CN111269504B - 一种用于pvc稳定剂的预分散多元醇酯及其制备方法 - Google Patents
一种用于pvc稳定剂的预分散多元醇酯及其制备方法 Download PDFInfo
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- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
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Abstract
本发明公开一种用于PVC稳定剂的预分散多元醇酯及其制备方法，该预分散多元醇酯按组分重量份计包括：多元醇酯100份，分散介质30～1000份，分散剂0～30份；所述多元醇酯为多元醇与含羧基或酸酐的化合物酯化反应制得；所述分散介质为有机酸金属皂、蜡类润滑剂、酰胺类润滑剂和/或抗氧剂；所述分散剂为阴离子表面活性剂、非离子表面活性剂或该二者的混合物。本发明制备方法为将酯化组分加入容器中进行酯化反应制得多元醇酯，然后加入分散介质和分散剂进行预分散，或者将分散介质和分散剂先入容器中，再加入酯化组分进行酯化反应制得。该多元醇酯的稳定性好、流动性强，具有良好的抗析出性和润滑性，且使用方便，在PVC中分散良好，具有良好的应用价值。
Description
技术领域
本发明涉及一种用于PVC稳定剂的预分散多元醇酯及其制备方法。
技术背景
聚氯乙烯(PVC)因其良好的性能和低廉的价格，广泛应用于制造管材、异型材、百叶窗帘、薄膜、人造革、电线电缆等等，是重要的通用塑料之一。为了避免加工过程中的热氧分解，一般需要加入稳定剂，常用的稳定剂有铅盐、镉盐、有机锡、锌基稳定剂以及有机稳定剂等。其中铅镉类因其毒性和对环境的严重影响，已被逐步淘汰；有机锡类稳定效果好，但价格高、有臭味，使用范围受到限制；有机稳定剂正在发展中，目前单独使用时效果不太好。最符合环保方向是钙锌复合稳定剂，最近几年得到了大力发展，使用范围越来越大。
钙锌复合稳定剂一般由有机酸的钙盐和锌盐及协效成分组成，加入锌盐的PVC有良好的初期色泽，但单独使用会发生突然严重分解的“锌烧”现象。为此需加入钙盐、水滑石等具备长期稳定效果的物质。多元醇类化合物能络合游离的锌离子，也能大幅度延长稳定时间。常用的多元醇有季戊四醇、双季戊四醇、三羟甲基异氰尿酸酯等，但它们与PVC相容性差，易迁移到产品表面或附着在加工设备表面，形成析出现象，影响加工过程和产品性能。将部分羟基酯化能改善相容性，当羟基含量降低或连接的碳链较长时，多元醇酯的稳定效果会下降，而用较低比例的短碳链的有机酸酯化对多元醇的稳定效果影响不大，但与PVC相容性改善不多，仍有析出现象。短碳链部分酯化之后的多元醇被破坏了结晶结构，熔点大幅下降，常温下为粘附性很强的固体或液体，不仅难包装、称量，而且在配方成分混合过程中易与其他组分结成难以分散的团块，很难被使用。因此，目前亟需合成一种稳定效果和相容性较好的多元醇酯，以用于PVC稳定剂。
发明内容
针对上述存在的问题，本发明提出一种用于PVC稳定剂的预分散多元醇酯制造方法，通过对合成的多元醇酯做预分散处理，得到一种便于使用，并与PVC相容良好的多元醇酯分散物。具体技术方案如下：
首先，本发明提供一种用于PVC稳定剂的预分散多元醇酯，该预分散多元醇酯按重量份计包括的组分如下：
多元醇酯 100份，
分散介质 30～1000份，
分散剂 0～30份；
所述多元醇酯为多元醇与含游离羧基的聚合物酯化反应制得；所述分散介质为金属有机酸皂、蜡类润滑剂、酰胺类润滑剂和/或抗氧剂；所述分散剂为阴离子表面活性剂、非离子表面活性剂或该二者的混合物。
优选的，所述多元醇为季戊四醇、双季戊四醇、三季戊四醇、甘露糖醇、葡萄糖和蔗糖中的一种或几种。
优选的，所述含羧基或酸酐的化合物为一元酸、二元酸及其酸酐或单酯中的一种或几种。
进一步优选的，所述一元酸包括C2～C18的脂肪酸，苯甲酸和丙烯酸及二元酸的单酯；所述二元酸及其酸酐包括马来酸、马来酸酐、草酸、酒石酸、丁二酸、己二酸、葵二酸、苯二酸和苯二酸酐。
优选的，所述金属有机酸皂包括钙、锌、铝、钾、钠、镁及稀土元素的C8～C30的有机酸酸皂化物；所述蜡类润滑剂包括石蜡、硬脂酸、烯烃低聚物及其氧化物；所述酰胺类润滑剂为乙撑二硬脂酰胺。
前述的用于PVC稳定剂的预分散多元醇酯的制备方法，包括步骤如下：
步骤1：合成多元醇酯：将准备的酯化组分一次性或分次加入容器中，高温条件下进行酯化反应并分出反应过程中分出产生的水分，待无水分被分出时，再进行减压蒸馏，分离出带水剂；
步骤2：预分散处理：将准备的分散介质和分散剂加入到合成的多元醇酯中，充分搅拌，使分散介质、分散剂与多元醇酯混合均匀，对多元醇酯预分散处理；
步骤3：冷却成型：将含有分散介质和分散剂的多元醇酯冷却获得蜡状颗粒产物，即为预分散多元醇酯成品。
作为优选的技术方案的，步骤1中，酯化组分包括多元醇、含游离羧基的聚合物、催化剂和带水剂；所述催化剂为为酯化反应催化剂，所述带水剂为甲苯、二甲苯或其二者的混合物；所述多元醇与含游离羧基的聚合物的加入量为：1mol多元醇，加入羧基0.2～2mol。
作为优选的技术方案的，步骤1中，所述酯化反应的温度为100～250℃，反应时间为0.1～10h；反应结束减压馏出带水剂，蒸馏压力为2～30kPa。
作为优选的技术方案的，步骤2中所述分散介质和分散剂可以先加入容器，再加入步骤1中所述的酯化组分进行酯化反应；所述搅拌的速度为20～100rpm，时间为0.1～10h。
作为优选的技术方案的，步骤3中，所述冷却成型的方法包括冷却粉碎、喷雾冷却、结片冷却；冷却成的形状为颗粒状或片状。
本发明的有益效果是：
本发明通过多元醇与含游离羧基的聚合物酯化反应制得多元醇酯，并加入分散介质和分散剂对其进行预分散处理，有利于提高多元醇酯的稳定性、改善其颗粒的流动性，并具有良好的抗析出性和润滑性。本发明制得的多元醇酯常温下为蜡状固体，使用方便，在PVC中分散良好，减少了析出现象。可以提供给稳定剂生产厂家用于复配含锌复合稳定剂，也可以给PVC制品生产厂家直接用于配方中。
附图说明
图1为本发明流变实验获得流变曲线图。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚，下面将结合实施例，对本发明的技术方案进行清楚、完整地描述。实施例1～2为配制预分散多元醇酯，实施例3为效果例。
实施例1
取季戊四醇30g，对苯二甲酸16g，催化剂0.8g，二甲苯10g作为酯化组分；将上述组分一次性加入到250ml的四口烧瓶中，升温至180℃，以30rpm的速度搅拌，回流反应6h，同时分出反应产生的水份，然后以10KPa的压力值减压蒸馏出二甲苯。降温至120℃，取出少量反应产物，冷却得到粘性固体，备用。余下的反应产物再次升温至135℃，继续搅拌以相同的速度搅拌，并缓慢加入硬脂酸锌42g，单硬脂酸季戊四醇酯5g，搅拌均匀后，倒入容器中冷却结块粉碎，得到长条形的蜡状固体，即为预分散多元醇酯，备用。
实施例2
取季戊四醇30g，苯甲酸26g，月桂酸5g，催化剂0.8g，二甲苯10g，作为酯化组分；在250ml的四口烧瓶中加入单硬脂酸甘油酯57g，然后加入酯化组分，搅拌均匀，升温至180℃，以80rpm的速度搅拌，回流反应2h，并分出反应产生的水份，然后以20KPa的压力值减压蒸馏出二甲苯；然后采用喷雾冷却方式得到颗粒状的蜡状固体，即为预分散多元醇酯，备用。
实施例3 效果例
本实施例是将实施例1和2配制的预分散多元醇酯及实例1中配制的酯化物应用于制作PVC材料中(3#、4#、5#)，并做流变实验，同时以季戊四醇对比做对比实验(2#)，并设立空白对比实验(1#)，观察各组样品的稳定作用和析出现象。本实施例中各实验配方如表1所示，配方中多元醇的质量、硬脂酸锌、润滑剂品种和质量均一致。
表1.本实施例中各组实验配方表
上述各组配方制得的PVC材料，进行流变实验获得的流变曲线如图1所示，观察各组试验机与物料接触表面的析出现象结果如表2所示。
表2.本实施例中各组实验析出现象结果
由以上实验结果分析：预分散的多元醇酯具有良好稳定效果，大幅延长稳定时间，并具有良好的抗析出性和润滑性。可以提供给稳定剂生产厂家用于复配含锌复合稳定剂，也可以给PVC制品生产厂家直接用于配方中。
对于本领域技术人员而言，显然本发明不限于上述示范性实施例的细节，而且在不背离本发明的精神或基本特征的情况下，能够以其他的具体形式实现本发明。因此，无论从哪一点来看，均应将实施例看作是示范性的，而且是非限制性的。此外，应当理解，虽然本说明书按照实施方式加以描述，但并非只包含一个的技术方案，说明书的这种叙述方式仅仅是为清楚起见，本领域技术人员应当将说明书作为一个整体，实施例中的技术方案也可以经适当组合，形成本领域技术人员可以理解的其他实施方式。
Claims (5)
1.一种用于PVC稳定剂的预分散多元醇酯的制备方法，其特征在于：包括步骤如下：
步骤1：合成多元醇酯：将准备的酯化组分包括多元醇、含羧基或酸酐的化合物、酯化反应催化剂和带水剂一次性或分次加入容器中，100～250℃条件下进行酯化反应0.1～10h，分出反应过程中分出产生的水分，待无水分被分出时，再进行减压蒸馏，分离出带水剂，蒸馏压力为2～30kPa；所述带水剂为甲苯、二甲苯或其二者的混合物；所述多元醇与含羧基或酸酐的化合物的加入量为：1mol多元醇，加入羧基0.2～2mol；
步骤2：预分散处理：将准备的分散介质和分散剂先加入容器，再加入步骤1中合成的多元醇酯，并以20～100rpm的速度搅拌0.1～10h，使分散介质、分散剂与多元醇酯混合均匀，对多元醇酯预分散处理；所述分散介质为有机酸金属皂、蜡类润滑剂、酰胺类润滑剂和/或抗氧剂；所述分散剂为阴离子表面活性剂、非离子表面活性剂或该二者的混合物；
步骤3：冷却成型：将含有分散介质和分散剂的多元醇酯冷却获得蜡状颗粒产物，即为预分散多元醇酯成品。
2.根据权利要求1所述的用于PVC稳定剂的预分散多元醇酯的制备方法，其特征在于：步骤1中，所述多元醇为季戊四醇、双季戊四醇、三季戊四醇、甘露糖醇、葡萄糖和蔗糖中的一种或几种；所述含羧基或酸酐的化合物为一元酸、二元酸及其酸酐或单酯中的一种或几种。
3.根据权利要求2所述的用于PVC稳定剂的预分散多元醇酯的制备方法，其特征在于：所述一元酸包括C2～C18的脂肪酸，苯甲酸和丙烯酸及二元酸的单酯；所述二元酸及其酸酐包括马来酸、马来酸酐、草酸、酒石酸、丁二酸、己二酸、葵二酸、苯二酸和苯二酸酐。
4.根据权利要求1所述的用于PVC稳定剂的预分散多元醇酯的制备方法，其特征在于：所述有机酸金属皂包括钙、锌、铝、钾、钠、镁及稀土元素的C8～C30的有机酸酸皂化物；所述蜡类润滑剂包括石蜡、硬脂酸、烯烃低聚物及其氧化物；所述酰胺类润滑剂为乙撑二硬脂酰胺。
5.根据权利要求1所述的用于PVC稳定剂的预分散多元醇酯的制备方法，其特征在于：步骤3中，所述冷却成型的方法包括冷却粉碎、喷雾冷却、结片冷却；冷却成的形状为颗粒状或片状。
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