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- 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
. .,
.
- TDI
IZOXIANURAT CUA 2,4
A , "" ,.,
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'
6-'~
1.
Lu{m lm dU'Q'c holm thanh t1;\i PhOng Hoa Ly. Hihl cO' cua Trwng
N
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 bao v(? tnrac H{li d6ng chiim Lu~n fm Nha mrac
hQpt~i Tru&ng D~i hQc Tbng hgp Thanh phf> H6 Chi Minh VaG Hic
gio-. ngay thfmg 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
Ar C Ar
'N/ """-N/
Xuc lac
3 Ar NCO ;>
d b
O~ 'N/ ~O
I .-- ,~..,..._.
.
Ar ,
!,:
- - 2-
. Loi.iixuc lac mly co th~ tang hoi.itbAngcach su d\lIlgchdt
dimg xUc lac nh\!" hQ'p chAt cpoxi. cacbamat ho~c m(lt baza khic cimg
loti xUc tAc [32J. ,
HQ'P chdt dbng xUc tac' epoxi chAng hi.iD. lac d\lIlg vao xUc lac
amin tarn ti.iO thanh m(}t ion lwDg Ulll nh\!" sau :
+b
R3N + CH2-CILR' ~ R3N GHz_CH_R'
"01 "...01
-~
~R N@-CH -CH-cP
3 2 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
- - -
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
- NCD.
va II leu
.
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
- - 4-
, I
-tfi- ~ -OH + ArNCO ~ -~ -O-CO...:NH-Ar
~
I I
TuO'ng tg nhu tren. nhom uretan t~o thanh nay se dong vai tro
obng xUc Lac m~ clio phan Ung trime bOa vong izoxianat t~o sg phim
cgc tren nhom NCO. lam clio nguyen tu cacbon cang ngheo di~n tu. U'U
diii sg Lac kich than h~ch cua anion xuc tac'vao -NCO.
- - -
5
2. MOl TRlJONG 01.TlJONG :
2.1 - Di6u eM :
Nam 1985. W.BRODA. E.V.DEHMLOW VA H.J.SCHULZ da cong bb
phan img trime hoa vong cac chAt monoizoxianat dtr6-i di~u ki~n xUc lac
chuyim pha (XTCP). K~t qua cho thAy phan (mg xay ra r.lt hl111hi~u
dtr6-i di~u ki~n oo~ OO
- - 6-
-
II MlJC TIEU NGHIEN CU-U
.. Ti~p theo c6ng b6 cua W.BRODA. E.V. DEHMLOW va
H.J.SCHULZ nam 1985. chUng t6i su d\illg phtro"ng phiip XTCP d~ di~u ch~
1(li va nh~n danh them mQt s6 chill arylmonoizoxianat.
.. Su d\illg phtrong phiip XTCP d~ di~u ch~ chili trime cua
2.4- TDI.
.. Kbao sat di)ng h9C pbiin u-ng trime boa yong cua arylizoxianat.
mono- va diizoxianat. trong di~u ki~n cij tu6'ng XTCP. Ben c
- - 7-
III- KETQUA THl[C NGHI~M VA BI~N LU~N
1. TONG HQP IZOXIANURAT CUA ARYLMONOIZOXIANAT
ChUng toi sir d\ffig phmmg philp XTCP khOng dung moi d~ di~u
ch~ va nh~ danh mt)t s6 chAt aryhnonoizoxianat : C6H5NCO.
p-QQ;H4NCO. m-CIC6H4NCO va m-CH3C6H4NCO. Mubi sir d\illg la
NaCN. chAt XTCP Aliquat 336. San phAro sinh ra dUQ"cco l~p va k~t tinh
lili trong MeOH. va dUQ"cnh~n danh bAng do di~m Dong chay. phi> hbng
ngolli va phan tich nguyen tb.
l
3 @- NCO 10%NaCN. 2.57.Aliquat 336) Trime
to {Xlong. hong dung moi
k
: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
Ip- CIC6H4NCO CIC6H4N1m-CH3C6H4NC
m- I
2 Iz
I2
I2
Therigian I
(phut)
I I 97 I 97
Hieu suAt I 97
97
(%)
I 205
I 318 I 214
Dim nong I 280
ch3.y (0Q
Ph6 h6ng
1710; 1412 1724 1400 1724 1408 1710 ; 1414
; ;
.~olli
vKBr ( cm-l )
'
Phan ticl: C21H1503N3 C21H1203N3C13!C21HIZ03N3Q3 C24H2103N3 I
nguyen to 71.00:4.17;11.36 54.40;2.59;8.87 54.74;2.62;8.81 72.07;5.21;10.241
I
1
CHN (%) !
!
- - 8-
- Bi~n luf,n
b :
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
- - -
9
BANG 2
MuM
2.4- TDI XTCP TMi gian HSI
to(OC)
(gia)
(I.)!
roo'
I
NaCN 4% Aliquat 2% Toluen/benzen pbOng( 30) 24
0.05mol 57
4OmI
70
4OmI 10
CHCI3
.
. Toluen 20ml 18 48
0.02mol
. . . .
. 20
. . . . 51!
. 24 55
. . . .
. 30 59
. . . .
. 36 62
.
. . CH3CN20ml 5 1 46
. KCN8% Dibenzo Toluen 2Oml pbOng(30) 26 41
18-crown
-6 3%.
I
. NMndanh : Ila bQt trAng mjn va dinh co di{lctnmg sau day:
- Ham hrgng NCO duQ'c do bAng phuung phap bOa h9C sir d\IDg ill
n-butylamin [16J trong CH3CN : 96.8% so v6'i ly thuy~t.
- Phi>hbng ngo~i \) KBr (cm-l)
: :
(\) CH~. 2278 (\) Ncd' 1716 (\) c =0 cua vong trime)
2926
1593-1515 (\) Nhan thom). 1407 (\) cua swn 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
- - 11 -
!If Nh~n danh :
Sim phAro la Iii mgt bgt trAng cSn ~. khOng co tinh barn dinh
nhtr 1. co d~c trung sau day:
- PhcS hlmg \) KEr
ngo~ (em-I) :
3436 (\)NH ). 2960 (\) CH:3). 1708 (\) C=O cua vong trime). 1418
(\) cua swn izoxianurat), 1234 (\) CO- 0).
Phi>eho thAy mill d~e trung eua nhom NCO {y 2278 eml dii mAt hAll.
- Phan tieh nguyen tb : C3OH3009N6
C% H% N% ,...---..-- ..,
-~-
i"" c-;-~;'--,.,
,';,:;
- 12
- -
b Di~u ch~ Ib
-
NCO
~
"3
013
0
0 ~
N/C'-N@NCO
I 1+
C" 2 -O-I-n-IOB
30-1 dung moi cua J
C / _°"2 ..
~0
0~ 0 holm 3 gi&
hru
./
N 0 ~
!'.'B-C-OOI -CH-rJI
r
2 '- 2
~ 0 II3C 0 0 013
0 0
NCO C
@N/ '-N.@lNlJ-C-OaI -aI-a',
CH " 2 ,I
3 d h 0 0
o~ N./ "'0 .
r81
~~ NIH- am - OJ-OJ
.
2 \/2
0 0
3 II
1b (937.)
d~ dang va cl1ng khong cAnxu~ tlic.
(mg xay ra .do hidro
TI18.n-
linh d(Jng dla glLxi
- - -
13
- DONG HQC CUA PHAN LING TRIME HOA yaNG
3
ARYLMONOIZOXIANAT
ChUng tei kMo sat dQng hQc phan Ung trime bOa vang cua
aryimonoizoxianat C6HsNCO. p-CIC6H4NCO. m-ClC6H4NCO va
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].
)(
~ J8J , y.
,~ NCOIOX 5X .
NaCN. ~
twa du 50m1l d b
,~ "3
'- ./
. Allq..! 336 N/ 'N
07
~
CH CN
~m~ ~
~o
l8J 0
= O. [aryimonoizoxianat] =
°
Cr th&i di&m t a )<
= X
= t. [arylmonoizoxianath a - 3x
t
a : n6ng dQ ban dAu cua arylmonoizoxianal
x : n6ng dQ cua izoxianurat t1J.Othanh
= koo't + ~
PhU'O'Ilg trinh dQng hQc b~c 2 : 1
- 3x)
3(a 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].
- - 14 -
3.1 - K6tqua :
3.1.1 - C6HSNCO
BANG 3 : Hftng s6 v~n t6c k. khoang tin c{ty KTC(k) +u6i v&i )}ac su§.t
. . .,.
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 pMn \rng trime boa
vong C6H5NCO thee nhi~t QQ. .
I
316
290 311
306.5
i T( oK)
I
2.39
0.64 1.53 1.77
k.lO+ 3mo}-l.s-l
I
i
iKTC(k).1~3moH.s-l 0.13 0.37 0.49
I
r 0.998 0.995 0.997
0.998
i
f
6H~ :t KTC(LJt- )
I
I 8.5 ~ 1.6
kcal .mol-l
i
, +
I/;;,s -:t KTC(/;;,S :t)
I -43.86:' 5.10
calX~ mol-l
I
r 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+
suii.~ P = 0.95. M so ttro'ng quan r. cae thOng so ho~t hOa 6H- va
.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) 293 307 311 316
I
I
ik.1O+3mo1-l.s-1 1.17' 1.~
I
:
I
I ,
, I I :
I
0.26
I
i KTC(k).lOt3moH.s-l I 1.48
0.40 0.89
,
I
, I
I
I
,
I i
r I 0.994 0.995 0.997
0.996
, I I I
I
I I I
I I
Lili~! KTC(L6H~ ) !
I
i 5.5.! 1.0
kca1.mo1-l
j
+ ... I
I
6s -:t KTC(/;;,S '"') I
!
cal.Wl .mol-l -53.20::' 3.20
r 0.998
- - -
15
3.1.3 - m-C1C6H4NCO
BANG5 : HAng sO v~n tOe k, khoang tin e~y KTC(k) ubi v6i xae
=
suilt P 0,95, h~ sO tU'O'llg quan r, cae thong sO ho~t h6a Lili.! va
=
L,S=, khoang tin c~y KTC (Lili-!.) va KTC (L,S!) v&i P 0,95 cua
phan (mg trime bOa yang ')"11.- lC6H4NCO thee nhi~t at)
C
BANG 5
T
I
293 307 311 316
T(OK)
I
k.lO+ 3moH.s-l 2.45
1.51 2.88
2,29
I
KTC(k) .10+3mol-l.s-l 0.24 0.34 0.53 0.65
r 0.992 0.993 0,998 0.990
I
Lili! KTC(Lili-!. )
1:
kcal.moH 4,5.! 1.0
L,s !:t KTC(Lili 1: )
-56.rn : 3,20
ea1.K-l.mol-l
r 0.997
3.1.4 - m-CH3C£fi4NCO
chUng toi chi khilO sat hAng so
Rieng uOi v6i m-tolylizoxianat,
v~n tOe k & 38°C va eo k~t qua sau day
r :0,993
k.1O+3morl.s-1: 1.62 KTC(k).10+3.mol-l.s.1: 1.35
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
~ I
~y~ono- i
I
! p-ClC6H,j'lCO
C6H5NCO m-ClC6H4NCO
~Q}aanat
I I
,... - i
I
,
I
IThOng ,
I
s6 ~I
boat bOa I I
I
;
I. t i
I
.
I
,+ + I
I DB- + KTC( DB-) I
I '
I
+
+ I +
- -
I
1.6 5.5 - 1.0
8.5 I 4.5 1.0
kcaLmol-1 I
I ! i
I I
I
I
! + ,+ I I :
i I
I6s - + I I
KTC( 6S -) I
I
-43.86 !. 5.10 ' -53.20!. 3.20 -56.08!. 3.20 i
I
caLK-I.mol-l I
I
I
I
! ,
I !
I
I
!
r 0.998 0.998 0.997
j
[ i
I 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 k.IO+ 3mol-l.s-1 log k
I I
I I
I
I
m- Cl 0.373 2.45 -2.6108
I I
p-Cl 0.227 2.12 -2.6737
H 0 i 1.77 i -2.7520
m- CH3 -0.069 1.62 -2.7905
I
: I
Tit phlrO'ng trinh hbi quy tuyfm HIm bi~u di6n cho log k theo O. La
guy ra 1.1'1b p va h~ s6 tlrO'ngquail r i:r 38°C nhu san:
s
= 0.95
p : 0.39 KTC(p) : 0.08 vo-i P r : 0,998
~
3.3 - BiOn :
a - Tit cac k~t qua th1,l'C
nghi$m. ta co th~ th~y dmg pMn
ftng trime hOa vang arylmonoizoxianat trong di~\1 ki~n XTCP nhu dii mo
tA cling thee dUng b?c 2 nhu trong trwng h?'P phim (mg dUQ'c th\rc
hi~n trong di~u ki{m dbng tuemg.
b - Hfmg s6 k ho~c kdo tinh thee phiill \rng b~c 2 co trj s6
khi cb dinti cho mbi nhi$t d{\. Di~u mly rlit 15' tM va dua-ng bi6u
- - -
17
log kdolT
theo lIT hi mQt threrng thlmg ch(mg to r~g v&i
= ko[Q+.
kdo CN- (dung Q;HsNCO
Th~ t'! nay ph\l h
- - -
18
- ~'.(~
Nh6m the cling rut di~n tu-.\(\,[.,..t~o n6i giila C va N cua hai phan
tu- arylizoxianat cling d~ dang va nhi~u. him cho tr~ thai chuy~n ti~p
cang kern t\l' do. do d6 lili 1: cling it dU'O'ngva .6.51: cling am.
4 - aONG HOC CUA PHAN lING TRIMEH6A VONG CUA
2,4- TDI
DQng hQc cua phan Ung trime bOa vong 2.4-TDI cUng dUQ'c khao
sat trong dung moi axetonitril v6i bazO' Ia mu6i NaCN va chAt XTCP
Aliquat 336 trong khoang nhi~t dQ tft 50C dim 21oC [3].
NCD
~ /Q{3
.
0 @x
~
/C.........
47. NaCN. 27. Aliquat 336 N N/ NCD
3
d b
Cl\CN (vfta diI 50mlT
~NCO
NCD
O.OSmol
O~C$i:o
CH3
a thai = O. =a
di~m : t D
[TDI] 0
= a - 3x
= t.
t [TDIh x
a nOng dQ ban dAu cua 2.4-TDI : x ; nOng di) cua izoxianurat
;
tl,\O thanh. PhU'O'ng trinh dQng hQc b~c 2 :
I
= kdo.t + I
- 3x) 3a
3(a
4.1 - K6t qua :
K~t qua th\lC nghi~m cOng cho thAy. dQng hQc cua phan irng
trimc h6a vong 2.4-TDI v&i muOi NaCN va chAt XTCP Aliquat 336 cOng
thuQc lo
nguon tai.lieu . vn