CN105705577A - 加工助剂及加工助剂用母料 - Google Patents

加工助剂及加工助剂用母料 Download PDF

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CN105705577A
CN105705577A CN201580000682.9A CN201580000682A CN105705577A CN 105705577 A CN105705577 A CN 105705577A CN 201580000682 A CN201580000682 A CN 201580000682A CN 105705577 A CN105705577 A CN 105705577A
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fluoropolymer
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金秀琓
金恩敬
李大浩
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HANNANOTECH CO Ltd
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Abstract

发明涉及一种非氟化可熔融加工聚合物的加工助剂及加工助剂用母料，它包含由偏二氟乙烯和六氟丙烯的共聚物构成、直径为0.02～0.5 的含氟聚合物一次粒子聚合成粒子大小为2 ～2mm的聚合型二次粒子的含氟聚合物。本发明即使不含有界面活性剂（interfacial agent）也能缩短消除熔体破裂的时间，并且加工时的挤出负荷小而可提高生产效率。

Description

加工助剂及加工助剂用母料
技术领域
本发明涉及一种用于挤出成型非氟化（non-fluorinated）可熔融加工聚合物的加工助剂及加工助剂用母料，特别是涉及一种即使不含有界面活性剂（interfacialagent）也能缩短消除熔体破裂（Meltfracture）的时间、延迟形成口模积料（Diebuild-up）的时间，并且加工时的挤出负荷小而可提高生产效率的加工助剂及加工助剂用母料。
背景技术
加工非氟化可熔融加工热塑性聚合物时，为了提高生产效率、降低成本，需要快速挤出。但是，非氟化可熔融加工热塑性聚合物组成物有临界切变速率，当超过该速率时会引起熔体破裂而使表面变粗糙，致使无法获得优质成形产品。
为了改善上述不足，并达到更快的挤压速度，通常用含氟聚合物作为加工助剂。
韩国授权专利第1996-0000511号（1996.01.08）中公开了用于可熔融加工聚合物的含氟聚合物加工助剂。
所述含氟聚合物加工助剂虽然有助于改善可加工性，但是，消除熔体破裂所需时间较长。
据知，缩短消除熔体破裂时间的最佳方法是将含氟聚合物加工助剂均匀地分散于非氟化可熔融加工聚合物内。韩国授权专利第10-0870388号（2008.11.25）中公开了可提高在非氟化可熔融加工聚合物内分散速度的含氟聚合物加工助剂。
所述含氟聚合物加工助剂由于有界面活性剂（interfacialagent），因而可以缩短消除熔体破裂的时间，但是，由于界面活性剂的热分裂温度低而易生成碳化物，且容易发生模具沉积（Die-Deposit），从而可形成口模积料（DieBuild-up）。
现有技术，将含氟聚合物用作为氟化可熔融加工聚合物的加工助剂使用时，主要是利用界面活性剂来提高含氟聚合物加工助剂在非氟化可熔融加工聚合物内分散度。但是，通过添加界面活性剂的方法加快消除熔体破裂的同时，也可引发口模积料的形成。
[在先技术文献]
[专利文献]
（专利文献1）KR1996-0000511B11996.01.08。
（专利文献2）KR10-0870388B12008.11.25。
发明内容
本发明的目的是弥补现有技术的不足，提供一种不含界面活性剂（interfacialagent）也能缩短消除熔体破裂的时间、控制口模积料（Diebuild-up）的形成，并且加工时挤出负荷小而可提高生产效率的用于非氟化可熔融加工聚合物的加工助剂及加工助剂用母料。
本发明发现作为加工助剂的含氟聚合物是由小粒子聚合而成的聚合型粒子，而非单粒子时，即使不使用界面活性剂（interfacialagent）也能缩短消除熔体破裂的时间、控制口模积料（Diebuild-up）的形成。
为了达到上述目的本发明采用的技术方案如下：
本发明加工助剂包含由偏二氟乙烯和六氟丙烯的共聚物构成、直径为0.02～0.5?的含氟聚合物一次粒子聚合成粒子大小为2?～2mm的聚合型二次粒子的含氟聚合物。
所述含氟聚合物100重量份里还添加有1～20重量份的分配剂（partitioningagent），不包含界面活性剂。
所述分配剂（partitioningagent）可使用平均粒子尺寸为0.5?～10?的无机物粉末或平均粒子尺寸小于1mm的有机物粉末中的至少一个，所述无机物粉末为选自由滑石、硅石、碳酸钙构成的群中的至少一种，所述有机物粉末为选自由抗氧化剂、紫外线吸收剂、阻燃剂、热稳定剂、光稳定剂、金属钝化剂、强化剂、塑化剂、润滑剂、乳化剂、颜料、光学漂泊剂、抗静电剂及发泡剂构成的群中的至少一种。
本发明提供一种包含加工助剂和非氟化可熔融加工聚合物的加工助剂用母料。
所述加工助剂用母料包含0.5～20重量百分比的所述加工助剂和80～99.5重量百分比的非氟化可熔融加工聚合物。
本发明加工助剂的有益效果是：即使不含有界面活性剂（interfacialagent），也能在挤出加工非氟化可熔融加工聚合物时缩短消除熔体破裂的时间、延迟口模积料时间，并且，因加工时挤出负荷小而可提高生产效率。本发明含氟聚合物加工助剂特别适用于可熔融加工聚烯烃的挤出。
附图说明
图1是通过本发明的实施例1制造的含氟聚合物二次粒子的光学显微镜照片。
图2是通过本发明的实施例2制造的含氟聚合物二次粒子光学显微境照片图。
图3是3M公司的加工助剂DynamarTMFX-9613的光学显微镜照片图。
图4是Daikin公司的加工助剂DA-810X的光学显微镜照片图。
图5是实施例1、比较例1及比较例5的消除熔体破裂时间照片图。
图6是实施例4及比较例5的口模积料形成时间照片图。
具体实施方式
下面对本发明进行详细说明。
众所周知，非氟化可熔融加工聚合物组成物挤出成型时，在挤出机内以熔融（melt）状态受到剪切力（shear），使含氟加工助剂与模面（Diesurface）接触而形成润滑层（lubricantlayer），从而消除非氟化聚合物的熔体破裂。
加工助剂有助于提高非氟化可熔融加工聚合物组成物的加工性能。当加工助剂内含有界面活性剂（interfacialagent）时，可以缩短消除熔体破裂的时间，但是，由于热分解温度低而易生成碳化物，而且容易发生模具沉积（Die-Deposit），从而会形成口模积料（DieBuild-up）。
而当加工助剂组成物里不含有界面活性剂（interfacialagent）时，可以延迟形成口模积料（DieBuild-up）的时间，但是，消除熔体破裂的时间较长。
本发明的特点是，即使加工助剂内不含有界面活性剂（interfacialagent）也能缩短消除熔体破裂的时间、控制口模积料的形成，而且，加工时挤出负荷小。
本发明的加工助剂包括将直径为0.02?～0.5?的含氟聚合物一次粒子聚集成粒子大小为2?～2mm的聚合型二次粒子的含氟聚合物。
包含于现有加工助剂里的含氟聚合物是由直径小于2mm的单粒子构成的，因此，挤出时含氟聚合物分散，经过较长时间之后才能与模具表面接触并形成润滑层。
然而，本发明的加工助剂将直径为0.02?～0.5?的含氟聚合物一次粒子聚合成粒子大小为2?～2mm的聚合型二次粒子，挤出时，构成聚合型二次粒子的一次粒子易于分离，可快速与硬模表面接触而形成润滑层。
进行共重合而形成适当的含氟聚合物的含氟单体包括含氟乙烯叉、六氟丙烯、氯三氟乙烯及全氟烷基乙烯基醚。可使用的含氟聚合物包括含氟乙烯叉、六氟丙烯、氯三氟乙烯、1-五氟丙烯及2-五氟丙烯、或者1-五氟丙烯或2-五氟丙烯的共聚物，但不局限于此。
本发明的加工助剂还可以包括分配剂（partitioningagent），所述分配剂（partitioningagent）用于防止含氟聚合物粒子相互粘连。所述分配剂（partitioningagent）也被称为抗粘连剂（antiblockingagent）。在100重量份的所述含氟聚合物里可添加1～20重量份的所述分配剂（partitioningagent）。所述分配剂（partitioningagent）可选用由滑石、硅石及碳酸钙构成的群中的至少一种，但不局限于此。所述分配剂（partitioningagent）最好是平均粒子尺寸为大于0.5?，小于10?的粉末。
本发明的加工助剂除了所述分配剂（partitioningagent）外，还可以包括抗氧化剂、紫外线吸收剂、阻燃剂、热稳定剂、光稳定剂、金属钝化剂、强化剂、塑化剂、润滑剂、乳化剂、颜料、光学漂白剂、抗静电剂、发泡剂等添加剂。
本发明中，分配剂（partitioningagent）不但可以使用滑石、硅石、碳酸钙等无机物粉末，而且还可以使用平均粒子尺寸小于1mm的有机物粉末。所述有机物粉末可选用抗氧化剂、紫外线吸收剂、阻燃剂、热稳定剂、光稳定剂、金属钝化剂、强化剂、塑化剂、润滑剂、乳化剂、颜料、光学漂泊剂、抗静电剂及发泡剂构成的群中的至少一种。
本发明还提供加工助剂用母料。
本发明的加工助剂用母料包括所述加工助剂和含氟可熔融加工聚合物，特别适合用作烯烃系列聚合物树脂成型时的加工助剂。
本发明加工助剂用母料是所述加工助剂均匀分散于烯烃系列聚合物而形成的，烯烃系列聚合物树脂挤压成型时添加母料，以提高挤压扭矩或挤压压力低下等成型加工性能。
所述烯烃系列聚合物优选烯烃基单体的均聚物或烯烃基单体及α烯烃共单体的共聚物。
所述烯烃基单体有乙烯、丙烯、丁烯、戊烯、己烯、辛烯、癸烯、十二烯、十四烯、十六烯、十八烯、二十烯等，但不局限于此。
用于共聚反应的共单体可使用碳数大于4的α-烯烃。碳数大于4的α-烯烃有1-丁烯、1-戊烯、1-己烯、4-甲基-1-戊烯、1-辛烯、1-癸烯、1-十二烯、1-十四烯、1-十六烯、1-十八烯或1-二十烯等，但不局限于此。其中，优选碳数为4～10的α-烯烃，但也可以由一种或多种α-烯烃作为共单体使用。
所述烯烃基聚合物最好是聚乙烯。
本发明加工助剂用母料可为粉末状、颗粒状、丸状等，但优选熔融混炼而成的丸状。
本发明加工助剂用母料最好包括0.5～20重量百分比所述加工助剂和80～99.5重量百分比非氟化可熔融加工聚合物。
本发明的加工助剂用母料可在所述加工助剂及所述非氟化可熔融加工聚合物的基础上根据需要添加其他成分混合而成。对所述其他成分没有特别的限制，可以是上述的添加剂。
本发明的加工助剂用母料可在120～200℃温度下将所述加工助剂和所述非氟化可熔融加工聚合物混炼而成。
下面通过实施例对本发明的构成及效果做进一步详细的说明。实施例只用于说明本发明，但本发明不局限于下述实施例。
[实施例1]
加工助剂是由偏二氟乙烯和六氟丙烯的共聚物构成、直径为0.02～0.5?的含氟聚合物一次粒子聚合而形成粒子尺寸小于1mm的聚合型二次粒子的90重量百分比的含氟聚合物和10重量百分比的分配剂（partitioningagent）混合而制成。所述分配剂使用滑石（KOCH公司KC5000）。所述含氟聚合物二次粒子的光显微镜照片如图1所示。
[实施例2]
加工助剂是由偏二氟乙烯和六氟丙烯的共聚物构成、直径为0.02～0.5?的含氟聚合物一次粒子聚合而形成粒子尺寸小于2mm的聚合型二次粒子的90重量百分比的含氟聚合物及10重量百分比的分配剂（partitioningagent）干混而制成。所述分配剂使用滑石（KOCH公司KC5000）。所述含氟聚合物二次粒子的光显微镜照片如图2所示。
[实施例3]
加工助剂是由偏二氟乙烯和六氟丙烯的共聚物构成、直径为0.02～0.5?的含氟聚合物一次粒子聚合而形成粒子尺寸小于1mm的聚合型二次粒子的97重量百分比的含氟聚合物及3重量百分比的分配剂（partitioningagent）干混而制成。所述分配剂使用滑石（KOCH公司KC5000）。
[实施例4]
加工助剂是由聚偏二氟乙烯和六氟丙烯的共聚物构成、直径为0.02～0.5?的含氟聚合物一次粒子聚合而形成粒子大小小于2mm的聚合型二次粒子的97重量百分比的含氟聚合物及3重量百分比的分配剂（partitioningagent）干混而制成。所述分配剂使用滑石（KOCH公司KC5000）。
[比较例1]
准备好3M公司的加工助剂DynamarTMFX-9613（90重量百分比的含氟聚合物及10重量百分比的分配剂）。3M公司的DynamarTMFX-9613的光显微镜照片如图3所示。3M公司的加工助剂DynamarTMFX-9613为单粒子，粒子尺寸小于1mm。
[比较例2]
准备好Daikin公司的加工助剂DA-810X（97重量百分比的含氟聚合物及3重量百分比的分配剂）。Daikin公司的DA-810X的光显微镜照片如图4所示。3Daikin公司的加工助剂DA-810X为单粒子，粒子尺寸小于2mm。
[比较例3]
准备好ShinePolymerTechnology公司的加工助剂3511N。所述ShinePolymerTechnology公司的加工助剂3511N包括50重量百分比的含氟聚合物和50重量百分比的界面活性剂（interfacialagent）。ShinePolymerTechnology公司的加工助剂3511N为单粒子，粒子尺寸小于2mm。
[实验例1]
按照表1所示的量，将所述实施例1至实施例4及比较例1至比较例3中的加工助剂和茂金属线型低密度聚乙烯（大林产业，mLLDPEXP9000，熔融指数0.6g/10分，密度0.935g/?）进行干混后，利用布拉本德仪器公司（BrabenderInstrument）的转矩流变仪（Plasti-Corder,长度/直径＝32/1）在170℃、200℃、200℃的温度下以60rpm熔融混合，然后在水箱里冷却挤出线料(extrudedstrand)形成丸粒。
在布拉本德仪器公司的单螺杆挤出机PlastographECPlus（长度/直径=32/1）上设置长度为80mm、直径为1.5mm的模具后，在气缸温度170℃、230℃、230℃，模具温度230℃下，以150rpm螺旋旋转数挤出所述每个丸粒，然后观察消除熔体破裂的时间和口模积料形成时间，并将模具压力记录在表1中。
测定熔体破裂消失时间时，把所述丸粒放入料斗的时间点设定为0，然后通过肉眼及触摸方式测定熔体破裂现象消失、成品的整个表面变平滑的时间。。
实施例1、比较例1及比较例5的熔体破裂现象消失的时间如图5所示，实施例4及比较例5的口模积料形成时间如图6所示。
表1
如表1及图5所示，实施例1至实施例4中的加工助剂与比较例1、比较例2的加工助剂相比可大幅缩短消除熔体破裂的时间，而且模具压力小。
并且，实施例1至实施例4的加工助剂与包含有界面活性剂（interfacialagent）的比较例3相比，消除熔体破裂的时间缩短。
如表1及图6所示，实施例1至实施例4的加工助剂在60分内未形成口模积料，而比较例3的加工助剂由于包含有界面活性剂（interfacialagent）而不到30分便形成口模积料。
由此表明，本发明的加工助剂虽然不包含界面活性剂（interfacialagent），但也能缩短消除熔体破裂的时间，并且，加工时挤出负荷小、可提高生产效率。
将图1、图2所示的本发明光显微镜照片与图3、图4所示的目前市场上销售的光显微镜照片进行比较，其结果如下。
如图1、图2光显微镜照片所示，本发明的含氟聚合物粒子是由小的一次粒子聚合而成的聚合型二次粒子。本发明的加工助剂是将所述聚合型二次粒子和分配剂干混而制成的。采用干混方法，无需施加热、压力等外部作用，因此，不会使所述聚合型二次粒子变形，从而可使本发明的加工助剂始终保持图1及图2所示的最初形态。
另外，如图3及图4的光显微镜照片所示，市场销售的加工助剂为单粒子。

Claims (5)

1.一种加工助剂，其特征在于：包含由偏二氟乙烯和六氟丙烯的共聚物构成、直径为0.02～0.5?的含氟聚合物一次粒子聚合成粒子大小为2?～2mm的聚合型二次粒子的含氟聚合物。
2.根据权利要求1所述的加工助剂，其特征在于：所述含氟聚合物100重量份里还添加有1～20重量份的分配剂，不包含界面活性剂。
3.根据权利要求2所述的加工助剂，其特征在于：所述分配剂可使用平均粒子尺寸为0.5?～10?的无机物粉末或平均粒子尺寸小于1mm的有机物粉末中的至少一个，所述无机物粉末为选自由滑石、硅石、碳酸钙构成的群中的至少一种，所述有机物粉末为选自由抗氧化剂、紫外线吸收剂、阻燃剂、热稳定剂、光稳定剂、金属钝化剂、强化剂、塑化剂、润滑剂、乳化剂、颜料、光学漂泊剂、抗静电剂及发泡剂构成的群中的至少一种。
4.包含权利要求1所述的加工助剂和非氟化可熔融加工聚合物的加工助剂用母料。
5.根据权利要求4所述的加工助剂用母料，其特征在于：包含0.5～20重量百分比的所述加工助剂和80～99.5重量百分比的非氟化可熔融加工聚合物。
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