Luận án Nghiên cứu phản ứng giảm cấp cao su latex tự nhiên bằng hệ Phenilhidrazin - FeCl2 và một số phản ứng biến tính cao su giảm cấp

hgpv6iketquaphantfchnguyento:Khi ditucaosubanGaudencansulong,chIsoN% tang(b~mg1.16). - !) - Ban&..!:1&: Phf.liltlchnguyentocaDsubanGauvacaDsulong. 1 .2.PhdRMN H: Bfmglll : Ph6RMN 1H cmcaDsubanGau,caDsugiamdIp[17]=0,50,va caDsu long [1]]= 0,27. SIT 1 MAu <5(ppm) 5,34 2,24 1,81 5,12 2,03 1,68 1,25 D~ctrul1g 3 CaDso lcmg [1]]=0,27 5,12 2,03 1,68 1,25 -CH= . -CH2- -CH3 (cis-l,4) -CH= -CH2- -CH3 (cis-l,4) -C-H (a) -CH= -CH 2- -CH3 (cis-l,4) -C-H (b) CaosubanGau 2 CaosugiamdIp [1]]=0,50 . Ch6thlch cuangde)cua(b) > (a) PhiSRMNIH elmcaDsogiamcap,ngooinhGngmuid~ctnmgcuacis-l,4-poliisopren,con oot hi~nmuiiJ<5= 1,25ppm,d~ctnmgcuaprotonH cmcarbontamcap(-~-H), chUngt() cos\!'khaum?chd?iphantut?ivj trl Ca-Metilen.Cui.mgdOcuamuin~lYdmg100khimtrcd(J .. ,... 'A gmmcapcuacaDsucangsail. CH3I - - CH2 -' C = CH - CH-t - CH- CH =: C-I a CH3 a CH2- C% H% N% " Poliisopren(CsHs)n, 1.1. . 88,24 11,76 - CaosubanGau 87,94 11,59 1,02 Caosulong[1]]=0,27 86,76 11,36 1,40 ** POLY1S1PRENE NATURELLE DANS C6D6; 297K ** ~.. CAO SU BAN DAU I J': ' I : I" I I I ' I , " I! ', ' I , i , i I ': , 1 ', " I' , ! , 'I l ' , ' , ' i I :' ;;" . ' , ! I ' , , I' , ' I' ! I 1 ,: . ," , 1 " '11 I I I '" '1' 1 1 ',i " I~ 1"~N : I [I,!':'01 ~1VV\f\/'\ rf'VJ~ , , I, , I I, I II I ,I , 1/, Ii' 'I \, Ctl ( ,? \UI;l--C::::- C\I-CM27~.- k\ /' L. l , I , I. r-, I;' "I' 5.0 ~_5 4_0 3_5PPM , ,---r- ,,--.---. 3_0 I II ! i i 'i I , I ~ I : , , I 11'1 i i I I , , I, I I ,1 ! i ! : ! ,I' 1 1 -~., ,,; -rAJ2- .--/ .x --- J rn ( <0 rn r--'-- c-,T-' , r- ~---.-----.-- 2.5 2.0 , i ". , .-, ", B~R P1S0PREN. j 0 1 DATE 26-3-9j SF 200.132 01 4179.000 SI 16304 TO j63B~ SW 2092.050 HZ/rT .255 . r, 0 0 0 23,00 12.50 5. 'toor 36.019 - 180 _60 LB GB CX CY F1 HZ/C~' PPM!CM sn 2343 AO 3.916 RG 64 NS 310 TE 303 DR 16 FW 2650 02 0.0 OP tOL PO "I "r i" ;;} \ ,'\'!i,'(' ',I,'-,,' " I !1i I!! !J i i, i """ , III I '! i I , , " " l' , I , I ,.u ' I ' , , , " , "'-1" . ,-- I I I " I ' I ." "C,," IRP" 1190 11011 J200 IODI' ':' I ri r I n I n J ,t' I'rA,I'li~.1:'/,1 il" I ~1 ~(I (\1', I1":1 I (fl' Ir - -, -- -, ", . 'n- -- - ( ! : I !' I'" ,I, , ,,j, ! ! (I "I " !I I '\i , ",' ,1 5 6 I g !; , , I I I I , i I ' " , , I, ' I ' ' ~ "I I," I \ '" I I I , '1 , ' 1 ' , \,1""II I i'l, !I I I ',I III i , ;1 III, '1 1 1:1 '; 1 ,'ll,L I ,t l l l , 1.l iI,l ! I ii,', i' "' I I!, I 1,1 11, iT! 1l " ,,' 'I ", ," CAOSULONG [It] =0,27 i! ,I ii' ' I' , ' . i, I' 1 ,1 - , 1 II ' : , , ' ,,1, 1 1,1 ' , i i I 1 " ,1 ' , ' , ' 1 ' . ': , 'J , ' ',i'," 1 1 ' 1 ' I, I I ': I Ii " II;:;I i .. j , I , !I: - .. ' ,!I I -, , ! i 1 ' , ' 1 1 I i1 , ' 1 11 I ' ii, II' I I' 'I I ',I' I III:j i \" Ill 'I!il, ' 1 1 1 '1 , 1- i_:I - \ I ,I 1 \J , , , " ,1 ' , " -I l l ' 1,,1; II "! I ! I) I I ' I I I I I, II' i j iI I I" 1! I :r ',' II 'II i!"'. +~ I ' I" fi tI I I 1 -11- " - 'I' L ; I ,I t ' I ' I,I I I i, " ii, III II' I ' I' i i!I ! ,I ' r ' i ' I I C , '.' )',1' n , j - ,- I ! fiI ,I ' " ' I I I " II :' \,, 1 1 i ' ,j I' i'; ! ' 'i i !'I" ,, " , 1 ' ,' \" ", : " " , '1 , ' 1 " i _,' II" I I " ,". , II .11.1: - ,-,. II, I I ., ' t ' ,I, , ,! ,i II I, "'",. ',' ,,' ,'i i IJJ"J-11Jjl.~ 1:11 : i :.d' ,i [, ,,' I', I I i i III ;! i ', i i .i,)I,i : ,i i'" ;i" I ,I I ,'I , I ] 600 1~(l02000 lBOO'1'1\1 i""r) ,r:li, "' ] ,I I j i L II.. 'I ' , '\ I '), ! I ,;(10 1" KW POLYISOPRENEDEGRADE (HTI) [CDCL3: 297K! K. 1 , , 1 ~ A J 'j (1 "'--' 1 A' .. -Co. .)T /J- J' ~ - ..------. CAO SU GIAM CAP [~] = 0,50 l~ J ~ .,. _._,-- "-,-T' ..-"'-~-'--,'--'-~-"--r-r-'---r-r-~--'--'--'--'-~-~- i,_, '--'r--r--,-,--' '-'-'- 4.') 4 0 3.5 3.0 2.5 2.0 i'" 1 r; 1.0 PPM ~' J - r---- )(- /' ( ~ <D ." r , I , I l l n88n .. POLY ISOPRENE OEGRADE-H3-[COCL3: 297KJ KW PIsopnEN.120 DATE 6-5-<11 SF 200. 132 u: 4179.000 SI 1"38,1 TO 16304 5W 2092.t8J HZ/PT.255 AO nG N5 TE OR FW 02 01' 3.g1G 32 10 303 Hi ;>';<;0 0 0 101. PO LB GfJ r~x CY FI HZ/U1 PPf.I!CM sn ;>'~40 0,',) 0 0 23.00 12.50 5 100 "r; 039 200 03 -'He, -~ " ' ---- l._~~_J_. CAO SU LONG [11] = 0,27 r-rrr'r--. r-, r-.-, r-, ",--, ,--r--r--r-r , ,-.-,- r-.-r ,-r-r--r---r-r -,--, ,--r-,'--'-'-"""-'-'-"" ~'-T ",0 4,5 40 3') 3.0 2.5 20 I,') 1.0 'j 00 'i PPM - III I I i I I i 5i?e"l "",gn."..,, 3(PPM' Assignment 3(PPMI ASSignment: 1 1 52 !-CHz i I,2.23M2.t5 ; -eH,- I 11.75 i -en, i I' I' I; ~ I' I I " I i : i I : I I, I ' i Ana,ysiseondIUo"" NucJeus:'H $alvem:C,D, I;:.eouenev:60MHz Tam08",fu,":75"CI Sp8C1rOms'ar:V ianOA.oo.IL Retare""": MOS I De/""""" rBCtlntque:CW I I I -,-CH"""",C" CH-/CH,-i.- CH, \ SAMPLE ooly.s,,'oo. ".o,cal,"""UCI I I . i I I -(-C.H,-~.H-',- ~~ I I I I cAMPLE ,00l".,soo,eO$ILaiax. 1,4c", ; (PPM) i7.5.6.8) 7,0 (6.8-6.2) 6.6 (2.5-1.75) 1.95 (1.75-1.11 1,5 liPPM) I(PPM) ~ T I i I i I Aulgnment As.."nm.n! Assignment II H H, . 1 1 Hi ' II' H, . Ih I AnaIYs" conditions Nuelous:'H F,.quencv ,250 MHz SOBCfrome'ar:eameca250 DetBCticn/BCtIniqus:CW Sew.nf :CGI, =ec:, Tamcenllurs',100'C Reference:HMOS loci<:nons " \ il Ii II II II ,I' I! il 'I : I :I 1\ I\I \I I I ' \ i \ \ I I I. , V 'y/ " J ~ <~ /\ r"J ' I I I '~- I : : , , ------ .~' ' ,. ~°l" OOM :,5 so -76- .. '" '" A . .. ,t' [I.PHAN UNG GHEP POLISTIREN TREN CA0 SU LATEX GlAM CAP: Chungtoith\}'Chi~nphan6nggheppolistiren(PS)ireDraosulatexthongqua2giaid~m: -Giai d~ 1:gifuncapraosulatexbangh~khaimaGPhenihidrazin- FeClz. - Giaid~n2:ghepPS ireDraosudagiamcapngaytrangh~latex. 11.1.LtplchQnye'ut6vaquiho~chviing~h1fcnghi~m: Phan6nggheppolistirenireDraosulatextv'nhiencoth~ph\!thuOcVaGnhieuyelltonhu: lugngmcchat,lugngchatkhaimaG,nhi~tdO,lugngchath~t dOngbem~t(LaurilSullfat), tr9nglugngphfmfirraosu,t6cdOkhuay,pH coomOltruOngv.v...M6iyellt6vem~tnayhay m~tkhacc1eUcOanhhuOngnhatdjnhdendOngh9Ccoophan6ng.Saukhi tieDhanhmOtso phan6ngthamdb,chungtoich9nnhGngthongs6biend6ivavungkhaosattuong6ngnhusau: NhGngthongsocOdjnh la : -Tr9nglugngraosulatex60%:8g -Nhi~tdOphantmg:72°C -Toc dOkhuay: 400vang/min - pH coomOltruOng: 7 - 7,5 -LUQIlgNazHPO4 banglugngchatkhaimaG 11.2.Phuungtrinhh'Uiquivanh~nxet: D~coth~thaydUQ'cmoiquaDh~giiiadOchuy~nhOOvacaethongsoanhhuOngdenphan ilngghepstiren,eungnhusl!tuongIDelfu1nhaugiiiacaethongso,chungtoi datieDhanhke h~chhOOth\}'Cnghi~mtn,fCgiaocapmOtmarOngv6icacbiendUQ'emahoatheoeongthoc[1,3] (z' - z')x' = J J J. =12345J !!!.z' , , , ,J Trangdo: ZJ' =Zjrnax+ Zjrnin2 vi!: !!!.Zj = Zjrnax- Zjrnin2 SIT Thong56bin d6i Z' - + 1 Tr9nglugngphfmtirraosuMy Zl 110.00055.000 2 LugngK2S208(g) Zz 0,18 0,30 3 LugngStiren(g) Z3 7,2 14,4 4 LlK!llgchatH.D. bemt (g) Z4 0,17 0,26 5 ThOigianphantmg(h) Zs 5 7 -77- Zj : danvi biende>ih~c khoangbiende>icmyelltothuj. Xj :giatrj macm yelltothuj ZOj : giatrj thvca mtrccO'sac~ yelltothuj. . Zj :giatrj thvccmyelltothuj. V~yphoongtrinh hOiquibi~udi~ns\!'ph\)thue>cgiGade>ghepVaGcacbiendamahOOe6 d~ng: v6i: = bo + blxl + b2X2+ b3x3+ b4x4+ bsxs + bl2XIX2 + b13XIX3+ b14xIX4+ b15xlx5+ b23X2X3.+b24x2X4+b25X2X5+ b34x3X4+ b35x3x5+ b45x4X5. Trangdo: Y: de>ghepcmphan(mg. Xj: bienmacuaZjU=1,2,3,4,5) bj : coh~sobi~udi~nhi~utrngtuyentinh bju:caeh~sobi~udi~nhi~utrngtoongtaedoL Ma tr~nkeho.;'lcht vcnghi~mbanphanb~enhatmare>ngv6ibi~uthtrcsinh: X5=Xl.X2.X3.X4 . . Dungd~xacdjnhcach~socmmahinh(1) duvechob6ibang11.1,trangd6Xo= +1 duvcg9i]abienao. Tir ketquathvcnghi~mcoduvctheomatr~nkehO<;lCh,taxacdjnhh~sobj theoctmg thuc[3]: y (1) bj = XjiyiN Trangdo: N :sothinghi~mcmkehO<;lch(N =16) Yi :de>ghepcmthinghi~mthui C11chi~utrngtoongtacdoibjuciingduqcxacdjnhnhahi~utrngtuyentinh.Tir dotaeo: bo~53,02 b12=-2,13 b23= 0,46 bi =-3,26 b13=0,86 b24= 0,27 b2= 0,72 b14=-1,36 b25= 2,83 b3= 3,58 bi5 =5,01 b34= 2,88 b4= 3,62 b35= 1,92 b5 = 3,81 b45= -2,89 STT Zl 1 55.000 2 110.000 3 55.000 4 110.000 5 55.000 6 110.000 7 55.000 ~110.000 9 55.000 10 110.000 ~55.000 12I 110.000 13 55.000 14 110.000 15 55.000 16 110.000 BIEN THL!C Z2(gr) Z3(gr) 0,30 14,40 0,30 14,40 0,18 14,40 0,18 14,40 0,30 7,20 0,30 7,20 0,18 7,20 0,18 7,20 0,30 14,40 0,30 14,40 0,18114,~0- 0)8 I 14,40 0,30 I 7,20 I 0,30 7,20 0,18 7,20 0,18 I 7,20 (*) BANGIT.l: Ma?tr?~ke ho,~chthlfCnghi~mbanph~inb?c \md ~9ngcua phanLlngghepPolystirentrencaosu Latexgiamcap. (S6thfnghi$m: 2 k-1= 24 = 16) BIENMA Z4(gr) Z5(gia)1 xO 1 xl 1 X2 1 x3 I x4 I x5 IXl21x13!X14!XIS! X231X241X251x341x35 1x4S 0,26 71+1+1+1+1+1+1+1+1+1+1+1+1+1+1+1+ 0,26 51+1_1+1+1+11 I 1 1+1+1+1 1+ 0,26 51+1+11+1+1 11+1+1 I 11+1+ 0,26 71+111+1+1+1+111 I 111+1+1+ 0,26 5 + + + + + + + + : I 0,26 7 + + + + + + + I + 0,26 7 + + + + + + + I + 0,26 5 + - - _1+1_1+1+1_1+1+1 1+1 1+ o,n 0,17 0,i7 0,17 0,17 0,17 0,17 0,17 I Yi% ,(i% j 7 7 5 7 +1+1+ +1++ + + t- 1+ ++ + + + +--t +1+1+ + +II~ + I I + 1+i + ~I++' 'LJ2 +I I I I-r I - I +1+1+ J + I +1+l I + I_I _I +1+ + + + I +1+ +1 I I I I Ii I! 1+ i + 1 + i+ I + I + I + I_! + I+ I +1+ 5 5 ~ 1+1+ r--l +7 89 ghepdo bangph110ngphapd110ngchuantLtphoIR . 89 gheptinhtLtph110ngtrinhheiqui £)9 GHEP Yi Yi + 68,7 68,79 70,4 69,05 54,4 55,73 58,9 59,01 36,9 36,45 "- 54,5 55,33 48,1 47,29 61,2 61,65 32,0 31,19 60,0 60,43 61,7 161,27 46,7 47,51 55,8 57,15 51,6 I 51,71 40,5 40,39 46,9 45,55 + - 78- D~danhgiftcach~socrnmohlnh,chungtoitieDhanh4 thinghi~m(No=4)atamke ~ch(bang11.2). BfmgII.2 :DOghepcrncacthinghi~mt?itamkehO<;lch. 01 Di"Cuki~nphanth1g: -TrQnglrn;mgphantllcaDsu:Mv =82.000 - Lrn;mgKzSzOs(g) : 0,24 -Lrn;mgStiren(g) : 10,8 -Lrn;mgchatHDBM (g) :0,215 -Thaigianph8.n(mg(h) :6 * cacdieuki~nkhactumtgtvnhutrongcacthfnghi~mabfmg1.1 Nhuv~ytrj trungblnhcrncacthinghi~mt?itamkehO<;lchsela:yo =54% Thea[3],tinhynghiflcrncach~sodugcWClrn;mgtheachufinstudentbhngcachtfnhdiC giair; tj : b' tj =~ V6i Sbjlaphumtgsaicrnh~so,dugctinhbOicongth6c: Sz. - sllioJ--W- Sthlaphumtgsaitaihi~n,dugctin~bOicongth6c: Sn.= ~~--lYO)- The sovaGtacO: . sn.=0,78 Sbj=0,22 Tir dotacoC{lCgifltr; tj (bfmgII.3) Thi nghim ti tam D()ghepyOu(%) 1 55,1 2 54,2 3 53,7 4 53,0 - 79- Bfmg111: Oia tr; Clk~tj tuong(mgv61bj h~c bju Chi conhfmgh~sobj haybjll cotj > tp(f) moicoy nghia[3]tp(f) lagiatr}tm bangelm leUchillln Student v61mucyp =0,05vab~ctvdocmphuongsaitalhi~nla3. :Theobfmgto,OS(3)= 3,18[4] Ta thaydlCh~sob23vab24trongbfmgII.3 cocacgiatr; t23vat24nhahem3,18Den chongcoynghiatrongphuongtrinhh'Oiqui. Nhuv~yphuongtrlnhh'OiquimotftSllph\!thu\>cd()chuy~nhdlcllaphlm(mgghepstiren reocaosuv~1OdlCthongsonghiencootrongvUngthllCnghiemcoth~13: Y =53,02-3,26xl+ 0,72x2+3,58x3+3,62x4+3,8lx5-2,13xlx2+ 0,86xIX3-1,36xIX4+ 5,01xIX5+2,83x2X5+2,88x3X4+ 1,92x3X5- 2,89x4X5 (a) SIl tuangthichcuamohlnhnayv61thvcnghi~mdUQ'cki~mtrabOitieuchilllnFisher[1,3]: . S2F , h - du tm - Sth V61S2dulaphUlmg~JldudUQ'ctinhbOirangthuc: a ( y - yo) 2 . S - I I u- N-L Trongdo: L Yj :soh~socoynghiatrongphuangtrinhh'Oiqui (L= 14) : giatr; cm dOchuy~nhoatinhtuphuangtrlnh11"l'1iqu (a). bj hoc bju tj bo 53,02 / 241,00to bl -3,26 tl 14,82 b2 0,72 t2 3,27 b3 3,58 t3 16,27 b4 3,62 t4 16,45 bS 3,81 ts 17,32 b12 -2,13 t12 9,68 b13 0,86 t13 3,91 b14 -1,36 t14 6,18 b15 5,01 tIS 22,77 b23 0,46 t23 2,09 b24 0,27 t24 1,27 b25 2,83 t25 12,86 b34 2,88 t34 13,09 b35 1,92 t35 8,73 b45 -2,89 t45 13,14 -80- Yj Taco: : giatrj coodOchuy~nhOOdotiTthvcnghi~m. 2 S du = 5,3564 Suyra. F ' h =5,3564=687. till 078 ', Giatrj trabangcootieucnufu1Fisher[5]: FO,95(fl,f2)= FO,95(2,3)= 9,6 " V6i: h=N-L=2 f2= No-1= 3 DoFtinh <Fo,95(2,3),nenphuongtrinhhoiquinoitrentuongthichverithvcnghi~m. Ngoaifa,chungtoiclingdoIU9TIghopolime(Polistiren)t~othanhtuongtmgvo;cacphlm mgtrongmatr~nthvcnghi~m,dOchuy~nboacmmonomeVaGhopolime(HO %) daDdOng rangkhoangtiT1-3% (bangIIA) Bang11.4:DOchuy~nhOOcoomonomeVaGphantmgghep(MG%), dOghep(DG%), dOchuy~nhOOcoomonomeVaGHomopolime(HO%), dOchuy~nhOO teingcOng(TC%), tuong(mgv6icacphantmgtrongmatr~nkehO<;1ch thvcnghi~m. SIT MG% HO% TC% DG% Ym% ! 1 65.9 2.2 . 68.1 664 687 , 2 73.8 20 75.8 689 704 3 36.3 2.1 38.4 52.1 544 4 44.5 1.8 46.3 572 589 5 35.1 2.1 37.2 345 36.9 6 73.4 30 76.4 524 54.5 7 56.3 32 59.5 45.8 48.1 8 95.5 24 97.9 58.9 61.2 9 13.7 13 15,0 292 32.0 10 466 17 48.3 583 60.0 11 482 12 49.4 59.1 61.7 12 260 14 27.4 438 46.7 13 746 15 76.1 52.8 55.8 14 646 23 66.9 49.2 51,6 15 402 20 42.2 37.6 40.5 16 539 2.2 56.1 44.7 46.9 PP PhuongphaptrQngIl1\mg Ph6IR I do -81- cac ket qilll trangbfmgII.4 rho thaycacgiatr}de>ghepdobangphUffilgph{lpphantkh tn;mglrn;mgvaphantkh bangph6hongng~ chenhnhaukhoang2-3%. . TuphUffilg trinh hoiqui(a),chungtoic6me>tsonh~nxetsau: * TrangvimgkhfK1sat,de>ghepph\!thue>ctuyentint theecacthongso: tn}nglll\mgphfm tu trungbinh Clk~caosu(My), lrn;mgchatkhcrimao,nongdOstiren,lrn;mgchathO<;1tdOngbe111~lt vathmgianphfm{mg.Trangd6,anhhuOngCUachatkhcrimaolayellnhat. * H~sob1 > 0 chUngto de>ghepgiamtheosvgiamtr9ngIll\mgphfmtu trungbinh cllCl caosuoDieu nayrho thay: Tam phan{mg,maa d6PS ghepvaotrenm<;lchd<;liphfmt&cuacaD so,dab}gifll11trangquatrlnh giamcapcaosutruacd6.Phan{mgghepPS tren caosuchuyell xayfa t<;livj tr] Ca-Metilen [8],neutrangphfmUnggiamcapcaoso,sv cat111~lChoxi hoaV~lsv khflu111~lChd~iphflntu clingxayfa 6 vj tr] nay,thi mucdOgia111capcangsfmdIng lmh hLimg dende>ghep. * Dic h~sob2,b3,b4,bs > 0, chUngto de>ghepsetangkhi tanKIll\mgchatkhoi 111~ID, nongdOstiren,lrn;mgchathOngbeill?t vathmgianphanUng. * H~sob12.vabI4 < 0 chothayphanUngse-thti?nlqi khi tlwc hi~ntrangdieDki~n: trQnglll\mgphantucaosua milccaov6i111(1tlrn;mgchatkhcrimaovachathO<;ltd(mgbem?tIon trangvungkhaosat. * H~sob25vab35> 0chUngtosvtUffilgtarthu~ngiliathengianphanUngveriIll\mgchat khcrimaovanong,dOstiren. * H~so b34> 0 chUngto c6 sv tUffilglac thu~mgilianongdOstirenV~llll\mgchathC~lt dOngbem?t. * H~sob45 < 0 chUngtC)sv'tUffilglac nghjchgilialrn;mgchathC~ltd(mgbe m~ltV~lthen gianphfmUng. * H~sob13vabI5>0 chothaytrangvungkhaosat,phanUngsethufinI(,rikhith\fChi~nc..y dieDki~n: Tn;mgIrn;mgphant&caosutMp di kemv6imQtnongd()Stirencaohc~lcthmgian phanUngkeDd~li. Dieu nay c6 th~dm;rcgiai thkh nhu sail : Khi giamdip caosu L'ltex b~mgh~ PhNHNHz-FeCI2,vaitro trQnglrn;mgphantu thapcUacaosugiamcapgayhaihi~ntll\mg ngll\rcnhautrenqillltrinhghepPSxayfasaild6: -Hi~ntll\mgkhaum~lchd~iphantut<;livj tr]Ca-Metilensecantr6svtancCmgcuaStiren trentamcuaphfmUngghep. -Ngm;rc]~li,v6itrQnglrn;mgphantuthap,Calltrued~liphantucuacaosucokhuynhhu6ng du6ithlmg,t~odieDki~ncholTIOnOmeStirend~dangkhuechtanmOtdlChdOngOeudentam phanUng[23]. Vi~cthvchi~nphanUngghepv6i1110tIll\mgStiren16nhC~lCthmgianphlm{mgkeodhise h6tr(,)'chohi~ntll\mgthu2,vadod6lamtangdOghep. -82- Ph~mtmgdoi chUngdUQ'cth\fChi~nv6iSt,rghepPS tr\fCtier trencaDsuLatexkhCmgyua giai do~mgiam cap,caedieu ki~nthl nghi~m(tru yell tc>tr9ngIrn;mgphan tir) tUtmgtv till .nghi~mthu2coobfmgmatr~nkeh~ch.KetquachobCribangII.5. Bfmg11.5: SosanhdOghepcUaphantmgghepPS trencaDsuLatexc6vakh6ngc6gifU11 '" cap. Ketquaa bang11.5rhothaydOghepcUaphantmgphepPS trencaDsuL'ltexchuagiam capthaphemcuaphantmg2.NhuV?y,caDsuc6trQngluvngphEmtuIOndocautrucd~iphEmtu a d~ngcuOnxoan,nenmonomesekh6khuechtanmOteachdongOeudencaetamphantmg trenPoliisopren,lamh~nthedOghepcUapha~tmg[23]. Toml~i: * Dtmgvem~tdQghep,chungtoidftthvchi~nphfmtmggheppolistirentrencaosulatex dftgi~l.lnCc:fpcodOghepcaD(70%)maIll\mghopolimel~lit (1-3%),sov6i cCmgtrlnhcua G.BOCCACCIO [7]eachtienhanhphantmgcUachungtoidemgianhlm(i'rtinhlienWccua tientrlnh). * D~rhophfmtmgcodOghepcaD,mOttrongc[lCdieuki~nlagiamtn,lngIU\mgphfmtl.1' caDsudenmtrcthfchh9JJ.St,rgiamcapSElUlamgiamtamphantmgvadododQgheprunggiflm theo;conneukhonggiamcapcaDsu,tIllyelltokhuechtanselw.ncheqUatrlnhphfm(mg. * Dtmgvem~ltdQchuy~nhOOcuamonomestirenvaocopolime(MG),thl thi nghi~mR (bang11.4.)elmketquacaDnhat(95,5%),tuongtmgv6idOghepkhoong61%. Hi~usufitphfm tmgtinh trendOchuy~nh6acUamonomecaDratcoynghia trong thvc ti~n. 11.3.Nh~ndanhsanpharo: Sanph5mcopolimeghepcaDsu-PSdUQ'cnh?ndanhbangph6IR vaRMN 1H. 1/Phd IR : Ngoaicacmuid~ctrungcUacaDSUtvnhien: 840,1666,1350cm-I,ph6IR cUacopolime ghepconxuathi~nCc1Cmuid~lCtrungcuaPS : -700va756cm-I:DaodOngbiend~ngcuaC-H trongnhfmthmnmQtranthe. - 1494va 1604cm-I :vc=c cuanhfmthO111. 2/PhdRMNIH : Thf nghim Zl (Mv) Z2(g) Z3(g) Z4(g) Zs (h) DG% 2 110.000 0,30 144 ' 026 5 68,9 70,4 2' 650.000 0,30 144 026 5 - 48,0 Phuongphapdo Trongluong Ph6IR -83- PheJRMNIH cuacopolimeghepngoainhGngmuid~etnmgcuacis-l,4-Poliisopren(J: 5,12ppm,2,O3ppm,1,68ppm,conxuathi~neaemuid~lCtnmgcuaPS : - 7,25va7,07ppm : HmvaHpcilanhfmthmD..' - 6,6ppm :. Hortacilanhanthmn. - 1,90ppm : Ha. - 1,43ppm :. Hf3. {3 a -CH2-~H - C6H6 ** CS-STYRENE (CDCL3;297K) ** VI 1, '> --(Olt-C ~ c,\I,-WL\ (r) -{:C'f!,H2,.-Cc<l-It (5), \ x. ~~\o L9~~ r t~t -cll,- -LAll~ , '"', " ~\\r(q H"(~! \l\" :::rH- (-I) lfr,>(s) ~-1 I' , , , , ' , , , , ' , , , , ' , , , I ' , , , , ' , , , , ' , , , 1 ' , , , I ' , , , , ' , , , 1 ' , , , , ' , , , I ,0 6.5 6.0 5,5 5.0 4.5 4.0 3,5 3,0 2,5 2 0 1.5 1,0 PPI-I " ,I !i Iii I I : ! I , I ' ' I ' ,,','" I [ I ' I , " I ',II!ilil , I'I!!:I: [ 1!1' I " I :I'I'II! 1'1'1111,11'1'I '! I!J ,I h:'sl" !~,U':!r,i .~,'; II i I CAO SU - STIREN!I I', I '; . ", - I' i I I; , :,-.t-"""", (IH"'C"~" ," "" '" ' ~! 'it. i I .",d,., " Ir", : I I I ; ,'. I I,,!, I ~ i i ' I ' i ' " : I ' i:' ,: ' I ' I , !:; , , I: I i ,,' " , i , . " ill' ; I ; I , !" " " II" I I I " , "", ' I ' " " , '" I" I, ", " ~: : " I : I 1, " I i ' I ; ' , ,I i , ': I i I !! " i , ' I ' , h" ! " i I I, ' , r, i ': ",: " , f, ' i ., " '~ ,, " , ' , ' J L . , , :) ..i . ' , "' , ":':' " I ""' , ':' , ,:1 , ' ' ,1 1 ,1,.:, I, : , I , ' I ' I '::! I1 II '1":"f. . h' , . '. . ': ' , ' I I I I ' " , "',j. '"" <'-: -~'i.j '(I, " , 'c, of ,",,' I, i I ' ',!! I , i' , :':,;1:r';f l :ri':i , "i:,,~:::t l f " 1 ' :';li;III\1 '" " ; , I " 'I ,I ! 'I I ' , ..'. i, ! ! I,' I, i ! !, , , ,0" .I, :' 1":" ".;. t ,J",:, I ; , 'i ' r ' j ' 1 ' , I , " "'" " I " , " ' I ' """, I ' " , i I " I ' I I, I ', I I! Iii I I ' , ,! I I II i ,; 1 I ',L I I , i !: ,,' Ii! I : ~i ' I , ; I, I ' i I I, I ': I I I ,!, ii" I I : 'I I " 'I I I, " ' , , , ' I, 'I, , ,I "" . ..:' , 1 ' :' ." ' I "' , I' ! I I : , " I I ' '" .. ': ' ',', ' ; ',: .' j',~, hi I' ,'t,t " " t ",..', i ,I , " I I( , ,; r',: Ir,{ " 1 il ';'" ' I I ," ," I " I ' I I ' I : , , I'I!, I ':!, " I: i . I i :: i I "!, ,i, :' 'i, '! i i : " ,1-:: , ' , ! i . i I I, I I: ,1,lj! Ii !;!, "I ' ,!I '. II 'i" i i i I I ' II : II " I Ii f " I i i i ' ,J"":"""'::' I "':'!:" ' , " ;';' ~ : ,!;' , " , :;: I I "I ' " ' , ;! I " ' I ' . I' ,. , I ., ! ' I, ," I I I " , , " [ ,~,:, , ~,,:j' , '-I~,j,t:j"""J~:"J::'S' : 1 ' ..,1 ,,:'1 " ""'" I ":" "l' ", , ',' ~" 'j , t ", ' , , 0:; , ' f ::, ,t, " , J 1,1,'" '.: ~I 'f' .I. ", ~"..I 'f' I , : " I r " I ' , " " " ! I ' II ' r " I i" '" ," ,'", I't' , J I' I I I I '; I ' I, ' I ! ' ! .., ,' I ' ' I I I " I, " " , ,I I, I , ;' " i' I I ' '! I ,[ ';, i-:,: :,':.::!':, i! if : i :,,'" , I ' 1,,1 ,' " , r:I'" ( , ,, ! :,..,I " ! !". , :- ' " ' I, I! " , ' ," , ' I , ' , ' ' I ' i I "," ! i I " "..I , : ."',, ;, \ ' 1 ; 'I' I I , I ', I " ' I ' I 1 I ':, " " ' I i i I ' I 10: ','!; ! I,! !" ii' !, i I 'i, i, ; " ' I " I . : '" ,'"" :""" ,"I"" I,g"" '", " "1'1)1 I ' 1 ' ,I , : I . , " , : , , , , '! I I I i' , II II I I i 1 "! t., ""~I!I """':' I'" o8§n C55TYREN,100 DATE 6-5--91 5F 200,132 01 4179,000 51 16384 TO 16384 5W 2092,050 HUrT ,255 0 0 0 0 23,00 12 50 1, Boor 60,036 ,300 ,02 LO GO ex Ci F1 HZ/CM PPM/r.M SA 2341 , I AU 3.91G RG 32 N5 184 TE 303 OR 16 FW 2650 02 0,0 OP 10L PO - U""T- [II. pHAN UNG C9NG ANHIDRID MALEIC (AM) vaoCAO SU .. ,(' GlAM CAP: V6i phfmlmgnay,truacbetchungtoitienhanhgiamcapcaosulatexbangh~khoim~lo Phenilhidrazin-FeCl2 dentrQnglugngphantiTmongmuon; saud6 th\,lChi~nphfmlmg c('mg AM VaGcaosudflgiamcaptrongdungmoitoluen,v6ichatkhoimaGlaperoxidbenzoil. ChungtoisiTdl,mgphuongphapquih~cli th\,lCnghi~md~khaosatphilolmgn6itren, nhamtlmhi~uanhhtimgcUacacyelltonhu: trQnglugngphantiTcaosu, lugngAM , lugng peroxidbenzoil,nhi~tdOvathmgianphan6ngdendOchuy~nhOOcuaAM VaGcansuoTrong d6,yelltotrQnglugngphantiTtrungblnhlayelltoduvcchungtoichuynhat. D~thayrovaitrocUayelltotrQnglugngphantirtrungblnhMv tacdOngdenphfmlmg, chungtoikhaosatphanlmgCr2vimgtrQnglugngphantir : vimgc6Mv =30.000- 70.000va vimgc6Mv=84.000- 136.000. 111.1.Khaosatphanthtgd)ngAM V80caosugiamdi'ptrongvungcotn;mghrc;mgphilohi' trungblnh Mv =30.000-70.000. . III.I.I. L~mchfJll ytu t(1vaqui hO!f£hvilllgthf,lCIlghi?m : Dt,rdvannhlmgketquathfimdovatheeilii li~uthamkhan[19,20],chungtoich9nnhlmg th~ngsobiend5inhusau: alC thongsocodjnh: -NOngdOcansugiamcaptrongdungdjchtoluen:5% -TocdOkhlk~y:400vong/min DOehuy~nhOOellaph~mlmgdll\1edjnhngrualasophfmtirAM eOngvan100matxfch isopren,vadll\1exaedjnhbangphuongphapth~tfch. SIT ThongseJbin d6i Zj - + 1 TrQnghn:.mgphantucansu(My) Zl 30,000 70.000 2 LlI\mgperoxidbenzoil(g) Z2 0,035 0,071 3 LugngAM (g). Z3 0,288 1,152 4 Nhit dO(aC) Z4 80 110 5 Thmgianphan6ng(h) Zs 3 5 -~) - ill.l.2. Phumlg(rinhh'oiquivanh~1lxet: . - Zj - zf ' - 1'2 3 45 xJ - /).Zj J - "" ," Phuangtrlnhhoiquibi~udi~n51!ph\!thuOegifmdOehuy~nh6avadlCbiend~lm~lh()(lC() d?ng: [1,3] Y = bo+ blXI + b2X2+b3X3+b4x4+bsxs+bl2XIX2+b13XIX3+ b14xlx4+ blSXIXS + b23X2X3+b24x2X4+b2Sx2XS+b34x3x4+b3sx3xS+b4sx4xS. (1) Trangd6: Y : dC)ehuy~nh6acrnphfmfu1g. Xj : bienmacrnzj U =1,2,3,4,5) bj : coh~sobi~udi~nhi~ulmgtuyentinh bju :caeh~sobi~udi~nhi~ufu1gtuangtaedoi. Ma tr?nkeh~lehthl,l'Cnghi~mbanphanb?cnhatmarC)ngvo;bi~uthuesinh: , xs =Xl.X2,X3.X4 Dungd~xaedjnhcaeh~socrnmohlnh(1) drn;rcrho bCribfmgIIL1, can cuV~IOmatr?nkehC\;'leh,taxaedjnhdrn,recaeh~sobj vabjuthene6ngthilc [3]: x" Y . bJ ' = IJ 1 N b' - ---B.u YiJU- N bo=9,62 bI =0,79 b2=2,33 b3=2,69 bI2=0,86 b13=0,96 b14= 0,066 blS=-0,17 b23=0,43 b24=-0,81 b4= 1,08 b2S= -0,12 b34=0,37 b3S=0,08 bs=0,43 b45=0,38 D~danhgiae{leh~soeuamohlnh,chungtoitienhanh4thlnghi~m(No=4)songsong atamkehO~ICh(bfmgIII.2). BANG Ill.l: Ma tr?n ke ho~ch?thLfcA,ngri$[T1bar]phan b$c 1md[Qngc0a phan t1ngGong AM vaGcaosu giamcapd vung co trQng1LJ'~ngphantv tv 30.000-70.000 (s6 thinghi$m:2k-1= 24= 16) Yi% 89 chuyenhoadotti thl/c nghi$m. 09 chuyenhoatfnhtti phuongtrinhhoiqui C) Yi% A' THl/C A' MA . .'BIEN BIEN £)QCHUYEN HOl\ SIT Zl Z2(gr)I Z3(gr)Z4(oC)Z5(gia'xO xl x2 x3 x4 x5 xl2 x13xl4 xl5 x23x24 x25X34 x35 x45 *Yi . Yi 1 70.0000,071 1,152 110 5 + + + + + + + + + + + + + + + + 19,00 19,13 2 70.0000,071 0,288 80 5 + + + + + + + + 9,25 9,67 3 70.0000,035 1,152 80 5 + + - + .+ + + + + 8,20 8,23- - - - - - 4 70.0000,0350,288 110 5 + + + + + + + + 6,25 6,33 5 70.0000,071 1,152 80 3 + + + + - + + + + 17,13 16,99- - - - - - 6 70.0000,0710,288 110 .., + + + + + + + + 9,05 8,61" '" 7 70.0000,035 1,152 110 3 + + + + + + + + 11,92 11,89 8 70.000.0,035I 0,288I 80 3 + + + + + +1+ + 2,49 2,43 19 30.000 0,07111,152 80 5 1+ +1+ + + + + + 12,0911,87. 10i30.000I 0,071 0,288 110 5 + + + + + + + + 8,75 8,85 11 30.000 0,03511,152I 110 5 + I 1+ + + +1 + + + 12,05 11,73I I 12: 30.0000,035I 0.2881 80 I 5 1+ + + + + + + + 4,87 4,59 113 I 30.000 0,071 11,152 110 I 3 1+ + + + + + + + 12,09 12,29I 14 i 30.000I 0,071I 0,288 I I ' +1 I 8,29I 8,1980 .., 1+ + + + + + +" 15 ! 30.000I 0,035 : 1,152! 80 I .., I + I 1+ i + +J+ + + + I 6,05 6,35I" 16 I 30.000I 0.035! 0.288 : I .., I I I +1+ i+ + 6,51 I110i " i + i + + + 6,77I -86- B~mg111.2.DQchuy~nhOOcoocacthfnghi~mt~lit~llnkehQach. Dieu ki~nphilO.mg: - TrQnglw;mgphfmtll cansu: 50.000 - Lw;mgPeroxidBenzoil(g) : 0,053 -Lw;mgAM (g) :0,72 - Nhi~tdQthfnghi~m(oC) :95 -Tho;gianph~ml g(h) :4 - WongdQcansu trong toluen : 5% Gia tr; trungblnh cooC{lCthfnghj~mt~jtfllnkeh~lChselh :yo =9,285 Tfnhynghiftcoocach~sodll\1COOClll\mgthenlieuchu5nstudentbangdlCht1nhc:k gift trjtj:[1,3] V6i: 2Sth =O~ Sbj=V ~ =V~ =0,055. N Tirdotacocacgiatr;tj: tj=bj/Sbj (bangIlL3.) BangIlL3. Giatr;cuatj tUtmglmgv6ibjhC$cbju Thi nghim ti HIm DOchuyn hoaYu0 (%) 1 9,03 2 9,37 3 9,20 4 9,54 bjhoc bjl! tj bo 9.62 to 174.9 b1 079 t1 14.36 b2 2.33 t2 42.36 b1 2.69 . t3 48.90 b4 1.08 t4 19.64 bs 043 ts 782 b12 0.86 t12 15.64 b13 0.96 t13 17.45 . bl4 0066 t14 1.20 bls -0.17 tl5 3.10 b71 0.43 - t73 7.82 - 87- Ta cotp(f) = to,05(3)= 3,18 [4] Chi conhiiTIgh~sobj haybjucotj > tp(f)millcoy nghiatrangphuungtrinhhoiqui. Trangb~mgIIL3. cach~sob14,b15,b25vab35codicgiatrj t14, tIS,t25vat35nhahem3,18Den khongcoynghia. Nhuv~yphuungtrinhhOiquimotaS\Jph\!thuOcdi)chuy~nboacuaph~mlrngci)ngAM vaocaosuvaocacthongsonghienClrutrongvimgth\Jcnghiemcoth~nl: Y =9,62+ O,79xl+2,33x2+2,69x3+ 1,O8x4+ O,43x5+ O,86xIX2+ O,96xIX3+ O,43x2X3-O,8lx2X4+ O,37x3X4+ O,38x4X5 (b) S\Jtuungthkhcuamohinhnayvillth\JCnghi~mdrn:./cki~mtrabCritieuchu5.nFisher[1,3]: Ftinh=sau . Vill S2ctuUlphuung~l~dUdUQ'ctinhbCriGongth(rc: S2 = (Yi - Yi)2 =022 (lu N - L ' Trangdo: L =12 va N =16 Suyra: Ftinh= 4,58 Giatrj trabangcilatieu.chu5.nFisher[5]: FO,95(4,3)= 9,1. DoFtinh< FO,95(3,3),Denphuongtrinhhoiquinoitrentuungthfch. Tir phUlmg trinh h<)iqui tren , chungtoicOmOtsonh~nxetsau: * Trangvimgkhaosat,dOchuy~nboaph\!thui)ctuyentinhtheocacthongso: tr~mgIrn:.mg phfmtutrllngblnhcuacaoSlI,llJ911gchatkhaimao,llJ\mgAM, nhi~td()vathengianph{m(mg; trangdofmhhlltmgcualacchat(llJ911gAM) vachatkhoimaolam~mhnhat. * H~sobl > 0rhothaytrongvUngtr~mgllJ911gphfmtutir30.000- 70.000,dOchuy~nh(x! gi~l111khigiamtr9nglUt,mgphfmtucaDSUoDieunaycoth~dUQ'cgiaJthkh Ihkhigiflllldip canSlI bhngh~khai maoPhenilhidrazin- FeCI2 , a mocdOgi~lmdip SflU,mOtso phfmd~mcanSlIbj khallm~cht[lihc;rp,s\J khflllm~chnaychuyeux5yrat~liCa-metilenerncaDSU,vadf!ycung chinhlanaim~lAM tancCmgValltrongphanlrngc(mgdUt,YClienhanhsalldo[6,10,13,19,20], ketqrulladOchuy~nhOOsegiamkhimocde)gifundiprangsau. * H~sob12vab13> 0 elmthays\JtUlmglacthu~ngifmyelltotrqngJtJ{;mgphfmtuveri lln,mgchatkhaim~lovalrn:.mgAM. b24 -0.81 t?4 1473 b25 -0.12 t25 2.18 b1L1 037 't1L1 6.73 b1'i 0.08 i t15 1.45 b4'i 0.38 t45 6.91 -88- * H~sob23,b34vhb45> 0, rho thaySI,1'tUtmgt{lCthu~ngiuayell to IUt.mgchatkhoi mllo vah.n,mgAM; yelltonhi~tdt>V~lhn,mgAM, rungnhuyeutonhi~td()vathtrigianph~m(mg. * H~sob24> 0 ch(mgtosl,1'tUtmgt{lCnghjcpgiuaIm.mgchatkhtrimllovanhi~td()ph~m (mg. III.2. Khaosatphanul1gc(mgAM vaocaDsugiamdIptrongvungcotn;mglu,!!ngphfinhi' trung blnh My =84.000-136.000 //1.2.1.LlfUchfJllytutffvaquihorchvimgthlfCIlghi?11l: Chungtoich<;mnhfmgthongsobiend6ivacodinhnhusail: cacthongsocodjnh: -N6ngdt>caosugi~llndiptrongdungdjchtoluen:5% 1." d" I ?, '90'oC-n lI~t 9plan ling : - Toc d()khuay : 400vang/min 11/.2.2.Plulfmgtrillh h'o;quivallh(ulxet: cac yelltodu9'Cm~lh6aved'imgkh6ngthunguyenv6i: [1,3] (Z' - zo) x' = h J J' = 1234I z. ", PhUtmgtrlnh h6iquib~~udi~nS,!ph\l thut>cgiuad0chuy~nh6avac{lCbiendflmflh6aCl) d~mg: Y =bo + blXl + b2X2+ b3x3+ b4x4+ bl2XIX2+ b13X1X3+ b23X2X3 Ma tr~nkehO~lChtlwc nghi~mb{mphanb?cnhatmer0ngvrnbi~uthtrcsinh: (2) X4=Xl,X2.X3 Dung d~xacdjnh cach~socuam6hlnh (2)du\}crho b6ib~mgIlIA C1)nClfvaomatr~nkeh0<;1Ch,taxacdjnhdm/cc~ch~sobj vabjuthencfmgth{rc[3]:" SIT TI" "'b"" d,\" Z' +10ngso leu 01 ,I - 1 Tr<;lngh){imgphantllcaosu(Mv) Zl 84.000 136.000 2 Lll\mgperoxidbenzoil(g) Z2 0,025 0,071 3 LlI\mgAM.(g) Z3 0,48 0,72 4 Thaigianphan(mg(min) Z4 60 90 SIT ZI 136.000 84.000 136.000 1 2 "" ,) 4 5 6 7 8 84.000 136.000 84.000 136.000 84.000I (*) Yi% Yi% BANGffi.4L:M?atran?ke,ho~c~thlfCngri$mbanp~fmb~,c1?mqrQng, cua phan LIng<;i9ng,AM vaGCao su gramcap 0 vung co tr9ng 1L1~ngphantLl Mv = 84.000-136.000. BIEN THl/C Z2(g) Z3(g) Z4(PhUt) 0,071 0,72 90 0,071 0,72 60 0,025 0,72 60 0,025 0,72 90 0,071. 0,48 60 0,071 0,48 90 0,025I 0,48I 90 I 0,025 I 0,48 I 60 BIEN MA ili I. X2 + 1+1+ ~ ~ +,- X3 + + + + + - +- I + 1+I + I + ' + I:I + I - + -I . I I - I.- I £>9chuyenhoado tU'thlfc nghi$m. £>9chuyenhoatinhtU'phuongtrinhhoiqui X4 IXIX2 IXIX3 IX2X3 + + + + + + + + + + + + +, ~+ + £>9CHUYEN HOA *Yi% 13,6 9,50 8,38 11,22 6,67 9,86 7,55 3,98 Yi% 13,44 10,02 7,90 11,32 6,36 9,78 7.66 424 -89- bo=8,84 b3.=1,83 b12= 0,02 bi = 0,20 b4= 1,71 b13= 0,11 b2= 1,06 b23=-0,19 D~d{mhgiacach~socuamohinh,chungtoitieDhanh4thfnghi~m(No = 4)songsongtr mkeh~ch(blmgIII.5). BfmgIlI.5.Dl)chuy~nhoacUacacthfnghi~mt~itflmkeh~)(lCh. Dfeuki~nphanUllg: - Tr9ng lm;rngphflll ti'rcaosu (M"v): 11o 000 - LlI\mgperoxidbenzail(g) :0,048 - Lrn;mgAM (g) :0,60 - Nhi~tdl)thinghi~m(aC) :90 -Thc,;gianphanfutg(min) :75 -Wongdl)caasutrongtaluen :5% Trj trungbinh cuacacthi nghi~mt~itfllllkehlK;lChselh : Nhu v~ytrj trungbinh cuacacthfnghi~mt~litfllllkehO~lChselh : yo =9,10 TfnhynghiacuaC{lCh~sodugctitrCIUQTigtheotieDchuflnstudentbhngdlCIl tfnh dlc gi{1 trjtj : [1,3] V(ri: S2th =0,112 Sbj =0,118 Tir d6tac6giatrj : tj =bj/Sbj (blmgIlI.6) Thi nghim ti tam D(}chuyn boaYu (%) 1 8,72 2 8,90 3 9,35 4 9,40 - 90- Bfmg111.6.Gia trj cuatjtuangfu1gveribj h~c bju Ta cotp(f) = to,05(3) = 3,18 [4] Chi co nhfmgh~so bj haybjuco tj > tp(f) mOlcoy nghiatrongphuangtrlnh hoi qui. TrangbfmgIlIA. ec'1Ch~sobl, b12vab13vab23cocacgifttrj 11,tI2,t13vat23nh6hem3,18nen khong coynghia. . Nhuv~yphuangtrinhhoiquimotaSI!ph\.!thuOcdOchuy~nhO[lcuaphlmfu1gc(mgAM vao caDsu vao cac thong songhien cUu trang vimgthIJCnghiem co th~la : . Y = 8,84+ 1,O6x2+1,83x3+ 1,7lx4 (c) SI!tUlmgthic~CUaIDahlnhnayv6ithlJCnghi~mdUt;Ycki~mtrabentieuchufmFisher [1,3]: V6i: S2du= 0,18 suyra : Flinh = 1,61 gifttrj trabangcUatieuchuflnFisher[5]: FO,95(fl,f2)= FO,9S(4,3) = 9,1 Do Flinh < FO,9S(3,3),nenphuangtrlnhhoiquinoi trentuangthich. Tir phuangtrlnhhfliquitren,chungtoicomOtsonh~nxetsail: *Trang viIng khao sat, dOchuy~nh0£1ph\.!thuOctuyentrnh theocac th6ng so : Im,mgchat khaimaD,Irn;mgAM, nhi~tdOvathaigianphan(mg;trongdoanhhtimgcuat{lCchat(h.n.mg AM) lam~nhnhat(b3= 1,83). * Yeu to tr9nglrn;mgphfmtu (lYIv)khong xufithi~ntrang plllltmg trlnh hoi qui (bi khfmg coy nghifl),ch(mgt6 trongvimgkhaosat,yellto naykhonganhhuangdendl)chuy~nh6acua phanfu1g. Dieu nayelmthfly: Khi khaosatphanfu1gcl)ngAM vaocaDsugif1mcfipco tn;mgIm.mg phfmtutrungblob kha1611(lYIv >80.000),Sl!khflUm?chd?iphfmtut?ivjtrfCx-metilenXllYra khongdangk~,vadodoh~lUnhukhonganhhUtmgdend()chuy~nhoacuaphanfu1gn6itren. bj hoc bju tj " bo 884 tn 7490 bl 0.20 tl 1.69 b2 1,06 t2 8,98 b1 1.83 t1 1551 b4 1.71 t4 1449 bl? 0.02 t12 0.17 bn 0.11 t13 0,93 b23 -0,19 t23 161 -91- D~lamfOnh~nxetnay,chungtoid5th\,I'Chi~ncacphfmtmgd6ichUngnhusau: (b~mg III.7) Bfmg111.7.Sos{mhfmhhuangcuatn,mglll\mgtrungbinhcuadlosudend()chuy~nhl)(1 cmphfmtmgcOngAM vacaosugi~llncap. Ket quatrongbangIIL7 chothay:amtrcdOgiamcapcaosusflU(Mv = 15.000,caosu long),dt)chuy~nhoacuapMn tmg l' va4' giamr6 f~tsov6i philo tmg1va4 dll\YCthvc hi~n trongcungdieuki~nthi nghi~m.Trong khi dt)chuy~nhOOgallnhu khtmgthayd6i'giGaphlm tmg4va9. * C'1Ch~sotUtmgmcdoikhongxuathi~ntrongphUtmgtrinh hl'1iqui (c), chothaycacyell totacdOngIt~nquatrinh ph~mtmgmOtcachdOcl~p. 111.3.Nh~ndaubsanph5m: S~mphflmchJl:Jcnh~ndanhb~mgph6IR. Sos{mhph6IR cuamflUdoichlmgcaDsugiamcapv6imflUcuas~mphflm,tathay: - V~nxuathi~nCc'1CmGid~ctfungcuacaDsugillll1cap,callhinh cis hinh nhu khCmgthay doi. - Xuathi~nthemcacmGia: 1850va1775cm-ld~ctfungchodaDdOnglienkefcuanh6m carboni!trongAnhidridvbng.Ngooifa,yangAnhidridSuccinicfatnlwyv{ridOtim,SI!mtYvlmg cuan6d~clluy~nthanhAciddugcnh~nthayaSl!xuathi~nmGi1716cm-l[10]. Thl nghim AM (g) My Chiltkh(n Th(ngian Yj% maD(g) (Olin) 1 0,72 136.000 0,071 90 13,60 l' 072 15.000 0,071 90 9,28 4 0,72 84.000 0,025 90 11,22 4' 0,72 15.000 0.025 90 7.45 9 072 136.000 0,025 90 1133 4 5"': !j, (, 7 ~ ' .I ' ,, ' I. -!I. ~' ,j :'-I' . ( I 'i l 'i , '-l;JI1 1 ~"! . ' ~" ~ .. I ,, IJ "',, 1 ,, 1 1 1-IJ " rl _ ! 'rl ~ \_ ~ I , : . IIl!\ ,t " j l .T r ., -~;'II\1;11(:'1': . ] ,1]'i';lil:",I~ , i]:II]"'ill! I ,'",' ,T I ' ll , " li j~t"' lj r+l !' llfI I11 '1 ] ,,11 1,'r.,o:,r,"""""r'-'~"("1::I" :,.,,"t).l.'l],II'LIII,,',,'::::' -J""',""""1T'I"""' l"-,,,:," , .,'».t,:t:,..J:t j"1,:i ll i \iI11 ',I'".'~;:"""V':':,I(:"'rf,."",I",,,n't), ""I, " ) ,:-"[,.::.",,1,, ,,1] ,'I" ", I ,',..it 'I' 1-;n[' .' [ ,,' ., . eo, " ' ."... "I!L':"'I I "" I~" \ ":I.! ,, "'I:"-i ,, ':'-I"'r',,', : , " ]' i :", j , ' I :,' ,I: "i CAOSU-AM Y/=8,29%, ' I I I ' I ' ' I ' . l,I ::,' ",'" ».:" , "", , I'Iii " 11:1-:-1' ~:"T l:;-I;'-ll l ,:J:'i" l :titt~'LI I :T': 1 i I ' ',",~"!"",:;"o;:"""o;,,c::,-:,,:>:,('C.:,,,':',', ,!I:'rdji:'.j:!j"!!1 PI:: "I; ,I"; ~;':r:~&i~~~~iff!ii:I,;'j:r'(J,"'":"'1' i ' , J i i'ii:Ii' i ' '. l I ' i " , i I I I I I I I 11,,:1 ,i I, ,: -;" " ,i ' 1 :11 !' r ' , .' : ,,1:,,!J,~ . I , J , "_i; " "" "---,1- ,,,, ' j'j-r-- I--'T-'I- ii i i Ji,: i:~' ' I', I ,I ,'..: ,:: ' ,: ,j: "I : ",'C"(""""",("',:,,o,,.!,,!),; I II"'IT' Iii ~~: "" 't_ " ",; " j: ,, "'L;i<,:, ,, ,:,tl .. . . i .. ."I . l -' " " . :' . 1. . 11 . _1 . " . 1 ] '- , "! v" , 'f' 1 " , 1"" ,] ' ,11' . '-""-" " ",, ' . ,'- . 1 . ' ' " I . : " 1 " ~ : . '_i " , I ' I" ," ,," ; Ii" I ' I ,I J i' 'I; Ij I ! ,,! : !' ; ,,:Ii'! ,:111_1-1 i:I.11 liL.L.I"I.:",I: ",,'I' ""ill I: ,, '- I ,.; ,1, I ,J 1 _'--'- ,, " 1 ' +1 - .j-, -lirl. Li.':: l i l.!'>:.:i Ili:ijllir , , ,: , '! -."'" .. .. , ,,! ,. '" J., " j,, " ,~ " " " " , i'- " . . ! " " " C: " !i ! l " , ,, ; ,, .':>:' ,, ;""""" f ":''" . ' ,, ';' . "-" ,, " 0,1 . 1" " " , 1 . : ,, "' 1 : . : . ,1 1. : .. : 1 : . " 1 ::"" 1' "" .[ . ' 1 + . : . 1: " "1: ,, 1 ,, . , ' ,, ' I'I,':',I'I~'I' j l'[-- ".""",".t.l- 1": ~ " ! 1 ' " " . J:(' ,, :~:." . J" " ) . "(~ ,, :" . f::' ,, r.'f""" . "i- " ' " ,~ " j " 't: "f" :. ,, ": "" " ',,,, - .,,. L ,, : , ~ .""" , . ": . " " : . ,,, . ,,- ,, ~ . : ,,! :l. . <-~ ,, : . : ." "' . ": i.':!,',"r')""',r'r'I')"'~"H--' j ' I ' . 1"""J "" 1 " ~ ' I ' ~ " :,-,~;,:(...t~')~J.,'J.'r"!':>:"~:'<ll):"'" "",c:" I,-"".r: ." i' "". ' ,,I - - t' 'e"I"I" '" ",,' "" ,"" " j '" "" "-,, I 'c: .' 1 '1 ' j " i' r"", - -' ',» ,,- - "". '1-' . ',. - "'-; (I I 1 I I' ; ,,:'.:: ]- t ".:,,:" """"'::."" m !il . I "f ' ! , I Ie .: - _. I, -.:::l: - : ""J! ' , ". ' , 'l- i 1 Ii: I ! I ; », " ! ' r ' !' I L "'" . I',:i ,,' I'" ,:, "".' , " fI'(' ,I j' " ,,' ,,' '("'" 1'1: ,, '" [i "I,, ' . 1 "" ,, ' i" . " t . " .1.1:, ,, " ' ,, ' ' I '" , c, ' .,, ;: " ,, " , " . ' ,, "" -!""" I ' ,, " . " , ' I i',ki!LLi ";':,, '.;j,,:'I;;'t" 1 ; I .- ifJ!J. "ttE~~dJt~,:..,::'~-:cJ:I I!t:+t:[ J~! ,",OJ 1000" 2500 ;! '2000 '11000 IGI,O IIAIHHeM' r ' t' In ! \:'i t~on \?OO 10')1) ""'{ ]"0 ""-,-:1-'-" , I ' l_) "--, ",--..- 1 J;' I' ,., I', I 11,,1'I , ; ,i I ' 'n i',no . !,1U[J,:CM ' " 2~;no 1200' 1000 0'10 ',II" -92- ~, A ... ~ K IV. PHAN UNG C9NG 1,2-DICLOROCARBEN VAO CAO SU GIAM CAP ~ , " ;t BANGPHUONG PHAPXUCTACCHUYEN PHA: Phfm(mgcl)ng1,2-dic1orocarbenVallcallsulatexdagiamcapdugcthvchi~ntrongdung moi toluen,tar nhflOt~10carbenla CHCh/NaOH dm v6i WC lac chuy~npha la elorur trietilbenzilamonium(TEBA), Phuongphapquih0c;1Chthvcnghi~mdugcsirdt,mgd~khaoS(lt anhhtimgcuacacyelltolienquaDdenphfm(mg, IV.I. LIpl ehQncaeyC"ut6vaquiho~ehviingth1!enghi~m: G'1cphilO(mgdUt,rclienhanhphongtheaphuangphapcuaMAKOSZA [18]dflthvchi~n v6iphim(mgcl)ng1,2-DiclorocarbenVallcachQpchatolefinthongthUtmgv6im(1tIt thayd6i: -Sirdt,mgNaOHdmthayvidungdjchNaOH50% -DungmoitoluenthayviCHCh. Gic yelltofmhhUt"mgvavtingkhaosatdugcchQll"nhusau: NhfmgthongsocOdjnh la : -TrQnglUt,mgcallsugifl111cap .: 2,04g(30mmol) -Nhi~tde>phim(mg : 30°C -Tocde)khufly :400vang/min -LUt,mgdungmoitoluen :20ml De)chuy~nhOOcuaphan(mgdugcxacdjnhthongquaSl!phflOtkh hamlUt,mgelmtrong sfmph5mbtmgphUtmgph{IPYOLHARD, IV.2.Phm:mgtrinhh()iquivanh~nxet: G'1cyelltodugcmahoaved~ngkhongthunguyen[1,3]. Phuangtrinhh'l'1iquib0cnhatmotaquatdnhphanlIngtrongquaDh~plWthu('>cV~IOc{\C yelltoneuireDc6d~ng: Y =bo+ bjxj Y =bo+ bjXl +bzxz+b3X3+ b4x4+ bsxs (1) SIT ThongsobiC"ndGi Z' - + 1 TrQngIUQT1gpha.ntircaDsu Zl 30.000 70.000 (My) 2 LtJ911gNaOH(mmol) Zz 40 60 3 LtJ911gTEBA (mmoI) Z3 0,176 0,352 4 LUt,mgCHCh (mmal) Z4 40 60 5 Thengianphan(mg(h) Zs 2 4 BANG IV.I: MAatr$nke ho~chthL!Cngri$m ban ph~nb~c1cua phEinl1ng c9ng 1,2- diclorocarbenvaGcao su giam cap. ( s6 thi nghi$m : 2 k-1= 24 = ,16) Z2(mmol)'Z3(mmol)Z4(mmol)ZS(gia)I xO I xl 60 ,0,352 60 4 I + I + 60 0,352 40 4 I + 60 0,352 40 2 I + I + 60 0,352 60 2 I + 40 0,352 40 4 I + I + 40 0,352 60 I 4 I + 40 0,352 60 I 2 I + I + 40 0,352 40 I 2 i + ~141+1+ 60 I 0,176I 60 I 4 - I + ~ 60 I 0,176I 40 I I ~ 40 I 0,176! 40 40 i 0,176i--.iQ 40 ! 0,176 I 60 S TT IzI 1 70.000 2 30.000 3 70.000 4 I 30.000 5 70.000 6 30.000 7 70.000 8 I 30.000 ! 9 I 70.000 I ' !2J30.000I 11 I 70.000I 112 I30.000I I 13 I 70.000II i14 I 30.000I - i ! I 1.)I 70.000: I , 16 ;30.000i C*) Yi% Yi% BIEN THl!C BIEN MA 2 + + x2 + + + + - + + + + x3 + + + + + + + + I 1+, x4 I xS + + + + + ~ -I + + + % ham ILfqngclor trong san pham do tl1thL!Cnghi$m. % ham ILfqngc!or trong san pham tinh tLrphLfongtrlnh hoi qui 2 4 4 II~ + 1,+ 1+ 2 2 i + I +I : +! I *Yi Yi + + 33,6 34,30 35,1 34,30 35,5 34,30 34,2 34,30 31,1 31,84 31,3 .31,84 31,7 31,84 32,0 I 31,84 30,7 30,84 31,0 30,84 30,4 I 30,84 30,0 130,84 28,1 I 28)8 28.7 : 28.38 - I . 28,6 i 28,38 I 29,4 ! 28,38 - + + - + + -93- Trang d6Y IahamIlJ911gelmc6trangs~mph~m. Anh lnltmgdongthmClk-15 yelltotrendenph~m6ngdl19'ckhansattrangC[ICthi nghi~m tienh~mhthenphuungan2k-l (24=16). Ma tr~nkeho.;'lchthvcnghi~mb~cnh~tv6ibienthvcsinh: xs=xpCZ.X3.X4 Dungd~xacdjnhcach~socoomohinh(1)drn;rcrhobCrib~mgIV.l. TirketqUathvcnghi~mc6dUQ'cthenmatr~nkehO<;1ch,taxacdjnhcach~sobj [3]: bo=31,34 bi =-0,13 b2= 1,23 b3= 1,73 b4= -0,13 bs = -0,14 D~danhgiacach~socoomohint, chUngtoitieDhanh3thinghi~m(No= 3)songson~lY tamkehO<;1ch(b~mgIV.2). . BangIV.2.H'amIlJ911gelmtrangsanphrimcrncacphan6ngt~itamkeh~lCh. Dietlki~nphi'm.mg: - TrQngIlJ911gphantucansu - Ltn,mgTEBA (mn1ol) -LlJ911gNaOH (mmol) - Ltn,mgCH CI3 (mmol) -Thm gianphanfuIg(h) :50.000 :0,246 :50 :50 :3 Nlm v~ytrj trungbinh cuacacthinghi~mt~itfllTIkehO<;1chla : Y =33,07% Tinhyngmacrncach~sodUQ'croc ltlQTIgthoochillinStudent:[1,3] Ta c6phuungsaitaihi~n:S2th=0,363 PhUlmg sai cooh~so : Sbj=~=~ =0,023 ~ Sbj=0,15 ~' Thi nghim ti HIm DOghepYu (%) 1 32,5 2 33,0 3 33,7 -94- Tll'd6tac6cacgiatrj tj (b~mgIV.3) B~mgIV.3. Gia trj CU~ltj tuangUngvOibj bj " tj bn 3134 to 208.90 bl -0.13 tl 087 b7 1.23 t7 820 b1 1.73 t1 11.53 b4 -0.13 t4 087 b5 -0,14 t5 0.93 Theob~mg[4]: tp(f) = to,05(2)= 4,3 Ta thaycach~sobI, b4,b5cOtI, t4,t5tuangUngnhahanto,O5(2),dod6chungk~ongc6y nghratrongphuangtrlnhhOiqui. Nhu v~yphuangtrinh hoi qui mo ta S11ph\l thuc)chi~usuatcrn rhEinUngc(mg 1,2-dicIorocarbenVaGcaDsuvOidlCthongsonghienClmtrongviIngthlJCnghiemc6th~la: Y =31,34+ 1,23x2+ 1,73x3 (d) S11tuongthichcrnmohinh nayvOithvcnghi~mdrn;rcki~mtrabOitieuchu5nFisher [1,3]: Tac6: Ftinh= 1,2 Gia trj trabangcUatieuchu5nFisher[5]: FO,95(fl,f2)= FO,95(13,2)= 19,4 Do Ftinh< FO,95(13,2),Denphuangtrinhhoiquinoitrentuongthichval thlJCnghi~m. Tll'phUtmgtrinhhoiqui (d), chungtoicomc)tsonh~nxetsail: * TrangviIngkhaoS[lt,hi~usuatphanUngc()ng1,2-dicIoracarbenVaGcaDsuph\lthu('>c tuyentinh V~lOlll\mgNaOHv~11rn;rngxUctarTEBA; khongph\l thuc)cVaGmtrcdOgilllTIdip CUll caDsu,Irn;rngCHCh vathmgianphanUng. * Yell to tr9ngIrn;rngphfu1tu (bI) khongxuathi~ntrangphuangtririh h'r>iqui chUngtll trangviIngkhaoS[lt,S11ctltm~chcaDsuhallnhukhonglamthayd6isolienketdeliCUlld~liphfm tu caDsu,vadod6khonganhhuOngdenhi~usuatphanUng.Khaosatchi sobram cuacaosutr trang viIng khao sat (bang IVA) rung rho thay S11 giam lien ket d6i traaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaaa -95- BfmgIVA : Chi soBrom(IB) cill caDsugiamdip. (*) Tn;mgIugngphant11Mycill caDsubandati. IV.3. Nh~ndanhsanph£1m: W3.1. PhiJ IR cooSlulph511l: TheoPinazzivaLiebmann[17,22]th1nhom-CClz- cill vlmgDicJorocycJopropanc6 muihapthod~ctnmga khdmg835-845cm-l,muinaydugcphanbi~tv6imuihapthocualien kefC=C 3ranthe(biend~ngngohim~tphf1ng)cDacaDsubillcUtmgdOhapthom~mhem. Khi sostmhphiSIR cill caDsugiamcapvacuasanph~mc0ng1,2-DicJorocarben(san ph~ cohamhn;mgcJor33%),chungtoinh?nthflycahaiphiSOeucomuihapthocr836cm-I, nhtmgmuihapthutrong's~mph~mcOngcoc~g dOIOnhem;ch(mgtocoSlJhi~ndi~ncua nhom-CCIz- cill vangcycJopropan. Nga)ifa,trongphiSIR cuasanph~mcOng,mui3036cm-l,d~lCtrtmgrhoV=C~-Hgiamr() r~t,rhothaycoSlJgiillnlienkefdoitrongqu.:'ltrinhcOng1,2-DiclorocarbenVaGcaDSUo IV.3.2.PhiJ RMN13Ccuaslutphd11l: V6i caDsucis-l,4-poliisopren,phiSRMN13Ccocacmuihapthodrn:;rcghitrongbfmgIV.5 BangIV.5 PhiSRMN13Ccill caDsutlJnhiencis-l,4-Poliisopren: fCHz-<;::=CH-CHz-tn CH3 ," Trmg Im;mg Chi so philot.rMyciia [1]) Brom caoso 650.000(*) 3,94 215 70.000 0,89 207 30.000 0,50 204 0 (ppm) Di;ictrullg 135,3 -C= 125,6' =CH- 32,6 -CHz- (b) 26,9 -CHz- (a) 23,7 -CH3 - 96- VOi sanph5rncaoSllcQng1,2-diclorocarbenIDachungt6ikhllC)S{lt,clmrnQtsodonv,i isoprenchuaph~mlmg,dod6trongcalltruccUam~chd~liphantutl>nt~lihaiIO:;lidlmvj coSlY: isopren(I) vacarben(Ca), n, --~ ~~~~---- . CH3 CH3 -E I b t fc2. '1,1> 1CH-- C- CH CH dl CH - C-CH -CH 2 - 2 .- 2 '>< 2 aU I Cq. PhiSRMN13c c~ sanph~mcaDsu d)ng 1,2-Dielorocarben(ham lm;mgelor 30%) co nhfmgmuid~lCtnmgdUt;YCphangillitrongbangIV.6. BangIV.6 PhiSRMN13C cUas~mph~ caDSllcQng1,2-dicIorocarben. d (ppm) . SIT Dc trullg Chi cho 1 134,73(rnGi4) C' C 1+01- =va- G 2 125,28(niui3) =CH- I 3 72,093 71,809 CI CI 01 71,736 'C/ 71,652 / \ 4 39,704 )(CH- 01 39,269 5- 32,087 31,643 -CH2- (b) 1+01 30,592 . 30,433 6 26,403' .' 24,529 23,967 -CH2- (a) .I +01 22,126 7 23,354 -CH3 I 22,304 -CH3 01 -97- D~xacnh~ncactInhi~ucilaRMN13C,kythuJ;ltDEPT (DistortionlessEnhancementby PolarisationTranfer)[24]d~ldUQ'cStrd\1ng.Trongky tht$tnay,v6i gacphatxung(angle d'impulsion)Po=135°,thlcactInhi~u-CH2-'- va-~- sebi~nmat. !rong ph5chi conl~icactinhi~ucila=CHL-, -CH3 va-yH; vanhuv~ysegiup1a phanbi~tdUQ'ccacmGid~ctrungtuongilng(bangIV.7). BanlZIV.7 Ph5RMN13Ccoosanph~mcallsuc~ng1,2-Dic1orocarbenkhisirdl}ngky tht$tDEPT (Po=135°). SIT 0 (ppm) Dc tnmg Ghi chu 1 125,81 125,26 =CH- I 124,46 2 39,71 XCH- Ca 39,26 3 23,39 -CH3 I 4 22,309 -CH3 Ca . .. ----------...- ' --_m--_- (I) Kw cs-cAnAENE ICOCl3: 303KI vr ~ ~ i ," -. '1 1,: [ '1. ','" b.. ] " ,:1\-'11,-\ [\1 - e- . -ell (II> ..~: - I '\.1 ,- "J /(1) ""' ((--cr I' ",W-P..(c\ " I hie) (1-) I _--L 0'11 alii' ~ " ~ftJ e ~~ "' 1~ ~ ' I ~.'~~r:'~"~~;~::','~'; / ( (\;>°;' (C) rC (~ '-../ /(, (~ \ '\,(11 Ll -->\~..,;. ~ ---,--~j U ,..J.Jl;ll, ,- -..,,--)C ,-, -T , ,~~JL-, -T--- r - ---, \L 'T" m, HO 130 \20 110 100 90 00 70 (;0 50 ~(J lCl 20 PPH CAG SU - CARBEN .--..-.---.. \ I' ) Kw-cs-tAndENErCO~L1:30JKJ ... , 1 ~ ~:' _ ~ ~ r ! - :I~':;-~ '~ ~~ '; ! '~ ~ '- I ". , "",.." - ,... ~,; ~-:" : -~:~ I ..,-'I (r)f.r) --'. ..('II, ~-~ " !~ w (() --:7(11 .. (I) :.(\\ -- 1 ~wt~ (t~~~~~~~'~~~~YI! . i ,,\tn'\'Yt\tr'~ . I , ',. SU DUNG KY THUAT DEPT '" ,.1' :> ,. ; !; ,\:!: 'r;~;,;,,~,,!-:,':ir; ',:~ ' ;;t;'~~t:~~i':i,:~ i i ",=-;:: ;,~; : : \:,~ " '! i ! '! -p I I " rJ'V\'t/\r'IJ ,-" "" . , , i , .', 'r' ,,-:-r-: ,. -II " ',' , , ,,': "; to: ", ",I', \ ;", ~;: ;::::. ';..:,: "':".":":""';'::;'::::'" i i 'I ;, 'f,' ':,1 ',:oo"., ",' ',I ,(, "j', 'J' ',', j,', i :- ,'J 'J ,):' -oj ' :' 'C., '.. ;, II: ,- , '~, , ' CAO SU - CARBEN "","'i"I, ": c', I,' --" "---' ~" 2".-!:!_I'JI'.GIH ,C!,'~:;,ltiO_2?O--ll! i , "'-'-"' "---""'-'- -98- 9 '" " .. 9,(' V. PHAN UNG CQNG HIDROCLORUR VAO CAO SU GIAM CAP: Phfm (mg c<)ngHCI VaGcaDsu giamear dUQ'cth\}'Chi~ntrong h~ dung moi Dioxan-l,2-Dieloroetan(tyI~1/4theoth~tich)v6ikhi HCI dUt"chapth1,1trongDioxanden Hongd<)xacdjnh(6,O3M). . Phuangphapquih0<;1ChthiJcnghi~mdrn;rcSlrd1,1ngd~kh~10sat~1l1hhuOngelk'1cacyellto denphfm(mgnoitren. V.l. Lt}'achl)nyeuto'vaquiho~chvungthtrcnghi~m: D1[dvaoketqilllthamdo, chungtoich9ncacyelltoanhhUtmgvavtingkhansatnhusail: NhGngthongsocodjnhIa: -NOngd<)cansu3% : 1,7g(tronglOmIdioxanva40mll,2-dicloroetan) - NOngd<)HCI trongdioxan: 6,O3M. D<)chuy~nhoacuaphan(mgdrn;rexaedjnhth6ngquaS1,1'phantichh~lmIUt,mgelmtrong sfmph5mbangphUtmgph{lPYOLHARD. i V.2.Phmmgtrlnhh(,)iquivanh~nxet: cacyelltodlJ{}'cmf1hoaved~1l1gkhongthunguyen[1,3].. Phuangtrlnh11'6iquib~cnh5tmotaquatrinhphan(mgtrongquanh~ph1,1thu<)eV~lOdIe yelltoneutrencod~ng: . Y =bo + blXl + b2X2+ b3x3+ bl2XIX2+ b13Xlx3+ b23x2X3+ b123XIX2X3 Trong doY lahamIll\mgeIorcotrongsanph5m. Anh hUtmgd('mgtheneilll3 yellto trendenph~m(mgdll\rckhansM trongdlCthl nghi~m tienhanhthenphUtmg{1l12k(23=8) Ma tr~nke h0 hlnh (1) dll\reehobOib~1l1gY.1 Tir ketqUllth1,1'cnghi~mcodrn;rctheomatr~n.keh0<;1eh,taxaedjnh dic h~sobj [3]: bo=20,53 bl= 0,125 b2=2,025 b3=3,075 bl2=-0,225 bl3=-0,075 b23=0,075 b123=0,025 (1) SIT .ThongsO'biend6i . Zj - + 1 Tn}ngIuvngphfmtucaDsuMy Zl 30.000 70.000 2 Thaigianphantmg(h) Z2 2 4 3 Nhit de)(oC) Z3 20 36 BANG V.I: M~tr~nke?hoCilc~th}!cnQhi~mb$c,1toanphaf!? m,,9r9ngcuaphanling c9ng.HC!vaocaosu gram cap . (S6 thfnghi~m:2k=23~ 8 ) .o~. ~-~ ~"'. ,._~- (*) Yi% % ~amIvqngClor trongsan phamdothl!Cnghi$m. % hamILrqngclortinhtLrphvangtrlnhhoiquiYi% A' THlfC A' MAS BIEN BIEN *Yi% Yi% IT Zl Z2(gia) Z3(oC) xo Xl. X2 X3 XIX2 XIX3 x2X3 XIX2X3 1 30.000 2 20 + + + + 15,1 15,43 2 70.000 2 20 + + - + + 15,9 .. 15,43 ,., 30.000 4 20 + + + + 19,4 . 19,48.:I - - 4 70.000 4 20 + + + - + - - - 19,4 19,48 5 30.000 2 36 + + . +1 - - + 21,2 21,58 6 I 70.000 2 36 + + + I + 21,8 21,58- - - - I 7 30.000 4 36 + +. + - - + - 25,9 25,63 8 70.000 4 36 + +\+ +1+ + + + 25,5 25,63 -99- D~dflllhgiftCflCh~socmmohl~h,chungtoiti~nhanh3thinghi~m(No= 3)songsongtr tfllllk~h~1Ch(bflllgV.2). . BangV.2. !-fam]rn;mgelortrongsanphflmcm cacphanlmgt~itfllll kehQ<:1Ch. oj Di'euki~nphan.mg: - Tn,mglrn;mgphfllltucaDsu :,50.000 - NOngde)HC] trongdioxan :6,03M -NOngde)caDsu :3% -Nhi~tde)phahlmg :28°C -ThOigianphanlmg(h) :3 -Dungmoi1,2-Dieloroetan- Dioxan(t5']~4/1theoth~tich). Trj trungbinh cuadlCthi nghi~mt(;litfllllk~hO<;lchPel: Y = 21% Tinh <;nghiacm cach~sodU9'cu6c]rn;mgtheochillinstudent: Ta cophUtmgsaitaihi~n:52th=0,16 Phuongsaicm h~so: . S2bj=0,02 Sbj= 0,141 Tir dotacocacgifttrj tj (bangV.3) BangV.3. Gia trj cuatj tu(mglmgVOlbj ho?cbju Thi nghim ti tam DOghepyOu(%) 1 21,4 2 21,0 3 20,6 bj hoc bjll tj bo 20,53 to 145,60 bl 0,125 tl 0,886 b2 2,025 t2 14,36 b3 3,075 t3 21,81 b12 -0,225 t12 1,59 b13 -0,075 tI3 0,53 b23 0,075 t23 0,53 . b123 0,025 t123 0,18 -100- Theob~mg[4]: tp(f) = to,005(2)= 4,3. Ta thaycach~so bI, b12,b13,b23vabI23cotI, t12,t13,t23.va1123tuongUngnhll hem to,05(2),dodochungkh6ngcoynghiatrangphucmgtrinhhoiqui. Nhu v~yphuongtrinh hoi qui mo w.Sl!ph\}thue)chi~usuatcuaph~mUngc0ngHCI V~IO caDsuv6icacth6ngsonghiencUutrangvUngthvcnghi~mcoth~Ia : Y =20,53+ 2,025x2+ 3,075x3 (e) Sv tuongthichcill m6hinhnayv6ithvcnghi~mdtn;Ycki~mtrabCritieuchu5nFisher [1,3]: Ftinh=0,78 Oia trj trab~lllgcuatieuchu5nFisher [5]: FO,95(fl,f2)=FO,95(5,2)= 19,3 Do Ftinh < FO,95(S,2), nenphucmgtrinhhoiquinoitrentuongthfch.. Tir phucmgtrinh hoiqui(e) , chungt6icomc)tsonh~nxe~sau: * Trang vUngkJ;taosat,hi~usuatphanfutgce)ngHCl VaGcaosuph\}thue)ctuyentinhvao cacth6ngsothmgianvanhi~tdOphanfutg; trangdoanhhu6ngcill nhi~tdOphantmgla m~lllh nhat. * Yell totrpngItn;rngphfllltu(bI) khongxuathi~ntrangphuorigtrinhhoiquichUngt6 trongSI!giamCcl'}pCc'10suCrvungkhaosat,solienketd6itrenm~chd~iphantuIt thayd6ivado d6kh6nganhhUtmgdenhi~usuatphanfutgce)ngHCl VaGlienlienketd6icill caDSUo * cachi~utmgtuongtard6ivatucmgtarbakh6ngco<;nghia,rhothaysl!cacthongsot{lC dOngIen'hi~usuatphantmgmOtdlChdOcl~p. V.3.Nh~ndanhslmphfim: Sanph5mcill phantmgcOngHCI VaGcaDsugiamCcl}pdll\1Cnh~ndanhbfingphe)IR. So sanhphe)IR cill sflllph5mvacill caosugiamcap,tathay: * co SI!giamcuOngde)hapthocill mlii3036cm-I(v =C-.H) va836cm-1(daod(mgbien d~ngngoaim~ltphrlllg-cualienketC=C 3Janthe). * Xuathi~ncaemlii696va732cm-Id~lCtrungcUalienketC-CI. Ngooifa,khi sos{mhphe)IR cill sanph5mdochungtoidieuchev6icaDsuHidracIorur 6athucmgm~liPliofilmST75clingthayconhfmgmliid~lCtrunggiongnhau.