Synthesis and properties of phosphorus polyesters with systematically altered phosphorus environment

Abstract

Monomers with phosphorus-containing substituents were incorporated into aromatic–aliphatic polyesters to develop polymeric halogen-free flame retardants as additives for poly(butylene terephthalate) (PBT). They were built into the polyester backbone of PBT substituting 1,4-butane diol as monomer by phosphorus-containing aromatic–aliphatic diols. Starting from 10-(2,5-bis(2-hydroxyethoxy)phenyl)-9,10-dihydro-9-oxa-10-phospha-phenanthrene-10-oxide (DOPO-HQ-GE), the chemical structure of the phosphorus monomers was systematically varied resulting in new polymers with diphenyl phosphine oxide substituents and bridged phosphine oxide units. The polymers were prepared by transesterification polycondensation in the melt in lab-scale as well as in a 2.4 l-autoclave. The properties of the polyesters were determined and compared to the DOPO-based polyester with respect to the achieved molar mass and polydispersity, solid state structure, glass transition temperature, thermal stability and combustion behavior. It was found that the different phosphorus substituents lead to different glass transition temperatures. The polymers containing bridged phosphorus structural units showed higher glass transition temperatures T g and resulted in higher char yields after thermal decomposition. Both phosphine oxide structures showed only one-step decomposition with a shoulder at the end of the step. In contrast, two separate steps were observed in the polyesters with DOPO-substituents. The results indicated that the phosphorus polyesters under discussion are suitable to adjust the flame retarding mechanism.