The Method Of Surface Polymerization To Synthesize Polyurethane

Firstly,an overview of the research of polyurethane synthesis and structure adjustment methods,surface grafting and solid phase organic synthesis;then raised a surface polymerization method for the synthesis of polyurethane regular structure.First completed the single selective protection and deprotection reactions of 1,n-symmetric diols,and discussed the impact of various factors on the yield of a single protection;then blocked isocyanate according urethodione,on the condition of appropriate deprotection feasibility study,the monomer AB was synthesized,while the kinetics of urethodione capping reaction was researched;Finally,we researched the surface of polymerization for synthesis low dispersion of polyurethane step from AB monomer,wang resin as a carrier,meanwhile investigated the impact of various factors on the stepwise polymerization rule.The main contents include:(1)Using 3,4-dihydro-2H-pyran as the protective agent,the selective monotetrahydropyranylation of 1,n-symmetrical diols(n=2,3,4,5,6)was catalyzed by pyridinium 4-toluenesulfonate.The effects of reaction time,reaction temperature etc were investigated.The orthogonal experiment with four factors and three levels was designed to optimize the yield of monotetrahydropyranylation.It was found that the order of importance is as follows:reaction time>reaction temperature>the amount of catalyst>the molar ratio of reactants.The optimized condition of monotetrahydropyranylation was also obtained.That reaction time is 10 h,the reaction temperature is 40?,ndiol:nDHP=1:1,mPPTS:mBD=3%,the yield of 4-(tetrahydropyran pyran-2-oxy)-1-butanol is 84.84%.(2)Uretidione reacted with a 4-(tetrahydropyran-2-oxy)-1-butanol,2-ethyl tertiary butyl amine-terminated polydimethylsiloxane and then opened ring,prepared two kind s AB type monomers,and the reaction kinetics of urethodione reacting with 4-(tetrahydropyran-2-oxy)-1-butanol by useing online infrared spectrometer? Uretdione reacted with 4-(tetrahydropyran-2-yloxy)-1-butanol in chlorobenzene,researching the influence of different catalysts(DBTDL,DABCO)and reaction temperature(30?,40?,50?,60?,70?)on urethodione capping.Sealing reaction conditions were determined:under 60?,5%(m/m)P(Bu)3 as catalyst,the reaction finished after 40 min.Urethodione reacted with 2-ethyl tertiary butyl amine reactive polydimethylsiloxane in chlorobenzene at room temperature for 40min.? According to kinetic and thermodynamic data,the urethodione capped and ring-opening reaction conditions were determined,the structural characterization of two AB monomer was analyzed by 1H NMR,13C NMR,IR and other test methods.(3)Wang resin was selected as carrier,2-ethyl tertiary butyl amine-terminated polydimethylsiloxane as monomers for the surface of polymerization,after alternating coupling,deprotecting,elution,and then polyurethane was cut from the resin,obtaining low polydisperse distribution polyurethane.The surface polymerization reaction was investigated and defined by IR?online infrared spectrometer,but by elemental analysis quantitatively investigate the gradual aggregation rule reactions,and discuss the temperature,solvent,material ratio,catalyst and dosage,reaction time and mixing method for stepwise polymerization influence the reaction yield,the polymerization reaction to determine the surface temperature of embodiment 80?,the reaction time was 12 h,DMSO as solvent and tri-n-butylphosphine(5%,m/m),DABCO(10eq)as a catalyst.Finally,determine the molecular weight and structure by IR,MALDI-TOF-MS.