Organosilicon compounds

Details Organosilicon compounds Organosilicon compounds

2001-10-05

2002-12-31

Shaver, Paul F. (Department: 1621)

Organic compounds -- part of the class 532-570 series

Organic compounds

Silicon containing

C556S434000, C556S435000, C549S214000

Reexamination Certificate

active

06500976

ABSTRACT:

BACKGROUND OF THE INVENTION
1. Technical Field
This invention relates to novel organosilicon compounds which are added to various thermosetting elastomer compositions as adhesive aids.
2. Background Art
Known adhesive aids added to conventional thermosetting elastomer compositions include those having alkoxysilyl groups, acid anhydride groups and SiH groups. Although some adhesive aids achieve good adherence, there is a desire to have compounds more effective as adhesive aids.
SUMMARY OF THE INVENTION
It has been found that organosilicon compounds having in a molecule (A) a perfluoroalkyl group of at least 3 carbon atoms which may be separated by an etheric oxygen atom, (B) a monovalent hydrocarbon group containing a carboxylic acid anhydride structure, and (C) a hydrosilyl group are effective as adhesive aids, especially as adhesive aids in elastomer compositions containing fluorinated compounds for enhancing their adhesion to metals.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The organosilicon compound of the invention has in a molecule (A) a perfluoroalkyl group of at least 3 carbon atoms which may be separated by an etheric oxygen atom, (B) a monovalent hydrocarbon group containing a carboxylic acid anhydride structure, and (C) a hydrosilyl (SiH) group.
Specifically, the organosilicon compound has the average compositional formula (1) and preferably the general formula (2), (3) or (4).
 Rf
a
R
1
b
R
2
c
H
d
SiO
(4−a−b−c−d)/2
  (1)
In formula (1), Rf is a monovalent organic group containing a perfluoroalkyl group of at least 3 carbon atoms which may be separated by an etheric oxygen atom,
R
1
is a substituted or unsubstituted monovalent hydrocarbon group,
R
2
is a monovalent hydrocarbon group containing a carboxylic acid anhydride structure,
a, b, c and d are numbers satisfying:
0.01≦a≦50.5, preferably 0.05≦a≦0.3,
0≦b≦2, preferably 0.5≦b≦1.5,
0.01≦c≦0.5, preferably 0.05≦c≦0.3,
0.01≦d≦0.5, preferably 0.05≦d≦0.3, and
2≦a+b+c+d≦3.
In formula (2), R
3
is a substituted or unsubstituted divalent hydrocarbon group,
R
4
and R
5
each are a substituted or unsubstituted monovalent hydrocarbon group,
R
6
is independently hydrogen, Rf, R
1
or R
2
, wherein Rf, R
1
and R
2
are as defined above, at least one hydrogen, at least one Rf and at least one R
2
are contained in a molecule, and
e is an integer of 0 or 1.
In formula (3), R
4
is a substituted or unsubstituted monovalent hydrocarbon group; R
6
is independently hydrogen, Rf, R
1
or R
2
, wherein Rf, R
1
and R
2
are as defined above; at least one hydrogen, at least one Rf and at least one R
2
are contained in a molecule; and m is a positive integer of at least 3 and preferably 3 to 8.
In formula (4), R
4
is a substituted or unsubstituted monovalent hydrocarbon group; R
6
is independently hydrogen, Rf, R
1
or R
2
, wherein Rf, R
1
and R
2
are as defined above; at least one hydrogen, at least one Rf and at least one R
2
are contained in a molecule; n is a positive integer of at least 1, preferably 1 to 500 and more preferably 5 to 200; and R
7
is R
4
or a group of the following formula (5):
wherein R
4
and R
6
are as defined above.
More illustratively, the substituted or unsubstituted monovalent hydrocarbon groups represented by R
1
, R
4
and R
5
are preferably those of 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, for example, alkyl groups such as methyl, ethyl and propyl, cycloalkyl groups such as cyclohexyl, aryl groups such as phenyl and tolyl, and the foregoing groups in which some hydrogen atoms are substituted with halogen atoms.
The monovalent hydrocarbon group containing a carboxylic acid anhydride structure, represented by R
2
, is not critical as long has it has a carboxylic acid anhydride structure. Groups of the following formula are preferred.
Herein R
7
is a divalent hydrocarbon group having 1 to 15 carbon atoms, and especially 2 to 10 carbon atoms, for example, an alkylene or alkenylene group.
Illustrative examples are given below.
The substituted or unsubstituted divalent hydrocarbon groups represented by R
3
are preferably those of 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, for example, alkylene groups such as methylene, ethylene and propylene, cycloalkylene groups such as cyclohexylene, arylene groups such as phenylene, and the foregoing groups in which some hydrogen atoms are substituted with halogen atoms.
The monovalent organic groups containing a perfluoroalkyl group of at least 3 carbon atoms which may be separated by an etheric oxygen atom, represented by Rf, include
F(C
x
F
2x
)CH
2
CH
2
—,
F(C
x
F
2x
)CH
2
CH
2
CH
2
—, and
F(C
y
F
2y
O)
p
C
z
F
2z
—A—,
wherein x is 3 to 20, y is 1 to 4, z is 1 to 10, p is 1 to 100, y multiplied by p is at least 2, and A is a divalent organic group, for example, an alkylene group such as methylene, ethylene or propylene.
Illustrative, non-limiting examples of the organic groups represented by Rf are given below. Note that Me is methyl.
C
4
F
9
CH
2
CH—
C
8
F
17
CH
2
CH
2
CH
2
—
C
3
F
7
O(CF
2
CF
2
CF
2
O)
h
CF
2
CF
2
CH
2
CH
2
—(e.g., h=1 to 50)
F—(CF
2
O)
h
(CF
2
CF
2
O)
i
CF
2
CH
2
CH
2
—(e.g., h=1 to 50, i=1 to 50)
Illustrative examples of the organosilicon compounds according to the invention are given below. They are typical examples, and the inventive compounds are not limited thereto. Note that Me is methyl.
The organosilicon compounds of the invention can be synthesized, for example, by the following method. The starting compound is an organosilicon compound having fluorine-modified groups, represented by the formula:
Rf
a
R
1
b
H
d
SiO
(4−a−b−d)/2
wherein Rf and R
1
are as defined above, and 0.01≦a≦0.5, 0≦b≦2, 0.01≦d≦0.5, and 2≦a+b+d≦3. By effecting addition or hydrosilylation reaction of an acid anhydride having an ethylenically unsaturated group to the organosilicon compound having fluorine-modified groups in the presence of a hydrosilylation catalyst such as a platinum complex compound, the end compound is obtainable.
The reaction temperature is usually about 50 to 150° C., preferably about 70 to 120° C. If necessary, the reactants are diluted with a solvent such as toluene, xylene or 1,3-bistrifluoromethylbenzene.
Most often, the organosilicon compounds of the invention are added to thermosetting elastomer compositions as adhesion aids whereby the compositions are improved in adhesion to various materials including metals and alloys such as aluminum, iron, stainless steel, nickel alloys, chromium alloys and copper alloys, plastics such as acrylic resins, nylon, PPS, PBT, PET, epoxy resins, polyimides and polyvinyl chloride, and ceramics such as alumina and silicon nitride.


REFERENCES:
patent: 5117001 (1992-05-01), Okinoshima et al.
patent: 5362887 (1994-11-01), Shiobara et al.

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