Synthesis Of Polyether Ester Plasticizers And Its Applications In Rubber

The low molecular weight plasticizers have high plasticized effect, but heat-resistanceand durability are unsatisfactory. And the high molecular weight polyester plasticizers havelow volatility, low migration and high temperature resistance, but low temperatureperformance and plasticizing efficiency are poor. In this paper, novel polyether esterplasticizers were synthesized. These polyether ester plasticizers contain both ether and estermolecular structure. The introduction of ester group helps plasticizers improve compatibilitywith the polar rubber and the introduction of ether helps to improve flexibility, oil resistanceand heat resistance of plasticizers. These polyether ester plasticizers can be used in productswhich need not only low temperature performance but also high-temperature performance.Seven polyether ester plasticizers were synthesized in this thesis by using thecondensation reaction of adipic acid, polyols, diethylene glycol monobutyl ether or n-octanol,they are AAPEGE, AAPEGO, GAAE, AADEGE, AADEGO, AABE and GAAO, respectively.The structural characteristics of plasticizers were investigated by using FT-IR,~1H-NMR andTGA testing. And polyether ester plasticizers were used in the acrylic rubber and nitrile rubbercompared with DOP plasticizer which is commonly used in plastic and rubber, to investigatethe compatibility of the rubber and plasticizers, rheological properties, curing characteristics,mechanical properties, heat resistance, low temperature properties and heat oil performance.Test results of Mooney viscosity and capillary rheometer show that the plasticizing efficiencyof polyether ester plasticizers of GAAE, GAAO, AADEGE and AADEGO is better than thatof the DOP plasticizer. Test results of quality-change, TGA, and heat oil show that the massloss of vulcanizates which contain polyether ester plasticizers was significantly lower thanthat of DOP vulcanizates, indicating that polyether ester plasticizers have excellent volatileresistance, high temperature resistance and oil resistance. Test results of low temperaturebrittleness, DSC and DMA show that GAAE, GAAO and AADEGO, have favorable lowtemperature performance, close to the DOP.Data results of the solubility parameter indicate that three-dimensional Hansen solubilityparameter δ and the IR value which derived from the Hansen method are very useful methodto predict the compatibility between the plasticizers and polar polymers. The comparison ofdifferent plasticizers by using solubility parameter method, calculation method, observationmethod and water-value method shows that the polarity order of plasticizers is AAPEGE,AADEGE> AAPEGO, AADEGO> GAAE, AABE> GAAO> DOP. And the compatibilitybetween ACM rubber and plasticizers is a positive correlation with polarity order while the compatibility between NBR rubber and plasticizers is a negative correlation with polarityorder. Experimental results show that ether group helps to improve the compatibility ofplasticizers and ACM rubber, but not conducive to improve compatibility of plasticizers andNBR rubber.Some of the polyether ester plasticizers which have the better overall performance in thecarbon black rubber compounds were applied in NBR/silica compounds. The propertiestesting results of comparison of different plasticizers in NBR/silica compounds indicate thatdue to the silica surface containing a large number of hydroxyl group, it’s easy to formhydrogen bonds with ester group and ether group of plasticizers, improving the compatibilityand mechanical properties of the polyether ester plasticizers and NBR rubber, but weakeningplasticizing efficiency and low temperature performance between the polyether esterplasticizers and NBR rubber.