CN110691642A - 生产聚合物掺混物的方法 - Google Patents

生产聚合物掺混物的方法 Download PDF

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CN110691642A
CN110691642A CN201880035667.1A CN201880035667A CN110691642A CN 110691642 A CN110691642 A CN 110691642A CN 201880035667 A CN201880035667 A CN 201880035667A CN 110691642 A CN110691642 A CN 110691642A
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zone
extruder
starch
thermoplastic starch
polyolefin
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J·P·A·马腾斯
R·J·P·施普尔
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SABIC Global Technologies BV
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Abstract

本发明涉及生产热塑性淀粉和聚烯烃的掺混物的方法，其中应用第一挤出机和第二挤出机，所述第一挤出机和第二挤出机均包括含第一区、第二区、第三区和第四区的连续区，所述方法包括如下步骤：1a)在第一挤出机的第一区中引入聚烯烃和相容剂，1b)在第一挤出机的第二区中熔融混合所述聚烯烃和相容剂，1c)在第一挤出机的第三区中向步骤1b)的混合物中加入热塑性淀粉，和1d)在第一挤出机的第四区中熔融混合步骤1c)的混合物以得到掺混物，其中通过包括如下步骤的方法在第二挤出机中生产热塑性淀粉：2a)在第二挤出机的第一区中引入淀粉，2b)在第二挤出机的第二区中向步骤2a)的混合物中加入增塑剂以获得热塑性淀粉，2c)在第二挤出机的第三区中使步骤2b)的热塑性淀粉脱气，和2d)在第二挤出机的第四区中使步骤2c)的脱气后热塑性淀粉加压以被移入第一挤出机的第三区。

Description

生产聚合物掺混物的方法
本发明涉及生产热塑性淀粉和聚烯烃的掺混物的方法。本发明还涉及如此获得的掺混物及其用途。
掺混高粘性和低粘性聚合物为良好分散的聚合物/聚合物配混物最通常在合适配混条件下在具有合适螺杆设计的双螺杆挤出机中实施。一个例子是生产聚乙烯(PE)和热塑性淀粉(TPS)的掺混物。将用于形成热塑性淀粉的组分以及聚乙烯和相容剂进料至双螺杆挤出机的喉部。在挤出机的第一部分通过天然淀粉、甘油和添加剂的胶凝作用形成TPS，而PE和相容剂仍处于固态。在双螺杆挤出机的第二部分升高筒温。PE和相容剂开始熔融，TPS相和PE相充分混合为均匀材料。
如果低分子量聚合物和高分子量聚合物之间的粘度差过大，则可能不能产生这些聚合物良好分散的掺混物。所得的掺混物可能包含凝胶和/或可能具有不均匀外观。
对于大规模生产掺混物来说，这种问题更明显。在大规模生产系统中有可能出现高温点，这将形成不均匀掺混物。
调节双螺杆挤出机的螺杆设计可能并不总是足以生产良好分散的这些聚合物的掺混物，特别是大规模生产时。
本发明的一个目的是解决上述和/或其它问题。
本发明提供一种生产热塑性淀粉和聚烯烃的掺混物的方法，其中应用第一挤出机和第二挤出机，所述第一挤出机和第二挤出机均包括含第一区、第二区、第三区和第四区的连续区，所述方法包括如下步骤：
1a)在第一挤出机的第一区中引入聚烯烃和相容剂，
1b)在第一挤出机的第二区中熔融混合所述聚烯烃和相容剂，
1c)在第一挤出机的第三区中向步骤1b)的混合物中加入热塑性淀粉，和
1d)在第一挤出机的第四区中熔融混合所述混合物以得到掺混物，
其中通过包括如下步骤的方法在第二挤出机中生产热塑性淀粉：
2a)在第二挤出机的第一区中引入淀粉，
2b)在第二挤出机的第二区中向步骤2a)的混合物中加入增塑剂以获得热塑性淀粉，
2c)在第二挤出机的第三区中使步骤2b)的热塑性淀粉脱气，和
2d)在第二挤出机的第四区中使步骤2c)的脱气后热塑性淀粉加压以被移入第一挤出机的第三区。
按照本发明方法，在不同与第一挤出机的单独挤出机(第二挤出机)中生产热塑性淀粉，和第一挤出机用于熔融聚烯烃和制备热塑性淀粉和聚烯烃的掺混物。当其与聚烯烃和相容剂的掺混物混合时，已完成了热塑性淀粉的形成。这确保可获得均匀组合物。
热塑性淀粉的生产需要足够的停留时间。当用于生产热塑性淀粉的工艺条件改变时，可以有利地独立于第一挤出机调节第二挤出机以确保足够的停留时间。
脱气步骤2c)减小了热塑性淀粉的水含量。在这个阶段实施脱气步骤比对包含热塑性淀粉和聚烯烃两者的组合物实施脱气(例如在单个挤出机中实施)更有利。按照本发明，可以在不含聚烯烃时在更低温度下实施脱气。在单个挤出机中，脱气只能在包含聚烯烃在内的所有组分的存在下实施。聚烯烃熔体的存在需要脱气步骤温度较高，这将导致淀粉分解的风险。另外，当温度很高时，脱气导致大量蒸气从挤出机排出，这具有使所产生的掺混物被带出挤出机的风险。这会堵塞排气通道和系统。按照本发明方法，可以避免这种过程不稳定性。
应注意US9045625公开了一种生产热塑性淀粉/聚合物掺混物的连续方法，其中通过向双螺杆挤出机中引入淀粉和增塑剂以形成热塑性淀粉和随后引入干态固体聚合物以形成热塑性淀粉/聚合物掺混物。在这种方法中，首先在双螺杆挤出机中产生热塑性淀粉，随后引入干态固体聚合物。通过双螺杆挤出机的设计限制用于形成热塑性淀粉的时间。如果在引入固体聚合物之前还没有完成热塑性淀粉的形成，则所得的组合物可能不均匀。
第一挤出机
在第一挤出机中形成聚烯烃和热塑性淀粉的掺混物。第一挤出机包括含第一区、第二区、第三区和第四区的连续区。
将聚烯烃和相容剂引入第一挤出机的第一区。聚烯烃和相容剂在第一挤出机的第二区中熔融混合。在第一挤出机的第三区中将热塑性淀粉加入到聚烯烃和相容剂的熔融混合物中。聚烯烃、相容剂和热塑性淀粉的混合物在第一挤出机的第四区中熔融混合以获得热塑性淀粉/聚合物掺混物。
配混期间各区的典型温度范围为：
-第一区[℃]：120-130，例如121-129
-第二区[℃]：130-161，例如138-161
-第三区[℃]：130-160，例如135-160
-第四区[℃]：130-160，例如140-154
第一挤出机中的停留时间例如可以约1分钟。
第二挤出机
与聚烯烃混合的热塑性淀粉在第二挤出机中形成。第二挤出机包括含第一区、第二区、第三区和第四区的连续区。
在第二挤出机的第一区中引入淀粉和任选的添加剂。所述淀粉和任选的添加剂可以单独或作为混合物引入。在第二挤出机的第二区中加入增塑剂。选择第二区的条件从而完成热塑性淀粉的形成。例如，第二区的温度为至少110℃和停留时间为至少30秒。在第三区，为所形成的热塑性淀粉脱气。在第四区中，将脱气后的热塑性淀粉移至第一挤出机的第三区。
配混期间各区的典型温度范围为：
-第一区[℃]：70-90
-第二区[℃]：110-140
-第三区[℃]：110-140
-第四区[℃]：100-140
第二挤出机的停留时间例如可以为约1-2分钟。
聚烯烃
聚烯烃优选选自丙烯均聚物、乙烯丙烯共聚物、聚乙烯如高密度聚乙烯、中密度聚乙烯、低密度聚乙烯、线性低密度聚乙烯和前述聚烯烃中至少两种的混合物。聚烯烃的密度优选至少0.910g/cm3。在一个优选的实施方案中，所述聚烯烃为聚乙烯，特别是低密度聚乙烯(LDPE)。
以掺混物为基准，聚烯烃的含量优选为10-70wt％，例如15-50wt％。
相容剂
正如这里所应用，术语“相容剂”定义为对淀粉相和聚烯烃相两者均具有亲和性的材料，和所述材料能够提高在界面处两相的粘合性，从而所述热塑性相和聚烯烃相可以在同一制品中共存而不会造成相的物理分离。适用于本发明的相容剂包含对热塑性淀粉具有高亲和性和/或混溶性的分子部分和对聚烯烃有高亲和性和/或混溶性的另一分子部分。
由于聚烯烃相的非极性性质和淀粉相的极性性质，相容剂可以为具有非极性骨架和结合在骨架中或接枝于骨架上的极性基团的聚合物材料。这种极性基团可以对淀粉具有反应性和与至少部分淀粉反应。相容剂也可以是具有非极性和极性单体的嵌段的嵌段共聚物。
合适相容剂的例子包括乙烯-丙烯酸共聚物、乙烯-乙烯基醋酸酯共聚物、具有至少1wt％接枝于其上的马来酸酐的聚烯烃、乙烯-乙烯醇共聚物、嵌段的皂化聚乙烯基醋酸酯、乙烯、丙烯酸丁酯和马来酸酐的无规三元聚合物、无规部分水解和皂化的聚乙烯基醋酸酯以及这些相容剂中至少两种的混合物。
相容剂优选选自乙烯-乙烯醇共聚物、嵌段的皂化聚乙烯基醋酸酯和乙烯、丙烯酸丁酯和马来酸酐的无规三元聚合物和它们的混合物。
相容剂的含量以掺混物计优选为3-30wt％。相容剂的含量以掺混物计优选为4-15wt％，更优选为5-10wt％，甚至更优选为5-7.5wt％。
热塑性淀粉
本领域熟练技术人员将会理解热塑性淀粉为包含一种或多种增塑剂的淀粉的解构形式。因此，为了避免怀疑，应该理解的是用于由淀粉制备热塑性淀粉的处理助剂如增塑剂被认为是热塑性淀粉的一部分。
以掺混物计，热塑性淀粉的含量优选为10-70wt％，例如50-70wt％。
淀粉
淀粉主要在植物种子、水果、块茎、根部和茎髓中存在，和是天然聚合物，其由在1-4碳位上通过糖苷链连接的重复葡萄糖基团组成。淀粉主要由分子量约1 x 105、基本为直链聚合物的直链淀粉和具有1 x 107数量级的非常高分子量的高度支化聚合物的支链淀粉组成。
所述淀粉可以来自任何合适的淀粉源如玉蜀黍、木薯、玉米、小麦、大米、土豆、大豆或这些淀粉源中至少两种的任意组合，土豆淀粉由于其易获得性而优选。
每个重复的葡糖单元通常具有三个游离羟基，因此为聚合物提供亲水性和反应性官能团。大多数淀粉含有20-30％的直链淀粉和70-80％的支链淀粉。但取决于淀粉来源，直链淀粉与支链淀粉的比可能会变化很大。例如，有些玉蜀黍杂交品种提供含有100％支链淀粉的淀粉(蜡状玉蜀黍淀粉)，或进一步更高的直链淀粉含量为50-95％。
除了天然的淀粉形式外，在本发明中也可以应用化学改性的淀粉。化学改性的淀粉包括但不限于氧化淀粉、醚化淀粉、酯化淀粉或这些化学改性(如醚化和酯化淀粉)的组合。合适的醚化淀粉包括但不限于用乙基和/或丙基取代的淀粉。合适的酯化淀粉包括但不限于用乙酰基、丙酰基和/或丁酰基取代的淀粉。
化学改性的淀粉通常通过使淀粉的羟基与一种或多种反应剂反应而制备。反应的程度通常称为取代度(DS)，相比于对应的天然淀粉，反应程度可以明显改变改性淀粉的物理化学特性。天然淀粉的DS以0表示，和对于完全取代改性的淀粉来说可以至多为3。取决于取代基的类型和DS，相对于天然淀粉，化学改性的淀粉可以展现出相当不同的亲水/疏水性质。
相对于淀粉和增塑剂的总重量，淀粉的含量通常可以为约30-90wt％，例如35-80wt％、35-70wt％、35-60wt％或40-50wt％。
增塑剂
增塑剂优选为多羟基醇增塑剂。多羟基醇的合适例子包括甘油、乙二醇、丙二醇、二乙二醇、二丙二醇、三乙二醇、三丙二醇、聚乙二醇、聚丙二醇、1,2-丙二醇、1,3-丙二醇、1,2-丁二醇、1,3-丁二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、1,5-己二醇、1,2,6-己三醇、1,3,5-己三醇、新戊二醇、三羟甲基丙烷、季戊四醇、甘露醇、山梨醇和它们的乙酸酯、乙氧化物和丙氧化物衍生物。
所述增塑剂优选为甘油和/或山梨醇增塑剂。
相对于淀粉和增塑剂的总重量，淀粉的含量可以通常为约10-70wt％，例如20-65wt％、30-65wt％、40-65wt％或50-60wt％。
添加剂
当存在时，相对于掺混物，添加剂的含量通常可以为0.1-5wt％。典型的添加剂包括脂肪酸和硬酯酸酯，其用作热塑性淀粉的处理助剂和粘度调节剂。
掺混物
相对于掺混物中的聚烯烃和热塑性淀粉的总量，聚烯烃的含量优选为20-80wt％，例如25-75wt％或30-70wt％。
本发明的掺混物主要由聚烯烃、热塑性淀粉和相容剂组成，即至少80wt％的掺混物为聚烯烃、热塑性淀粉和相容剂。优选至少90wt％或至少95wt％的掺混物为聚烯烃、热塑性淀粉和相容剂。
本发明还涉及由本发明方法获得或可获得的热塑性淀粉和聚烯烃的掺混物。
本发明还涉及由本发明方法获得或可获得的热塑性淀粉和聚烯烃的掺混物，其中由所述掺混物产生的膜的透明度可以为至少60％，优选70％，更优选75％。
本发明还涉及包含本发明掺混物的制品。
所述制品可以为由所述掺混物制成的双轴向拉伸膜。
本发明还涉及生产双轴向拉伸膜的方法，包括在高温下沿纵向和横向拉伸本发明的掺混物。这种方法例如在WO2013/178746中详细地进行了描述，其作为参考在这里引入。如此获得的膜具有包含淀粉和聚烯烃层的多层结构。本发明的膜组合了低氧渗透性和低水蒸汽渗透性。因此，本发明制品的合适例子包括食品包装。
本发明的双轴向拉伸膜的厚度可以为例如2-250μm，更通常为5-100μm、20-80μm或40-60μm。
由所述方法获得或可获得的双轴向拉伸膜的透明度可以为至少60％，优选70％，更优选75％。
多层膜包含双轴向拉伸膜和在双轴向拉伸膜每一侧提供的聚合物膜，该多层膜的透明度为至少60％，优选70％，更优选75％。
从淀粉相角度来看，拉伸时热塑性组合物的温度不可以太高，因为太高的温度会造成热塑性淀粉变黄或变棕。太高温度下热塑性淀粉也可能变脆，这是不想要的。实际上限为130℃。拉伸温度下限在某种程度上取决于掺混物，但通常可以认为该下限由聚烯烃相的熔化和结晶温度决定。实际下限可以为100℃，虽然熟练技术人员可以很容易地通过常规实验确定实际下限。优选地，掺混物拉伸在高于热塑性淀粉和聚烯烃两者的熔点的温度下实施。
获得本发明膜的拉伸方法不限于具体拉伸方法，但优选应用吹塑膜技术，因为该技术非常适合制备薄膜。但也可采用其它拉伸技术如压延。
所述制品也可以为包含本发明双轴向拉伸膜和在本发明双轴向拉伸膜每一侧提供的聚合物膜的多层膜，其中所述聚合物膜优选包含聚烯烃如聚乙烯和相容剂。合适的例子包括针对本发明掺混物描述的相容剂。这种聚合物膜可以在沿纵向和横向拉伸前或之后通过层压或共挤出在本发明的双轴向拉伸膜上提供。
本发明多层膜的厚度例如可以为2-250μm，更通常为5-100μm、20-80μm或40-60μm。多层膜中双轴向拉伸膜与剩余膜间的厚度比例如可以为5:95至95:5，例如40:60至60:40。在一些实施方案中，本发明多层膜的厚度为40-60μm和所述双轴向拉伸膜的厚度为2-25μm。
应注意本发明涉及这里描述的特征的所有可能组合，特别优选的是权利要求中给出的那些特征的组合。因此，应理解这里描述了与本发明掺混物相关的特征的所有组合、与本发明方法相关的特征的所有组合以及与本发明掺混物相关的特征和与本发明方法相关的特征的所有组合。
还应注意术语‘包括’不排除其它要素的存在。但应理解对包含某些组分的产品/掺混物的描述也公开了由这些组分组成的产品/掺混物。由这些组分组成的产品/掺混物可能是有利的，因为它提供了制备所述产品/组合物的更简单、更经济的方法。类似地，还应理解对包含某些步骤的方法的描述也公开了由这些步骤组成的方法。由这些步骤组成的方法可能是有利的，因为它提供了更简单、更经济的方法。
当对一个参数提到下限和上限值时，应理解也公开了由这些下限值和上限值组合形成的范围。
下面通过实施例的方式描述本发明，但本发明不限于此。
实验
由表1所示组分通过双螺杆挤出机制备LDPE和热塑性淀粉的掺混物。
应用该掺混物作为中间层制备三层吹塑膜。三层吹塑膜的外层由LDPE和相容剂的干掺混物组成，所述相容剂为乙烯、丙烯酸丁酯和马来酸酐的无规三元聚合物(Lotader3410)。挤出机的温度(进料单独的材料至吹塑挤出机)为125-140-135-130-130℃，螺杆速度为50rpm，线速度为9m/min和总流通量为约20kg/hr。所有三层材料的吹塑放大比(BUR)为3。
在对比实验A-D和E-G中，在单个双螺杆挤出机中生产，LDPE和热塑性淀粉的掺混物。在对比实验A-D和对比实验E-G中改变螺杆类型、挤出机长度与直径的比和流通量。
在对比实验A-D中，熔体指数为1.1-3.2dg/min。视觉观察膜显示获得的中间层掺混物是透明的，但不均匀，和所有实验均形态粗糙。
在对比实验E-G中，熔体指数为25.5-33.3dg/min。视觉观察膜显示获得的中间层掺混物的透明度和均匀度好于对比实验A-D，但对于所有情况，所获得的掺混物仍不够均匀。
在本发明的实施例1-6中，由本发明两个双螺杆挤出机系统生产掺混物。在所有实施例中，中间层是透明的并具有良好分散的均匀结构。
表1
Figure BDA0002294637990000091
在23℃和50％RH下测量膜的透明度。测量在来自BYK-Gardner GmbH的设备上实施。方法基于ASTM D1746。与ASTM D1746相比，BYK定义了小角度散射，因为散射光线量(通过膜样品后)不超过2.5°，而ASTM D1767应用的角度为0.1°。但所有其它特征均如ASTMD1746所述。
表2
实施例 透明度，％
1 77.0
2 82.9
3 88.0
4 81.1
5 80.4
6 76.7
A 29.6
B 24.9
C 24.0
由表2可以清楚地看出，相比于对比例A-C，本发明实施例1-6显示出更高的透明度。

Claims (15)

1.一种生产热塑性淀粉和聚烯烃的掺混物的方法，其中应用第一挤出机和第二挤出机，所述第一挤出机和第二挤出机均包括含第一区、第二区、第三区和第四区的连续区，所述方法包括如下步骤：
1a)在第一挤出机的第一区中引入聚烯烃和相容剂，
1b)在第一挤出机的第二区中熔融混合所述聚烯烃和相容剂，
1c)在第一挤出机的第三区中向步骤1b)的混合物中加入热塑性淀粉，和
1d)在第一挤出机的第四区中熔融混合步骤1c)的混合物以得到掺混物，
其中通过包括如下步骤的方法在第二挤出机中生产热塑性淀粉：
2a)在第二挤出机的第一区中引入淀粉，
2b)在第二挤出机的第二区中向步骤2a)的混合物中加入增塑剂以获得热塑性淀粉，
2c)在第二挤出机的第三区中使步骤2b)的热塑性淀粉脱气，和
2d)在第二挤出机的第四区中使步骤2c)的脱气后热塑性淀粉加压以被移入第一挤出机的第三区。
2.权利要求1的方法，其中以掺混物计，聚烯烃的含量为10-70wt％，相容剂的含量为3-30wt％和/或热塑性淀粉的含量为10-70wt％。
3.前述权利要求任一项的方法，其中聚烯烃选自丙烯均聚物、乙烯丙烯共聚物、聚乙烯如高密度聚乙烯、中密度聚乙烯、低密度聚乙烯、线性低密度聚乙烯以及前述聚烯烃中至少两种的混合物。
4.前述权利要求任一项的方法，其中相容剂选自乙烯-丙烯酸共聚物、乙烯-乙烯基醋酸酯共聚物、具有至少1wt％接枝于其上的马来酸酐的聚烯烃、乙烯-乙烯醇共聚物、嵌段的皂化聚乙烯基醋酸酯、乙烯、丙烯酸丁酯和马来酸酐的无规三元聚合物、无规部分水解和皂化的聚乙烯基醋酸酯以及这些相容剂中至少两种的混合物。
5.前述权利要求任一项的方法，其中相对于淀粉和增塑剂的总重量，淀粉的含量为约30-90wt％，例如35-80wt％，35-70wt％，35-60wt％或40-50wt％。
6.前述权利要求任一项的方法，其中增塑剂为甘油和/或山梨醇增塑剂。
7.前述权利要求任一项的方法，其中步骤2c)在110-140℃的温度下实施。
8.前述权利要求任一项的方法，其中第一挤出机和第二挤出机均为双螺杆挤出机。
9.一种生产双轴向拉伸膜的方法，包括按权利要求1-8任一项生产掺混物的方法和在高温下沿纵向和横向拉伸所述掺混物。
10.由权利要求1-8任一项方法获得或可获得的热塑性淀粉和聚烯烃的掺混物。
11.由权利要求9的方法获得或可获得的双轴向拉伸膜。
12.由权利要求9的方法获得或可获得的双轴向拉伸膜，其中所述膜的透明度为至少60％，优选为70％，更优选为75％。
13.一种多层膜，包含权利要求11-12的双轴向拉伸膜和在双轴向拉伸膜每一侧提供的聚合物膜。
14.一种多层膜，包含权利要求11-12的双轴向拉伸膜和在双轴向拉伸膜每一侧提供的聚合物膜，其中所述膜的透明度为至少60％，优选为70％，更优选为75％。
15.权利要求11-14的膜用于食品包装的用途。
CN201880035667.1A 2017-05-30 2018-05-28 生产聚合物掺混物的方法 Pending CN110691642A (zh)

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