CN101326056A - 聚(对苯二甲酸丙二醇酯)/聚(α-羟基酸)薄膜 - Google Patents
聚(对苯二甲酸丙二醇酯)/聚(α-羟基酸)薄膜 Download PDFInfo
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Abstract
本发明涉及聚(对苯二甲酸丙二醇酯)/聚(α-羟基酸)薄膜,制备该薄膜的方法和其最终用途。
Description
发明领域
本发明涉及聚(对苯二甲酸丙二醇酯)/聚(α-羟基酸)薄膜,其制备方法和最终用途。
发明背景
聚(对苯二甲酸丙二醇酯)(“PTT”)和其在多种应用中的用途已经在文献中记载,所述用途包括模塑成型产品。PTT为衍生自对苯二甲酸或其酯与三亚甲基二醇(也称作1,3-丙二醇)(“PDO”)的聚酯。PDO可通过多种化学或生物化学途径,包括由多种糖来源如玉米制备,从而可由可再生资源制备。期望具有改进的韧性、伸长率和表面性质的新型PTT制品。另外,由于对苯二甲酸和其酯目前由石油基物质制备,所以提高PTT组成的绿色度(可再生资源基物质)而不损害产品的总体性质是期望的。
日本专利公开第2003-041435号公开了PTT与1-10wt%基本由聚乳酸组成的聚酯的混合物。该混合物用于制备中空、卷曲短纤维。聚(乳酸)也可由可再生资源制备,由乳酸(2-羟基丙酸)和其分子间酯制备,所述乳酸和其分子间酯又通过乳酸发酵从碳水化合物制备。日本专利公开第2003-041435号关注于使用聚乳酸提供更加稳定的卷曲,而没有记载薄膜或对其的改进。
发明概述
本发明涉及一种薄膜,其包括聚合物组合物,该聚合物组合物含有基于聚合物组合物重量约20-约98wt%的聚(对苯二甲酸丙二醇酯)和基于聚合物组合物重量约80-约2wt%的聚(α-羟基酸)。
优选地,该聚合物组合物包括基于聚合物组合物重量至少约30wt%,更优选至少40wt%,更加优选至少50wt%,更加优选大于50wt%,甚至更优选至少60wt%和最优选至少75wt%的聚(对苯二甲酸丙二醇酯)。优选该聚合物组合物包括最高约95wt%的聚(对苯二甲酸丙二醇酯)。
优选所述聚合物组合物包括基于该聚合物组合物重量最高约70wt%,更优选最高约60wt%,更加优选最高约50wt%,更优选少于约50wt%,更优选最高约40wt%和最优选最高约25wt%的聚(α-羟基酸)。优选该组合物包括基于聚合物组合物重量至少约5wt%的聚(α-羟基酸)。
优选地,所述聚(对苯二甲酸丙二醇酯)使用采用可再生生物资源通过发酵工艺制备的1,3-丙二醇生产。
优选所述聚(α-羟基酸)为聚乳酸,更优选为源自生物的聚乳酸。
优选所述薄膜为约0.1密耳-约100密耳厚。在一个优选实施方式中,所述薄膜为约0.1密耳-约15密耳厚。在另一个优选实施方式中,所述薄膜为约15密耳-约100密耳厚。
在一个优选实施方式中,所述薄膜为双轴取向薄膜。在另一个优选实施方式中,所述薄膜为流延薄膜。
在一个优选实施方式中,所述薄膜为单层膜。在另一个优选实施方式中,本发明涉及多层膜,其包括至少一个包括聚合物组合物的薄膜层,其中该聚合物组合物含有基于聚合物组合物重量约20-约98wt%聚(对苯二甲酸丙二醇酯)和基于聚合物组合物重量约80-约2wt%聚(α-羟基酸)。在一个优选实施方式中,所述多层膜通过层压至少一个薄膜层到至少一个其它薄膜层或基材制备。在另一个优选实施方式中,多层膜通过共挤出所述至少一个薄膜层与至少一个选自聚烯烃、乙烯共聚物、离聚物、聚酰胺、聚碳酸酯、丙烯酸类树脂、聚苯乙烯、乙烯乙烯醇、聚偏二氯乙烯和其它合成聚合物薄膜层的其它薄膜层制备;和其中所述多层膜任选地包括一个或多个粘合固定层(adhesive tielayers)。
在一个优选实施方式中,所述薄膜为吹塑薄膜。
本发明还涉及由该薄膜生产的制品。所述制品可由单层或多层膜制备。制品的例子为容器(如瓶和化妆品容器),和其它多层层压结构体。包括热成型和真空热成型制品。
本发明还涉及制备所述薄膜,包括所述单层膜和多层膜,以及制备制品。例如,在一个实施方式中,涉及制备薄膜的方法,包括如下步骤:(a)提供含有基于聚合物组合物重量约20-约98wt%的聚(对苯二甲酸丙二醇酯)和基于聚合物组合物重量约80-约2wt%的聚(α-羟基酸)的聚合物组合物,和(b)形成薄膜。
本发明的薄膜、薄膜层和制品具有与仅使用PTT制备的那些相比相似或更好的性质。更特别地,模量和表面外观已经得到改进。这是出乎预料的,因为聚(α-羟基酸)聚合物具有明显低于PTT的物理和机械性质。从而,使用聚(α-羟基酸),技术人员可提高薄膜、薄膜层或制品中的绿色含量(可再生资源百分数),而不会显著劣化最终产品的性质。
优选实施方式的详细描述
所有这里提及的出版物、专利申请、专利和其它参考文献均全文结合在这里作为参考。除非另外定义,否则这里使用的所有技术和科学术语均具有与本发明所属领域普通技术人员的通常理解相同的含义。在存在冲突情况下,将遵循本说明书,包括定义。
除非明确记载,否则商标以大写字母表示。
除非特别说明,否则这里的材料、方法和例子仅为解释性的,而非限制性的。尽管在本发明的实践和试验中可使用与这里描述的那些类似或等价的方法和材料,但适宜的方法和材料描述如下。
除非另外说明,否则所有百分数、份数、比例等均基于重量计算。
当数量、浓度或其它值或参数以范围、优选范围或上限优选值与下限优选值的列表给出时,应理解为特别公开了所有由任意范围上限或优选值与任意范围下限或优选值的任意组合形成的范围,无论该范围是否单独公开。当一个数值范围记载于本文中时,除非另外说明,否则该范围应包括其端点和在该范围内的所有整数和分数。当限定一个范围时,并不代表将本发明的范围限制于该列举的特定数值。
当使用术语“约”描述数值或范围的端点时,该公开内容应理解为包括相关的特定数值或端点。
如这里使用的,术语“包括”、“包含”、“含有”、“含”、“具有”或其任意其它变型均应涵盖非排除性的包含。例如,包括一组要素的工艺、方法、制品或装置不必仅限于那些要素,而是可包括其它未明确列出的或该工艺、方法、制品或装置固有的其它要素。进一步地,除非明确作出相反说明,否则“或”表示包含性的或,而不是排除性的或。例如,以下任意一种都满足条件A或B:A为真(或存在)和B为假(或不存在),A为假(或不存在)和B为真(或存在),和A和B均为真(或存在)。
应用“一个”或“一种”用于描述本发明的要素和组分。这仅仅是基于简洁和提供本发明的总体理解。该表述应理解为包括一个(种)或至少一个(种),并且单数形式同样包括复数形式,除非其明显表示相反含义。
本发明涉及聚合物组合物,包括该聚合物组合物的熔融共混混合物、薄膜、薄膜层和制品(或制品层)。所述聚合物组合物和熔融共混混合物包括聚(对苯二甲酸丙二醇酯)和α-羟基酸的聚合物。一种或多种α-羟基酸的聚合物的量为至少约2%,更优选至少约5%和在一些情况下更优选至少约10%。α-羟基酸聚合物的量最高为约80%,优选最高约75%,在另一个实施方式中最高约60%,在再一个实施方式中最高50%,在另一个实施方式中低于50%,在再一个实施方式中最高约40%和在一个额外的实施方式中最高约25%。优选该聚(对苯二甲酸丙二醇酯)以最高约98%的量使用,在另一个实施方式中优选最高约95%和在一个额外的实施方式中优选最高约90%。优选以至少约20%,在另一个实施方式中至少约25%,在另一个实施方式中至少约40%,在再一个实施方式中优选至少约50%,在进一步的实施方式中大于50%,在一个额外的实施方式中至少约60%,和在一个额外的实施方式中至少约75%的量使用。上述为重量百分数,并分别基于所述聚合物组合物和熔融共混聚酯混合物的总重量。基于方便的目的,本发明的聚合物组合物有时称作“PTT/PAHA聚合物”。
聚(对苯二甲酸丙二醇酯)或PTT意图包括均聚物和含至少70摩尔%对苯二甲酸丙二醇酯重复单元的共聚物。优选的聚(对苯二甲酸丙二醇酯)包含至少85摩尔%,更优选至少90摩尔%,甚至更加优选至少95或至少98摩尔%,和最优选约100摩尔%的对苯二甲酸丙二醇酯重复单元。
聚(对苯二甲酸丙二醇酯)通常由1,3-丙二醇和对苯二甲酸/二酯的酸催化的缩聚生产,任选的存在少量其它单体。
当所述PTT为共聚物时,其可包含最高30摩尔%,优选最高15摩尔%,更优选最高10摩尔%,更加优选最高5摩尔%和最优选最高2摩尔%的包含其它单元的重复单元。这些重复单元优选包含具有4-12个碳原子的二羧酸(例如丁二酸、戊二酸、己二酸、十二双酸和1,4-环己烷二甲酸);不同于对苯二甲酸并具有8-12个碳原子的芳香族二羧酸(例如间苯二甲酸和2,6-萘二甲酸);和不同于1,3-丙二醇的具有2-8个碳原子的线型、环状和支化脂肪族二醇(例如乙二醇、1,2-丙二醇、1,4-丁二醇、3-甲基-1,5-戊二醇、2,2-二甲基-1,3-丙二醇、2-甲基-1,3-丙二醇和1,4-环己二醇)。
所述聚(对苯二甲酸丙二醇酯)可包含少量其它共聚单体,这类共聚单体通常选择为使得它们对性质不具有显著负面影响。这类其它共聚单体包括间苯二甲酸-5-磺酸钠(5-soditm-sulfoisophthalate),例如在约0.2-5摩尔%范围水平。可结合极少量的三官能共聚单体例如偏苯三酸用于粘度控制。
特别优选的聚(对苯二甲酸丙二醇)为其中用于制备所述聚合物的1,3-丙二醇包括(优选基本上(substantially)包括)采用可再生生物资源通过发酵工艺制备的1,3-丙二醇的那些。作为由可再生资源获得的起始材料的说明性例子,已经记载了制备1,3-丙二醇(PDO)的生物化学途径,其采用由生物的和可再生的资源如玉米原料生产的原料。例如,在克雷伯氏菌属(Klebsiella)、Citrobacter、梭菌属(Clostridium)和乳酸菌属(Lactobacillus)菌种中发现了能够将甘油转化为1,3-丙二醇的菌株。该技术公开于数个公开文献中,包括前面引入的US5633362、US5686276和US5821092。其中,US5821092公开了一种由甘油采用重组生物体(recombinant organisms)生产1,3-丙二醇的生物学工艺。该工艺结合用异源(heterologous)pdu二醇脱水酶基因转化的大肠埃希菌(E.coil)细菌,对1,2-丙二醇具有特异性。该转化的大肠埃希菌在作为碳源的甘油的存在下生长,和从该生长介质分离1,3-丙二醇。由于细菌和酵母均可将葡萄糖(如玉米葡糖(corn sugar))或其它碳水化合物转化为甘油,所以在这些公开文献中记载的工艺提供了快速、廉价和环境友好的1,3-丙二醇单体源。
所述源自生物的1,3-丙二醇,如通过上文所述和参考的工艺生产,包含通过植物结合的来自大气中二氧化碳的碳,其构成了用于所述1,3-丙二醇生产的原料。这样,优选用于本发明的源自生物的1,3-丙二醇仅包含可再生碳,不含化石燃料基或石油基碳。从而,基于以上的使用源自生物的1,3-丙二醇的聚(对苯二甲酸丙二醇酯)对环境具有较少影响,因为在该组合物中使用的1,3-丙二醇没有消耗日益减少的化石燃料,和在降解时,将碳释放回大气中供植物再次使用。
优选所述用作反应物或作为反应物组分的1,3-丙二醇通过气相色谱分析测定以重量计,具有大于约99%的纯度,更优选大于约99.9%。特别优选在US7038092、US2004-0260125A1、US2004-0225161A1和US2005-0069997A1中公开的纯化的1,3-丙二醇。
所述纯化的1,3-丙二醇优选地具有以下特征:
(1)紫外吸收在220nm处低于约0.200,在250nm处低于约0.075,和在275nm处低于约0.075;和/或
(2)组成(composition)具有低于约0.15的L*a*b*”b*”色值(ASTMD6290),和在270m处低于约0.075的吸光度;和/或
(3)低于约10ppm的过氧化物组成;和/或
(4)通过气相色谱测量,总有机杂质(不同于1,3-丙二醇的有机化合物)浓度低于约400ppm,更优选低于约300ppm,和更加优选低于约150ppm。
本发明聚(对苯二甲酸丙二醇酯)的特性粘度为至少约0.5dL/g,优选至少约0.7dL/g,更优选至少约0.8dL/g,更优选至少约0.9dL/g,和最优选至少约1dL/g。本发明聚酯组合物的特性粘度优选最高约2.5dL/g,更优选最高约2dL/g,更加优选最高约1.5dL/g,和最优选最高约1.2dL/g。
聚(对苯二甲酸丙二醇酯)和用于制备聚(对苯二甲酸丙二醇酯)的优选生产技术公开于US5015789、US5276201、US5284979、US5334778、US5364984、US5364987、US5391263、US5434239、US5510454、US5504122、US5532333、US5532404、US5540868、US5633018、US5633362、US5677415、US5686276、US5710315、US5714262、US5730913、US5763104、US5774074、US5786443、US5811496、US5821092、US5830982、US5840957、US5856423、US5962745、US5990265、US6232511、US6235948、US6245844、US6255442、US6277289、US6281325、US6297408、US6312805、US6325945、US6331264、US6335421、US6350895、US6353062、US6437193、US6538076、US6841505和US6887953中,其均结合在这里作为参考。
可用作本发明聚酯的聚(对苯二甲酸丙二醇酯)可由E.I.du Pont deNemours and Company,Wilmington,Delaware在SORONA商标下面业获得,和可由Shell Chemicals,Houston,Texas在CORTERRA商标下商业获得。
在本发明实践中使用的聚合的α-羟基酸(“PAHA”)包括以下物质的聚合物:乳酸(包括其有规立构二聚体L(-)丙交酯的聚合物)、羟基乙酸(包括其二聚体乙交酯)和2-羟基丁酸。同样包括在术语“聚合的α-羟基酸”中的为PLA的共聚物,如PLA和ε-己内酯(2-氧杂环庚酮(oxepanone))和/或γ-己内酯(5-乙基-2-氧杂环戊酮(oxolanone))的共聚物。
本发明实践中可以使用任何等级的PLA。在本发明实践中使用的优选聚(乳酸)(PLA)为由L(-)丙交酯催化制备的100%源自生物的聚合物,优选具有130-200℃的熔点。该在本发明实践中使用的PLA的特性粘度优选为至少约0.7dL/g,更优选至少约0.9dL/g,和优选最高约2.0dL/g,更优选最高约1.6dL/g。
适用于实施本发明的PLA可由Cargill,Inc.,Mine-tonka,MN,一种优选等级是PLA Polymer 4040D,和其它供应商获得。
所述PTT/PAHA聚合物组合物可采用任意已知技术制备,包括物理共混和熔融共混。优选将所述PTT和PAHA熔融共混和配混。优选地将PTT和PAHA混合并在足以形成共混物的温度下加热,一旦冷却,将该共混物形成为成形制品如粒料。PTT和PAHA可通过多种不同方式形成共混物。例如,可将它们(a)同时加热并混合,(b)加热前在独立装置中预混合,或(c)加热然后混合。作为例子,该聚合物共混物可通过输送管线注射(transfer line injection)生产。所述混合、加热和成形可通过为所述目的设计的常规设备如挤出机、Banbury混合机等实施。所述温度应高于每种组分的熔点,但低于最低分解温度,从而必须基于PTT/PAHA聚合物的任何特定组成调节。根据本发明的特定PTT和PAHA,温度典型地在约180℃-约260℃范围内,优选至少约230℃和更优选最高约250℃。
如果需要,所述聚合物组合物可包含某些添加剂,例如热稳定剂、成核剂、粘度促进剂(viscosity booster)、荧光增白剂、颜料和抗氧化剂。
根据预计的最终应用,所述聚合物可包含少量其它热塑性树脂或常规加入至热塑性树脂中的已知添加剂,例如稳定剂如紫外吸收剂,和抗静电剂。当然,这些添加剂应该以不会负面影响通过本发明获得的优点的量使用。
基于所述聚合物组合物重量,聚酰胺如尼龙6或尼龙6-6可以约0.5-约15重量%的小数量添加,以改进本发明组合物的性质(如强度)和可加工性。
优选的成核剂,优选0.005-2wt%的选自对苯二甲酸单钠盐、萘二甲酸单钠盐和间苯二甲酸单钠盐的二羧酸单钠盐,作为成核剂,可以如US6245844中所述添加。
本发明的组合物可形成为流延或双轴取向薄膜、板材或其它制品。这些薄膜典型地具有约0.1密耳-约100密耳的尺寸。所述薄膜可为单层膜或与其它薄膜层包括聚烯烃、乙烯共聚物、离聚物、聚酰胺、聚碳酸酯、丙烯酸类树脂、聚苯乙烯、粘合固定层、乙烯乙烯醇、聚偏二氯乙烯或其它合成聚合物共挤出形成的多层膜。所述单层膜还可层压至其它薄膜或基材上。
所述聚合物组合物可使用常规设备制成薄膜,所述薄膜包括流延和双轴取向薄膜。涉及的步骤典型地为:制备聚合物的干混物,熔融共混聚合物,挤出所述聚合物以形成粒料(包括其它形状如薄片等),再熔化该颗粒,通过模头挤出所述粒料,并可在约180℃-约260℃范围下的温度实施。本发明的聚合物组合物在物理性质方面提供了优于PTT本身的新变化。
以下实施例基于解释而非限制本发明的目的提供。除非另外说明,否则所有份数、百分数等均基于重量。
实施例
材料
使用的PTT为SORONA明亮聚(对苯二甲酸丙二醇酯)(E.I.du Pontde Nemours and Company,Wilmington,DE),具有1.02dl/g的特性粘度。
使用的PLA为由Cargill,Inc.,Minetonka,MN获得的PLAPolymer4040D聚(乳酸)。
试验方法1.特性粘度测量
PTT和PAHA特性粘度(IV)采用以Viscotek Forced Flow ViscometerY900(Viscotek Corporation,Houston,TX)在19℃下以0.4克/dL浓度,对于溶解在50/50重量%三氟醋酸/二氯甲烷中的聚合物,按照基于ASTM D 5225-92自动方法测量的粘度确定。将测量的PTT IV值与在60/40wt%苯酚/1,1,2,2-四氯乙烷中根据ASTM D4603-96手工测量的IV值相关联。参见US5840957。
试验方法2.物理性质测量
所述薄膜的物理性质采用试样使用Instron Corp.的1125型拉伸试验仪(Instron Corp.,Norwood MA)测量。
所述拉伸性质根据ASTM D-638测量。
实施例1-3和对比例A
薄膜通过挤出本发明的聚合物和PTT对比聚合物制备。
PTT在空气烘箱中于120℃干燥16时。PLA聚合物4040d在80℃下干燥16小时。
PTT和PLA聚合物共混物在28mm双螺杆挤出机中于249℃下制备。薄膜通过标准模头挤出,并通过经过水冷辊骤冷,冷却至室温并缠绕。制备各种厚度的薄膜,4密耳厚薄膜的数据示于下表1中。每个数据点均为10个独立试样的平均值。
表1-PTT/PLA薄膜性质
XD=横向
MD=加工方向(纵向)
样品的模量(横向和加工方向)随着PLA含量的增加而增加。横向应力同样随着向PTT中加入PLA而获得改善。
由于与PTT相比PLA通常具有明显较差的强度性质如模量,因此这些变化是特别出乎预料的。
已经基于解释和说明的目的提供本发明实施方式的上述公开。其不是穷举性的,或不应将本发明限制为该精确的公开形式。根据本公开,本文所述实施方式的多种变型和改进对于本领域普通技术人员而言将变得显而易见。
Claims (7)
1.一种包含聚合物组合物的薄膜,所述聚合物组合物包括基于该聚合物组合物重量约20-约98wt%的聚(对苯二甲酸丙二醇酯)和基于该聚合物组合物重量约80-约2wt%的聚(α-羟基酸)。
2.权利要求1的薄膜,其中所述聚(α-羟基酸)为聚乳酸。
3.权利要求2的薄膜,其中所述聚乳酸为源自生物的聚合物。
4.权利要求1的薄膜,其中所述聚(对苯二甲酸丙二醇酯)使用由采用可再生生物资源通过发酵工艺制备的1,3-丙二醇生产。
5.权利要求3的薄膜,其中所述聚(对苯二甲酸丙二醇酯)使用由采用可再生生物资源通过发酵工艺制备的1,3-丙二醇生产。
6.权利要求1的薄膜,其中所述薄膜为约0.1-约100密耳厚。
7.一种多层膜,其包括至少一个包含权利要求1-6中任意一项所述薄膜的薄膜层。
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-
2006
- 2006-11-29 US US11/605,662 patent/US7666501B2/en active Active
- 2006-12-01 AU AU2006322085A patent/AU2006322085A1/en not_active Abandoned
- 2006-12-01 CN CN200680045602.2A patent/CN101321828B/zh not_active Expired - Fee Related
- 2006-12-01 JP JP2008544395A patent/JP2009518555A/ja active Pending
- 2006-12-01 CN CN200680046132.1A patent/CN101326056A/zh active Pending
- 2006-12-01 BR BRPI0620556-9A patent/BRPI0620556A2/pt not_active IP Right Cessation
- 2006-12-01 WO PCT/US2006/046052 patent/WO2007067435A2/en active Application Filing
- 2006-12-01 KR KR1020087016128A patent/KR20080074206A/ko not_active Application Discontinuation
- 2006-12-01 CA CA002628565A patent/CA2628565A1/en not_active Abandoned
- 2006-12-01 EP EP06838813A patent/EP1957582A2/en not_active Withdrawn
-
2010
- 2010-01-06 US US12/652,756 patent/US8066923B2/en active Active
Also Published As
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US8066923B2 (en) | 2011-11-29 |
US20070128436A1 (en) | 2007-06-07 |
CN101321828A (zh) | 2008-12-10 |
CA2628565A1 (en) | 2007-06-14 |
CN101321828B (zh) | 2012-07-04 |
BRPI0620556A2 (pt) | 2011-11-16 |
EP1957582A2 (en) | 2008-08-20 |
WO2007067435A2 (en) | 2007-06-14 |
US20100105841A1 (en) | 2010-04-29 |
US7666501B2 (en) | 2010-02-23 |
AU2006322085A1 (en) | 2007-06-14 |
JP2009518555A (ja) | 2009-05-07 |
KR20080074206A (ko) | 2008-08-12 |
WO2007067435A3 (en) | 2007-08-16 |
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