Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – From silicon reactant having at least one...
Reexamination Certificate
1999-06-08
2001-06-12
Dawson, Robert (Department: 1712)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
From silicon reactant having at least one...
C524S588000, C525S466000, C525S477000, C528S024000
Reexamination Certificate
active
06245875
ABSTRACT:
CROSS-REFERENCE TO RELATED APPLICATIONS
Not applicable
FEDERALLY SPONSORED RESEARCH
Not applicable
1. Field of the Invention
The invention relates to high durometer, low structuring, low specific gravity heat curable silicone elastomers.
2. Brief Description of the Related Art
Silicone heat curable elastomers (HCE) generally consist of diorganopolylsiloxane gum, fluid and silica filler. Silica filler acts as reinforcing component to provide mechanical strength. Current fumed silica filler reinforced high durometer HCE compounds have a structuring problem which is characterized by a significant rise in plasticity over time. The severe structuring problem causes processing difficulties such as feeding these compounds into extruders and injection molding machines, and difficulties in mixing catalysts, pigments and blending with lower durometer compounds because the material will not soften readily on the mill.
SUMMARY OF THE INVENTION
The present invention is directed to a curable composition comprising: (a) 50 to 90 parts by weight of an alkenyl terminated linear diorganopolysiloxane gum having a viscosity in the range of 1,000,000 to 200,000,000 centipoise at 25° C. and having an alkenyl concentration of about 0.01 to 0.05 mole percent of siloxy units; (b) 10 to 30 parts by weight of an alkyl terminated diorganopolysiloxane gum having a viscosity in the range of 1,000,000 to 200,000,000 centipoise at 25° C.; (c) 3 to 20 parts by weight of an alkenyl containing diorganopolysiloxane gum having a viscosity varying from 100,000 to 200,000,000 centipoise at 25° C. and having an alkenyl concentration of about 0.5 to 15 mole percent of siloxy units; (d) 40 to 60 parts by weight of treated fumed silica with surface area varying from about 130 to 350 m
2
/g; and (e) 0.5 to 3.0 parts by weight of a hydroxy terminated polysiloxane fluid having about 0.5 mole percent alkenyl, and to a silicone elastomer formed by curing the composition. The silicone elastomer composition has a high durometer with low specific gravity. The silicone elastomer composition of the present invention exhibits “low structuring”, i.e., it has improved stability with respect to plasticity.
DETAILED DESCRIPTION OF THE INVENTION
In a preferred embodiment, the composition of the present invention comprises, from 50 to 90 parts by weight (“pbw”), even more preferably from 60 to 80 pbw, of the alkenyl terminated diorganopolysiloxane gum; from 10 to 30 pbw, even more preferably from 20 to 30 pbw, of the alkyl terminated diorganopolysiloxane gum; from 3 to 20 pbw, even more preferably from 3 to 10 pbw, of the alkenyl-containing diorganopolysiloxane gum; from 40 to 60 pbw, even more preferably from 50 to 60 pbw, of the treated fumed silica; and
from 0.5 to 3.0 pbw, even more preferably from 1.3 to 2.2 pbw of the hydroxy terminated polysiloxane.
Compounds suitable as the alkenyl terminated gum component of the composition of the present invention include, for example, vinyl, propenyl, and butenyl terminated gums. In a preferred embodiment, the alkenyl terminated diorganopolysiloxane gum is vinyl terminated dialkylpolysiloxane gum, more preferably vinyl terminated dimethylpolysiloxane gum, even more preferably vinyl terminated poly(dimethylsiloxane-co-methylvinylsiloxane) gum.
In a preferred embodiment, the alkenyl terminated diorganopolysiloxane is one according to the formula:
M
vi
D
x
D
vi
v
M
vi
where M
vi
is R
1
R
2
2
SiO1
/2
D is R
3
2
SiO
2/2;
D
vi
is R
4
R
5
SiO
2/2
where R
1
and R
4
are C
2
-C
6
alkenyl, preferably vinyl, R
2
, R
3
and R
5
are C
1
-C
6
alkyl or C
2
-C
6
alkenyl, preferably methyl, and x and v are chosen so that the viscosity of the gum is in the range of 1,000,000 to 200,000,000 centipoise at 25° C., and having an alkenyl concentration of about 0.01 to 0.05 mole percent of siloxy units.
As used herein, “C
1
-C
6
alkyl” means a straight or branched chain alkyl group containing from 1 to 6 carbon atoms per group, such as, for example, methyl, ethyl, propyl, and butyl.
As used herein, “C
2
-C
6
alkenyl” means a straight or branched chain alkenyl group containing from 2 to 6 carbon atoms per group and at least one double bond between two carbon atoms per group, such as, for example, vinyl, propenyl and butenyl.
Compounds suitable as the alkyl terminated diorganopolysiloxane gum component of the present composition include, for example, methyl, ethyl, propyl, and butyl terminated gums. In a preferred embodiment, the alkyl terminated diorganopolysiloxane gum is a methyl terminated gum, even more preferably trimethyl-terminated polydimethylsiloxane.
In a preferred embodiment, the alkyl terminated diorganopolysiloxane gum is one according to the formula:
MD
w
M
where M and D are R
6
SiO
3/2
and R
3
SiO
2/2
, respectively, where w is chosen so that the viscosity is in the range of 1,000,000 to 200,000,000 centipoise at 25° C.
Compounds suitable as the alkenyl-containing diorganopolysiloxane gum component of the present composition include, for example, vinyl-, propenyl- and butenyl-containing gums. In a preferred embodiment, the alkenyl units are on-chain. As used herein, “on chain” mean that the alkenyl units are on di-organo-functional siloxane units of the gum. In a preferred embodiment, the alkenyl-containing diorganopolysiloxane gum is a vinyl-containing dialkylpolysiloxane, preferably a vinyl-containing dimethylpolysiloxane, even more preferably trimethyl-terminated poly(dimethylsiloxane-co-methylvinylsiloxane).
In a preferred embodiment, the alkenyl-containing diorganopolysiloxane gum is one according to the formula:
MD
y
D
vi
z
M
where M is R
6
SiO
3/2
,
D
vi
is as previously described, R
6
is C
1
-C
6
alkyl or C
2
-C
6
alkenyl, where y and z are chosen so that viscosity ranges from 100,000 to 200,000,000 centipoise at 25° C. and having an alkenyl concentration of about 0.5 to 15 mole percent of siloxy units.
The composition of the present invention may, optionally, further comprise from 0 to 1.0 parts by weight of tetramethyldivinylsilazane. The composition of the present invention may, optionally, further comprise from about 0.5 to 5 parts by weight of trimethylolpropane trimethacrylate.
Optionally, a curing agent is added to cure the rubber composition of the present invention. Any of the conventional curing agents can be used. The preferred curing agents are organic peroxides conventionally used to cure silicone elastomers. Preferred peroxide curing agents include t-butyl-hydroperoxide, cumene hydroperoxide, decaline hydroperoxide, di-t-butyl-peroxide, dicumyl peroxide, &agr;,&agr;-bis(t-butylperoxy)di-isopropylbenzene, t-butyl-cumylperoxide, 2,5-dimethyl-2,5-di-(t-butylperoxyhexyne-3 and 2,5-dimethyl-di (tert-butylperoxy)-hexane. The most preferred of these peroxide curing catalysts is 2,5-dimethyl-di(tert-butylperoxy)-hexane which is available commercially under the trade name VAROX®, available from R. T. Vanderbilt Co, Inc.
Other optional additives used in the compositions of the present invention are coloring agents and pigments.
A highly preferred embodiment of the present invention further comprises: 0 to 1.0 parts by weight of tetramethyldivinylsilazane; and 0.5 to 5 parts by weight of trimethylolpropane trimethacrylate.
The process for forming this composition can be either cold mix or hot mix at temperature above 100° C. The cold mix can be achieved using Banbury or Doughmixer equipment. The hot mix can be achieved using either a Doughmixer batch process or an extruder-type continuous process.
The composition of the present invention is used alone or by first applying it to a substrate, and then curing it to form a cured silicone elastomer. Curing is generally high temperature curing, i.e., at a temperature of about 100° C. or higher.
The silicone elastomer composition of the present invention may be used in a variety of applications, including, for example, forming gaskets, keypads, electronic parts, O-rings and wire and cable coatings.
All United States patents referenced herein are herewith and hereby specifically incorporated by reference.
The examples given belo
Dawson Robert
General Electric Company
Zimmer Marc S.
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