阻燃PVA-g-AN的制备、表征及性能
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摘要
以K2S2O8-NaHSO3氧化还原体系为引发剂,将丙烯腈(AN)接枝到聚乙烯醇(PVA)上,得到聚乙烯醇接枝丙烯腈聚合物(PVA-g-AN),将其与磷酸-尿素反应制备阻燃聚乙烯醇接枝丙烯腈聚合物(FR-PVA-g-AN).利用傅里叶变换红外光谱(FTIR)、X射线能谱(XPS)和X射线衍射(XRD)对其结构进行表征,并用热重分析(TGA)对其热性能进行研究.结果表明,当引发剂用量占反应物总质量的1%,n(K2S2O8)∶n(NaHSO3)=5∶1,m(丙烯腈)∶m(聚乙烯醇)=3.5∶1,70℃反应4 h时,接枝率可达190%;在m(磷酸)∶m(尿素)=5∶1,85℃条件下处理接枝产物PVA-g-AN 4 h时,获得阻燃性能良好的FR-PVA-g-AN,700℃马弗炉热处理后,残炭量达到63%.TGA结果显示,FR-PVA-g-AN的热降解过程较PVA减慢,且800℃后残炭量由PVA的3.12%增加到54.3%,说明FR-PVA-g-AN具有优异的热稳定性和成炭性.
Flame retardant polyvinyl alcohol(PVA) grafted with acrylonitrile(AN)(FR-PVA-g-AN) was prepared via grafting copolymerization of AN onto PVA(PVA-g-AN) using K2S2O8-NaHSO3 as initiator followed by the chemical modification reaction with phosphoric acid and urea.The structure of FR-PVA-g-AN was characterized by Fourier transform infared spectroscope(FTIR),X-ray photoelectron spectroscopy(XPS) and X-ray diffraction(XRD),and the thermal property was studied by thermogravimetric analysis(TGA).The results show that the grafting percent reaches 190% under the condition of the mass fraction of initiator being 1% of the total reactant,the molar ratio of K2S2O8 to NaHSO3 being 5∶ 1,the mass ratio of AN to PVA being 3.5∶ 1,and reaction temperature being 70 ℃,and the reaction time of 4 h.The FR-PVA-g-AN with excellent fire retardancy can be obtained with the mass ratio of phosphoric acid to urea being 5∶ 1 and reaction temperature of 85 ℃ for 4 h.There is about 63% char residue left after FR-PVA-g-AN was treated at 700 ℃ with muffle.The TGA curves indicate that the thermo-oxidative degradation of FR-PVA-g-AN is slower than that of PVA,and the char residue of FR-PVA-g-AN increases to 54.3% at 800 ℃,while the char residue of PVA is only 3.12%,which fully proves that FR-PVA-g-AN has better thermal stability and char forming capability.
Flame retardant polyvinyl alcohol(PVA) grafted with acrylonitrile(AN)(FR-PVA-g-AN) was prepared via grafting copolymerization of AN onto PVA(PVA-g-AN) using K2S2O8-NaHSO3 as initiator followed by the chemical modification reaction with phosphoric acid and urea.The structure of FR-PVA-g-AN was characterized by Fourier transform infared spectroscope(FTIR),X-ray photoelectron spectroscopy(XPS) and X-ray diffraction(XRD),and the thermal property was studied by thermogravimetric analysis(TGA).The results show that the grafting percent reaches 190% under the condition of the mass fraction of initiator being 1% of the total reactant,the molar ratio of K2S2O8 to NaHSO3 being 5∶ 1,the mass ratio of AN to PVA being 3.5∶ 1,and reaction temperature being 70 ℃,and the reaction time of 4 h.The FR-PVA-g-AN with excellent fire retardancy can be obtained with the mass ratio of phosphoric acid to urea being 5∶ 1 and reaction temperature of 85 ℃ for 4 h.There is about 63% char residue left after FR-PVA-g-AN was treated at 700 ℃ with muffle.The TGA curves indicate that the thermo-oxidative degradation of FR-PVA-g-AN is slower than that of PVA,and the char residue of FR-PVA-g-AN increases to 54.3% at 800 ℃,while the char residue of PVA is only 3.12%,which fully proves that FR-PVA-g-AN has better thermal stability and char forming capability.
引文
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[21]Li P.Z.,Li X.R.,Xu X.,Polym.Mater.Sci.Eng.,2009,25(1),19—22(李培枝,李小瑞,徐旋.高分子材料科学与工程,2009,25(1),19—22)
[22]Jiang X.C.,Xia C.,Ye D.Z.,Liu L.,Dai H.,Zhang X.,Chem.J.Chinese Universities,2012,33(8),1872—1876(江献财,夏超,叶德展,刘磊,代华,张熙.高等学校化学学报,2012,33(8),1872—1876)
[23]Wei D.Q.,Luo X.J.,Deng P.,Tao J.L.,Acta Polym.Sinica,1995,(4),427—433(魏德卿,罗孝君,邓萍,陶家良.化学学报,1995,(4),427—433)
[24]Wu G.S.,Mu J.G.,Zhang G.,Fine Chemicals,1993,10(1),12—16(巫拱生,慕建光,张国.精细化工,1993,10(1),12—16)
[2]Hall M.E.,Zhang J.,Horrocks A.R.,Fire Mater.,1994,18(4),231—241
[3]Zhang J.,Horrocks A.R.,Hall M.E.,Fire Mater.,1994,18(5),307—312
[4]Wyman P.,Crook V.,Ebdon J.,Hunt B.,Joseph P.,Polym.Int.,2006,55(7),764—771
[5]Ren Y.L.,Cheng B.W.,Xu L.,Jiang A.B.,Lu Y.C.,J.Appl.Polym.Sci.,2010,115(3),1489—1494
[6]Ren Y.L.,Cheng B.W.,Jiang A.B.,Lu Y.C.,Xu L.,J.Appl.Polym.Sci.,2010,115(6),3705—3709
[7]Akovali G.,Gundogan G.,J.Appl.Polym.Sci.,1990,41(9/10),2011—2019
[8]Tsafack M.J.,Levalois-Grutzmacher J.,Sur.Coat.Tech.,2006,200(11),3503—3510
[9]Xu J.Z.,Tian C.M.,Ma Z.G.,Gao M.,Guo H.Z.,Yao Z.H.J.,Therm.Anal.Calorim.,2001,63(2),501—506
[10]Wang D.L.,Liu Y.,Wang D.Y.,Zhao C.X.,Mou Y.R.,Wang Y.Z.,Polym.Degrad.Stab.,2007,92(8),1555—1564
[11]Zhao C.X.,Liu Y.,Wang D.Y.,Wang D.L.,Wang Y.Z.,Polym.Degrad.Stab.,2008,93(7),1323—1331
[12]Xu S.J.,Ding Q.W.,Zhejiang Chem.Eng.,2001,32(1),59—60(徐胜杰,丁琦伟.浙江化工,2001,32(1),59—60)
[13]Lin J.S.,Zhao C.X.,Liu Y.,Wang D.Y.,Wang Y.Z.,Flame Retardant Mater.Technol.,2008,(6),1(林建盛,赵春霞,刘娅,王德义,王玉忠.阻燃材料与技术,2008,(6),1)
[14]Ma Z.L.,Zhao W.G.,Hu H.F.,Liu Z.G.,Polym.Mater.Sci.Eng.,1998,14(6),99—101(马志领,赵文革,胡汉芳,刘志广.高分子材料科学与工程,1998,14(6),99—101)
[15]Ma Z.L.,Zhao W.G.,Polym.Mater.Sci.Eng.,2002,18(1),44—46(马志领,赵文革.高分子材料科学与工程,2002,18(1),44—46)
[16]Zhou X.D.,Dyeing and Finishing,2001,(6),27—28(周向东.印染,2001,(6),27—28)
[17]Zhan Y.Z.,Zhou W.F.,Appl.Chem.Ind.,2008,37(3),279—282(詹友镇,周文富.应用化工,2008,37(3),279—282)
[18]Lu J.H.,Gao B.J.,Zhang G.H.,Acta Polym.Sinica,2009,(6),540—545(卢金华,高保娇,张国海.化学学报,2009,(6),540—545)
[19]Liu Y.C.,Lu C.,Cheng S.J.,Zhou D.F.,J.Funct.Polym.,2003,16(4),483—488(刘颖春,陆冲,程树军,周达飞.功能高分子学报,2003,16(4),483—488)
[20]Zhang M.,Na Y.,Jiang Z.H.,Chem.J.Chinese Universities,2005,26(1),170—174(张梅,那莹,姜振华.高等学校化学学报,2005,26(1),170—174)
[21]Li P.Z.,Li X.R.,Xu X.,Polym.Mater.Sci.Eng.,2009,25(1),19—22(李培枝,李小瑞,徐旋.高分子材料科学与工程,2009,25(1),19—22)
[22]Jiang X.C.,Xia C.,Ye D.Z.,Liu L.,Dai H.,Zhang X.,Chem.J.Chinese Universities,2012,33(8),1872—1876(江献财,夏超,叶德展,刘磊,代华,张熙.高等学校化学学报,2012,33(8),1872—1876)
[23]Wei D.Q.,Luo X.J.,Deng P.,Tao J.L.,Acta Polym.Sinica,1995,(4),427—433(魏德卿,罗孝君,邓萍,陶家良.化学学报,1995,(4),427—433)
[24]Wu G.S.,Mu J.G.,Zhang G.,Fine Chemicals,1993,10(1),12—16(巫拱生,慕建光,张国.精细化工,1993,10(1),12—16)
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