(LLDPE)、丙烯均聚物、丙烯无规共聚物、丙烯抗冲共聚物等等，及其混合物。马来酸化聚烯烃的方法是已知的。例如，美国专利6,716,928教导了马来酸化丙烯抗冲共聚物。
优选地，所述马来酸化聚烯烃是马来酸化HDPE。制备马来酸化HDPE的合适的HDPE包括乙烯均聚物和乙烯与α-烯烃的共聚物。合适的α-烯烃包括1-丁烯、1-己烯和1-辛烯等等，及其混合物。优选地，所述HDPE包含少于5wt％的α-烯烃。HDPE的密度优选约0.93到约0.97g/cm3且更优选约0.95到约0.965g/cm3。优选地，所述马来酸化HDPE含有约0.05wt％到约5wt％接枝的马来酸酐。更优选地，所述马来酸化HDPE含有从约0.5wt％到约2.5wt％接枝的马来酸酐。
在本发明的方法中使用的合适的聚烯烃弹性体包括乙烯-丙烯橡胶(EPR)、乙烯-丙烯-二烯单体橡胶(EPDM)等等，及其混合物。此处使用的，术语“弹性体”指的是具有类似橡胶的性质和很少或没有结晶的产品。优选地，所述聚烯烃弹性体含有约10wt％到高达约80wt％的乙烯单体单元。更优选地，所述聚烯烃弹性体含有10wt％到70wt％的乙烯单体单元。示例性的商用的聚烯烃弹性体包括Lanxess公司的BUNAEPT 2070(22门尼ML(1+4)125℃.，68％乙烯，和32％丙烯)；BUNA EPT2370(16门尼3％亚乙基降冰片烯，72％乙烯，和25％丙烯)；BUNA EP T 2460(21门尼，4％亚乙基降冰片烯，62％乙烯，和34％丙烯)；ExxonMobil Chemical的VISTALON707(72％乙烯，28％丙烯，和22.5门尼)；VISTALON722(72％乙烯，28％丙烯，和16门尼)；和VISTALON 828(60％乙烯，40％丙烯，和51门尼)。合适的从商业来源可以获得的EP弹性体也包括ExxonMobil Chemical的VISTAMAXX系列弹性体，特别是VISTAMAXX级6100、1100和3000。这些材料是乙烯含量分别为16、15和11wt％的乙烯-丙烯弹性体，Tg为约-20到-30℃。VISTAMAXX 6100、1100和3000在230℃各自具有3、4和7g/10min的熔体流动速度；0.858、0.862和0.871g/cm3的密度；和48、47和64℃的200g维卡软化点。其它合适的EP弹性体包括Dow Chemical的VERSIFY弹性体，特别是级别DP3200.01、DP3300.01和DP3400.01，其分别具有9、12和15wt％的乙烯含量。这些级别具有在230℃为8g/10min的熔体流动速度；各自0.876、0.866和0.858g/cm3的密度；各自60、29和＜20℃的软化点；和各自-25、-28和-31℃的Tg。
在本发明的方法中使用的合适的LLDPE包括乙烯和α-烯烃的共聚物。α-烯烃包括1-丁烯、1-己烯和1-辛烯等等，及其混合物。LLDPE的密度优选在约0.865到约0.925g/cm3的范围内。LLDPE是市场上可以买到的，例如来自EquistarChemicals，LP的GS707和GS710LLDPE。特别优选的LLDPE包括具有可变剪切网络结构(shear modifiable network)的那些。例如，美国专利6,713,585教导了具有可变剪切网络结构的LLDPE。合适的LLDPE可以通过齐格勒、单中心或任何其它烯烃聚合催化剂制备。
优选地，根据本发明的方法制备的基于聚烯烃的粘合剂包含约2wt％到约30wt％的马来酸化聚烯烃，约1wt％到约30wt％的聚烯烃弹性体，和高达约97wt％的LLDPE。更优选地，根据本发明的方法制备的基于聚烯烃的粘合剂包含约5wt％到约15wt％的马来酸化聚烯烃，约2wt％到约10wt％的聚烯烃弹性体，和高达约93wt％的LLDPE。所述基于聚烯烃的粘合剂任选地包含添加剂，例如抗氧剂、UV-吸收剂、助流剂等等，及其混合物。所述基于聚烯烃的粘合剂任选地包含粘合促进剂。有用的促进剂包括有机碱、羧酸和有机金属化合物，有机金属化合物包括有机钛酸盐和铅、钴、镍、锌和锡的络合物或羧酸盐，例如二月桂酸二丁锡、马来酸二辛基锡、二乙酸二丁基锡、二辛酸二丁基锡、乙酸亚锡、辛酸亚锡、环烷酸铅、辛酸锌、环烷酸钴等等，及其混合物。
首先将所述马来酸化的聚烯烃与所述聚烯烃弹性体混合；然后将得到的混合物与LLDPE混合。可以采用任何合适的方法进行所述混合。优选地，所述混合在高于所述组分熔点的温度下进行。例如，所述混合可以在Banbury混炼机或在挤出机中进行。对于商业产品更优选挤出。双螺杆挤出机，例如Coperion在市场上销售的名称为ZSK-53、ZSK-83、ZSK-90和ZSK-92的那些是特别优选的。我们惊奇地发现，通过依次将所述马来酸化聚烯烃与所述烯烃弹性体然后与LLDPE混合，生产的基于聚烯烃的粘合剂显示了显著改进的透明度和粘合性，与通过将马来酸化聚烯烃与预混合的聚烯烃弹性体和LLDPE共混制备的那些相比。
优选地，本发明的方法结合了向聚烯烃上接枝马来酸酐、将所述马来酸化聚烯烃与聚烯烃弹性体混合，和然后将得到的混合物与LLDPE混合。更优选地，所有这三个步骤在多阶段挤出机中进行。多阶段挤出机是已知的。例如，美国专利申请公开No.2006/0076705教导了多级挤出机装配。
在所述多阶段挤出方法中，所述接枝反应优选是在自由基引发剂存在下。合适的自由基引发剂包括1，1-双(叔丁基过氧基)环己烷，正丁基-4，4-双(叔丁基过氧化戊酸酯)，1，1-双(叔丁基过氧)-3，3，5-三甲基环己烷，2，2-双(叔丁基过氧)丁烷，过氧化二异丙苯，过氧化叔丁基异丙苯，α，α’-双(叔丁基过氧异丙基)苯，二叔丁基过氧化物，2，5-二甲基-2，5-二(叔丁基过氧基)己烷等等，及其混合物。优选在马来酸酐和所述聚烯烃已经被彻底地混合后，将自由基引发剂加入到挤出机中。在接枝反应基本完成后，所述马来酸化聚烯烃转移到所述挤出的第二个步骤，在其中将聚烯烃弹性体进料到所述挤出机并和所述马来酸化聚烯烃混合。在所述马来酸化聚烯烃和弹性体被彻底混合后，所述混合物转移到挤出的第三个步骤，其中将LLDPE进料到所述挤出机中并与之混合。
优选地，本发明的方法与LLDPE的生产结合。这就是所谓的“联机”方法。在该方法中，将马来酸化聚烯烃与聚烯烃弹性体混合，然后将得到的混合物与来自LLDPE聚合线的LLDPE反应器粉末在造粒前混合。
本发明也包括含有根据本发明的方法制备的连接粘合剂层的多层聚烯烃薄膜。对于多层，我们意思是所述薄膜除了所述连接粘合剂层外具有至少两个以上的层。所述连接粘合剂层将其它的层粘接在一起。多层薄膜的一个实施例是具有HDPE/连接层/EVOH/连接层/HDPE结构的五层薄膜。乙烯-乙烯醇共聚物(EVOH)层用作氧阻隔层。多层薄膜的另一个实例是具有LLDPE/HDPE/连接层/EVOH/连接层/HDPE/LLDPE结构的七层薄膜。在多层薄膜中使用的合适的LLDPE和HDPE与上述讨论的相同。本发明的多层薄膜可以通过不同的方法制备。所述多层薄膜可以通过共挤出、涂覆和其它层压方法制备。所述薄膜可以通过浇铸、吹膜或双泡取向方法制备。吹膜方法包括高注道(high-stalk)和型腔内(in-pocket)成膜方法。在高注道方法中，挤出物以从挤出模膨胀了一定距离(通常是茎的长度)的管式“茎”的形式离开模具的环形开口。对于型腔内吹膜方法，管膨胀作为管从挤出模离开。等所述管压平和冷却后，其可以裂开形成薄膜。
以下实施例仅仅是举例说明本发明。本领域技术人员将会认可在本发明的精神内和权利要求范围内的许多变化。
实施例1
将马来酸化HDPE(PMG 2300，Equistar Chemicals，LP的产品，10重量份)与乙丙橡胶(EPR V722，ExxonMobil Chemicals的产品，5重量份)在ZSK-30双螺杆挤出机中在220℃和230RPM下混合。然后将得到的混合物与LLDPE(GA602040，Equistar Chemicals的产品，LP，85重量份)在同样的条件下混合生产出粘合剂树脂。
在Killion挤出机上制备具有HDPE/连接粘合剂/EVOH/连接粘合剂/HDPE结构的五层薄膜，其中上述的粘合剂树脂用作连接粘合剂。HDPE是Alathon M6210，Equistar Chemicals，LP的产品，具有0.95dg/min的MI2和0.958g/cm3的密度。EVOH是SoarnolDC3203FB级，Nippon Gohsei Kagaku K.K.，日本的产品。层分布分别为43％、3％、8％、3％和43％。根据ASTM D1876测试薄膜样品的粘合性。使用Instron拉伸测试机测量将所述薄膜以25.4mm(10”)/min以T-剥离构型分离所需要的力。五个样品的平均粘合性用剥离强度lb/in记录。对于3密耳的薄膜，粘合性为1.7lb/in；对于5密耳的薄膜，粘合性为3.1lb/in。
对比实施例2
按照实施例1的总体步骤，但是通过将所述马来酸化的HDPE与EPR和LLDPE的预混物混合来制备所述粘合剂树脂。对于3密耳的薄膜，粘合性为1.4lb/in；对于5密耳的薄膜，粘合性为2.6lb/in。
实施例3
在Killion挤出机上制备具有EVA/连接粘合剂/EVOH/连接粘合剂/EVA结构的五层薄膜，其中实施例1中制备的所述粘合剂树脂用作连接粘合剂层。EVA(乙烯-乙酸乙烯酯共聚物)是UE624，Equistar Chemicals，LP的产品，具有2dg/min的MI2和VA含量为28％。EVOH是SoarnolDC3203FB级，Nippon GohseiKagakuK.K.，日本的产品。层分布分别为36％、7％、14％、7％和36％。使用窄角散射(NAS)测试薄膜样品的透明度。使用Zebedee CL-100透明度计进行所述NAS测量。将所述薄膜样品切成10cm×10cm并通过吸气将其粘接到光源前面的测试单元上。七个标本的平均透明度记录为平均透明度。对于7密耳的薄膜，平均透明度为26。
对比实施例4
按照实施例3的总体步骤，但是使用比较实施例2中的粘合剂树脂。对于7密耳的薄膜，平均透明度为24。

Claims (11)

1. 一种基于聚烯烃的粘合剂的生产方法，包括将马来酸化聚烯烃与聚烯烃弹性体混合，然后将得到的混合物与线性低密度聚乙烯混合。
2. 根据权利要求1的方法，其中所述马来酸化聚烯烃是马来酸化高密度聚乙烯。
3. 根据权利要求2的方法，其中所述马来酸化高密度聚乙烯含有0.05wt%到5wt%接枝的马来酸酐。
4. 根据权利要求3的方法，其中所述马来酸化高密度聚乙烯含有0.5wt%到2.5wt%接枝的马来酸酐。
5. 根据权利要求1的方法，其中所述聚烯烃弹性体是乙丙橡胶。
6. 根据权利要求1的方法，其中所述粘合剂包含1wt%到30wt%的所述弹性体，2wt%到20wt%的所述马来酸化聚烯烃，和50wt%到97wt%的线性低密度聚乙烯。
7. 一种由权利要求6所述的方法制备的粘合剂。
8. 一种包含权利要求7所述的粘合剂的层的多层薄膜。
9. 一种用于制备基于聚烯烃的粘合剂的挤压方法，包括：(a) 将马来酸酐接枝到聚烯烃上；(b) 将所述马来酸化聚烯烃与聚烯烃弹性体混合；和(c) 将线性低密度聚乙烯与来自(b)的产品混合。
10. 根据权利要求9的方法，其中所述接枝马来酸酐的聚烯烃是高密度聚乙烯。
11. 根据权利要求9的方法，其中所述聚烯烃弹性体是乙丙橡胶。
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