有机硅改性没食子酸非异氰酸酯聚氨酯的制备及性能研究
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摘要
在氯铂酸催化作用下,由聚甲基氢硅氧烷(PMHS)与烯丙基缩水甘油环碳酸酯(AGC)经硅氢加成反应合成有机硅环碳酸酯(CCPS),并通过交联反应引入到没食子酸非异氰酸酯聚氨酯(GNIPU)中,制备得到有机硅改性的GNIPU(GNIPU-CCPS)。采用FT-IR、1H NMR及13C NMR表征了CCPS化学结构,考察了CCPS改性对NIPU聚合物材料热力学性能的影响。研究结果表明:经CCPS改性的GNIPU涂膜具有优异的柔韧性(0.5 mm)、附着力(1级)和抗冲击性能(≥50 kg·cm),且随着CCPS含量的增加,材料的热稳定性、柔韧性及耐水性逐渐增强,玻璃化转变温度及铅笔硬度逐渐降低。
A cyclic carbonate-functionalized polysiloxane( CCPS) was successfully synthesized by hydrosilylation of poly(methylhydrosiloxane)(PMHS) with allyl glycidyl carbonate(AGC) by using H_2PtCl_6 as catalyst. The CCPS was subsequently incorporated into gallic acid-based non-isocyanate polyurethane( GNIPU) networks to form GNIPU-CCPS composites. The chemical structure of CCPS was characterized by FT-IR,~1H NMR and~(13)C NMR,as well as,the effects of CCPS on mechanical and thermal properties of GNIPU were investigated. The GNIPU-CCPS coatings exhibited excellent properties such as flexibility(0.5 mm),adhesion(grade 1) and impact strength(≥50 kg·cm). Furthermore,with the increase of CCPS content,the thermal stability,flexibility and water resistance of the coatings were increased,while the glass transition temperature and pencil hardness of the coatings were decreased.
A cyclic carbonate-functionalized polysiloxane( CCPS) was successfully synthesized by hydrosilylation of poly(methylhydrosiloxane)(PMHS) with allyl glycidyl carbonate(AGC) by using H_2PtCl_6 as catalyst. The CCPS was subsequently incorporated into gallic acid-based non-isocyanate polyurethane( GNIPU) networks to form GNIPU-CCPS composites. The chemical structure of CCPS was characterized by FT-IR,~1H NMR and~(13)C NMR,as well as,the effects of CCPS on mechanical and thermal properties of GNIPU were investigated. The GNIPU-CCPS coatings exhibited excellent properties such as flexibility(0.5 mm),adhesion(grade 1) and impact strength(≥50 kg·cm). Furthermore,with the increase of CCPS content,the thermal stability,flexibility and water resistance of the coatings were increased,while the glass transition temperature and pencil hardness of the coatings were decreased.
引文
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[29]YU Y T,WANG J.Synthesis and properties of block and graft waterborne polyurethane modified withα,ω-bis(3-(1-methoxy-2-hydroxypropoxy)propyl)polydimethylsiloxane andα-N,N-dihydroxyethylaminopropyl-ω-butylpolydimethyl-siloxane[J].Polymer Engineering&Science,2014,54(4):805-811.
[2]CORNILLE A,AUVERGNE R,FIGOVSKY O,et al.A perspective approach to sustainable routes for non-isocyanate polyurethanes[J].European Polymer Journal,2017,87:535-552.
[3]BLATTMANN H,FLEISCHER M,BHR M,et al.Isocyanate-and phosgene-free routes to polyfunctional cyclic carbonates and greenpolyurethanes by fixation of carbon dioxide[J].Macromol Rapid Commun,2014,35(14):1238-1254.
[4]陈彩凤,刘贵锋,孔振武,等.新一代环保型聚氨酯-非异氰酸酯聚氨酯的研究进展[J].生物质化学工程,2012,46(6):47-54.CHEN C F,LIU G F,KONG Z W,et al.Research progress of nonisocyanate polyurethane-novel environmental-friendly polyurethane[J].Biomass Chemical Engineering,2012,46(6):47-54.
[5]POUSSARD L,MARIAGE J,GRIGNARD B,et al.Non-Isocyanate polyurethanes from carbonated soybean oil using vmonomeric or oligomeric diamines to achieve thermosets or thermoplastics[J].Macromolecules,2016,49(6):2162-2171.
[6]SAMANTA S,SELVAKUMAR S,BAHR J,et al.Synthesis and characterization of polyurethane networks derived from soybean-oil-based cyclic carbonates and bioderivable diamines[J].Acs Sustainable Chemistry&Engineering,2016,4(12):6551-6561.
[7]GRIGNARD B,THOMASSIN J M,GENNEN S,et al.CO2-blown microcellular non-isocyanate polyurethane(NIPU)foams:From bio-and CO2-sourced monomers to potentially thermal insulating materials[J].Green Chemistry,2016,18(7):2206-2215.
[8]BAHR M,MULHAUPT R.Linseed and soybean oil-based polyurethanes prepared via the non-isocyanate route and catalytic carbon dioxide conversion[J].Green Chemistry,2012,14(2):483-489.
[9]BOYER A,CLOUTET T,TASSAING T,et al.Solubility in CO2and carbonation studies of epoxidized fatty acid diesters:Towards novel precursors for polyurethane synthesis.Green Chemistry[J],2010,12(12):2205-2213.
[10]徐文杰,单玉华,鲁墨弘,等.非异氰酸酯路线由微藻油与CO2合成聚氨酯[J].现代化工,2013,33(9):61-65.XU W J,SHAN Y H,LU M H,et al.Microalgae oil-based polyurethane prepared from microalgae oil and CO2via the non-isocyanate route[J].Modern Chemical Industry,2013,33(9):61-65.
[11]KATHALEWAR M,SABNIS A S,D’MELLO D.Isocyanate free polyurethanes from new CNSL based bis-cyclic carbonate and its application in coatings[J].European Polymer Journal,2014,57:99-108.
[12]BESSE V,AUVERGNE R,CARLOTTI S,et al.Synthesis of isosorbide based polyurethanes:An isocyanate free method[J].Reactive&Functional Polymers,2013,73(3):588-594.
[13]Liu G F,Wu G M,Kong Z W.Synthesis,modification and properties of rosin-based non-isocyanate polyurethanes coatings[J].Progress in Organic Coatings,2016,101:461-467.
[14]刘贵锋,吴国民,孔振武.POSS改性萜烯基非异氰酸酯聚氨酯的制备及性能研究[J].林产化学与工业.2017,37(3):31-37.Liu G F,Wu G M,Kong Z W.Synthesis and properties of terpene-based non-isocyanate polyurethanes modified with POSS[J].Chemistry and Industry of Forest Products,2017,37(3):31-37.
[15]TRYZNOWSKI M,S'WIDERSKA A,OEK-TRYZNOWSKA Z,et al.Facile route to multigram synthesis of environmentally friendly nonisocyanate polyurethanes[J].Polymer,2015,80:228-236.
[16]CORNILLE A,SERRES J,MICHAUD G,et al.Syntheses of epoxyurethane polymers from isocyanate free oligo-polyhydroxyurethane[J].European Polymer Journal,2016,75:175-189.
[17]REN Z,YAN S.Polysiloxanes for optoelectronic applications[J].Progress in Materials Science,2016,83:383-416.
[18]CHRUS'CIEL J JS'NIAK E.Modification of epoxy resins with functional silanes,polysiloxanes,silsesquioxanes,silica and silicates[J].Progress in Polymer Science,2015,41:67-121.
[19]JI X,WANG H Z,MA X L,et al.Progress in polydimethylsiloxane-modified waterborne polyurethanes[J].RSC Advances,2017,7(54):34086-34095.
[20]PILCH-PITERA B.Polyurethane powder coatings containing polysiloxane[J].Progress in Organic Coatings,2014,77(11):1653-1662.
[21]OCHIAI B,KOJIMA H,ENDO T.Synthesis and properties of polyhydroxyurethane bearing silicone backbone[J].Journal of Polymer Science Part A:Polymer Chemistry,2014,52(8):1113-1118.
[22]HOSGOR Z.Nonisocyanate Polyurethane/silica hybrid coatings via a sol-gel route[J].Advances in Polymer Technology,2012,31(31):390-400.
[23]LIU G F,WU G M,KONG Z W,et al.Synthesis and properties of POSS-containing gallic acid-based non-isocyanate polyurethanes coatings[J].Polymer Degradation&Stability,2015,121:247-252.
[24]刘贵锋,陈彩凤,孔振武,等.腰果酚基环碳酸酯及其季铵盐衍生物的合成与表面活性研究[J].林产化学与工业.2013,33(2):85-90.LIU G F,CHEN C F,KONG Z W.Synthesis and surface active properties of cardanol-based cyclic carbonate and its quaternary ammonium salt derivatives[J].Chemistry and Industry of Forest Products,2013,33(2):85-90.
[25]KAMINO B A,BENDER T P.The use of siloxanes,silsesquioxanes,and silicones in organic semiconducting materials[J].Chemical Society Reviews,2013,42(12):5119-5130.
[26]CHENG J Y,CAO Y,SUN F,et al.Synthesis and performances of UV-curable polysiloxane-polyether block polyurethane acrylates for PVC leather finishing agents[J].Industrial&Engineering Chemistry Research,2015,54(21):5635-5642.
[27]LIU G F,WU G M,HUO S P,et al.Synthesis and properties of non-isocyanate polyurethane coatings derived from cyclic carbonatefunctionalized polysiloxanes[J].Progress in Organic Coatings,2017,112:169-175.
[28]DU Y,ZHANG J S,ZHOU C,et al.Synthesis and properties of waterborne polyurethanebased PTMG and PDMS as soft segment[J].Polymer Bulletin,2016,73(1):293-308.
[29]YU Y T,WANG J.Synthesis and properties of block and graft waterborne polyurethane modified withα,ω-bis(3-(1-methoxy-2-hydroxypropoxy)propyl)polydimethylsiloxane andα-N,N-dihydroxyethylaminopropyl-ω-butylpolydimethyl-siloxane[J].Polymer Engineering&Science,2014,54(4):805-811.