BQ GIAo Dl)C vA oAo TAO
TRUONGO~I HQCTONG HQP TP. He CHI MINH
1ted g'~
., , "
PHAN lJ'NGTRIME HOA VONG
ARYLIZOXIANAT BANG
, " K
PHUONG PHAPXUCTACCHUYEN PHA&
THAMDOvAl (mG DUNG
.
. .,
IZOXIANURAT CUA 2,4 -TDI
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'
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 :

Cac k~t qua nghien cuu cua DAVIS cho bi~t a nhi~t d(i cao. m(it
phAn 000 cua 2.4-toluendiizoxianat(2.4-TDO dime bOa va trime bOa
khOng chl)n Il)c [17J.
a700c trong vong 600 gia. san phAro trime thu
dU'Q'c Ia 27. va dime 4.27 Trong dieu ki~n khong xUC lac nay. nfmg
IU'Q'Dgho~t bOa eiia phlin (mg trime bOa vang eua 2.4-TDI dA eong hi> 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 va eang cMm ubi v6'i hgp ch5.t
poliizoxianat. LU'Q'ng xUc lac sir dl,lllg ciing kha l&n so v6'i lU'Q'ng
izoxianat ban dAu.
- 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
-~

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-pv6i 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 1iimu6i 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<!c xUc taco DQ chgn 19c cua phan irng trime bOa giam
theo thir t'! cua nhom th~ R cua RNCO nhu sau [12J
aryl> 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+ 0- 0
I II
-N = C = 0 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 irng tang [21J.
e - Xuc tac 1ii muM amoni ho!)c pholphoni l(r cJ.p CUB
hidraxil vo cO' va cua axil cacboxylic
Ho<;lt tinh cua xuc lac tuy thuQC vao tinh than h'.lch cua anion
trung tam ho<;lttinh
cua xuc taco

- Rbi xUC tac khOng co d~ng ion, o{lng hQc phan irng thu{lc lo~i
phU'O'ngtrinh b~c 1 tileD n6ng o{l cua maDame izoxianat 'va b~c 1 theo
nbng o{l cua xUC lac.
- Rbi xuc lac co d/!-Dgion. o{lng hQc phan
trinh b~c 2 tileD n6ng 09 cua maDame va b~c 1
lac.
irng thu{lc lo~ phU'O'ng
tileD nbng 09 cua xuc
- 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<lngkhong dung moi er nhi~t d() phOng.
. Tuy nhien. pbin 1mg trime h6a vc}ng Dh1mg chAt poliizoxianat
nhU' 2.4-TDI du6i di6u kiOn XTCP vin clura c6 cOng b6.
. M~t khAc. chling Wi dugc bi~t san phAm trime h6a:ua 2.4-TDI
dii!u ch~ trong moi tl'U'o-ngdtmg ttr6-ng. do Tr<ln Thanh SO'I1cong bb Dam
1985 [8]. khOng duQ'c bi!n. OO6mNCO bi mAt d<ln theo thai gian. do tac
d(}ng cua kill h~u nhi~t deri va co v~t cua xUc lac con sot l~ ma khO
rua s~ch. ChUng Wi hy vgng rfing dtr6-i di~u ki~n XTCP v&i vi~c su d\lI1g
sa luQ'ng bazO' rAt 006 er th~ rAn. trime co th~ dU'Q'crua s~ch va 6n
dtnh hO'n.
2.2 - DOng hQc trong mOi trmhIg ell tuang
Cho db nay. vi~c khao sat dOng hQc cUa phin Ung trime h6a
vc}ng cae chAt izoxianat (mono-vi poli-) du6i di6u ki~n XTCP chua dUQ'c
cOng bOo
- 6 -
II -MlJC TIEU NGHIEN CU-U

l
a -K6t qui : Cac san phAro trime la bt)t trimg mjn. co k~t qua
di~u ch~ vanh~ danh nhu sau :
Ph6 h6ng
.~olli
( )
1710; 1412
vKBr cm-l
'
I
Phan ticl: C21H1503N3 C21H1203N3C13!C21HIZ03N3Q3
1
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
CHN (%) !
1724 ; 1400 1724 ; 1408 1710 ; 1414
BANG1
C6H5NCO
Ip- CIC6H4NCOI m- CIC6H4N1m-CH3C6H4NC1
Therigian I 2
I 2 I 2 Iz
(phut)
Hieu suAt
I 97
I 97 I 97
I
97
(%)

a - Ki!t qua:
Di~u chi? :
- 9 -
BANG 2
. 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) :
2926 (\) CH~. 2278 (\) Ncd' 1716 (\) c =0 cua vong trime)
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
2.4- TDI
MuM
XTCP
I roo'
to(OC)
TMi gian
HSI
(gia)
(I.)!
0.05mol

20ml 5 1 46
.
KCN8% Dibenzo
Toluen 2Oml
pbOng(30)
26 41
18-crown
-6
3%.
I
- 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 CURnhorn 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

i"" c-;-~;' ,.,
;
-~-
I'i/:., ,';,:;<'t.,-,i.:.J
!
Tlljf1iF 'P-' :}(;j-'-
_~~:_i_~5-i \~ ~~: ~_.:
I j
L
I
~~-
:
,
H2SO4 dd + 2NaCl HCl dd) 2HClt + NazS°4
90 - 1200C
CH20H-CHOH-CHZOH + HClt ~ ClCHZ-CHOH-CHZOH
10 gi& 3- cloro-1.2- dihidroxipropan
+ 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.
!IfPhan (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
' /

TI18.n- (mg xay ra d~dang va cl1ngkhong 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: .
SilOphAro 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
17!0 (\) C=O cua yang trime), 1422 (\) cua
(\) C- c)
\ I
0
- Phiin lIch nguycn t6 : C36H36012NG
(\) NIl). 2928 (\) ~tJ ),
soon izoxianllrat). 1228
C% = 57.90. 11%= 5.25. N% = 11.60
- 13 -
3 - DONG HQC CUA PHAN
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°Cdim 430C [2].
LING TRIME HOA yaNG
)(
, ~ NCOIOXNaCN.5X . ~ ~
J8J
, y.
,~ CH CN . Allq !336 N/ 'N

+
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
tin c~y KTC(Lili-) va KTC(/;;,S-) v&iP = 0.95 cua pMn \rng trime boa
vong C6H5NCO thee nhi~t QQ. .
I
i T( oK)
I
I k.lO+ 3mo}-l.s-l
i
290
306.5
311
316
0.64 1.53 1.77
2.39
iKTC(k).1~3moH.s-l
I
0.13 0.37 0.49
r
0.998
0.998 0.995 0.997
i
f
I 6H~ :t KTC(LJt- )
I kcal .mol-l
i

I I
I Lili~! KTC(L6H~) !
kca1.mo1-l i
j
I
I
I
!
293 307 I 311 I 316
1.17' 1.~
I :
0.26 I
I
0.40 I 0.89 I 1.48
, I
0.996 I 0.994 I 0.995 I 0.997
I I
5.5.! 1.0
-53.20::' 3.20
0.998
+
6s -:t KTC(/;;,S '"')
cal.Wl .mol-l
r
- 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'llgquan 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

kcal.moH
4,5.! 1.0
L,s !:t KTC(Lili1: )
ea1.K-l.mol-l
-56.rn : 3,20
r
0.997
- 16 -
BANG 6
I ~ ~y~ono- i
i
'
I , - ~Q}aanat
IThOngs6 ~I
I boat bOa I
I . . t
,+ +
I
I DB- + KTC(DB-)
I
'
I kcaLmol-1 I
I I
! + ,+ I
I6s - + KTC(6S -) I
I caLK-I.mol-l I
I I
I r [
i I
i I

X 0 Hammett I k.IO+ 3mol-l.s-1 I log k
I I
m- Cl 0.373 I 2.45 I -2.6108
p-Cl 0.227
I 2.12 I -2.6737
H 0 i 1.77 i -2.7520
m- CH3 -0.069 : 1.62 I -2.7905
I
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 KTC(p) : 0.08 vo-i P = 0.95 r : 0,998
3.3 - BiOn~ :
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 <li~n
- 17 -
log kdolT theo lIT hi mQt threrng thlmg ch(mg to r~g v&i
kdo = ko[Q+. CN- (dung <f!ch)J c6 nbng d<) [Q+, CW] c6 dj.nh trong
dung <f!ch. c6 nghia la S,! ly trieh ion CN- ta muM NaCN leD Fha hihl cO'
dil d<;itmuc can bflng v~ nbng de? va muc can b~g nay kh6ng thay dbi
dang k~ trong khoang nhi~t de?khao sat, ta tr& 11}.itnrerng hr;rp nhu xUC
Hic dbng tU'&ngv&i hrQ'ng xuc lac cho VaGban diu dU'Q'cxac dj.nh,
- d[arylmonoiz.] =ko[Q + ,CN-(dd)] [arylmonoiz. J2 = kdo[arylmonoiz.] 2
c - amQt nhi~t dQ xac c1jnh, hflng s6 v~n tbc k giam theo
thu tl! cac monoizoxianat sau day

I:
I
! C
I [-"-
I
! O""N I
! I I
l Ar J
dt
0
Ii
Ar C
"N/ 'CN
I
i
t:
o( ~ N
I
PI.
+
.Q
- 18 -
- ~'.(~
Nh6m the cling rut di~n tu \(\,[., t~on6i 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 PHANlING TRIMEH6A VONGCUA
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

= 0.95. h~ s6 tU'O'ngquan r. cac thOng s6 hol,\t bOa lili.t va
= kdo.t + I
3a
- 19 -
6s:t. khoang tin c~y KTC (Llli:t) va KTC (6s::) v{rj P = 0.95 eua
phim Ung trime bOa v6ng 2.4-TDI theo nhi~t 119.
BANG8
T(K)
i
ik.1O+4mol-I.s-I
I
KTC(k) .1O+Ltmol-I.s-I
f
I
l
6H:rz KTC(Llli:t)
keal.mol-I
r
t +
1
6S.:tKTC (6S-)
cal. K -I.mol-l
I
I
r
1.12
T
I 0.11
i
r

284
I
289
'
293.8
i
-
1.73
'
2.32
I
3.05
I
i
0.37
i
0.51
!
1.33
;
!
;
i
I
0.997
I
0.996
I
0.995
I

Trj s8 6S:!: kha am cUng pM hQ'P v6'i tr~ng thai chuy~n ti~p kem
t\l do h<YIlso v6'i tr~ng thai ban dAu.
- 21 -
5 - CO CHE CHUNG DE NGH!
TrEm ca sa cae k6t qua khao sat G{>ngh9C va ca ch6 pMn (mg
trime hoa vang monoizoxianat trong di~u ki('!nd6ng tu&ng do KRESTA va
dimg nghi~p d<i cong b5 [21. 23. 24J. chUng t6i d~ ngb! ca ch6 chung
du&i day cho phci.n irng trime bOa vang arylizoxianat v6'i muM NaCN
trong di~u ki~n XTCP.
!If Mu6i amoni tir cAp Q+a- (Aliquat 336) dua CN- VaG pha h\h1
ca (dung d!ch izoxianat)
Fha vo ca Q+CI- + NaCN (rim).;=-Q+CN- + NaCI
(r~n)
~
Q+CI-
11
+t
Q+CN- (dd
)
Izoxianat
)
Fha hii'u ca
(dung d!ch)
Trime
(M6i trmhlg izoxianat) NCO
Va' -AI : @ h", -@ CH,
Ca ch~ chung cho pnan irng trirne bOa vang arylizoxianat duQ'c d~
nghj xay ra nhu sau :
KHal MA~ k
Ar- N=C=O + Q+. CN:)(dung dicb) I ,

C G. .
O~ "11./ ""0
.
Ar
4
- 22 -
QIUYEN pHAN UNG
k"
4 + Ar-N=C=O
- 2
~
0
II
Ar C Ar
'N'" "N/
d b
01' 'N/ ~ + 2
I 0
Ar
5
NGUNG pHAN lrNG
0
I}
Ar C
'N'" ""-CN AI
d
'-=eW'"
;: +
" C~ . Q
0" 'N/ "b

2.4-TDI
Toluen
NaCN
Aliquat 336
to phOng
1
I
(thclnh phAn poliizoxianat)
CHCl3 (dung moO
DAu l<}.~ + Glixerin
Bu2SnD (:ruc tac)
21OoC
I
Monoglixerit (thanh phAn polio!)
I
. Xilen (chilt pha loang)
I Co-Ph (chilt lam kho)
fto phOng
vecni uretan 2 thinh pbAn
Tinh chAt cua vecni thu dUQ'c ph\}. thuQc chu y~u vao ty l~
NCD: DH va IUQ'ng%.Co
- %.Pb sir d\ffig [7. 16.27J.
b - Ki1t qua:
BANG 9 : co d!nh hl'Q'Ilgchill lam kh6 2%(;0 - 67 Pb va thay d(,i
ty l~ NCD : DH
I
I
TVIe NCD : DH r
. . I
I 1 : 1 i

Ifiu kh6
tOt
t6t

Trích đoạn izoxianurat cua m clorophenylizoxianat izoxianurat cua m tolylizoxianat

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