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I. Polymerization of vinyl monomers in the presence of inorganic substances

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Die Aiagewandte Makromolekulare Chemie 32 (1973) 177-180 ( N r . 450)
From the Department of Applied Chemistry, Faculty of Engineering,
Tohoku University, Sendai, Japan
Short Communication
I. Polymerization of Vinyl Monomers in the Presence
of Inorganic Substances
By TADASHI
YAMAGUCHI,
TAKAYUKI
ONO, and HIROSHIITO
(Received 17 November 1972)
Recently many patents for manufacturing composites which consist of
organic polymers and inorganic substances have been reported. Usually these
composites are molded after mechanical mixing. However, the mixing procedure has had some problems from the industrial aspect.
The purpose of this communication is t o report a novel method for preparation of composites concerning polymerization of methyl methacrylate in the
presence of calcium sulfite with sulfur dioxide in water medium.
Methyl methacrylate, sulfur dioxide and other reagents were purified by usual
methods. Calcium sulfite was prepared from double decomposition of calcium chloride and sodium sulfite at 50°C.
Calcium sulfite, methyl methacrylate and water were charged into a four necked
round bottom flask. At desired reaction temperature sulfur dioxide was introduced
in the reaction system with stirring and polymerization occured immediately. The
reaction products were separated according to Table 1.
Table 1. The treatment of reaction products.
Reaction
Mixture
I + Ether
Residue I
Benzene
+
Ether'Layer
.1
Water Layer
Evaporating up
+ Ethyl Alcohol
I
Residue I1
1 0 % HC1 Soh.
+
I
Unextrectable
Polymer
I
Extracted
Polymer
Water Soluble
Organic Products
CaSO3 . +HzO
(including CaSO4 . 2H20)
177
d
Polymerization time: 20.3 h.
Polymerization temperature : 60 "C.
(YO)
c
Yield
(g)
Po1y mer
content
Residue I
Calculated from the following equation : content =
Atmosphere
b
Run
No.
Water soluble
organic
products
(g)
total amount of the polymer
amount of unextractable polymer
(YO)
Polymer
yield
x 100.
(Yo)
Unextractablea
polymer content
in residue I1
(YO)
Unextractableb
polymer content
in total polymer
a
5
cc
P
a
[rll
0.60
0.32
Extracted
Conventionala
3
1.9
9.4
3.0
23.9
6.2
33.4
n
'
aw
0.32
0.12
2.24 . 105
1.19
1.27
0.74
(from G. P. c.)
En
0.62
6.77 . 105
2.84
7.94
2.49
1.10
aw
28.2
33.3
31.5
4.4
3.5
3.7
Steric triads (yo)
H.
I.
(from N. M. R.)
66.4
63.2
64.8
S.
Conventional polymer was prepared from radical polymerization with AIBN initiator (2% for added monomer) in benzene a t
40°C for 3 h.
2
1.95
0.85
2.33
1.03
at 25OC
in benzene
Extracted
Unextractable
Extracted
Unextractable
Polymer
Characterization of the polymers obtained.
1
No.
Run
Table 3.
k
%
3
0
3
-%
ix
2
3.
3
3
G-
T. YAMACUCHI,
T. ONO,and H. ITO
Although there was no conventional radical initiator in the reaction system,
polymerization carried out easily. Powder-like calcium sulfite capsulated with
polymethyl methacrylate and a small amount of water soluble organic compounds were obtained. There were scarcely polymer particles in residue I. The
results under various polymerization atmospheres are shown in Table 2. It was
obvious that oxygen accelerated polymerization rate and also the formation of
water soluble organic products. The ratio of unextractable polymer is considerably high in each experiment. The examples of characterization of polymer
obtained are shown in Table 3. The values of M,/M, of unextractable polymers
are much higher than that of homopolymers. And as increasing the amount
of oxygen in the reaction system, molecular weight of the polymers became
smaller and the molecular weight distribution became broader.
When calcium sulfite was absent under the same conditions, polymerization
of methyl methacrylate did not take place (Table 4).
Table 4. Reaction of MMA with SO2 in the absence of CaSO3 . & HzO.
Run
No.
6
7
8
Atmosphere
Argon
Air
Oxygen
Polymer Yield
(Yo)
0
0
0
Water soluble organic
products
(g)
0.17
1.36
2.33
Reaction conditions: MMA: 15 g; SOe: 4.7 g; water: 80 ml; 40°C; 5 h.
From above results polymerization mechanism seemed to be very complicated. But it is assumed that polymerization partly carried out by redox mechanism and also the surface of calcium sulfite crystal partly participated.
Residues I with polymer content more than about 10%were moldable directlyA detailed paper will be published in future.
180
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presence, monomerl, inorganic, substances, vinyl, polymerization
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