BQ GIAo Dl)C vA oAo TAO
TRUONG O~I HQC TONG HQP TP. He CHI MINH
1ted g'~
.,
,
"
PHAN lJ'NGTRIME HOA VONG
ARYLIZOXIANAT BANG
,
"
K
PHUONG PHAPXUCTACCHUYEN PHA&
THAM DO vAl (mG DUNG
.
.,
.
IZOXIANURAT CUA 2,4
A
,
- TDI
""
,.,
CHUYENNGANH HOA LY-HOALYTHUYET
~
,.,
MA SO 1.04.04
TOM TAT
A
~
~
~
-
~
LU~N AN PHO TIEN SI KHOA HQC HOA HQC
THANH PHO HO CHi MINH-1992
u'
1.
6-'~
N
Lu{m lm dU'Q'c holm thanh
t1;\i PhOng Hoa Ly. Hihl cO' cua
Trwng
l.>~i hQc Tbng hgp Thanh phf> H6 Chi Minh.
NguOi huVng din khoa hoc :
1. GSTS CHU PHAM NGQC SaN
2. PTS LE TH1 NffirT HOA
NgWi
Dl$1 x6t :
- Thtr nhAt
:
- Thtr hai :
Ca quaD nhtn x6t :
Lu~n an duvc
hQpt~i
Tru&ng
bao v(? tnrac
H{li d6ng
D~i hQc Tbng hgp Thanh
gio-. ngay
thfmg
chiim
Lu~n
fm Nha mrac
phf> H6 Chi Minh VaG Hic
Dam 1992.
Co th~ tim dQClu~n lm nay t~i :
. Thu vi~n Khoa hQc Tbng hgp TP. H6 Chi Minh.
. Thu vi~n truo-ng D~i hQc Tbng hgp TP. H6 Chi Minh
- I -
I - TONG QUAN TAllI~U :
Phlul (mg trime bOa vong arylizoxianat t~o thanh nhi'mg hgp chAt
izoxianurat b~n nhi~t. ph\! thuQc chit y~u VaG Io~ xiic lac va co ih~ vi~t
thee phU'O"llgtrinh phlul (mg sau :
0
II
C
"""-N/
Ar
3 Ar NCO
'N/
Xuc lac
;>
d
O~
Ar
b
'N/
I
Ar
~O
,
.
.--
,~..,..._.
!,: Ia
16.5 keal-moH (17J.
b - Xiic tac 1a bazu cua N. P. As. Sb
Cae lac giA Sorokin va dOng nghi~p [31] eho rAng a giai do~n
khoi maD cUa phlin (mg co S\l tiic kieh than h~eh eua xUc lac ch~ng
h~ R3N. ireD cacbon cua nhom NCO t~o thanh mQt ion IuO'ng C\rc phan
ly mQt philo hay loan philo dwi d~
ion hrcYngtinh (zwitterion) nhu sau:
R3N + O=C=N-Ar ~
R3~-C-~
II I
0 Ar
Ion Iu6'ng tinh trung gian co tinh than h~ch t6t d~ pMt trilm pb8.n
(mg.
Phan
Ung xay
ra
eMm
poliizoxianat. LU'Q'ng xUc lac
izoxianat ban dAu.
va
eang
cMm
sir dl,lllg ciing kha
ubi v6'i hgp
ch5.t
l&n so v6'i lU'Q'ng
- 2 -
. Loi.iixuc lac mly co th~ tang hoi.itbAngcach su d\lIlgchdt
dimg xUc lac nh\!" hQ'p chAt cpoxi.
loti xUc tAc [32J.
,
HQ'P chdt dbng xUc tac' epoxi
amin tarn ti.iO thanh
m(}t ion lwDg
R3N + CH2-CILR'
"01
~R
3
N@-CH
2
~
cacbamat
ho~c
chAng
hi.iD. lac
Ulll nh\!" sau
+b
R3N
m(lt baza
khic
d\lIlg vao
cimg
xUc lac
:
GHz_CH_R'
"...01
-~
-CH-cP
I
R'
Niiu co s\! hi~n di(!n cua dung m6i luUng C\!C phi proton. no se an
d!nh ion lwng tinh trung gian nay va do do tang v~ tOc phan \mg.
c - Xuc tac Iii h{Yp chAt cO' kim :
H<;rpchdt cO' kim co th~ chia thanh hai nhom [14J :
. Nhom I. co di.iDgchung 1<1MX (M
kim loi.ii lien kiit ; -x : -OR,
. Nh6m II. la ancoxit.
: kim loi.ii ho~c nh6m xuAt c6
-SR, -NR)
DOi vo-i xuc lac I1hom I. d~ tang hoi.it tinh cua n6 phcli su d\lIlg
dung m6i lwDg cvc phi proton nh\!" Qimetyl sunfoxit (DMSO) ho~c
N,N-Qimetyl fomarnit (DMF). Con nhom xUC lac II, chi cAn su d\lIlg mOt
nbng dO nha cua DMF ho~c DMSO la du diJ tang hoi.it cua xUc lac nay.
Xuc lac cua I1hom I cODg vao n6i N=C cua -N=C=O ti.iO thanh
mOt san phAm c{mg co nhom cacbonyl chAng hi.iD [l1J
0
II
BU3Sn-O-SnBU3 + Ar-N=C=O --7 Ar-N-C-O-SnBU3
I
SnBU3
Nguyen tu kim loi.ii lien ki!t v&i nitO' lam tang tfnh bazO' cua nitO'.
HQ'P chdt c(}Dg nay co mang tinh than hi.ich (dAu N) hun izoxianat ban
dAu va co th~ gia tang v~n t6c phan irng ~Ung vo-i hQ'P chdt phirc ti.iP
than di(!n tu ti.iO thanh b&i xUC lac nhom II va izoxianat. V~ m~t hinh
cua - NCO biiin tir di.ing ti.iP chUng sp sang sp2 lam d~ dang
s\! ti.iOphuc v&i xuc tac nhom II. ni!u co [15J.
h9C, cacbon
-
3
-
D6i v&i xUc lac cua nhom II khOng c('mg tn,rc ti6p vao - N=C=O
nhu nhom I. tU'O'nglac gifra ion kim lo~i v&i nguyen tir am w9n N ho{\c
0 cua izoxianat lam cho cacbon cua - NCO cang thi~u di{m tIT hall.
Dung m6i hrong c,!c phi proton DMF va DMSO co lac d\lIlg bn mrm ion
hrong tinh hay chAt phirc t~p t~o thanh do lac d~
cua xuc lac nhom I
va II leu
- NCD.
.
M6i xUc lac cua tUng nhom nay co th~ duqc tang ho~t bftng
cach sir d\lIlg kbt hQ-p v6i m~t xUc tac cUa nh6m khic cUng lov,i (k~t
hqp nhom I v&i nhom II). Vi~c dUng h~ d6ng xuc lac ciing nhom. nhom
I-I ho{\c nhom II-II. kh6ng co tac d~.
D6i v&i nhom I co th~ tang ho~t
bftng KI.
d - Xuc tac 1ii mu6i hotic Oxit CUBkim lo{ti kiJm va kii!m th6
Trong trwng hqp nay. ngm'ri ta phai sir d\lIlg dung m6i lu&ng
c,!c phi proton m~
nhu DMF ho{\c DMSO d~ gap phiin tang ho~t xuc
lac vii boa tan d\r benzyl. alyl > > ankyl
. Lo<;lixUc lac nay co th~ tang ho~t bftng hQ'p chit cacbamat t~o
thiinh do lac d\lIlg cua mQt ru<;yuv&i izoxianat tU"O'llgirng.
Tac d~
cua chAt dbng xUC lac cacbamat Iii gay hi~u irng earn
phan c,!c trim nhom NCO bAng s,! t~o thanh lien k~t hiaro.
-
0+
N
=
C
0-
=0
I 0II
H-N-C-O-
S,! tang tinh than di~n tIT cua nguyen
tIT cacbon
cang
\rU dai cho
s,! lac kich than h~ch cua chAt xuc lac tren nhom NCO, phan irng pMt
tri~n
d& dang va v~n t6c phiin
hidraxil
irng tang
e - Xuc tac 1ii muM amoni
vo cO' va cua axil cacboxylic
[21J.
ho!)c
pholphoni
l(r cJ.p
CUB
Ho<;lt tinh cua xuc lac tuy thuQC vao tinh than h'.lch cua anion
trung tam ho<;lttinh cua xuc taco
N€!u co s,! thay th& nhom ankyl tren cation amoni chimg h'.lll bftng
nhom hiaroxiankyl. ho<;lt tinh cua xuc lac sc tang rAt nhif!u. Nhom
hiaroxil
trim cation
amoni se lac d\lIlg v&i izoxianat
nhu sau
[22J.
- 4 ,
-tfi-
I
~
-OH + ArNCO ~
I
TuO'ng tg nhu tren. nhom uretan
obng xUc Lac m~
clio phan Ung trime
cgc tren nhom NCO. lam clio nguyen tu
diii sg Lac kich than h~ch cua anion xuc
-~
~
-O-CO...:NH-Ar
I
t~o thanh nay se dong vai tro
bOa vong izoxianat t~o sg phim
cacbon cang ngheo di~n tu. U'U
tac'vao -NCO.
hbng
ngolli va phan tich nguyen tb.
l
3 @-
NCO 10%NaCN. 2.57.Aliquat 336) Trime
to {Xlong.khong dung moi
:x
-
a K6t qui : Cac san phAro trime la bt)t trimg mjn. co k~t qua
di~u ch~ vanh~ danh nhu sau :
BANG1
C6H5NCO
Therigian
(phut)
I2
Hieu suAt I
(%)
97
Dim nong I 280
ch3.y (0Q
Ph6 h6ng
.~olli
vKBr ( cm-l )
1710; 1412
Ip-
CIC6H4NCOm- CIC6H4N1m-CH3C6H4NC
I
I 2
I
97
I 318
1724
2
I
;
Iz
I 97
I 97
I 214
I 205
1400
1724
;
1408
1710 ; 1414
'
I
Phan ticl:
nguyen to
C21H1503N3
C21H1203N3C13!C21HIZ03N3Q3 C24H2103N3
71.00:4.17;11.36 54.40;2.59;8.87 54.74;2.62;8.81
72.07;5.21;10.241
1
CHN (%)
!
!
I
b
- Bi~n luf,n
8 -
:
Ki!t qua cho thfly. phucrng phiip XTCP la mQt ph\lO'ng phiiP. r~t
hero hi~u dOi v&i phan irng trime hOa vang arylmonoizoxianat. Nhung
chUng ta phai cM y. khOng th~ tang v~t6c
ho{ic hi~u su§.t phan (mg
bAng cach vira tang nhi~t dQ vira tang nbng dQ cua mc laC va dbng thai
chgn mu6i co tinh baw r~t m~
di! co san phAm trime slJ-ch du,c.Phan
(rog se b~ clJ-Dhtranh v&i Sl! t~o thanh polime day thimg.
2
- TONG HgP
IZOXIANURAT CUA 2,4- TDI vA DAN XUAT [1J
2.1 - IzoxiaDuratcUa 2.4- TDI (1)
l1a m(H hQ'p chAt ~ vang triizoxianat b~n nhi~t (so v&i 2.4-TDI
ban dAu). ChUng toi tii!n hanh sir d\lDg phUO'Dg phiip XTCP trong diEm
ki~n co dung mOl d~ di~u chi! 1. Dung moi sir d\lDg co th~ chia thanh hai
lo?-i : mQt Iii dung moi khOng hOa tan d\lQ'c san phAm (toluen. benzen)
va hai la dung moi hOa tan san phAm (CHCl3. CH3COOEt. CH3CN). Mu6i
vo cO' su d\ll1g la NaCN. KCN. NaHCO3' ChAt xuc tac chuyi!n pha Iii
Aliquat 336 va dibenzo 18- c.,.own- 6. D~ tranh Sll tham gia cua nhom
NCO (y ~ tri ortho d6i v&i nhom Cl\ trong phan tu 2.4- TDI. co holJ-t
tinh thAp bO'Dnbom NCO (y para [28J. chUng Wi tbllc hi~n phcin img &
nhi~t dQ phOng.
c$r
Nee
3
Mu6i vo CO'. cbAt XTCP
dung maio to phang
NCO
a - Ki!t qua:
... Di~u chi? :
-
-
9
BANG 2
MuM
2.4- TDI
XTCP
to(OC)
roo'
I
0.05mol
NaCN 4% Aliquat 2% Toluen/benzen pbOng( 30)
4OmI
4OmI
CHCI3
.
.
0.02mol
.
.
.
.
.
.
.
Toluen 20ml
.
.
.
.
.
.
.
TMi gian HSI
(gia)
(I.)!
.
.
.
.
.
.
.
.
.
.
CH3CN20ml
KCN8% Dibenzo
24
Toluen
5
2Oml pbOng(30)
57
10
70
18
48
20
24
30
51!
55
36
62
59
1
46
26
41
18-crown
-6 3%.
I
. NMndanh :
Ila bQt trAng mjn va dinh co di{lctnmg sau day:
NCO duQ'c do bAng phuung phap bOa h9C sir d\IDg ill
[16J trong CH3CN : 96.8% so v6'i ly thuy~t.
- Ham hrgng
n-butylamin
- Phi>hbng ngo~i
2926
(\) CH~.
:
\) KBr (cm-l)
2278 (\) Ncd'
1593-1515 (\) Nhan thom).
:
1716 (\)
1407 (\) cua swn
c =0 cua
vong trime)
izoxianurat).
Phi> cho thAy khOng co SJ,rhi{m di~n mill di{lc trung \) C=O cua
vong dime a vUng 1785 cm-l [17. 18. 25. 30J va khong co SJ,rhi~n di~n
cua polime m~ch thAng dugc di{lctrung bAng mill hAp thu a khoang 1660
cm-l [20J.
. Tim hi~u dQ b~n cua 1
San phAro trime diI M~ trong chai d~y kin va cAt ky trong binh
him khO v~ mAt ddn cac nhom NCO theo thai gian. SJ,r ki{!n nay cho
thAy sau mQt thai gian da gift trong binh him khO. san ph1im tr& thanh
khOng bOa tan dugc trong dung moi dll bOa tan dugc trime hIC d&u. Phi>
hbng ngo~i cua ciIng mQt m~u san phAm. nhung
dugc ch1;ly cach nhau
- 10 hai tuhn. cho tht..y mOi dQ.c tnmg cua nhom NCO if 2278 cm'
cling ng~n
Jim va xuAt hi~n mt1i Nfl a vUng > 3400 cm '. ChUng to nh6m NCO dii
m~t mi>t phAn d~ tao thanh cacbamat. 51,1'kj~n nay ciing du,c mi>t sb
Uic gia d1\ gin chu truUc day [8]. D~ co th~ phan Hch nguyen tt> san
phAm bn dinh. ch(mg tai kh6a nhom NCO CUR1 bing MeOn ho~c glixidol.
b - Bi(m lu{ln
:
Phlm (mg trime hoa vDng 2.4-TDI
co th~ thl,l'c hi~n dlT,ctrong
di~u ki~n XTCP. PMn (mg co di> chgn Igc cao va chi cho trime. Hi~1l suAt
phan (mg ciing khn cao. Nhung cung khang Den keo dlli th<'ri gian qua
11Iu d~ trlinh kha nl\.ng phAn (mg CUR nhorn NCO a orIlla. Phan (mg
khOng thb thl,l'c hj~n trang di~u ki~n khong dung mM vi. xay ra qua nhanh
vii loa nhi~t rAt nhii;u. dAn dl!n Sl,l'hinh tMnll palime kh6ng tan do phlm
(mg xay ra khang nh(mg iY nhom NCO para dbi vb-i OJ3 ms. cDn iY nhom
NCO 0- orlha nfia.
Dung moi kha tbt Iii. toluen.
[rime khOng ta'n tach r<'ri kilOi mol
tHrong phfm (mg. Vi~c co I~p san phAm dO'lJgian hern. 1 ciing khong b~n
v&i th<'rjgian tuO'ng duerng nhu dibll ch/) trong dil!u ki~n dilng tuang. Co
thb gifr 1 iY tqmg thlii dung dlch trong m(jt thai gian tucrng dM IAIl hern
va sir d\mg dung djch nay db (mg d\lIlg trong vi~c ch~ t\lO vecni va chAt
k~t dinh.
2.2 - Din xuAt cUll. 1
2.2.1 - Trimclylcllcbamal
III CUB J
0
NOO
a~~
N./
I
&,C,-
0
~ ""N
,~'NCO
GY
I
./ C+~
~
?
013
a~ a(
0
0
"
.
0 ~! - C-;OI,
N./
""-N)0I
3cn 3on dung
I, d 'hoan mol
hru 2cua
gio-d
./ b '"
~~O
oP
~
y
~ ::'
-Omlocoom>
1/
013
la (96%)
0
~
-
11 -
!If Nh~n danh :
Sim phAro la Iii mgt bgt trAng cSn ~.
nhtr 1. co d~c trung sau day:
- PhcS hlmg
\) KEr
ngo~
(em-I)
khOng co tinh barn dinh
:
3436 (\)NH ). 2960 (\) CH:3). 1708 (\) C=O cua vong trime).
(\) cua swn izoxianurat), 1234 (\) CO- 0).
1418
Phi>eho thAy mill d~e trung eua nhom NCO {y 2278 eml dii mAt hAll.
- Phan tieh nguyen tb : C3OH3009N6
C%
H%
N%
Ly thuy€!t
58.25
4.85
13.59
Do dm.rc
58.23
4.80
13.22
2.2.2
a
-
- Dieu
Triglixidyl
cacbamat
CUB 1 (Ib)
ch~ hoa chAt glixidol
Phim (mg dtrQ'c th'!c
hi~n bfmg hai giai do{lIl
!If Dieu ch~ dAn xuAt monoclo
H2SO4 dd + 2NaCl
I'i/:.,
..,
c-;-~;'--,.,
,';,:;<'t.,-,i.:.J ;
Tlljf1iF--'P-'
!
HCl dd)
2HClt
+ HClt
:}(;j-'-
I
L---~~-
+ NazS°4
- 1200C
ClCHZ-CHOH-CHZOH
3- cloro-1.2- dihidroxipropan
~
10 gi&
+ CHZOH-CHCl-CH20H
2- cloro-1.3- dihidroxipropan
DAn xuAt monoclo dm.rc co l~p bfmg each chung d.t phan do~n
dwi lip suAt kern. Hi~u suAt Iii 50% vii dg s~ch cua san phAm d,!a tren
phep ~
phan Cl va sAc ky khi Iii 96% co 90% dlmg phan 1.2 va 6%
dong phan 1.3 [4J.
!If Phan (mg dong vong dAn xuAt monoclo dtr&i dieu ki$n XTCP
120%K2C03. 1%Aliquat 336
ClCHZ-CHOH-CH20H+ CH20H-CHCl-CH20H
"8Oml dietyl ete. heaD ItrU 4gi&
h5n hQ'p dong phan 0.1 mol
CH2-CH-CH20H
'
/
o
-~-
.._~~:_i_~5-i \ ~---~~: ~_.:
cua glixerin
90
CH20H-CHOH-CHZOH
:
,...---..-i""
glixidol (68%)
j
I
:
-
b
-
12
-
Di~u ch~ Ib
NCO
~
"3
013
0
0
~
N/C'-N@NCO
CI
1+
0~
N
./
30-1 -O-I-n-IOB
C"
2/
_°"2
~ 0
0
~
dung moi cua J
..
0
~
holmhru3 gi&
!'.'B-C-OOI -CH-rJI
2
'2
r
0
II3C
0
0
@N/
NCO
CH
C
0
013
0
'-N.@lNlJ-C-OaI
"
3
d
o~
h
N./
-aI-a',
2 ,I
0
.
"'0
0
r81
~~
.
3
TI18.n-
(mg xay ra
NIH- am 2
0
II
1b (937.)
d~ dang va cl1ng khong cAnxu~ tlic.
.do hidro
linh d(Jng dla glLxi<1o1tile kieh vao nhom NCO eua 1 h,IO thanh nhfmg
nh6m cecbamat. Hgp chAt 1b 10. m{jt triepoxi haa tan trong dung moi
Ol3CN co kM filIng su d~g him nguy~n Ii~u di6n ehb ch[;t kbt diOO
epoxi va chAt 6n dinh PVC [9].
. Nh~ndanh:
.
SilO phAro Ib Iii b(Jl trAng mill va khii bn diOOv~ hoiJt lIOO. eo d~c
tnmg san day:
- Ph6 hlmg ngo~i 'i) Kl3r (em-!)
: 3440 (\) NIl). 2928 (\) ~tJ ),
17!0 (\) C=O cua yang trime), 1422 (\) cua soon izoxianllrat). 1228
(\) Cc)
\ I
0
-
Phiin lIch nguycn
C%
=
t6
: C36H36012NG
57.90. 11%= 5.25. N% = 11.60
OJ-OJ
\/2
0
-
-
13
-
DONG HQC CUA PHAN LING TRIME HOA yaNG
ARYLMONOIZOXIANAT
ChUng tei kMo sat dQng hQc phan Ung trime bOa vang cua
aryimonoizoxianat C6HsNCO. p-CIC6H4NCO. m-ClC6H4NCO va
3
m -CH3C6H4NCO v6i bazO' 1a. mu6i NaCN vii chell XTCP 1a. Aliquat 336
trong dung mei axelonilril trong khoang nhi~t dQ tlI 17°C dim 430C [2].
)(
, ~
NCOIOX
NaCN.
5X .
,~
CN
07 N/'. Allq..! 336
~m~
Cr th&i di&m
,
y.
~
twa du 50m1l d
"3
CH
~
J8J
~
~
l8J
t
= O. [aryimonoizoxianat]
°=
t
= t. [arylmonoizoxianath
= a - 3x
a
./
'N
b
~o
0
X
)<
a : n6ng dQ ban dAu cua arylmonoizoxianal
x : n6ng dQ cua izoxianurat t1J.Othanh
PhU'O'Ilg trinh
dQng hQc b~c 2 :
1
3(a
- 3x)
= koo't + ~
3a
D6 theo doi v~n t6c phan Ung. chUng lei sir d\lllg phU'O'Ilgpilap
dp1h 1U'Q'ngnhom NCO can 1~ tll'ng th&i di~m (t) [16]. K~t qua lhgc
nghi~m kill dQ chuy~n hoa phan (mg d~t 70-80% cho thely. dQng hQc cUa
phan ii'ng lrime hoa vong cac aryimonoizoxianal v&i mu6i NaCN va. chell
XTCP Aliquat 336 thuQc lo~ phuO'Dg lrinh b~c 2 theo n6ng d{> cUa
monome. ChUng Wi Slr d\lIlg phep giai Uch h6i quy va. phllO'ng pMp binh
phllO'Dg t6i lhi6u ap d\mg cho phuO'ng trinh hbi quy tuy~n tinh d6 sur ra
cac hAng s6 v*n t6c k. cac thOng s6 ho~t hoa 6J{: va. 6.S:::. trt s6 p
cua Hammett va. khoang tin c~y tUO'DgUng ; va. kern theo do co cho tr!
s6 cua h~ s6 tllO'ng quaD r 116bi~l v~ muc dQ tuyim tinh cua cac di~m
dang quail sat [5].
-
3.1 - K6tqua
14 -
:
3.1.1 - C6HSNCO
)}ac su§.t
BANG 3 : Hftng
+u6i v&i
. s6 v~n t6c k. khoang tin. c{ty KTC(k)
A
.,.
!\
P = 0.95. h() so ;.tro'ng quaD r. c-rc thOng so ho?-t hoa illl- va uS-. khoimg
= 0.95 cua
tin c~y KTC(Lili-) va KTC(/;;,S-) v&iP
vong C6H5NCO thee nhi~t QQ.
I
i
I
i
290
T( oK)
I
311
1.53
1.77
0.13
0.37
0.49
0.998
0.995
0.997
iI KTC(k).1~3moH.s-l
r
i
0.998
316
306.5
0.64
k.lO+ 3mo}-l.s-l
pMn \rng trime boa
.
2.39
f
6H~ :t KTC(LJt- )
I
I
i
kcal
8.5 ~ 1.6
.mol-l
,
+
I/;;,s -:t KTC(/;;,S :t)
calX~ mol-l
II
-43.86:'
r
5.10
0.998
3.1.2 - p- C1C6H4NCO
BANG 4 : HfLngs6 v~n tbc k. khoang tin c~y KTC(k) ubi v&i xac
.
f +
.,
va
suii.~ P = 0.95. M so ttro'ng quan r. cae thOng so ho~t hOa 6H.65:'. khoang tin e~y KTC (Lili~) va KTC (/;;,S~) v&i P = 0.95 eua
puan trag trime hoa vong p- ClC6H4NCO thee nhi~t u{>
i
i recK)
iI k.1O+3mo1-l.s-1
I
I
,
i KTC(k).lOt3moH.s-l
,
I
r
,
:,
I
,i
0.26
0.996
311
I
:
I
I
I
0.40
,
I
0.994
I
I
I
Lili~!
KTC(L6H~)
kca1.mo1-l
+
...
6s -:t KTC(/;;,S '"')
cal.Wl .mol-l
r
!
i
5.5.!
1.0
j
I
II
!
316
I
1.~
I
I
I
I
307
1.17'
I
I
I
I
293
-53.20::'
0.998
3.20
0.89
0.995
II
I
I
1.48
0.997
-
-
15
3.1.3 - m-C1C6H4NCO
BANG5 : HAng sO v~n tOe k, khoang tin e~y KTC(k) ubi v6i xae
suilt P
L,S=,
=
0,95, h~ sO tU'O'llg quan r, cae thong sO ho~t h6a Lili.! va
khoang
tin c~y KTC (Lili-!.)
va KTC (L,S!)
=
v&i P
0,95
cua
phan (mg trime bOa yang ')"11.-ClC6H4NCO thee nhi~t at)
BANG 5
T(OK)
293
307
T
I
311
316
I
k.lO+ 3moH.s-l
1.51
2.45
2,29
2.88
I
KTC(k) .10+3mol-l.s-l
r
0.24
0.992
0.34
0.53
0.993
0,998
0.65
0.990
I
Lili!
KTC(Lili-!. )
1:
kcal.moH
4,5.!
1.0
L,s !:t KTC(Lili 1: )
ea1.K-l.mol-l
r
-56.rn : 3,20
0.997
3.1.4 - m-CH3C£fi4NCO
Rieng uOi v6i m-tolylizoxianat,
chUng toi chi khilO sat hAng so
v~n tOe k & 38°C va eo k~t qua sau day
k.1O+3morl.s-1: 1.62
KTC(k).10+3.mol-l.s.1:
1.35
r :0,993
BANG 6 : Cae trl sO thOng sO ho~t bOa. khoang tin c~y tren pMp
tinh dOi v&i xae xuilt P = 0,95 va h~ sO tU'O'ng quan r cua phan (mg
trime bOa yang tily thee tUng arylmonoizoxianat.
-
-
16
BANG 6
i
'
~
I
I
~y~ono-
,...
~Q}aanat
-
bOa
II boat
ThOng
s6
.
I
,+
II DB-
.
+ KTC(DB-)
I
+
I6s - +
I
It
I
'
-+
II
1.6
I
I
I
I
I
I
;I
II
5.5 -+ 1.0
!
i
I
:
iI
I
-43.86 !. 5.10 '
m-ClC6H4NCO
,
I
I
KTC( 6S -)
caLK-I.mol-l
I
IiI
I
,+
I
,
I
8.5
kcaLmol-1
I
!
+
I
! p-ClC6H,j'lCO
C6H5NCO
i
~I
I
i
i
-53.20!.
3.20
4.5
-+
1.0
I
I
I
I
-56.08!.
I
3.20 i
!!
I
r
I
0.998
[
I,
I
!
0.998
j
I
0.997
i
3.2 - Kbio I!t bi~u 'Cmg4i~n tU-cUa nhbmthb tron nhAn tham
BANG7 : S1,l'thay dbi cua log k theo 0 cua Hammett i:r38°C
Nh6m th~
1
r
I
I
X
0 Hammett
m- Cl
0.373
p-Cl
H
0.227
0
m- CH3
-0.069
I
I
I
I
k.IO+ 3mol-l.s-1
I
log k
I
i
2.45
2.12
1.77
:
1.62
I
I
i
I
I
-2.6108
-2.6737
-2.7520
-2.7905
Tit phlrO'ng trinh hbi quy tuyfm HIm bi~u di6n cho log k theo O. La
guy ra 1.1'1sb p va h~ s6 tlrO'ngquail r i:r 38°C nhu san:
p
: 0.39
3.3 - BiOn~
KTC(p)
: 0.08 vo-i P
= 0.95
r : 0,998
:
a - Tit cac k~t qua th1,l'Cnghi$m. ta co th~ th~y dmg pMn
ftng trime hOa vang arylmonoizoxianat trong di~\1 ki~n XTCP nhu dii mo
tA cling thee dUng b?c 2 nhu trong trwng h?'P phim (mg dUQ'c th\rc
hi~n trong di~u ki{m dbng tuemg.
b - Hfmg s6 k ho~c kdo tinh thee phiill \rng b~c 2 co trj s6
khi cb dinti cho mbi nhi$t d{\. Di~u mly rlit 15' tM va dua-ng bi6u
p-CIC6H~CO
> m-CH3CsH4NCO
Di~u nay cUng c6 th~ d,! doan dU'Q'cvi v&i cac nh6m th~ cang rut
di~n tu, C cua nhom N=C=O cang thiE!Udi~n tu. U"UdiU cho phan \i'ng
t§.n cong than h<;ich. HO'n nua, S,! ki~n nay ding duQ'c xiic nh~n b6-i tr!
s6
p
duang.
p=
Tr! s6
0,39 tuO'ng elM nho,
chi rang
6- tr<;ing thai
chuy~n
ti~p
co s,! tang di~n tieh am trai dai ta N qua O. Nhu v~y dQ nh~y cua phan
\i'ng a6i v&i hi~u \i'ng cua nh6m th~ kb6ng lem l~m.
d - Cac trj sb ll.y:!: tang din thee thfr t'! :
m-ClQ)H4NCO < p-CJC6H4NCO < C6HSNCO
.
A
..
+
va tq so wS-
am co tIi tuy{;t d6i pam dan thee thu tv
m-ClCeH4NCO > p-CIC6H4NCO > Q;HsNCO
Th~ t'! nay ph\l h
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