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Kinetics of the

Synthesis of Propyl and ButylAcrylatesin the Presence of

SomeHeteropolyacids asCatalysts

 JERZY SKRZYPEK,1 TERESA WITCZAK,2 MIROSŁAW GRZESIK,1 MARIUSZWITCZAK 21Institute of Chemical Engineering, Polish Academy of Sciences, ul. Bałtycka 5, 44!"" #li$ice, Poland2%aculty of %ood &echnology, 'ni(ersity of Agriculture, ul. Balicka !)), *"!4+ rak -o$, Polandecei(ed )* /anuary )""01 re(ised 4 /une )""01 acce2ted 4 /une )""03I !".!"")kin.)"*50

Pu6lished online in 7iley InterScience 8$$$.interscience.$iley.com9.ABSTRACT: Esterifcti!" recti!"s !# cr$%ic ci& 'it( n)*r!*"!% "& n)+t"!% 'ere crrie&!t i" t(e %i-i& *(se i" t(e *rese"ce !# ./PW12O0 !r ./PM!12O0 s ct%$st, t ri!ste3*ertres, 3!%r rti!s !# t(e rect"ts, "& c!"ce"trti!"s !# t(e ct%$st4 T(e 5i"etice-ti!"s (& "!"e%e3e"tr$ #!r34 C 6 27 Wi%e$ Peri!&ic%s, I"c4 I"t J C(e3 Ki"et 01:12819, 2

INTRODCTION

Acr$%tes re i3*!rt"t i"ter3e&ites i" t(e *r!&cti!"!# *%stics4 O'i"; t! t(e &ierse *r!*erties !# *!%$3ers "& t(e c!*!%$3ers !+ti"e& !" t(eir +sis,t(e$ (e 'i&e **%icti!" i" eer$&$ %i#e "&i" 3"$ i"&stries4 Esterifcti!" !# cr$%ic ci& 'it(%c!(!% (s c!33erci%%$ +ee" *er#!r3e& +$ si";%i-i& ct%$st sc( s s%#ric ci&, ($&r!<!ric ci&,"& *r)t!%e"es%#!"ic ci&, +t t(ese re t!=ic "&c!rr!sie4 .eter!*!%$ci&s re 5"!'" t! +e (i;(%$ ctieci&ic ct%$sts i" s!%ti!", "& s! t(e$ (e +ee"

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sccess#%%$ se& i" " ci& recti!" sc( s esterifcti!"4.eter!*!%$ci&s re %ess t!=ic4 Re*%ci"; 3i"er%ci&s 'it( (eter!*!%$ci&s !>ers 3e"s #!r e%i3i"ti";!r t %est re&ci"; t(e &";ers t(t t(!se c!"e")Corres2ondence to: T4Witc?5@ e)3i%: t'itc?5r45r5!'4*%4c6 27 Wi%e$ Peri!&ic%s, I"c4

ti!"% ct%$sts !# esterifcti!" cse t! t(e "tr%

e"ir!"3e"t4W(i%e t(e tec("!%!;ic% s*ects !# t(e esterifcti!"!# cr$%ic ci& 'it( *r!*$% "& +t$% %c!(!%s (e+ee" re%tie%$ 'e%% "&erst!!&, t(e 5"!'%e&;e !# t(e5i"etics "& t(er3!&$"3ics !# t(is *r!cess sti%% re3i"si"&e-te4 T(ere re *rctic%%$ "! &t !" t(e5i"etics !# t(e s$"t(esis !# *r!*$% "& +t$% cr$%te i"t(e *rese"ce !# (eter!*!%$ci&s4 O"%$ C(e" t %4 1s;;este& t(t t(e esterifcti!" !# cr$%ic ci& 'it(n)+t"!% i" t(e *rese"ce !# (eter!*!%$ci&./PW12O0 is sec!"&)!r&er recti!"4 .!'eer, t(eire=*eri3e"t% &t re scrce "& %i3ite& !"%$ t! t(ete3*ertre !# /D/ K4

 T(e *rese"t st&$ i3s t! &eter3i"e t(e 5i"etics!# t(e esterifcti!" !# cr$%ic ci& 'it(n)*r!*"!% "& n)+t"!% !er &!&ect";st!*(!s*(!ricci& ./PW12O0F "& &!&ec3!%$+&!*(!s*(!ricci& ./PM!12O0F s ct%$sts4KIETICS OH T.E SYT.ESIS OH PROPY A BUTY ACRYATES 1/

!"P!RI#!NTA$Ki"etic e=*eri3e"ts 'ere crrie& !t i" t$*ic%+tc( rect!r !# 1)3 c*cit$, '(ic( 's 3ec("ic%%$;itte& 'it( " i3*e%%er "& ftte& 'it( re<= c!"&e"ser4 T(e te3*ertre 's 3i"ti"e&'it(i" 4DLC4 T(e 3i=i"; s*ee& !# +!t 1 r*3's &eter3i"e& t! +e scie"t t! e%i3i"te "$ 3ss

tr"s#er %i3itti!"4 ! c(";e i" t(e recti!" rte's &etecte& '(e" t(e stirrer s*ee& 's rie& #r!3DD t! 1D r*34 T! i"itite " e=*eri3e"t% r", 5"!'" 3!"t !# %c!(!% 's c(r;e& t! t(e rect!r"& (ete& t! t(e &esire& te3*ertre4 Acr$%ic ci&'s &&e& t t(e &esire& 3!%e rti!4 e=t, t(e ct%$st./PW12O0 !r ./PM!12O0 's i"tr!&ce& t!t(e recti!" 3e&i34 T! !i& si&e recti!"s !# *!%$3eri?ti!",($&r!-i"!"e 's &&e& t! t(e rect!r4C(r!3t!;r*($ ree%e& t(t t(e recti!" 3i=trec!"ti"e& 3!st%$ t(e *r!&cts !# esterifcti!" ester"& 'terF "& !"%$ trce 3!"ts !# t(e *r!&cts!# si&e recti!"s4 T(ere#!re, it 's *!ssi+%e t! c(ec5

t(e *r!;ress !# t(e recti!" +$ &eter3i"i"; t(e ci&it$!# t(e recti!" s$ste34 T(e ci& "3+er 's est+%is(e&t(r!;( t(e titrti!" !# KO. s3*%es4 S3*%es!# t(e recti!" 3i=tre 'ere i33e&ite%$ &i%te& i"c!%& 2)*r!*"!%, "& recti!" st!**e& +ecse !# c!!%i";"& &i%ti!"4 T(e &rti!" !# t(e *r!cess "& t(e#re-e"c$ !# s3*%i"; 'ere se%ecte& #!r i"&ii&% e=*eri3e"ts,&e*e"&i"; !" t(e c!"&iti!"s !# t(e recti!"4

 T(e e=*eri3e"ts 'ere c!"&cte& ti%% t(e3!3e"t '(e"3i"i3% c(";es i" t(e c!"ce"trti!"s !# t(e rect"ts

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'ere "!tice&4 T(e 3!%r rti! !# %c!(!% t! ci& t t(e +e;i""i";!# t(e recti!" 's /:1, D:1, "& 1:14 T(e ct%$stc!"ce"trti!"s 'ere 142/, 24D, 042, "& 470 'tN#!r &!&ect";st!*(!s*(!ric ci& "& /412, 420, "&12407 'tN #!r &!&ec3!%$+&!*(!s*(!ric ci&4 T(e

e=*eri3e"ts 'ere crrie& !t t seer% te3*ertres#r!3 /17 t! /7 K #!r n)*r!*"!% "& #r!3 /0/ t!/9/ K #!r n)+t"!%4Ta%le I T(e Esti3te& Actiit$ C!ecie"ts #!r n)Bt"!% t Te3*ertre !# // K "& t(eI"iti% M!%r Rti! !# Acr$%ic Aci& t! A%c!(!% !# 1:/ ;  ;  A ; E ; 7 <  <  A < E < 7 

422D 492D 42D 42D 4/2 14 149 2472/42 49 4D 4D 47 1417 1422 247//419D 49D 49D 49D 47 14/ 1479 2470141D 4D 41 41 47/D 1402 147/ 24707412D 42D 412D 412D 47D 14DD 149/ 247D/41 4 41D 41D 499 149 149D1 247D749D 4D9D 419D 419D 4907 147 1491 24714D 4DD 42 42 492 142 149 2470

42D 4D2D 422D 422D 40 141D 14/ 247R!S$TS

 T(e esterifcti!" !# cr$%ic ci& 'it( %i*(tic %c!(!%is t$*ic% reersi+%e recti!" &escri+e& +$ t(e#!%%!'i"; e-ti!":.2C C. COO. R 6 O. Q .2C C.COOR 6 

.2O 1FBse& !" t(e st!ic(i!3etric e-ti!", " e=te"&e&5i"etic e-ti!", i" '(ic( cr$%ic ci& is re#ere"cerect"t, c" +e 'ritte" i" t(e #!%%!'i"; #!r3:r  k 1 6 ca

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 a 6 2F'(ere "& A re#er t! cr$%ic ci& "& %c!(!%, res*ectie%$,"& 7 "& E re#er t! 'ter "& !"e !# t(e*!ssi+%e esters, res*ectie%$4

 T(e", si"; t(e 3ss +%"ce !# t(e re#ere"ce c!"stite"ti" +tc( rect!r ss3i"; c!"st"t &e"sit$F,t(e #!%%!'i"; re%ti!" is !+ti"e&:&c 

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&t ca61F 

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  6 =

cdF 6  a 6 0F'(ere n A "& n  re t(e i"iti% "3+ers !# 3!%es4B$ i"te;rti"; E-4 0F #!r t(e &i>ere"t %es !# e=*!"e"ts ss3e&, 'e trie& t! f"& s!%ti!" t(tInternational /ournal of Chemical inetics OI 14125i"10 SKRZYPEK ET A4Ta%le II C%c%te& %es !# t(e E-i%i+ri3C!"st"ts "& E-i%i+ri3 e;ree !# C!"ersi!"s !# Acr$%ic Aci& t ri!s Te3*ertres& =V n AnB   ; <  an)Pr!*"!%/17 499D 1:/ 142 D49 479/27 4711 1:/ 14D D4 4

//7 47/1 1:/ 1477 D4D9 1407/07 470 1:/ 2422 D407 12419/D7 47 1:/ 241 D4/ 1049n)Bt"!%/0/ 4D 1:/ 241 94D 1D490/D/ 42D 1:/ 247 94/ 242// 4DD 1:/ 04 942/ 274/

'!%& e"sre t(e +est ft +et'ee" t(e recti!" rtee-ti!" "& t(e e=*eri3e"t% &t4 T! &! s!, 'e se& "3eric% i"te;rti!" 3et(!&4k 1t ca61F = 

 6 

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)*+&+'+(& ,& +&& +,& '&& ',& -&& -,&Time .min/

√

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./PW12O0  6 : & /07 K 

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1:/ ct%$st 042 'tN, 6 : & /D7 K 1:/ ct%$st 042 'tN, 2 : & /D7 K 1:D ct%$st 042 'tN,3: & /D7 K 1:1 ct%$st

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K 1:/ ct%$st 470 'tNF4

 > F 's &ic%t t! rec(, "& t(e 3!&e% !+ti"e& ;e3!r err!rs4 Si"ce t(e c(e3ic% recti!"s "&er st&$

t!!5 *%ce i" t(e %i-i& stte "& t(e rect"ts #!r3e& 3%tic!3*!"e"t 3i=tre !# *!%r s+st"ces, 'e &eter3i"e&t(eir ctiit$ c!ecie"ts4 T(e &eter3i"ti!"'s 3&e +$ t(e UIHAC 3et(!&, "& t(e "ecessr$&t 'ere &erie& #r!3 24 T+%e I s(!'s e=3*%es!# ctiit$ c!ecie"ts #!r t(e recti!" !# cr$%ic ci&'it( +t"!% t c!"st"t te3*ertre4 Becse t(e!r&er !# t(e %es !+ti"e& #!r t(e !t(er recti!"st ri!s te3*ertres 's si3i%r, 'e i"#erre& t(tt(e recti!" rte 's *r!*!rti!"% t! t(e ctiit$ rt(ert(" t(e c!"ce"trti!" !# t(e rect"ts4 T(ere#!re, t(e5i"etic 3!&e% 's e=*resse& i" ter3s !# +!t( t(e ctiities"& 3!%r c!"ce"trti!"s4 Becse t(e recti!"

s$ste3 's +etter &escri+e& '(e", 's ss3e& t! +e"!"i&e% !# t(e %i-i& 3i=tre, 'e re*%ce t(e c!"ce"trti!"!# t(e rect"ts i" E-4 2F 'it( t(eir ctiities4

 T(e", si"; t(e 3ss +%"ce 'e !+ti"e& t(e re%ti!"&c 

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 a 6 F'(ere < is t(e ctiit$ c!ecie"t !# t(e c!3*!"e"t4

 T(e &i>ere"ti% e-ti!"s /F "& F #ter tr"s#!r3ti!"'ere i"te;rte& "3eric%%$ +$ t(e Si3s!"Xs3et(!&4Usi"; t(e e-i%i+ri3 &e;rees !# c!"ersi!", &eter3i"e&!" t(e +sis !# t(e cr$%ic ci& c!"ce"trti!"est+%is(e& e=*eri3e"t%%$ i" t(e stte !# e-i%i+ri3,International /ournal of Chemical inetics OI 14125i"KIETICS OH T.E SYT.ESIS OH PROPY A BUTY ACRYATES 1D&,+&+,'&',& ,& +&& +,& '&& ',& -&& -,& (&&

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1:/ ct%$st /412 'tN, 6 : & /D7 K 1:/ ct%$st /412 'tN, 6 : & /7 K 1:/ ct%$st /412 'tN,2: & /7 K 1:D ct%$st

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/7 K 1:D ct%$st 12407 'tNF4

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 T+%e II s(!'s t(e %es !# t(e e-i%i+ri3 &e;rees!# c!"ersi!" #!r *r!*"!% "& +t"!% "& t(e%es !# t(e c!"st"ts t ri!s te3*ertres4 T(e

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a.D

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n)Pr!*"!% 1 1/n)Bt"!% 127 12

CONC$SIONS

 T(e res%ts !# !r e=te"sie reserc( *r!i&e& t(e +sis#!r '!r5i"; !t 5i"etic e-ti!"s "& &eter3i"i"; t(e%es !# c!"st"ts **eri"; i" t(e e-ti!"s4As i"&icte& +$ t(e ct%$tic ctiities !# t(e(eter!*!%$ci&s "&er st&$, &!&ec3!%$+&!*(!s*(!ricci& 's 3!re ctie t(" &!&ect";st!*(!s*(!ricci& +!t( #!r n)*r!*"!% "& n)+t"!%T+%e IF4 T(e ti3e "ee&e& t! rec( t(e &e;ree !# International /ournal of Chemical inetics OI 14125i"KIETICS OH T.E SYT.ESIS OH PROPY A BUTY ACRYATES 19

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c!"ersi!" 4 #!r t(e recti!"s crrie& !t i" t(e*rese"ce !# +!t( ct%$sts 's s(!rter #!r n)+t"!%T+%e IF,'(ic( s;;ests t(t t(is recti!" *r!cee&e&#ster4C!3*ris!" !# t(e 5i"etic 3!&e%s !# t(e(eter!*!%$ci&)ct%$?e& recti!"s "&er st&$ 'it(

t(!se !# t(e recti!"s ct%$?e& +$ c!33!"%$ se&s%#ric ci& %e&s t! s!3e "!te'!rt($ c!"c%si!"s4 T(e #!r3 !# t(e 5i"etic e-ti!" #!r t(e %tter &e*e"&e&!" t(e %e";t( !# t(e cr+!" c(i" i" t(e %c!(!%3!%ec%e: #!r n)+t"!% / "& (i;(er %c!(!%s 0t(e 5i"etics 's e%e3e"tr$, '(eres #!r n)*r!*"!%/ "& %!'er %c!(!%s D t(e recti!" 's #!rt(!r&er sec!"& !r&er i" ci& "& %c!(!% #!r esterif)cti!", "& sec!"& !r&er i" ester "& 'ter #!r ($&r!%$sisF4I" c!"trst, #!r (eter!*!%$ci&s i" t(is st&$ t(e5i"etic e-ti!" i" %% cses (& "!"e%e3e"tr$ #!r34

BIB$IO6RAPH7 14 C(e", 4@ , Z4@ O5(r, T4 A**% Ct% 1, 17,2182424 ."se", .4@ Rs3sse", P4@ Hre&e"s%"&, A4@ Sc(i%%er,M4@ G3e(%i";, J4 I"& E"; C(e3 Res 11, /, 2/D282/DD4/4 Gr?esi5,M4@ S5r?$*e5, J4@Witc?5,M4 St& Sr#ce SciCt% 1, 122, 01D8017404 Gr?esi5, M4@ S5r?$*e5, J4@ Witc?5, M4 Pr?e3 C(e32, 9, 291829/4D4 Witc?5, M4@ Gr?esi5, M4@ S5r?$*e5, J4 I"[? C(e3 Pr!c20, 2D, //18/04International /ournal of Chemical inetics OI 14125i"