Synthesis And Application Of Decomposable Functional Rosin Based Surfactants

As a kind of natural renewable forest resources,rosin is used to substitute petrochemical resource and develope new surfactants.The decomposable rosin-based surfactants could be more environmentally friendly owing to easy decomposition.In this paper,we use disproportionated rosin as raw materials to design and synthesize five novel rosin based ester(Ⅰ,Ⅱ,Ⅲ,Ⅳ and Ⅴ).SAA-III,SAA-IV and SAA-V were respectively obtained by salt formation.The self-assembly properties of V was discussed in ethanol-aqueous and utilized to construct three-dimensional micro-nano composite material of nickel hydroxide and hydroxyapatite functional materials.The study broaden the application field of rosin resources in functional materials.The results were as follows:(1)Five novel rosin based ester surfactants were obtained by acyl chlorination,esterification,phosphate reaction and salt formation using three times recrystallization from dehydroabietylamine.The structures were identified by FT-IR,NMR,MS,and CMC,surface tension,the krafft temperature,foam performance,and emulsifying properties were discussed.The research showed that I,II,SAA-III,SAA-IV and SAA-V had good surface activity,the CMC values were 4.69×10-3,5.15×10-3,2.65×10-3,1.71×10-3 and 1.38×10-3 mol/L,and respectively the γcmc values were 48.2、41.4、34.6、33.2 and 32.5 mN/m.The krafft points increased while carbon chain lengthened,and the times for 10 mL water out from paraffin/water emulsion system were 11、128、90、98and 153 s.The initial foam heights of the surfactants were 16、18.5、18、23 and 19 mm,and after 5 minutes,the heights were 6、4、4、11.5 and 3.5 mm.Five novel rosin ester surfactants had good emulsification and foaming properties.(2)The pH-responsive of V,namely DDPD was studied in aqueous-ethanol solution by studying the self-assembly properties.DDPD could be self-assembled to form vesicles and micelles by adjusting pH and concentration.The micelles were well dispersed at low concentration and self-assembly to form spherical.The micelles aggregated to form about 200 nm to 3 μm aggregates with the increasing of concentration.There existed strong intermolecular repulsion,and could formed relatively scattered vesicles in strong acid and alkali(pH=1 and pH=13),which the formation constant P<0.33 and the vesicle size was about 300 nm.However,the micelle aggregated to form aggregates when P=0.5 and the particle size was about 0.5-3 μm at pH=3-11 owing to the repulsive force between the molecules were weak.The research showed that there was strong antagonistic effect in DDPDS-SDBS systems.The CMC and γcmc values of DDPDS-SDBS complex system decreased significant when the mixed proportion were 90:10.However,obvious synergistic effect was existed in DDPDS-CTAB complex system.The CMC and γcmc values of DDPDS-CTAB complex system decreased significant when the mixed proportion were 90:10.Foam stability was increased obviously,while the emulsifying properties and wettability were weakened in two kinds of complex systems.The CMC and γcmc values of mixed DDPDS-SDBS system were 4.75×10-3 g/L and 37.80 mN/m,and the times for 10 ml water out from paraffin/water emulsion of combined system discussed from 153 s to 129 s.The CMC and γcmc values of mixed DDPDS and CTAB system were 0.14×10-3 g/L and 25.22 mN/m,and the times for 10 ml water out from paraffin/water emulsion of combined system discussed from 153 s to 104 s.The foam stability of the composite system was obviously improved,and the foam height of DDPDS-SDBS only changed 1.5 mm after 5 minutes,the heights of DDPDS-CTAB have remained virtually unchanged.(3)DDPDS was used for controlling morphology of micro-nano nickel hydroxide composite materials and DDPD was provided phosphorus source of hydroxyapatite functional materials.The 3D micro-nano nickel hydroxide composite materials were successfully prepared by DDPDS and mixed systems as annexing agent.The reaction solvents,reaction time,DDPDS concentration,mixed system in nickel hydroxide composite were investigated.Moreover,a possible formation mechanism of nickel hydroxide composite was proposed based on the effect of DDPDS.Study on nickel hydroxide composite showed that DDPDS could promoted the diffractions peak directions and improved the crystallinity of products.The morphology of nickel hydroxide became become more and more regular with the increase of reaction time.Hydroxyapatite functional materials were successfully prepared by calcium nitrate as calcium source,and NH4H2PO4 and DDPD as phosphorus source.The effects of different phosphorous source on the morphology of hydroxyapatite at different pH conditions were investigated.The result of hydroxyapatite indicated that DDPD as the organic phosphorus source could be completely hydrolyzed under alkaline conditions to produce PO43-and formed irregular flakes of hydroxyapatite structure.In acidic conditions,rosin based phosphate diester surfactant could be used as a surface modifier,not only provided the PO43-and hydroxyapatite.A dandelion-like hollow hydroxyapatite was obtained by DDPD as template.