植物油基PVC增塑剂化学合成与应用

Chemical synthesis and application of vegetable oil-based plasticizers

当前石油基增塑剂存在的诸多问题,尤其是邻苯类增塑剂被质疑具有持久性的生殖毒性,且在许多国家受到法规限制。而植物油脂作为精细化学品原料所具有来源广、产量大、可再生和价格低廉等诸多优势,已成为生物基增塑剂研究开发的焦点。综述了以植物油脂为主要原料通过不同的化学反应(环氧化、Diels-Alder反应、酯交换、氯代、酯化、缩聚、开环和双键加成等)对植物油脂结构中的不饱和双键、共轭双键、酯基、与酯基相连β碳上的氢、羟基和羧基进行改性,设计并合成出不同结构类型油脂基增塑剂,如环氧化植物油(环氧化脂肪酸酯)、C22-三酸酯、脂肪酸多酯、含硫脂肪酸酯、甘油酯、植物油聚酯型和阻燃型植物油基增塑剂等主要研究成果,包括合成工艺条件以及各类增塑剂对PVC制品的性能影响。与国外相比,我国油脂基增塑剂产品种类少、产量低,环氧类和氯代型油脂基增塑剂是比较成熟产品,开发其绿色的合成工艺是当下研究焦点。其他类型油脂基增塑剂除了要在结构设计、工艺开发上加大研究外,还需要加大在特定塑料制品中的应用研究。就国内情况而言,应重点开发量大价低的非食用油脂,以推动产业发展。

It is estimated that the global production value of plasticizers will exceed$19.5 billion by 2020,in which,90%will be used in polyvinyl chloride(PVC)products.However,there are many problems in petroleum-based plasticizers,in particular,phthalate accounts for 80%of the total plasticizer in China at present,which is questioned for its persistent reproductive toxicity and regulatory limitations.Compared with other environmentally friendly and bio-based plasticizers for PVC,vegetable oil-based plasticizers have many advantages,such as plenty available resource of raw materials,low price and versatility.Various vegetable oil-based plasticizers for PVC,such as epoxidized vegetable oil(epoxide fatty acid ester),C22-triacid ester,fatty acid polyesters,sulfur-containing fatty acid esters,glycerol ester,vegetable oil based polyester and flame retardant vegetable oil-based plasticizer,have been synthesized by modifying the unsaturated double bonds,conjugated double bonds,ester groups,hydrogen on ester-linkedβ-carbon,hydroxyl and carboxyl using the methods of epoxidation,esterification,transesterification,polycondensation,Diels-Alder reaction,chlorination,ring opening and double bond addition chemical reactions,etc.It is also included process conditions and performance of the vegetable oil-based plasticizers.The effects of chemical structure of the vegetable oil-based plasticizer on the plasticity,precipitation resistance,cold resistance and thermal stability of PVC materials and its application in some special materials are investigated in this study.It is reported that the epoxy vegetable oil-based plasticizers are the most popular ones.Soybean oil and palm oil are the main raw materials for the current research.Since the research on plasticizing mechanism for vegetable oil-based plasticizers is still insufficient,this study explored the chemical synthesis and application of vegetable oil-based plasticizers.Compared with other developed countries in the world,the species of oil-based plasticizers are limited and lower yield in China.Epoxy and chlorinated oil-based plasticizers are relatively mature products,and the focus of the research is to develop a green synthesis process.It is suggested that the future study should be focused on other types of oil-based plasticizers not only in terms of structural design and process development,but also their application research in specific products.In view of the domestic situation,it is recommended to focus on developing non edible oils with large production scale and low prices to promote the development of industrial production.