CN117285780A - 一种耐高温热灌装瓶用聚丙烯树脂组合物及其制备方法 - Google Patents
一种耐高温热灌装瓶用聚丙烯树脂组合物及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种耐高温热灌装瓶用聚丙烯树脂组合物及其制备方法，该耐高温热灌装瓶用聚丙烯树脂组合物包括：聚丙烯树脂、抗氧剂、成核剂和除酸剂；聚丙烯树脂、抗氧剂、成核剂、除酸剂的质量比为100:(0.06～0.15):(0.02～0.06):(0.02～0.10)。本发明的聚丙烯树脂组合物具有较好的刚性和耐热性，其弯曲弹性模量和热变形温度明显提高，同时又有较好的韧性和透明性，满足以注拉吹工艺生产的热罐装瓶的要求。
Description
技术领域
本发明属于聚烯烃树脂技术领域，具体涉及一种耐高温热灌装瓶用聚丙烯树脂组合物及其制备方法。
背景技术
罐装一般分为冷罐装和热罐装，常见的灌装机大多数是冷罐装，热罐装是比较特殊的罐装，罐装物料(茶、果蔬汁、运动饮料和保健饮料等)冷却后成固体或者粘稠度较高的时候选择热罐装较好。热罐装的时候，首先对物料进行瞬时超高温或短时高温杀菌，然后保持物料在80℃～90℃的温度下进行灌装，封盖后利用物料本身的温度对包装容器内壁及瓶盖进行杀菌。
聚对苯二甲酸乙二醇酯(PET)是目前市场上果汁饮料及茶饮料等产品的主要热罐装容器材料，其热变形温度一般不超过60℃，不耐高温，灭菌时使用的化学试剂也对食品的安全卫生存在威胁，因此有逐渐被安全卫生性能更高的PP塑料瓶代替的趋势。PP瓶能够承受的热罐装温度高达96℃，因此，在热罐装领域，PP瓶更具优势。
由于均聚聚丙烯(PP)制品透明性不好、韧性较差，限制了其在包装、医用、食品等领域的应用。通过丙烯与乙烯或其他α-烯烃的无规共聚，可降低聚丙烯材料的熔点和结晶度，改善其透明性和韧性等，拓宽了PP应用领域。目前应用最广的是乙丙无规共聚PP，在使用传统Z-N催化剂时，乙烯的竞聚率远高于丙烯，使得共聚物中低分子量部分的乙烯含量较高，导致产品的正己烷溶出物多，无法满足对卫生要求较高的食品和医疗用品的包装要求。丙丁无规共聚PP具有二甲苯可溶物少、正己烷溶出物少、刚韧平衡性好、透明性好等优点，在医用或食品包装领域有很好的应用前景。
中国专利CN201811246954.5公开了一种热罐装瓶用聚丙烯树脂，该热罐装瓶用聚丙烯树脂由聚丙烯树脂基料、抗氧剂、成核剂和酸中和剂经熔融混合造粒而成，得到的聚丙烯树脂具有更好的结晶能力，更高的耐热性和刚性，热变形温度达80～90℃、弯曲弹性模量达1200～1400MPa；但该技术开发的产品中，使用的助剂是有机磷酸盐类成核剂和硬脂酸钙或氢化滑石粉酸中和剂，得到的产品刚性和热变形温度值不高，不能满足加工要求条件更高的热罐装瓶料的要求。
中国专利CN201811246982.7公开了一种低析出注拉吹瓶用聚丙烯树脂，该低析出注拉吹瓶用聚丙烯树脂由聚丙烯树脂基料、抗氧剂、成核剂和酸中和剂经熔融混合造粒而成，得到的聚丙烯树脂具有较强的结晶能力，正己烷提取物减少50％以上，适合于注拉吹成型，满足热罐装瓶的食品卫生安全要求；但该技术开发的产品的效果偏重于正己烷提取物的测试，并没有考察产品作为热罐装瓶料的力学、热学和光学性能。
史建公等人发表的综述文章《二环[2.2.1]/[2.2.2]庚烷二羧酸盐成核剂研究及应用进展》，公开了二环[2.2.1]庚烷二羧酸盐和[2.2.2]庚烷二羧酸盐是一种分散型聚丙烯增强改性成核剂，可以提高聚丙烯的结晶温度和改性PP收缩的各向同性；但该技术着重介绍了有机羧酸盐成核剂本身具有的优良性能，并未将其应用到热罐装瓶用聚丙烯产品中。
发明内容
本发明的目的在于提供一种耐高温热灌装瓶用聚丙烯树脂组合物及其制备方法，该树脂组合物具有较好的刚性和耐热性，其弯曲弹性模量和热变形温度明显提高，同时又有较好的韧性和透明性，满足以注拉吹工艺生产的热罐装瓶的要求。
为达上述目的，本发明提供一种耐高温热灌装瓶用聚丙烯树脂组合物，其组成包括：聚丙烯树脂、抗氧剂、成核剂和除酸剂；聚丙烯树脂、抗氧剂、成核剂、除酸剂的质量比为100:(0.06～0.15):(0.02～0.06):(0.02～0.10)；
其中，所述聚丙烯树脂为丙烯/1-丁烯无规共聚聚丙烯；所述抗氧剂为受阻酚类抗氧剂与亚磷酸酯类抗氧剂形成的复配混合物；所述成核剂为复配成核剂，所述复配成核剂为有机羧酸盐HPN-68L与苯甲酸钠组成的混合物，有机羧酸盐HPN-68L与苯甲酸钠的质量比为1:0.5～1:4。
本发明的耐高温热灌装瓶用聚丙烯树脂组合物，所述丙烯/1-丁烯无规共聚聚丙烯中，丁烯含量为3.0～6.0wt％。
本发明的耐高温热灌装瓶用聚丙烯树脂组合物，所述丙烯/1-丁烯无规共聚聚丙烯的熔体流动速率为10～14g/10min。
本发明的耐高温热灌装瓶用聚丙烯树脂组合物，所述抗氧剂中的受阻酚类抗氧剂为1010和CA的混合物，即四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯和1,1,3-三(2-甲基-4-羟基-5-叔丁基苯基)丁烷；所述抗氧剂中的亚磷酸酯类抗氧剂为168，即三[2,4-二叔丁基苯基]亚磷酸酯。
本发明的耐高温热灌装瓶用聚丙烯树脂组合物，所述受阻酚类抗氧剂与亚磷酸酯类抗氧剂的质量比为1:0.8～1:4，其中所述受阻酚类抗氧剂中1010和CA的质量比为1:0.5～1:2。
本发明的耐高温热灌装瓶用聚丙烯树脂组合物，所述有机羧酸盐HPN-68L与苯甲酸钠的质量比优选为1:1～1:3。
本发明的耐高温热灌装瓶用聚丙烯树脂组合物，所述除酸剂为复配除酸剂，所述复配除酸剂为合成水滑石粉与氧化锌组成的混合物，合成水滑石粉与氧化锌的质量比为1:0.5～1:3。
本发明还提供一种耐高温热灌装瓶用聚丙烯树脂组合物的制备方法，该制备方法包括以下步骤：将聚丙烯树脂、抗氧剂、成核剂和除酸剂在高速混合机内高速搅拌出料，再将混料加入双螺杆挤出机造粒，得到耐高温热灌装瓶用聚丙烯树脂组合物。
相较于现有技术，本发明具有以下有益效果：
本发明的耐高温热灌装瓶用聚丙烯树脂组合物，在丙烯/1-丁烯无规共聚聚丙烯基料中加入复配成核剂有机羧酸盐HPN-68L与苯甲酸钠并调配其比例，得到的耐高温热灌装瓶用聚丙烯树脂组合物的刚性和热稳定性进一步提高，热变形温度达90～103℃、弯曲弹性模量达1500～1620MPa，本发明的耐高温热灌装瓶用聚丙烯树脂组合物热变形温度更高、弯曲弹性模量也更高，能较大程度地减少热罐装瓶产品的不良变形率。
本发明的耐高温热灌装瓶用聚丙烯树脂组合物在丙烯/1-丁烯无规共聚聚丙烯基料中加入的复配抗氧剂为受阻酚类抗氧剂与亚磷酸酯类抗氧剂形成的复配混合物；进一步地，受阻酚类抗氧剂优选为1010和CA的混合物，亚磷酸酯类抗氧剂优选为168，本发明的三元复配抗氧剂1010、CA和168，利用多元抗氧剂的协同作用，进一步增强了共聚物的耐热性能。
具体实施方式
下面通过实施例对本发明进行具体描述。有必要在此指出的是以下实施例只用于对本发明进行进一步说明，不能理解为对本发明保护范围的限制，该领域的技术熟练人员可以根据上述本发明内容对本发明作出一些非本质的改进和调整。
评价分析方法：
熔体流动速率按照GB/T 3682-2000测试；
乙烯和丁烯含量由红外光谱测得：由波数700～750cm-1处的乙烯特征峰得到乙烯含量，767cm-1处的丁烯特征峰得到丁烯含量；
拉伸屈服应力按照GB/T 1040.2-2006测试；
弯曲弹性模量按照GB/T 9341-2008测试；
简支梁缺口冲击强度(常温23℃)按照GB/T 1043.1-2008测试；
热变形温度按照GB/T 1634.1-2019测试；
雾度按照GB/T 2410-2008测试；
结晶温度由差示扫描量热仪(DSC)测得：在氮气保护下，取少量聚丙烯粒料，以10℃/min的速率升温至200℃，恒温5min，然后以10℃/min的速率冷却至室温，记录熔融和结晶曲线，得到熔点、结晶温度。
实施例1～19
实施例采用的聚丙烯树脂的特征见表1，成核剂为有机羧酸盐HPN-68L与苯甲酸钠组成的混合物，抗氧剂为受阻酚类抗氧剂四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯、1,1,3-三(2-甲基-4-羟基-5-叔丁基苯基)丁烷和亚磷酸酯类抗氧剂三[2,4-二叔丁基苯基]亚磷酸酯组成的混合物，除酸剂为合成水滑石粉与氧化锌组成的混合物。
聚丙烯树脂组合物按照下述制备方法制备得到：
将聚丙烯树脂、抗氧剂、成核剂和除酸剂按表2所示质量比，分别在高速混合机内高速搅拌3min后出料，再将各混料加入双螺杆挤出机造粒。将制取的粒料在注塑机上注射出拉伸、弯曲强度等测试的标准样条进行测试。造粒工艺条件：1段150℃，2段150℃，3段160℃，4段180℃，5段200℃，6段190℃，7段170℃，8段160℃，9段160℃，下料速度16r·min-1，螺杆转速120r·min-1，熔体温度210℃，机器电流13A。注塑加工条件：挤出温度210℃，模具温度40℃，注射压力30MPa，注射时间15s，保压压力30MPa，保压时间20s，冷却时间20s。
对比例1～6
对比例1～6采用的聚丙烯树脂的特征见表1。
聚丙烯树脂组合物按照下述制备方法制备得到：
按表2所示的物质及质量比进行添加，其他步骤同实施例1。
对比例7
对比例7采用的聚丙烯树脂组合物的特征见表1，树脂组合物中成核剂只添加有机羧酸盐类成核剂HPN-68L，其余物质及质量比见表2，其他步骤同实施例1。
对比例8
对比例8采用的聚丙烯树脂组合物的特征见表1，树脂组合物中成核剂为有机磷酸盐类成核剂2,2′-亚甲基-双(4,6-二叔丁基苯基)磷酸钠，其余物质及质量比见表2，其他步骤同实施例1。
各实施例和对比例的聚丙烯树脂组合物的物理机械性能测试结果见表3。
表1.实施例与对比例聚丙烯树脂的特征
表2.抗氧剂、成核剂和除酸剂的组成及比例
表3.实施例与对比例聚丙烯树脂组合物的性能测试结果
从表3来看，均聚聚丙烯尽管有较高的弯曲弹性模量和热变形温度，但其冲击强度较差、雾度较高；乙丙共聚聚丙烯的冲击强度虽然较高，雾度也较低，但其弯曲弹性模量和热变形温度较低。本发明在丙烯/1-丁烯无规共聚聚丙烯树脂中加入一定组成和比例的抗氧剂、成核剂、除酸剂后，其冲击强度、弯曲弹性模量和热变形温度均相对较高，雾度相对较低。结合实际加工生产中的要求，热罐装料物理性能需同时达到热变形温度＞90℃、弯曲弹性模量＞1500MPa、冲击强度＞3.6KJ/m2、雾度＜12％，才能满足大部分加工要求较高的热罐装料需求。本发明制备的聚丙烯树脂组合物能够同时满足上述要求，其综合性能优异，能够满足实际生产的需要。
从不加成核剂时聚丙烯树脂组合物的弯曲弹性模量和热变形温度来看，测试数据明显较低，因此，成核剂的选择使用在本发明中具有较大影响。本发明通过加入复配成核剂有机羧酸盐HPN-68L与苯甲酸钠并调配其质量比为1:0.5～1:4，提高了刚性、韧性、耐热性和透明性。
当然，本发明还可有其它多种实施例及其变形，在不背离本发明精神及其实质的情况下，熟悉本领域的技术人员可根据本发明作出各种相应的改变和变形，但这些相应的改变和变形都应属于本发明权利要求的保护范围。
Claims (8)
1.一种耐高温热灌装瓶用聚丙烯树脂组合物，其特征在于，包括：聚丙烯树脂、抗氧剂、成核剂和除酸剂；聚丙烯树脂、抗氧剂、成核剂、除酸剂的质量比为100:(0.06～0.15):(0.02～0.06):(0.02～0.10)；
其中，所述聚丙烯树脂为丙烯/1-丁烯无规共聚聚丙烯；所述抗氧剂为受阻酚类抗氧剂与亚磷酸酯类抗氧剂形成的复配混合物；所述成核剂为复配成核剂，所述复配成核剂为有机羧酸盐HPN-68L与苯甲酸钠组成的混合物，所述有机羧酸盐HPN-68L与苯甲酸钠的质量比为1:0.5～1:4。
2.根据权利要求1所述的聚丙烯树脂组合物，其特征在于，所述丙烯/1-丁烯无规共聚聚丙烯中，丁烯含量为3.0～6.0wt％。
3.根据权利要求1所述的聚丙烯树脂组合物，其特征在于，所述丙烯/1-丁烯无规共聚聚丙烯的熔体流动速率为10～14g/10min。
4.根据权利要求1所述的聚丙烯树脂组合物，其特征在于，所述受阻酚类抗氧剂为四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯和1,1,3-三(2-甲基-4-羟基-5-叔丁基苯基)丁烷的混合物，所述四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯和1,1,3-三(2-甲基-4-羟基-5-叔丁基苯基)丁烷的质量比为1:0.5～1:2；所述亚磷酸酯类抗氧剂为三[2,4-二叔丁基苯基]亚磷酸酯。
5.根据权利要求1所述的聚丙烯树脂组合物，其特征在于，所述受阻酚类抗氧剂与亚磷酸酯类抗氧剂的质量比为1:0.8～1:4。
6.根据权利要求1所述的聚丙烯树脂组合物，其特征在于，所述有机羧酸盐HPN-68L与苯甲酸钠的质量比为1:1～1:3。
7.根据权利要求1所述的聚丙烯树脂组合物，其特征在于，所述除酸剂为复配除酸剂，所述复配除酸剂为合成水滑石粉与氧化锌组成的混合物，所述合成水滑石粉与氧化锌的质量比为1:0.5～1:3。
8.一种权利要求1-7任一项所述的耐高温热灌装瓶用聚丙烯树脂组合物的制备方法，其特征在于，包括以下步骤：将聚丙烯树脂、抗氧剂、成核剂和除酸剂在高速混合机内高速搅拌出料，再将混料加入双螺杆挤出机造粒，得到耐高温热灌装瓶用聚丙烯树脂组合物。
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