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&
W. W. Y. Lau , S. H. Goh ~
aDepartment of Chemical Engineering, bDepartment of Chemistry, National University of Singapore, Republic of Singapore
(Received 2 May 1992; revised version received 6 October 1992; accepted 20 October 1992)
New polymerizable urethane-functional monomers containing hindered-amine
structures have been synthesized by reaction of m-isopropenyl-t~,otdimethylbenzyl isocyanate with hindered piperidines and their copolymers
with styrene and methyl methacrylate have been prepared by free-radical
initiation. The structures, thermal stabilities, solubility parameters and stabilizing effect of these new HALS have been assessed. The results show that the
monomers have good photoprotecting effect. The effect of the copolymers is
less good because of the lower content of the piperidine nitrogen. The
extraction resistance to water at 90C is good for the copolymers but poor for
the monomers. UV and ESR experiments confirm that the photoprotecting
mechanism is still due to the scavenging action of nitroxyl radicals.
I + II(II')
INTRODUCTION
dibutyltin dil . . . . te
80C
III(III') + M
, III(III')
-(--II I-)w-(LM-)-.
80C
-(--III'~4~--M-)~-..
CH3
I
H2C-=C
HO
H3C ~ x . . ~ C H 3
H~C ~
CH~
CH3
CH,
H~c/C\N~__.~C=O
(i)
(II)
CH3
I
H2C--C
EXPERIMENTAL
1 Synthesis of urethane functional HALS
H~/C/CH30
~C \ N H
1---~1~0. H
H3C~CH3
H~C
I
CH3
(Ill)
275
CH~
276
HALS
RESULTS A N D D I S C U S S I O N
2 Characterization o f HALLS
1 Determination o f H A L S structures
Ec
6=--.d
Sample
3 Polymer studies
Styrene
MMA
--
--
--
--
Ill-St
1720
3 060,700-800
3 250
1540
1 720
3 060,700-800
3 250
1540
1720
3 060
3 400
3 020
700,760
III'-St
1 720
3 400
3 060
3 020
700,760
1 720
III-MMA 3 400
3 060
1 720
III'-MMA 3 400
3 060
III
Carbamate
IIV
--
1 720-1 735
2 995
--
1 720-1 735
2 995
Sample
C%
H%
N%
III
III'
64-17
8-7
2-68
--2.28
I,,
1II'
2 T h e r m a l stability o f H A L S
jib, a
11I
a'
-st
/
1,
III '-st
~"
3 Solubility p a r a m e t e r s
III ' - M M A
277
1(3
6
4
2
Chemical shift (ppm)
a'
H2C__---C
gCH~
CH~ C H ~
j_~/
3
~ g ~
t II_ e/~
h~ - - N H - - C - - O - - ~ H
b
IN--CH~a
CH3 CH3
a~
a
IIl
CH3 ~
d H2~C
~ g
H3
I
g
a'
CH~ CH3 a
i V
CH~
b
III'
"
--A
CH3 C H 3
a~ a
278
HALS
Structure
Vinyl
III(III')
N%"
T= (C)
3.76
82.3-83.8
cn 3
H2~
III
H3
H2C-----C
III'
3"91
116-118
III-St
19.5:1
0-58
114-116
III'-St
18:1
0"63
120-122
7:1
1-34
147-150
8.75:1
1.14
138-140
CH3
I
III-MMA
C--=O
I
I
O
CH3
CH3
I
4-cH~-~---~IU'~
III'-MMa
C=O
I
O
I
CH3
300nm, so that the urethane-functional molecules are not able to function as UV absorbers.
The ESR signals during photo-oxidation of PP
films containing the urethane functional HALS
are shown in Fig. 4. They are the standard signals
from the nitroxide free radical in the solid
s t a t e . 7,s'12-t4A6-18 Thus the stable NO" free radical
can be formed during photo-oxidation. The g
value of the urethane-functional HALS is 2.0064,
similar to
other
low molecular weight
HALS. 1'3'7"15 Thus the stabilizing action of these
compounds remains the scavenging of alkyl
271
271
214
225
11
1I'
118 120
279
mechanism
III
III'
III-St
III'-St
III-MMA
III'-MMA
770
765
PDS
/~
Cal=/2/cm3/2
9-1
9.3
8-7
8.4
8-9
8.4
9.2
7-8
8.8
1.5~
O~ 6
13
t3
1.0
X
16
0.5
S
100
14
200
300
400
Irradiation time
//----
1400
(h)
1500
1600
1700
Fig. 2. Carbonyl formation in polypropylene film containing H A L S during photo-oxidation, (1-Ill, 2-111, 3-III-St, 6-III-St,
8-III-MMA, 13-III-MMA, 14-Tinuvin-765, 15-Tinuvin-770 and 16-PDS).
Table 6. Induction period of photo-oxidation and embrittlement time of thermo-oxidation for polypropylene containing HALS
Additives
Blank
III
III'
III-St
III'-St
IP (h)"
tem (h) b
N% c
25-5
22"5
/
1 385
85
3-76
1 480
110
3-91
122
62
0-58
44
62
0-63
III-MMA III'-MMA
80
134
1.32
76
156"5
1-14
765
1 412
540
5.5
770
PDS
264
1660
540
5-8
216
465
2-2
/
41
/
"Induction period.
h Embrittlement time.
c Content of nitrogen of piperidine ring in H A L S (effective N%).
The concentration of additive in PP is 0.3%. The structures of 765(Tinuvin-765 or 508), 770(Tinuvin-770) PDS and 264(BHT)
are in the literature. "'9.u
280
F
<
IlL
~qL
8
-" 4
ACKNOWLEDGEMENTS
n
I
20
I
40
I
60
I
80
I
100
I
120
7 9
140
REFERENCES
1. Usitton, J. J. Am. Chem. Soc. Polym. Preprint, 18 (1)
(1977) 393.
2. Klemchuk, P. P., Polymer Stabilization and Degradation. ACS Symposium Series 280, Washington, DC,
1985.
3. Gugumus, F., Develop. in Polym. Stab., 1 (1979) 261.
4. Murayama, K., J. Synthet. Org. Chem. (Japan), 31
(1973) 198.
5. Pan, J. Q. & Liu, Y. H., Addit. Communic. (1981) (3)
1.
10 G
i
I
rn
rn'
Tr[ - s t
Tn"-st
Trt'-MMA
m'-MMA
Fig. 4. The ESR signal of HALS (in PP film containing HALS at 0.3%, after photo-oxidation for 142.5 h)
281