CHNG I: QU TRNH ALKYL HA

Qu trnh alkyl ha l qu trnh a cc nhm alkyl vo vo phn t cc cht hu c hoc v c. Cc phn ng alkyl ha c gi tr thc t cao trong vic a cc nhm alkyl vo hp cht thm, izoparafin, mercaptan, sulfid, amin, cc hp cht cha lin kt ete... ngoi ra qu trnh alkyl ha l nhng giai on trung gian trong sn xut cc monome, cht ty ra...

1. C TRNG CA QU TRNH ALKYL HA

I. Phn loi cc phn ng alkyl ha S phn loi hp l nht cc qu trnh alkyl ha l da trn loi lin kt c hnh thnh.
1. Alkyl ha theo nguyn t C: cn gi l qu trnh C - alkyl ha

C - alkyl ha l th nguyn t H gn vi C bng cc nhm alkyl. CnH2n+2 + CmH2m Cn+mH2(n+m)+ 2 ArH + RCl ArR + HCl
2. Alkyl ha theo nguyn t O v S: cn gi l qu trnh O - alkyl ha v S -

alkyl ha O - alkyl ha v S - alkyl ha l cc phn ng dn n to thnh lin kt gia nhm alkyl v nguyn t O hoc S. ArOH + RCl + NaOH ArOR + NaCl + H2O

NaSH + RCl RSH + NaCl

3. Alkyl ha theo nguyn t N: cn gi l qu trnh N - alkyl ha

N - alkyl ha l th cc nguyn t H trong amoniac hoc trong amin bng cc nhm alkyl. y chnh l mt trong nhng phng php quan trng nht tng hp cc amin. ROH + NH3 RNH2 + H2O
4. Alkyl ha theo cc nguyn t khc:

Cc qu trnh Si -, Pb -, Al - alkyl ha... l con ng quan trng tng hp cc hp cht c nguyn t hoc c kim. 2 RCl + Si R2SiCl2 4 C3H7Cl + 4 NaPb (xc tc l Cu) Pb(C3H7)4 + 4 NaCl + 3 Pb Al(C2H5)3

3 C2H4 + Al + 3/2 H2 II.

Cc tc nhn alkyl ha v xc tc Cc tc nhn alkyl ha c th chia lm 3 nhm:

a) Cc hp cht khng no (olefin v acetylen), trong s ph v cc

lin kt ca cc nguyn t C. b) Dn xut Cl vi cc nguyn t Cl linh ng c kh nng th di nh hng ca cc tc nhn khc nhau. c) Ru, ete, este, oxyt olefin l cc tc nhn m trong qu trnh alkyl ha lin kt C - O s b ph v. 1. Tc nhn l olefin - xc tc v c ch Trong cc loi tc nhn th tc nhn olefin c gi thnh kh r, v vy ngi ta lun c gng s dng chng trong mi trng hp c th. Cc olefin (etylen, propylen, buten v cc olefin cao phn t) ch yu c s dng C - alkyl ha cc parafin v cc hp cht thm. Xc tc: acid proton (a.Bronsted) hoc acid phi proton (a.Lewis)

C ch: ch yu xy ra theo c ch ion qua giai on trung gian hnh thnh cacbocation. Kh nng phn ng ca cc olefin c nh gi bng mc to ra cacbocation: RCH = CH2 + H+ RC+H - CH3 Qu trnh ny chu nh hng ca s tng chiu di mch, phn nhnh

ca olefin: CH2 = CH2 < CH3 - CH = CH2 < CH3 - CH2 - CH = CH2 < (CH3)2C = CH2

 Tc nhn olefin c mch cng di, cng phn nhnh th kh nng phn ng cng ln. Ngoi ra trong rt nhiu trng hp, qu trnh alkyl ha bng olefin c th xy ra di tc dng ca cc cht khi mo phn ng chui gc, hoc tc dng ca nh sng hoc tc dng ca nhit cao. Khi cc phn t trung gian l cc gc t do v trong trng hp ny kh nng phn ng ca cc olefin c cu to khc nhau cng khng khc nhau nhiu. 2. Tc nhn l cc dn xut clo - xc tc v c ch Cc dn xut clo c xem l cc tc nhn alkyl ha tng i thng dng nht trong cc trng hp O -, S -, N - alkyl ha v tng hp phn ln cc hp cht c kim, c nguyn t; ngoi ra cn c s dng trong trng hp C - alkyl ha.

C - alkyl ha: xy ra theo c ch i in t di tc dng cht xc tc l cc acid phi proton (FeCl3, AlCl3) qua giai on trung gian hnh thnh cacbocation: RCl + AlCl3 R+ Cl -AlCl3 R+ + AlCl4Kh nng phn ng ca cc alkyl clorua ph thuc vo phn cc ca lin kt C-Cl hoc vo bn cacbocation v s tng khi chiu di v mc phn nhnh ca nhm alkyl tng: CH3CH2Cl < (CH3)2CHCl < (CH3)CCl3

O -, S-, N - alkyl ha: xy ra theo c ch i nhn v khng cn xc tc RCl + :NH3 RN+H3 + Cl- RNH2 + HCl Kh nng phn ng ca cc dn xut clo c sp xp theo dy: ArCH2Cl > CH2 = CH - CH2Cl > AlkCl > ArCl v AlkCl bc I > AlkCl bc II > AlkCl bc III

Trong tng hp c kim v c nguyn t: xy ra theo c ch gc t do di tc dng ca kim loi

4 NaPb + 4 C2H5Cl 4 Pb + NaCl + 4 C2H5 4 NaCl + Pb(C2H5)4 + 3 Pb

3. Tc nhn l cc hp cht c cha O - xc tc v c ch

Cc tc nhn alkyl ha c cha O nh ru, ete, este, oxyt olefin c th dng trong cc qu trnh C -, O -, N - v S - alkyl ha; tuy nhin trn thc t ngi ta s dng ch yu l cc oxyt olefin. Qu trnh xy ra theo c ch cacbocation di tc dng ca xc tc l acid proton lm t lin kt gia nhm alkyl v oxy: ROH + H+ R - +OH2 R+ + H2O III. c tnh nng lng ca cc phn ng alkyl ha Cc c tnh nng lng ph thuc vo tc nhn alkyl ha v dng lin kt b ph v trong cht alkyl ha. Mt s thng s nng lng trong qu trnh alkyl ha c trnh by bng sau: Tc nhn alkyl ha RCH = CH2 RCl ROH CH2 - CH2 O CH CH Lin kt b ph v C - H Car - H O-H Car - H O-H N-H O-H N-H O-H O-H -Ho298 , kJ/mol 84 100 96 104 50 63 34 42 0 0 25 0 21 21 42 88 104 100 117

2. ALKYL HA THEO NGUYN T CACBON

Qu trnh C - alkyl ha ch yu xy ra vi cc hp cht thm v parafin vi nhiu nghi thc t to ln. I. Alkyl ha cc hp cht thm

1. Ha hc v c s l thuyt 1.1. Xc tc Tu thuc vo tc nhn alkyl ha m c th s dng cc xc tc khc nhau. Cc tc nhn alkyl ha hydrocacbon thm s dng ch yu trong cng nghip l cc dn xut clo v olefin. Ru t c s dng cho qu trnh alkyl ha hydrocacbon thm v c kh nng alkyl ha km hn.

Khi tc nhn l cc dn xut clo: xc tc hu hiu nht l cc acid phi proton, ph bin nht l AlCl3. Hn hp phn ng trong pha lng khi alkyl ha vi xc tc AlCl3 bao gm 2 pha: phc xc tc v lp hydrocacbon.

Khi tc nhn l olefin: thng dng xc tc l AlCl3; ngoi ra c th dng a.H2SO4, HF, H3PO4 trn cht mang, aluminosilicat, zeolit... Trong :
o Khi xc tc l a.H2SO4 hoc HF: + qu trnh pha lng

+ t = 10 40oC + p = 0,1 1 MPa

o Khi xc tc l a.H3PO4 rn:

+ qu trnh pha kh + t =225 275oC + p = 2 6 MPa

o Khi xc tc l aluminosilicat, zeolit: kh

+ qu trnh pha lng hoc pha

+ t = 200 400oC + p = 2 6 MPa Nh vy, i vi qu trnh C-alkyl ha th xc tc AlCl3 chim v tr p o v c nhiu u th.