聚苯硫醚合成宏观动力学探讨-贺建业

:2002-02-17;:2002-08-08　＊96:1004-1656(2003)05-0706-02贺建业,黄光琳(,　610064):;;;:0643.1;0631.5　　:A　　(PPS)[1],,,AB,(A2B2)※AB。。1　[1]。(N-):Na2S+2xNMP2Na(NMP)+x+S2-(1),,,[2],,,:Cl-C6H4-Cl+S2-Cl-C6H4-S-+Cl-(2):nCl-C6H4-S-Cl-[-C6H4-S-]-n+(n-1)Cl-(3),1(1-PNaCl+PNa2S)=c0·k·t+1(4)c0,k,PNaCl,PNa2S,t。,(4),。,c02-2.3mol/kg,104,0.99。k,4-6h,。,≥0.35,≥280℃。2　1。1　Table1　Effectofreactionconditionsonthereactionandthemeltingpointoftheproduct　c0mol/kg℃dl/g1250℃4h20.8992650.342250℃4h20.8942630.343220℃1h+250℃6h2.30.9522740.354220℃1h+250℃6h2.30.9582750.35　　1,c0,。k,。AB,[3],K3=[Cl-(-C6H4-S-)-n]·[Cl-][Cl-C6H4-S-](5),。,(25℃,N-[4]0.0027mol/L)。(0.999)。,,。,。60,,,。,(0.2mol/kg),2。155200310　　　　　　　　　　　　ChemicalResearchandApplication　　　　　　　　　　　　Vol.15,No.5Oct.,20032　Table2　Effectofaddedsodiumsaltonthemeltingpointoftheprocduct　　Na2S℃dl/g4220℃1h+250℃6h0.9492750.355220℃1h+250℃6h　0.9492820.39　　＊,。,。(5)AB,,,(3),(1)(2),:K1=[Na(NMP)+x]2·[S2-][Na2S](6)K2=[Cl-C6H4-S--]·[Cl-][Cl-C6H4-Cl]·[S2-](7)K1K2K3=[Cl-(C6H4-S-)-n][Cl-]2[Na(NMP)+x]2[Na2S][DCB](8);(1)[Cl-]2,,,。(2),,,。。(8),[Na(NMP)+x]2,,[Na(NMP)+x],,[Cl(-C6H4-S-)-n],,。,,,,,。(3)(8)K1,K1,,N-,,K1,。:[1],,.ChemicalJournalofChineseUni-versities(),1997,Vol.18:633-636.[2]B.Paolo,J.Phys.Chem.1973,77:1258-1261.[3],,“”,,,1962,214.[4],,(SolventHandbook)(),,,1987:250.Apparentkineticsstudyofthesynthesisofpoly(phenylenesulfide)HEJian-ye,HUANGGuang-lin(CollegeofChemistry,SichuanUniversity,Chengdu,610064,China)Abstract:Inourperviousinvestigation,wefoundthatthesyntheticprocessofPPSwasdominatedbyacondensationwhich,inturn,wasfollowedbyaself-polycondensationofABtype.Inthefirstplace,thesolventactionofNa+wasinccuredbythetwosolvent(NMPandHMPA)Na2S+2xNMP=2Na(NMP)+x+S2-……(1)Therfore,theS=wasfullybaredanditisnueleophilicreactivitywasraised.ThereactionofthehighactivebareS=andp-dichlorobenzenewascarriedouteasilyCl-C6H4-Cl+S2-=Cl-C6H4-S--Cl-…………(2)Theproductivep-chloro-thiophenolanionwasfollowedbyaself-condesationnCl-C6H4-S--=Cl-[-C6H4-S-]-n+(n-1)Cl-……(3)Thusanapparentkineticesexpressionofthepolycondensationwasfoundas1(1-PNaCl+PNa2S)=c0·k·t+1(4)And,theequilibriumconstantofsynthesizingPPSwasexpressedasfollowsK1K2K3=[Cl-(C6H4-S-)-n][Cl-]2·[Na(NMP)+x]2[Na2S][DCB]………(5)InwhichK1,K2,K3areequilibriumconstantsofthechemicalreactions(1),(2),and(3),respectively.Keywords:poly-condensation;PPS;thermodynamicsequilibriumconstant(责任编辑　万家义)707第5期　　　　　　　贺建业等:聚苯硫醚合成的宏观动力学的进一步探讨