Poly(caprolactone)-based Plasticizers to reduce gas-check in PVC films

增塑剂用于增加硬质聚合物(如聚氯乙烯)的柔韧性和可加工性，用于各种商业产品，如电线、电缆、地板和泳池衬垫。几十年来，邻苯二甲酸二乙基己酯(DEHP；通常称为邻苯二甲酸二辛酯(DOP))是聚氯乙烯配方中使用的最常见的增塑剂。然而，DEHP及其代谢物，特别是其单酯，对健康造成了负面影响，例如成为内分泌干扰物。最近，DEHP被禁止在儿童玩具中使用，邻苯二甲酸盐替代品正在迅速被提供。我们开发了以琥珀酸酯为基础的酯，这种酯在被丢弃后可生物降解为无毒代谢物，同时在混合配方中的表现也与DEHP一样或更好。此外，我们利用绿色化学原理，使用可持续的积木，减少了溶剂、工艺步骤数和催化剂浓度，进一步优化了工艺。这些绿色琥珀酸酯增塑剂作为聚氯乙烯的主要增塑剂效果良好。然而，在我们之前的合作中，我们发现聚己内酯(PCL)嵌段共低聚物被发现作为二次增塑剂非常有效，几乎消除了气阻，这是一种限制生产率的现象，在压延或辊磨时气泡夹带在薄膜中。这些原因在文献中没有得到很好的描述。我们的目标是找出降低PCL嵌段共聚物/聚氯乙烯共混物(由于表面张力或流变效应)中气体止回阀的基本机理。我们将与工业合作伙伴一起，确定产生这种影响的根本原因，然后设计一套针对不同产品线量身定做的PCL基二次增塑剂。随后将对衍生的PCL增塑剂进行经济评估，以准备扩大规模。该项目潜在地具有巨大的工业和社会经济影响，因为在向市场提供另一种绿色增塑剂的同时避免了代价高昂的停机时间。这一CRD的创新将创造加拿大的知识产权、许可机会和就业机会，因为它是市场上第一个推出此类产品的公司。

Plasticizers are used to increase the flexibility and workability of rigid polymers like poly(vinyl chloride) (PVC) for a myriad of commercial products such as wiring, cables, flooring and pool liners. For decades, di-2-ethylhexyl phthalate (DEHP; often termed dioctyl phthalate (DOP)) was the most common plasticizer used in PVC formulations. However, DEHP and its metabolites, particularly its monoester, have caused negative health effects, such as being an endocrine disruptor. Recently, DEHP was banned from use in children's toys and phthalate alternatives are rapidly being offered. We developed succinate-based esters that biodegrade to non-toxic metabolites after being discarded while also performing as well or better than DEHP in blend formulations. Further, we further optimized the process using green chemistry principles, using sustainable building blocks and reducing solvent, number of process steps and catalyst concentration. These green succinate ester plasticizers worked well as primary plasticizers for PVC. However, during our previous collaborations, we discovered that poly(caprolactone) (PCL) block co-oligomers were found to be very effective as secondary plasticizers, virtually eliminating gas-check, which is a phenomenon that limits production rates where air bubbles are entrained in the film when calendaring or roll-milling. The causes are not well described in literature. Our goal is to find the fundamental mechanism for gas-check reduction in PCL-block co-oligomer/PVC blends (due to either surface tension or rheological effects). In tandem with the industrial partner, we will determine the root causes for this effect and then design a suite of PCL-based secondary plasticizers tailored to various product lines. An economic evaluation of the derived PCL plasticizers will follow in preparation of scale-up. This project has potentially enormous industrial and socio-economic implications, as costly down-time is avoided while delivering another green plasticizer to market. The innovation from this CRD will create Canadian-based intellectual property, licensing opportunities and job creation due to being first on the market with such a product.