Research On Synthesis Of Dehydroabietic Based Phosphorus(Phosphonic) Anhydride Derivatives And Hybrid Materials

Rosin is an important forestry biomass resource in China.It is widely used in food processing,medicine,new pesticides,ink,adhesives and surfactants.In this paper,the unique chemical structures of rosin resion,such as rigid ring skeleton,chiral structure,double bond,and carboxyl modified sites acid were used.Based on the abietic acid dehydroabietic acid of rosin as the raw material,the active sites of acyl chloride were designed.Four dehydroabietic phosphorus derivatives were synthesized.Two kinds of Dehydroabietic phosphorus(phosphnic)anhydride were used as phosphorus source,and dehydroabietic based derivatives/apatite hybrid materials were obtained by the sol-gel method in temperature and reaction conditions.(1)Synthesis of dehydroabietic based phosphonic anhydride derivativesTwo dehydroabietic based phosphonic anhydride derivatives-dehydroabietic based phenylphosphonic anhydride(DPPDA),Dehydroabietyl adenosine monophosphate monoanhydride(DAMM),and dehydroabietic based amide adenosine phosphate anhydride(DAAPD),were synthesized with dehydroabietic acid.The effects of reaction materials and extraction methods on the products were investigated,and the structures of the products were characterized.DPPDA has excellent emulsification and foam properties.When the mass concentration is between 0.01% and1%,the emulsifying time is over 230 S.When the mass concentration is 0.10%,the foam height reaches 2.5 m L.The optimal configuration of DPPDA and its hydrolysate were obtained by quantum chemistry calculation.(2)Preparation of hybrid materials by sol-gel method using dehydroabietic phosphorus(phosphine)anhydride as organophosphorusThe hybrid materials were prepared by sol-gel method using two dehydroabietic phosphorus(phosphonic)anhydride derivatives with high yields as phosphorus source.When DPPDA was used as phosphorus source,spherical structure hybrid materials assembled on nanoscale could be obtained at p H=3,80,6h and Ca/P=1:10 conditions.In alkaline conditions,the pomelo like hybrid materials assembled by rod like rods were obtained.Under acidic conditions,spherical structures could be formed under different calcium phosphorus ratios.However,the smaller calcium and phosphorus content is more regular than that of the obtained materials.When Ca / P = 3.34:1 and p H = 12,the organic matter content of the hybrid material could reach up to 60%.Increasing temperature was beneficial to the growth of hexagonal crystal,and prolonging reaction time was not conducive to the stability of the assembly structure.The molecular structure of Organic Ca(PMCa)complex formed in hybrid materials was calculated by quantum chemistry to explore the formation mechanism of hybrid materials.The results show that the hybrid materials have good adsorption capacity for phenol,and the adsorption capacity can reach 33 mg/g.Through the study on p H and phenol concentration,it is found that the adsorption of phenol on hybrid materials is a combination of physical adsorption and chemical adsorption.