Luận án phó tiến sỹ Phản ứng trime hóa vòng arylizoxianat bằng phương pháp xúc tác chyển pha & thăm dò và ứng dụng izoxianurat của 2,4 - TDI

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
,

.

.--

,~..,..._.

!,:
1. MOl TRUONG DONG TU'ONG :

!

~~

~

~~-~,'~-_.-

1.1 - aI6u chlt :
a

- Khong xUCtac - Tac dllDKcua nhi~t :

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

a

700c trong vong 600 gia. san phAro trime thu
khOng chl)n Il)c [17J.
dU'Q'c Ia 27. va dime 4.27.. Trong dieu ki~n khong xUC lac nay. nfmg
IU'Q'Dg
ho~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

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.

cacbamat

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

~

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<1 X (M
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\rtheo 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+
N

=

C

0-

=0

I 0
II

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.

Lo~i xUc Lac nay co th~ tang ho~t bAng sir d\lIlg k~t hQ'P vo-i
h9'P chAt halogenua axit ho*c anbidrit axit cua axil cacboxylic. tuy nhien
o{l chQn lQc phan Ung co th~ kem hD'll do co s\l' c~
tranh sg t~{) thanh
chAt trime va polime caD hO'n [29J.
[- Xue tae 111 1wng tinh eua sunfoni Yang:
ion
nhu phenolat 2-metyl-4-( I-thiolanyli) dihidrat
Xuc lac nay co ho~t tinh caD hD'll lo~ xuc Lac (b) va (d). No co
th~ clio phan irng xAy ra a nhi~t o{l thAp. nhung o{l chQn lQc tra thanh
kern a dwi cfc. do co s\l' c~nh tranh v&i polime day thAng t/!-othanh [23J.
Nhin chung. m{lt s6 xUc lac trim it co Lac dl,lng a nhi~t o{l phOng,
va s6 lU'9'Dgthuhi~n di~n cua dung moi lwng C\l'C phi proton m~nh va m{lt 86 it co thl?
thgc hi~n kh6ng cAn dung mol.
Dg chQn lQc cua phan Ung tuy theo vi~c chQn tUng xUC tac clio
phu h9'P vo-i nhom Ar cua ArNCO maDame.
1.2 - D(lng hQc trong c1i6uki~n 46ng tu6'ng :
Co nhi~u cong b6 v~ cO' ch~ o~ ngh! tily tileD tirng lo~ xuc lac
mg!. nhung v~ cO' ban. co hai cO'.ch~ c{lng than h~ch [23J :

- 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 irng thu{lc lo~ phU'O'ng
trinh b~c 2 tileD n6ng 09 cua maDame va b~c 1 tileD nbng 09 cua xuc
lac.


-

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. 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-ng dtmg ttr6-ng. do Tr1985 [8]. khOng duQ'c bi!n. OO6m NCO bi mAt dd(}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

.. 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
2.4- TDI.

d\illg phtrong

phiip XTCP d~ di~u ch~ chili trime

cua

.. 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<.J.nh khao
do
sat hi~u lmg di~n tu cua dic nhom th~ tren nhan thO-ill cua
arylmonoizoxianat. Tren cO"sO- nay. tim hi~u cO"ch~ phan lmg trime hoa
yang chill arylizoxianat du6'i di~u ki~n XTCP va so sanh v6'i cO" ch~ dii
sir d\illg xuc lac trong m6i truang dtmg tu6'ng.~
.. N~u difJu clill duQ'c trime cua 2.4-TDI bAng phtro"ng phiip XTCP.
till chUng t6i tim hi&u ui) bfJn cua no va xem kha nang u-ng d\illg trong
m(Jt s6linh ""c.


- 7 -

III- KETQUA THl[C NGHI~M VA BI~N LU~N
1. TONG HQP IZOXIANURAT CUA ARYLMONOIZOXIANAT
ch~

ChUng toi sir d\ffig phmmg philp XTCP khOng dung moi d~ di~u
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
Therigian
(phut)

I2

Hieu suAt I
(%)

97

Dim nong I 280
ch3.y (0Q

Ph6 h6ng
.~olli
vKBr ( cm-l )

1710; 1412

Ip-

CIC6H4NCO CIC6H4N1m-CH3C6H4NC
mI

I 2
I

Iz

I 97

I 318

;

I 97

I 214

97

1724

2

I

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(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.)!

.
.
.

.

.

10

Toluen

51!
55

36

5

70

48

20
24
30

.

20ml
CH3CN

57

18

.
.
.

.

KCN8% Dibenzo

24

62

59

1

46

26

2Oml pbOng(30)

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
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 mol2 gio-d d 'hoan hru cua I,

~ ::'

./ 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

I
C

1+

0~

N

./

30-1
C" 2 -O-I-n-IOB
/
_°"2
~ 0

0

~

dung moi cua J
..

0
~

holm 3 gi&
hru

!'.'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<1o1
tile 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~n
danh:

.

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
(\) C- I
c)

\
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 5X .
NaCN.

,~

CN

07
'. Allq..! 336 N/

~m~

~

./
'N

~
l8J

t

= O. [aryimonoizoxianat] =
°

t

Cr th&i di&m

,

y.

~

twa du 50m1l d

"3
CH

~

J8J
b

~o
0
X

= t. [arylmonoizoxianath a - 3x
=

a

)<

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
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

vong C6H5NCO thee nhi~t QQ.
I

i
I

i

290

311

1.53

1.77
0.37

0.49

0.998

0.995

0.997

0.64

k.lO+ 3mo}-l.s-l

iKTC(k).1~3moH.s-l
I
r

i

316

306.5

0.13

T( oK)

I

pMn \rng trime boa

.

0.998

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

I
I

-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)
ik.1O+3mo1-l.s-1
I
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

I
I
!

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

I
I
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.- lC6H4NCO thee nhi~t at)
C
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

0.65

0,998

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

-

boat bOa
IThOng
s6
I .
I

,+

I
I DB-

.

+ KTC(DB-)

I
+

I6s - +
I

I
t
I
'

+
-

I
I

1.6

I

I

;
I
I
I

+
5.5 - 1.0

!

I
I

I

+
-

1.0

I

:

i
I

4.5

i

I

I

m-ClC6H4NCO

,

I

I

KTC( 6S -)
caLK-I.mol-l

I

i
I
I

I

,+

I

,
I

8.5

kcaLmol-1

I

!

+

I

! p-ClC6H,j'lCO

C6H5NCO

i

~I

I

i

i

I

-43.86 !. 5.10 '

-53.20!.

3.20

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 1.1'1b p va h~ s6 tlrO'ngquail r i:r 38°C nhu san:
s

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'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

log

-

kdolT

kdo

17

= ko[Q+.

theo lIT hi mQt threrng thlmg ch(mg to r~g
v&i
CN- (dung dung 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}.inrerng hr;rp nhu xUC
t
Hic dbng tU'&ng v&i hrQ'ng xuc lac cho VaG ban diu dU'Q'cxac dj.nh,

= ko[Q

- d[arylmonoiz.]
dt

+ ,CN-(dd)] [arylmonoiz.

=

J2

kdo[arylmonoiz.]

2

a

c - mQt nhi~t dQ xac c1jnh, hflng s6 v~n tbc k giam theo
thu tl! cac monoizoxianat sau day
m-ClC#l4NCO
> 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 hkich cua hgp chAt phuc t~p t<;iothanh wi s,! lac dQng cua CN- vao phiin
ta izoxianat dati lien v6'i IDe?tph,in l& arylizoxianat

Ar-N~

C~~Q+

~

Ar

-

,

,-'no
-

0

Ii
C

Ar
"N/
I
i

t:

o(--.~ N
.Q
I
PI.

+

lAr-N";'C=O

C

jAr,

j
I:

'N~'

I
!

[-"-

!

!

l

Q+

CN

~.

1

0
!I

r
'CN

N=:~~

'CN

C

' 8
1

I

I

O""N

I

I

Ar

I

J

\ r

. Q+

.


-

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 TRIME
H6A 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

~

.

0

@x

~
/C.........

47. NaCN. 27. Aliquat 336

N

N/

Cl\CN (vfta diI 50mlT

3

/Q{3

d

NCD

b

~NCO
NCD

O.OSmol

O~C$i:o
CH3

a thai
a
tl,\O thanh.

;

di~m : t
t

= O.
= t.

[TDI] 0

[TDIh

=a

= a - 3x

D
x

nOng dQ ban dAu cua 2.4-TDI : x ; nOng di) cua izoxianurat
PhU'O'ng trinh

I
3(a

- 3x)

dQng hQc b~c 2 :

= kdo.t + I
3a

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<;1i htrO'Dg trinh b~c 2 theo n6ng dQ cua maDame 2.4-TDI.
p
BANG 8 : Hfmg s6 v~ tOc k. khoang tin c~y KTC(k) dOi v&i xac
suAt P = 0.95. h~ s6 tU'O'ngquan r. cac thOng s6 hol,\t bOa lili.t va


-

19

-

6s:t.
khoang tin c~y KTC (Llli:t) va KTC (6s::)
phim Ung trime bOa v6ng 2.4-TDI theo nhi~t 119.
BANG 8

284

T(K)
i

i k.1O+4mol-I.s-I

1.12

I

I
'

1.73

=

v{rj P

289

'

i

2.32

0.95

eua

293.8
3.05

I

T

I
i

KTC(k) .1O+Ltmol-I.s-I
f
I

0.11

0.37

i

!

r----

r

I

l

!
i

6H:rz KTC (Llli:t)
keal.mol-I

I

!

1.33

;
;
i

I

I

0.997
I

i

I

0.51

!

0.996

I

0.995

0.999

I
I
I
I

i
;
!

9.7 .:! 1.5

I
I

t...
+
6S.:tKTC (6S-)
cal. K -I.mol-l

i

I

1

.
I

-41.59 :t 5.40

I

I

I

r

4.2 - Bi~n~
a - Cae

!

0.999

:
ki!t qua trim chi rAng phuO"ng trL'lh dgng

119C phim

img trime h6a v6ng 2.4-TDI trong di~u ki~n XTCP cUng tucmg qr nhu
trong di~u ki~n dlmg tU'6'ng ita d1I!!e e6~g bb tru&e day [21. 23. 24J va
phim img trime bOa vang cae chAt arylmonoizoxianat d1.1'&idi~u ki~n
XTCP all khao sat tren. Himg s6 v~ tbe k b0~C kd~ tinh thee phan t.."Ilg
b{tc 2 co tri sO kha c6 di.nh cho m6i nhi~t 119. Dil!u mly rAt ly thu. va
dU'6'ng bi6u di{;n log keo:'T theo l/T hi IDgt dU't'yngthAng. chimg to rAng
v{ri kdo = ko[ Q+. CN-(dung d~ch)] e6 nong 09 [Q+. CN-] c6 d!nh trong
dung ~eh. co ngrua lei s1! ly trich ion CN- tir mu6i NaCt,j len pha hu-u cO"
da d{lt mire can blmg v~ nong C9 va mfre can b:mg mly kh6ng thay d6i
dimg k~ trong khoang nr.i(!t <19kbao sat, ta tro' 11].i ru-o-ng h9"P Th'1uxuc
t
lac dbng tU'6-ngwi hrq-ng xuc tac cho VaG ban cIau dU'Q'cxac dtIili.
- d[2.4-TDI]
dt

= kc[Q-i-. CN- (dd)][2.4-TDjJ2

= kdo[Z.4-TDI]2


-

20

-

b - Trong c'iing di~u ki~n thi nghi~m. phan Ung xay ra
nhanh hth~ giii thich la do CH3CN (f70= 37.5) phan C\lC h

C
Dung mOl cang phan C\lC. ci;ip ion Q+. CN- cang b~ phan ly d~ dang.
CN- cang dugc tang ho~t. cang co kha Dang khO'i mao phan ii'ng trime
bOa 2.4-TDI. Dung mOl pnAn c\lc mtr~ng thai chuy~n ti~p co nhi~u di~n tich hs
Th\lC chxay ra qua nhanh Den khOng do dugc hAng sO v~ tOc k trong di~u ki~n
hi~n tc - Trj sO 6H1: tUO'ng dUO'Dg v6'i cac trj s6 cua m(it sO
lac gia ail cong b6 tr€m phan (mg trime hoa vang cua 2.4-TDI trong
di~u ki~n mOl tru'tYng d6ng tu6'ng :
. H~ xUc lac Et3N- trimetylolmelamin v6'i dung mOl AcOBu. khao
sat trong vUng 2<1>C. 6H:!: = 9 kcal.mol-l [19] .
. Xuc tac lel feAA. khao sat trong khocing 25-78°C.
kcal.moI-l

6H1:= 10.5

[18] .

Di~u miy chUng to m(it IAn nua co th~ xem phan (mg crime hoa
yang izoxianat v6'i mu6i NaCN trong dii!u ki~n XTCP tUO'ng t\l nhu trong
di~u ki~n a6ng twng v6'i xUc tac du&i d~
ion.
Trj s8 6S:!: kha am cUng pM hQ'P v6'i tr~ng thai chuy~n ti~p kem
t\l do hs

5

21

-

- CO

CHE CHUNG DE NGH!
TrEm ca sa cae k6t qua khao sat G{>ng
h9C va ca ch6 pMn (mg
trime hoa vang monoizoxianat trong di~u ki('!n d6ng tu&ng do KRESTA va
dimg nghi~p ddu&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)
Fha hii'u ca
(dung

11

~

+t
Q+CN- (dd) Izoxianat )

Q+CI-

Trime

d!ch)

(M6i trmhlg izoxianat)

Va' -AI :

NCO

@

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

-' ,.

PRAT TRIEN

.

k-l

Ar- N",.C- CN. Q+
:1
0
2

,

:

0

II

C
Ar-N~~=O
;1
0

~

'->

k2

Ar'N/

I

,.
0'

~.
,,:.'el

0
It
:I + Ar-N=C=O

kz

Ar'N" C "CN
Ar
eN'" +
I
If'
C
G. .
Q

O~ "11./
.
Ar
4

""0

'CN

N
Ar
S

+

.Q


-

-

22

QIUYEN pHAN UNG

k"

4 + Ar-N=C=O

-

2

Ar
'N'"

0
II
C

Ar
"N/

~

d
01' 'N/

b
~ +
0

I
Ar

2

5
NGUNG pHAN lrNG
0
I}

Ar
C----'N'" ""-CN

'-=eW'"

AI

;:..

"d

0"

'N/
I
AI

...C~..
"b

.

Q

+

k3

~

5 +

Q+.

CN- (dung djch)

TU'O"ng v6i cO' ch~ trong h~ dOng tuUng. gill sir giro do~ dong
t\l
yang bAng giro do~ chuy~n philn \mg dU'Q'c\lU dai hO'Dgiro do1,\nngung
philn \mg. ta co k2 > k3. Cac maDame arylizoxianat dU'Q'csir d\IDg nhi~u
a giro do~ phat tri~n va chuyim philn \mg. ta cO kl > k-l. k2 = k'2 =
k~2. k2> > kl.
a tr1,\Dgthai lID djnh:
[2] = [3] = [4] = [X]
[X] = kl[Q+. CN-][AINCO]
k-l + k3
PhU'O"ng
trinh d{>nghQc co th~ dU'Q'cvi~t dwi d~g

-

d[ArNCO]
dt

= k2[X][AINCO] =
= ko[Q+.

v6"i

ko

=

k2k 1

[Q+.

CN-] [AINCO]2

k-l + k3

k2kl
k-l + k3

CN-][AINCO]

va.

kdo

2

= kdo[AINCO]2

= ko.

[Q+. CN-]


6

- THAM DO liNG

23

-

Dl,ING IZOXIANURAT CUA 2,4-TDI

6.1 - ChI: q.o vccni uretan 2 thinh ph!n
a - Qw trinh

:

:

2.4-TDI
Toluen

DAu l<}.~ + Glixerin

NaCN

Bu2SnD (:ruc tac)
21OoC

Aliquat 336
to phOng
I

1

(thclnh phAn poliizoxianat)

I

Monoglixerit (thanh phAn polio!)
I

CHCl3 (dung moO

.

Xilen (chilt pha loang)

Co-Ph (chilt lam kho)
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'Ilg chill lam kh6 2%(;0 - 67..Pb va thay d(,i
ty l~ NCD : DH
I

f to

ITV Ie NCD : DH
I

I

I
I

I

.

.
1 : 1
1 : 2

1 : 3

1 : 3.5

I

1 : 4

I

1 :. 4.5
1 5

I

I

.

r

I

i

I

I

Thai gian kh6
khO nhanh
khOnhanh
kh6nhanh
kh6 nha.'lh
10 - 15 phUt

I

50
!

i

!

- 60

Ifiu kh6

phut

I

;

i

I
I

I

i

l
I

I
I
I

I

D(j bOng cua mimg vecni
kh6ng t6t
,
khong t~t
khOng tot

- bi nirt

b~ m~t
.

- bi nirt b: m~t
- bi nirt,be m~t
khOng tot
t6t
tOt
t6t