Synthesis Of Ordered Super-microporous Materials By Rosin-based Templating Agents

Dehydroabietylamine has gathered considerable attentionis because of its excellent physical and chemical properties which is a natural rosin modified product,with a tricyclic diterpene rigid structure of the chiral primary amine.The development and application of surfactants with dehydroabietylamine as raw materials is one of the important ways of its high value utilization.However,the relevant research focused on the traditional emulsification,infiltration,solubilization,corrosion and other fields of application,in the synthesis of functional porous materials rarely reported.The special porous material of between the microporous and mesoporous of ordered super-microporous material is a pore size of 1-2 nm,which has become a hotspot in the field of material synthesis because of it through the pores of the porous material is too small to affect the mass transfer of the limitations and make up the mesoporous material pore size is too large without the function of defects.Therefore,this paper uses dehydroabietylamine and its derived quaternary ammonium salt as template to synthesis of ordered super-microporous materials,examine the influence of reaction parameters on the structural properties of the materials,and reveal the reaction mechanism.Specific results are as follows:1)Synthesis of the highly ordered super-mesoporous silica material using dehydroab-ietic trimethyl ammonium bromide?DTAB?as template and different organic amine?ammonium?modulation.The organic amine?amine?effects on structural performance significantly because of it has a dual function?alkali and templating agent?.When the primary amine is used,hexagonal phase of super-mesoporous material is compounded by using the molecular size of the primary amine is short??C4?,and the product structure changes from hexagonal phase to lamellar phase when hexylamine?C₆?is added.The order of sample decreases with the increase of methyl groups on the amine group when using methylamine,dimethylamine,trimethylamine and tetramethylammonium hydroxide.When tetramethylammonium hydroxide,tetraethylammonium hydroxide,tetrapropylammonium hydroxide and tetrabutylammonium hydroxide were used,the order of the samples decreased first and then increased with the increase of carbon chain.The introduction of methylamine will form highest order of hexagonal super-microporous silica material.The BET specific surface area of calcined super-microporous silicas is 1466.62 m³/g,the surface area of Langmuir is 2330.78 m³/g,the pore volume is 0.65 m³/g and the pore size is 2.17 nm.2)Single-head and multi-head group dehydroabietyl quaternary ammonium salts were synthesized from dehydroabietylamine.A novel ordered ultrafine silica material was synthesized by N,N-dimethyl-N-hydroxyethyl-N-dehydroabietylammonium chloride.The phase structure was a three-dimensional cubic phase.N,N-dimethyl-N-benzyl-N-dehydroa-bi-etylammonium chloride due to the introduction of a strong lipophilic benzyl and the water-soluble sharp decline,can not play the role of template.The polyalkylidene dehydr-oabietyl quaternary ammonium salt is synthesized by the growth of the hydrophobic chain.The samples formed are all lamellar phase structure,and the unit cells are increased and the pore size is increased to the mesopore.Indicating that the molecular size of the surfactant is the key to regulating the size of the unit cell and the pore size.3)Using DHAA and CTAB compounded system as template,NaOH as the alkali source,synthesis silica molecular sieve of lamellar phase ordered super-microporous.Adding a little DHAA changed the structure of the sample from the mesopores MCM-48ofcubic phase to the layered super-microporous structure.The high concentration of NaOH will again change the sample phase from the lamellar ultrafine structure to the hexagonal mesoporous MCM-41.In the synthesis of CTAB amount,crystallization time and temperature should be appropriate,too high and too low will reduce the order of the sample.When the ratio of the amount of each component in the reaction system is nTEOS:nCTAB:nDHAA:nNaOH:nH2O=1:0.114:0.00457:0.50:60,the sample has the high-est degree of sequencing by 373 K hydrothermal crystallization sample.The pore size is about 2 nm.4)Ti?SO4?2 as titanium source was prepared by sol-gel method using N,N,N-trimethyl-dehydroabulyl ammonium bromide as template,and hexagonal ordered super-microporous titanium-based materials were obtained.The ratio of nDTAB:nTi?SO4?2:nH2O=7:133:7500 and the water bath temperature is 318³33 K.The sample with long-range order is about 2 nm.The obtained thermal stability of the titanyl sulfate precursor is poor,and when the template was removed by calcination at 623 K,the pores collapsed.But after the treatment with phosphorus acid produced the thermal stability titanyl phosphate is better,after calcination still maintain a high degree of orderly structure.In this study,we have combined the excellent products of forest chemical industry and the frontier of inorganic materials to expand the synthetic route of ordered super-microporous materials,and open up new ways for deep processing and utilization of rosin resources.