CN102143991B - 软质丸粒化的聚氯乙烯增塑溶胶 - Google Patents

软质丸粒化的聚氯乙烯增塑溶胶 Download PDF

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CN102143991B
CN102143991B CN200980135106XA CN200980135106A CN102143991B CN 102143991 B CN102143991 B CN 102143991B CN 200980135106X A CN200980135106X A CN 200980135106XA CN 200980135106 A CN200980135106 A CN 200980135106A CN 102143991 B CN102143991 B CN 102143991B
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S·D·霍顿
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Abstract

本发明提供了一种肖氏A硬度低于约70的软质可丸粒化的聚氯乙烯增塑溶胶。在本增塑溶胶中使用的增塑剂可以为石油基增塑剂或生物基增塑剂或两者共用。一种在搅拌室中进行的凝胶化、熔融、控温冷却的方法使得常规的液态增塑溶胶转化为可丸粒化的增塑溶胶条料。若在冷却为条料或其他形状之后使用造粒机，就可得到丸粒化的增塑溶胶。这种转化不影响液态增塑溶胶制剂的硬度。固化增塑溶胶可以储存用于以后挤出或塑造为最终产品的形状。

Description

软质丸粒化的聚氯乙烯增塑溶胶
优先权声明
本申请要求2008年9月10日提交的律师案卷号为12008020的美国临时专利申请第61/095,699号的优选权，该文件通过引用结合在本申请之中。
发明领域
本发明涉及一类软质但坚固程度足以制成丸粒形式的增塑溶胶。
发明背景
工业和商业产品经常由聚氯乙烯化合物(PVC)制得，在形态上或为未熔融的PVC粘性液体(例如增塑溶胶)或为挠性PVC固体(例如丸粒、颗粒或立方体)。
根据肖氏A硬度量表，肖氏A硬度低于约70的挠性PVC固体非常难于制备。未熔融的PVC增塑溶胶因为是液体，除非其被熔融，否则不具有有效硬度。
发明内容
技术需要的是一种用于制造肖氏A硬度低于约70，优选低于约50，更优选约10-50范围内的任意硬度，甚至更优选约20-45范围内任意硬度的挠性PVC固体丸粒的方法。
技术也需要一种可丸粒化的增塑溶胶，基于增塑溶胶的固体形式，促进后续塑造或挤出的效率。
本发明通过控制增塑溶胶在搅拌室(例如挤出机)中的熔融搅拌解决了这两项问题，利用这一方式，得到了一种可丸粒化的增塑溶胶。
为本发明起见，“可丸粒化的增塑溶胶”指一种液体增塑溶胶，其已在具备条件允许凝胶化、熔融和冷却按顺序进行的搅拌室中经过了一次加热过程，使得增塑溶胶固化，需要时用于以后丸粒化。之后丸粒化的固化增塑溶胶就成为了“丸粒化的增塑溶胶”。
可丸粒化的增塑溶胶具有常规商业增塑溶胶的所有初始属性，并得到了凝胶化的、熔融增塑溶胶，后者经过之后的塑造或挤出可以形成最终的塑料制品。丸粒化的增塑溶胶也是如此。本发明两种中间产品的差异在于它们的操作形态，分别为条状与丸粒状。丸粒状为优选项，但条状也有其使用价值。
本发明中的方法不是化学反应，而是从增塑剂中的颗粒状PVC向增塑剂与可丸粒化形状的PVC颗粒形成的熔融固体溶液的物理转化。
作为转化过程的一项功能，增塑溶胶保持其非常低的硬度，落于上文所述的肖氏A硬度范围。如果初始液态增塑溶胶熔融后在塑造或挤出加工生产时被中断，则本发明中的方法提供了一种暂停生产加工的方法，这样常规增塑溶胶在其向最终制品的转化过程中仅完成了一半。
由于条料或丸粒的固体属性，硬度又非常软，因而可丸粒化的和丸粒化的增塑溶胶就成为具有巨大和通用价值的中间产品，成为可以在某一时刻制备，储存一段时间，之后用于完成最终产品生产的库存物品。
固体的储存、运输和利用通常比液体的储存、运输和利用具有优势。对于使用挠性PVC化合物的场合，尤其是那些需要肖氏A硬度低于70或甚至50的场合，通过本发明中的方法制备的可丸粒化和丸粒化的增塑溶胶对于塑料塑造或挤出操作技术人员而言是出乎意料的新的初始物质。由于固体的操作属性，增塑溶胶为这些人员提供了操作效率。
本发明一方面是一种包含聚氯乙烯的肖氏A硬度低于约70的可丸粒化的增塑溶胶。
本发明另一方面是一种制备可丸粒化的增塑溶胶的方法，包括以下步骤：(a)将液体增塑溶胶引入加热的搅拌室中；(b)使增塑溶胶凝胶化；(c)使增塑溶胶熔融；(d)在搅拌室中冷却增塑溶胶至足以使其形成固化的可丸粒化增塑溶胶的条料。优选地，该方法包括步骤(e)在搅拌室外冷却该固化条料，及(f)将固态条料分割成更小的部分来制备丸粒化的增塑溶胶，任选地，使用水槽，随后施以转刀条料造粒机。或者，也可以使用水下造粒机替代水槽和条料造粒机。
本发明另一方面在于由可丸粒化的增塑溶胶经过上述步骤(e)和(f)制成的丸粒化增塑溶胶。
本发明的特征及优点将在以下制图相关的各种实施方式中予以说明。
制图的简要描述
图1为用于将液态增塑溶胶转化为可丸粒化的增塑溶胶的典型搅拌室的侧视图。
本发明的实施方式
搅拌室
图1展示了一种典型的搅拌室10，其具有进料口20，加热部分30和出料口40。虽然搅拌室10看起来非常像挤出机，其实，任何分批或连续熔融搅拌设备只要能够按照特定的顺序安排温度变化均可以用于本发明。
优选使用挤出机因为其在操作上是连续的，且其在部分30内的加热区可以按照本发明方法的要求进行控制。该挤出机可以是具有常规长径比的单螺杆挤出机、同向双螺杆挤出机或异向双螺杆挤出机。
在搅拌室10中，加热部分30在进料口20和出料口40之间分为不同的四段，分别为I、G、F和C。
I段为邻近进料口20的导入区，其中液态增塑溶胶可以开始被加热和搅拌。
G段为邻近I段的凝胶化区域，其中液态增塑溶胶进行凝胶化。
F段为邻近G段的熔融区，其中凝胶化的增塑溶胶在足够的剪切作用下熔融从而产生均聚物熔体。应当注意的是，在某些配方中熔融过程在凝胶化过程之后发生的如此迅速以致无从判断凝胶区G段何处终止熔融区G段何处开始。但无论段G和段F的长度及可能的重叠，在大分子水平聚合物的凝胶化先于熔融是毋庸置疑的。
C段为邻近F段的冷却区，其中熔融的增塑溶胶开始冷却，优选在控制速度下，从其熔融温度降至足以使熔融增塑溶胶变为半固态从而通过出料口40出口产生条料的温度。
出料口40可以是单拉丝模头、多拉丝模头或任何从搅拌室形成塑料产品轮廓形状的其他常规出料口。
在考虑对挤出机的适应性时，本发明中的方法按顺序采用了段I、G、F和C，由于出人意料地已经发现可能在冷却之前使液体增塑溶胶发生凝胶化和熔融，优选在加热区30其余部分使用受控形式。C段的目的在于充分降低熔融增塑溶胶的温度至使其固化足以从出料口40以条状固体增塑溶胶挤出，该条料随后可被分为更小的部分，例如当出料模头轮廓为圆形时条料被分为丸粒状。
表1显示了加热区30中各段，包括出料口40，所占百分比的范围以及各段适宜温度和优选温的度范围。
Figure BPA00001328924300041
在增塑溶胶转化过程中，为提供随时间引入其中的稳定能量，I、G和F各段的温度可以相同或相似。因此，所加的能量总量可以从这三段的温度、搅拌及驻留时间计算出来。
段C优选分为不同的分区，其中温度从如表1所示的C起始温度向C终端温度降低。根据加热区30用于冷却步骤的长度，温度的降低可以近似为渐近式，也可控制为依照直线或非线性速率曲线。由于冷却步骤对于出现可条状化的半固体非常关键，因而从段C起点至段C终端温度降低优选采用斜率轻微弯曲的形式。
摇动或搅拌或其他机械作用可以在加热区30中的各段进行。如果在混合器或挤出机中，叶轮或螺杆可以约25-500rpm的速度旋转，优选为约75-250rpm。
固化增塑溶胶条料随后可以用空气冷却或水冷。空气冷却依赖于环境温度，而水冷可以进行温度控制。因此，后者为优选项。
图1也显示了固化后的增塑溶胶条料放入其中的水槽50和在适当冷却和固化后用于将可丸粒化的增塑溶胶条料转为丸粒的造粒机60。
作为选择，也可以使用水下造粒机，其安装在搅拌室的末端，这样可丸粒化的条料在从模头挤出后同时被进一步冷却并进行切割。这一替代方案减少了产生可丸粒化的增塑溶胶中间产物的可能，有利于丸粒化的增塑溶胶中间产物。
应当注意，出料口40的轮廓将产生条料截面的几何形状，其后续任选的切割操作得到的形状可以是圆柱、立方体、星型棒或其他固体几何形状。在本发明中，所有可能的形状均计为“丸粒状”。
任选水槽50的温度可以是约1℃-27℃，优选为约4℃-10℃，以确保造粒机60制得轮廓鲜明的移动条料，已充分固化但足够软，形成各个丸粒。
最后，任选地，但优选在进料口20的上游提供一个计量装置70，用于控制进入搅拌室10的液态增塑溶胶的量。该计测装置可以简单如阀控制的重力进料储器，亦可复杂如蠕动泵。此外，如果使用任选的计量装置，进入室10的进料速度近似等于造粒机60的造粒速度是有益的。由于即使完全变为固体，增塑溶胶也非常软，因而会在从出料口40涌出的条化半固体中产生线性张力，这一点在建立线速度和生产效率时必须予以考虑。
增塑溶胶
任何现有的增塑溶胶及任何未来开发的液态增塑溶胶均有望用于本发明。
聚合物处理技术与乙烯基增塑溶胶非常相似。这些增塑溶胶是由分散级、微悬浮级和乳剂级聚氯乙烯(PVC)树脂(均聚物和共聚物)和增塑剂形成的。示范性的分散级PVC可参见美国专利4,581,413、4,693,800、4,939,212及5,290,890，以及诸如以上四项专利所引用的参考文献等等。
在从乙烯基树脂制备流体增塑溶胶过程中所用的主要液态增塑剂为诸如邻苯二甲酸、磷酸、己二酸、癸二酸、柠檬酸、不饱和脂肪酸等各种酸的有机酯。其中，邻苯二甲酸酯是最经常使用的氯乙烯树脂的主要增塑剂。含有中等长度烷基(例如约6-12个碳原子长度)的邻苯二甲酸二烷酯在每100份喷雾干燥氯乙烯树脂粉末中使用约60-300重量份时实现了增塑溶胶性质的充分均衡。具体的用作液态增塑剂的例子包括：邻苯二甲酸二辛酯(DOP)、邻苯二甲酸丁苄酯(BBP)、己二酸二辛酯、癸二酸二丁酯、邻苯二甲酸二异壬酯(DINP)、氢化邻苯二甲酸二异壬酯(DINCH)、氢化邻苯二甲酸二(2-乙基己基)酯、硬脂酸甘油酯及其组合物。
不饱和脂肪酸的有机酯为邻苯二甲酸酯增塑剂的优良替代物，因其是从生物可再生资源制备得到的。美国专利6,797,753(Benecke等)通过在此处的引用构成本发明的一部分，揭示了增塑聚氯乙烯聚合物，其所用的增塑剂含有从植物油衍生而来的脂肪酸，该脂肪酸与醇(单羟基醇或多元醇)基本上完全酯化，具有不饱和键的脂肪酸基本上完全环氧化，并且其中的脂肪酸基本上随机加到醇的一个或多个羟基位。增塑剂的加入量为PVC树脂的约10-230phr。这些在Benecke等揭示的从植物油衍生得到的“环氧豆油酯类”增塑剂，例如环氧季戊四醇四豆油酸酯、环氧丙二醇二豆油酸酯、环氧乙二醇二豆油酸酯、环氧豆油酸甲酯及环氧蔗糖八豆油酸酯，属于一组常被称为“生物增塑剂”的增塑剂并且非常适合在本发明中使用。
普立万公司(PolyOne)(www.polyone.com)是日常消费市场上液态PVC增塑溶胶的一个商业来源。这些PVC树脂在增塑液中的分散体通过加入热或光稳定剂、着色剂(color pigment)、阻燃剂、起泡剂及目标产品所需要的其他添加剂而得到了增强。
优选的市场上可得到的PVC增塑溶胶包括由GeonTM 121A分散级PVC制成的GeonTM B 2536 Flesh和MB 2536A增塑溶胶。
任选的添加剂
在热塑性塑料工业中通常使用的大量成分也可以包含在本发明的产品之中。这些任选的添加剂的非限定性的例子包括：爽滑剂、防粘连剂、抗氧化剂、紫外光稳定剂、淬火剂、增塑剂、脱模剂、润滑剂、抗静电剂、滞火剂(fire retardants)及诸如玻璃纤维、滑石、白垩或粘土等填料，以及它们的组合。这些任选的添加剂在本发明混合物中的存在量为约0-150phr，优选为约0-100phr(每100份PVC树脂含添加剂的份数)。
任何可用于涂层和颜料常规着色剂也可以接受用于本发明。可以使用常规着色剂，包括如二氧化钛、氧化铁、氧化铬、铬酸铅、炭黑、二氧化硅、滑石、陶土、金属氧化物、硅酸盐、铬酸盐等无机颜料和如酞菁蓝、酞菁绿、咔唑紫、蒽嘧啶黄、阴丹士林黄、异吲哚啉黄、蒽醌蓝、喹吖啶酮紫、苝红、叠氮红及其他有机颜料。着色剂的数量从不添加至每100份PVC树脂中加入约5份，优选为约0-3份。
储存
可丸粒化的增塑溶胶，尤其是那些已丸粒化的，可以用与任何其他固体热塑性成分相同或相似的方式储存用于以后塑造或挤出为最终塑料制品的形状。
意外地，储存的本发明产品具有作为其来源的液态增塑溶胶的性质，呈现出固态PVC、非常软质化合物。换言之，先前不能得到的低肖氏A硬度的PVC固体被制造了出来。
本发明的用途
储存的可丸粒化的增塑溶胶条料或丸粒化的增塑溶胶丸粒可以随后用于现有的适用于PVC化合物的各种类型的塑造或挤出操作，仅受到制模机和挤出机操作人员想象力的限制。
后续的挤出或制模技术对于热塑性聚合物加工领域内的专业人员是众所周知的。为此，不使用过多试验而是引用如《挤出：最终处理指南和手册》(Extrusion，The Definitive Processing Guide and Handbook)、《成型零件收缩和翘曲手册》(Handbook of Molded Part Shrinkage and Warpage)、《专门成型技术》(Specialized Molding Techniques)、《滚塑成型技术》(RotationalMolding Technology)和《模具，工具和模具修复焊接手册》(Handbook of Mold，Tool and Die Repair Welding)等文献，所有文献均为塑料设计图书馆(www.williamandrew.com)出版，可以使用本发明的化合物制成任何可以想象到的形状和外观的物品。
本发明的增塑溶胶可以证明用作最终用途汽车，FDA、UL、ASTM、NSF、USDA、军事、医疗或消费特定用途。
进一步的实施方式描述于以下示例之中。
示例
表2显示了市场上可从普立万公司购得的两种液态增塑溶胶产品：MB2536 Flesh和MB 2536A Flesh的熔融搅拌条件，在具有9个加热区及1个加热条料模头出料口的Leistritz 27mm双螺杆挤出机中形成可丸粒化的增塑溶胶条粒，经与水槽相连，并在之后立即通过一台Conair品牌304型旋刀条料造粒机形成丸粒化的增塑溶胶。一个阀控制的重力进料储器用作计量进样器。MB 2536 Flesh液态增塑溶胶用于制成肖氏A硬度约为40的商业化熔融成型固体。MB2536A Flesh液态增塑溶胶用于制成肖氏A硬度约为30的商业化的熔融成型固体。形成约0.5cm长×0.4cm直径的丸粒。
Figure BPA00001328924300081
可丸粒化的增塑溶胶通过模头以条状进入水槽。丸粒化的增塑溶胶使用造粒机在上述速度下由条料制成，该速度非常接近挤出机进样口计量速度为25镑/hr(11.3kg/hr)时可丸粒化的增塑溶胶条料的出料速度。
两种增塑溶胶成功丸造化的关键在于，进入挤出机的增塑溶胶的仔细计量，控制构成段I、G、F和C的各区的加热过程，水槽的低温及与计量速度密切匹配的造粒速度，所有的操作均在螺杆速度约为150rpm转速下进行。
通过比较，先前使用螺杆速度为300rpm的试验，基于多个原因，不能产生可接受的可丸粒化的增塑溶胶。300rpm的螺杆速度过快；不使用用于冷却的段C——段F的温度一直保持至模头；计量速度与造粒速度失配导致在条料上产生内部张力。结果完全不可用，并且在多分钟内不能实现稳态、连续生产。
本发明不限于以上实施方式。

Claims (13)

1.一种包含聚氯乙烯和增塑剂的可丸粒化的增塑溶胶，所述增塑溶胶的肖氏A硬度为10-50，所述增塑溶胶通过包括以下步骤的方法制得：
（a）将液态增塑溶胶引入加热的搅拌室中；
（b）使增塑溶胶凝胶化；
（c）在剪切作用下使增塑溶胶熔融；并
（d）在搅拌室中冷却增塑溶胶至足够使其形成固化的可丸粒化的增塑溶胶条料，
其中所述增塑剂为邻苯二甲酸、磷酸、己二酸、癸二酸、柠檬酸、不饱和脂肪酸的有机酯或它们的组合，所述增塑剂的存在量以重量计为每100份聚氯乙烯树脂对应含有30-300份。
2.如权利要求1所述的增塑溶胶，其特征在于，所述增塑溶胶被分为丸粒状。
3.如权利要求1或2所述的增塑溶胶，其特征在于，所述聚氯乙烯为均聚物或共聚物树脂。
4.如权利要求1或2所述的增塑溶胶，其特征在于，所述增塑剂选自：邻苯二甲酸二辛酯、邻苯二甲酸丁苄酯、己二酸二辛酯、癸二酸二丁酯、邻苯二甲酸二壬酯、氢化邻苯二甲酸二异壬酯、氢化邻苯二甲酸二(2-乙基已基)酯、硬脂酸甘油酯类、环氧化豆油酯类及其组合。
5.如权利要求1或2所述的增塑溶胶，其特征在于，所述增塑溶胶为聚氯乙烯化合物，还包含爽滑剂、抗粘连剂、抗氧化剂、光稳定剂、热稳定剂、阻燃剂、发泡剂、著色剂、淬火剂、辅助增塑剂、脱模剂、润滑剂、抗静电剂、滞燃剂、填料及其组合。
6.一种制造可丸粒化的增塑溶胶的方法，包括以下步骤：
（a）将液态增塑溶胶引入加热的搅拌室中；
（b）使增塑溶胶凝胶化；
（c）在剪切作用下使增塑溶胶熔融；并
（d）在搅拌室中冷却增塑溶胶至足够使其形成固化的可丸粒化的增塑溶胶条料。
7.如权利要求6所述的方法，其特征在于，所述搅拌室为挤出机。
8.如权利要求6或7所述的方法，还包括以下步骤：
（e）在搅拌室外冷却固化的条料；并
（f）将固态条料分割为更小的部分，用于制造丸粒化的增塑溶胶。
9.如权利要求8所述的方法，其特征在于，所述冷却步骤在水槽中完成，所述分割步骤由造粒机完成。
10.如权利要求9所述的方法，其特征在于，所述造粒机为水下造粒机。
11.一种由如权利要求7-10中任一项所述方法制得的丸粒化的增塑溶胶。
12.如权利要求11所述的丸粒化的增塑溶胶，其特征在于，其肖氏A硬度为10-50。
13.一种由权利要求1或权利要求14所述的增塑溶胶塑造或挤出的塑料制品。
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BRPI0918422A2 (pt) 2015-11-24
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