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[]2002-05-12[](20010344)[](1971-),,;(1960-),,,,..[]1000-1832(2002)03-0053-07颜力楷,兰亚乾,苏忠民,邵琛,李宝利,刘东波,李学志,王占良,杨寿江,王荣顺(东北师范大学化学学院功能材料化学研究所,玉米淀粉深加工研究中心,吉林长春130024;)[]以玉米淀粉和丙烯基单体为主要原料,对淀粉接枝共聚高吸水性树脂进行中性一步法合成,优化合成反应路径.根据自由基聚合反应机理,在引发剂及交联剂作用下淀粉与丙烯基单体进行接枝共聚反应,定性及定量地分析反应物溶液pH值反应温度引发剂用量以及单体与淀粉的配比等因素对高吸水性树脂吸水性能的影响,从而找出最佳反应条件.同时采用量子化学abinitioUHF方法在6-31G基组水平上对两类淀粉链段自由基模型进行几何优化,分析体系的净电荷前线分子轨道分布规律,以及自由基的稳定性和反应活性特征,揭示接枝共聚反应机理.[]淀粉;高吸水性树脂;接枝共聚;吸水率;abinitioUHF方法[]Q539+11;O641112+1[]A1,,,.20,,.,,,,,.,,.,,,,,,;,,,第34卷第3期东北师大学报自然科学版Vol.34No.32002年9月JOURNALOFNORTHEASTNORMALUNIVERSITYSeptember2002.,[1~4].,C.R.Russell,300~1000.,,[5~8].,,,,,.80,1982,400,,[9~12].,,.2211主要试剂及仪器21111试剂(,);(,);(,);A(,);(,);B(,);C();(,).21112仪器(JB90-D,);(HHSS11-4,);(FW80,);.212高吸水性树脂的制备1.121211中和液的配制,NaOH,,.21212接枝共聚合反应,,30min,.AB,,115h.,C,,pH,15min.21213产物的后处理,,..213性能测定,[13,14].54东北师大学报自然科学版第34卷21311吸水率的测定015g,,,30min,,10min,[15]:=(g)-(g)(g)@100%.21312吸水速率的测定,,.21313保水率的测定10g,4000r/min1h,,[15]:=(g)(g)@100%.3311机理探讨,,,.,,,.Ce4+[16],.:A,2,3,,,CO,B1B2(2),,.[17,18],,.B1B22.,B1B2.Gaussian-98,abinitioHartree-Fock(UHF),6-31G.SGIOrigin200.2UHF/6-31G1,23,2.55第3期颜力楷等:淀粉接枝共聚高吸水性树脂的合成及其性质研究1B1B2nmB1B2O(1))C(2)011449011438C(2))C(3)011531011538C(3))C(4)011493011508C(5))C(6)011512011489C(6))O(1)011410011417C(4))O(7)011385011212C(5))O(8)0112130113852B1B2eB1B2O(1)-01799-01775C(2)0137201365C(3)0130201300C(4)0138601489C(5)0156901413C(6)0164901651O(7)-01330-01497O(8)-01536-013383B1B2EtB1B2ELUMO/a1u1011333011275EHOMO/a1u1-013373-013449$E/a1u1014706014724Et/a1u1-76013921-790138071030L/(C#m)61198121836,.,C(4)(B1),C(4)sp3,C(3))C(4),C(4))O(7),C(5)sp2,C(5))O(8),C(4))O(7).C(5),.)CHO)C#H),,.C(4)C(5),.,B1B2,.,,,.,B1,HOMO,.312中和液酸碱度对高吸水性树脂吸水性能的影响:12g60g20~30g25%16mL,170mL,34e.,.3.3,16~2756东北师大学报自然科学版第34卷g,,;27g.:,,,,,;,,,,)COOH)COONa,,.,,..(),1000.34313反应温度对高吸水性树脂吸水性能的影响(12g60g27g25%16mL,170mL),,4.20e,;40e,,,.423e~35e,;35e.,,,,,.,,,,.314引发剂用量对高吸水性树脂吸水性能的影响,,-.A.,,5.0135g,0165g..,,,.,,,.57第3期颜力楷等:淀粉接枝共聚高吸水性树脂的合成及其性质研究,,,.,.5,,.,,.,,,,,,.56315淀粉用量对高吸水性树脂吸水性能的影响(60g27g25%16mL,170mL,34e),,6.3~12g,,;12g,.,,,.4(1),,,.(2),,.(3),,B1B2,B14.[][1]AthawaleAD,LeleV1Recenttrendsinhydrogelsbasedonstarch-graf-tacrylicacid:areview[J].Starch-Starke,2001,53(1):7~13.[2]PompiliaIS,FrancoisR,ImanH,etal.Structure-propertiesrelationshipincross-linkedhigh-amvlosestarchforuseincontrolleddrugrelease[J].CarbohydrateResearch,2000(3):163~175.[3]JanaT,RoyBC,MaitiS.BiodegradablefilmÔ.Printabilitystudyonbiodegradablefilm[J].JournalofAppliedPoly-merScience,2001,79(7):1273~1277.[4]HanselmannR,BurchardW.Structuralpropertiesoffractionatedstarchpolymersandtheirdependenceonthedissolution58东北师大学报自然科学版第34卷process[J].Macromolecules,1996,29:3277~3282.[5].[J].,1999,27(3):20~21.[6]SensoA,FrancoP,OliverosL,etal.Characterizationofdoublysubstitutedpolysaccharidederivatives[J].CarbohydrateResearch,2000,329:367~376.[7]LiuH,RamsdenL,CorkeH.Physicalpropertiesandenzymaticdigestibilityofpyhydroxypr-oltedae,wx,andnormalmaizestarch[J].CarbohydratePolymers,1999,40(3):175~182.[8],.[J].,1999,12(2):211~216.[9],,.[J].,2000(1):24~26.[10],.[J].,2000,2:85~93.[11].[J].,1999,24(3):33~36.[12],.[J].,1994,24(3):71~76.[13],,.[J].,1994,9(4):12~18.[14],.[J].,1998,24(4):3~5.[15],,.[J].,1999,20(4):362~365.[16].[M].:,1991.1~16.[17],,,.1,3[J].,2001,17(1):27~34.[18],,,.[Si(S2Ph)n]m?(n=1~3)abinitioDFT[J].(),2000,32(2):44~47.Influenceofacidity,temperatureandinitiatoronsyntheesisandpropertiesofstarchgraftcopolymerizationsuperwater-absorbentresinYANL-ikai,LANYa-qian,SUZhong-min,SHAOChen,LIBao-li,LIUDong-bo,LIXue-zhi,WANGZhan-liang,YANGShou-jiang,WANGRong-shun(InstituteofFunctionalMaterialChemistry,FacultyofChemistry,NortheastNormalUniversity,Changchun130024,China)Abstract:Thesuperwater-absorbentresinwassynthesizedbyusingstarchfrommaizeandpropy-lenebasedmonomerastherawmaterial.Thereactionrouteofsynthesiswasimproved.Basedonthemechanismoffreeradicalpolymerization,graftpolymerizationbetweenstarchandpropylenebasedmonomerwascarriedoutundertheactionofinitiatorandcross-linker.Theyalsostudytheacidity,temperatureandinitiatoramountandmonomer/starchfeedratioseffectonthewaterabsorptionprop-ertyofsuperabsorbentresin.Thebestoperatingconditionwasfoundintheend.Atthesametime,twokindsofradicalmodelofstarchchainwereoptimizedatthelevelof6-31Gbasissetbyquan-tumchemicalabinitioUHFmethod.Theatomicnetcharge,populationoffrontiermolecularor-bital,stabilityandreactivepropertiesoffreeradicalswereanalyzed,themechanismofgraftpoly-merizationwasdiscussed.Keywords:starch;superwater-absorbentresin;graftpolymerization;absorptionofwater;abin-itiomethod59第3期颜力楷等:淀粉接枝共聚高吸水性树脂的合成及其性质研究