Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – From silicon reactant having at least one...
Reexamination Certificate
2000-06-14
2003-04-01
Dawson, Robert (Department: 1712)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
From silicon reactant having at least one...
C528S025000, C528S031000, C528S409000, C528S410000, C528S414000, C556S479000
Reexamination Certificate
active
06541593
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to a novel reactive silicon group-containing polyether oligomer for use mainly in a moisture-curable resin and to a process for the production thereof. More particularly, the present invention relates to a reactive silicon group-containing polyether oligomer which is produced by hydrosilylating an unsaturated group-containing polyether oligomer with a reactive silicon group-containing compound and to a process for the production thereof.
BACKGROUND OF THE INVENTION
The technology for producing a reactive silicon group-containing polyether oligomer comprising reacting an unsaturated group-containing polyether oligomer with a reactive silicon group-containing compound in the presence of a Group VIII transition metal catalyst, such as chloroplatinic acid, has been disclosed (Japanese Kokoku Publication Sho-45-36319, Japanese Kokoku Publication Sho-46-12154, Japanese Kokoku Publication Sho-8-36960, Japanese Kokoku Publication Sho-58-41291, Japanese Kokoku Publication Sho-63-37820). However, in the hydrosilylation reaction of the unsaturated group with said reactive silicon group-containing compound, the reaction yield of the reactive silicon group based on the unsaturated group is self-limited when the starting polyether oligomer contains allyl group as said unsaturated group, for the intramolecular rearrangement of allyl group to propenyl group occurs as a side reaction. Therefore, when the reactive silicon group-containing polyether oligomer so produced is used in a curable resin composition which is a principal application thereof, the cured product is deficient in hardness so that its application requiring strength is restricted. The use of a polyether oligomer having an unsaturated group substituted by a monovalent organic group of 1 to 20 carbon atoms has also been disclosed but there is no disclosure about its specific structure, the production process utilizing the particular oligomer or the characteristics of the reactive silicon group-containing polyether oligomer which can be obtained.
The object of the present invention is to inhibit the intramolecular rearrangement of an unsaturated group during hydrosilylation and thereby produce a polyether oligomer with the reactive silicon group introduced at a high rate.
Having explored with diligence for enhancing the reaction yield of a reactive silicon group based on an unsaturated group, the present inventors found surprisingly that when a polyether oligomer having an unsaturated group of a specific structure, which can be easily produced, was used as a starting material, the above-mentioned side reaction of an unsaturated group during hydrosilylation could be inhibited so that the rate of introduction of a reactive silicon group based on the unsaturated group was dramatically increased; thus, a polyether oligomer could be produced with an average reactive silicon group introduction rate of not less than 85%. The present inventors found further that, in the production of said oligomer, a platinum catalyst having a specific ligand is remarkably effective in catalyzing the reaction. It was also discovered that the cured product of a polyether oligomer with a reactive silicon group introduced into the molecular terminus at a rate of not less than 85% on the average, which could be provided for the first time by the process of the present invention, exhibited exceptionally satisfactory physical characteristics as compared with the cured product of the conventional polyether oligomer with a reactive silicon group introduced into the molecular terminus only at a rate of about 80% on the average.
SUMMARY OF THE INVENTION
The present invention, therefore, relates to a process for producing a reactive silicon group-containing polyether oligomer, which comprises reacting (a) a polyether oligomer the backbone chain of which comprises a polyether and which contains in a side chain or at a terminus of its molecule at least one unsaturated group of the following general formula (1):
H
2
C═C(R
1
)—R
2
—O— (1)
(wherein R
1
represents a hydrocarbon group of not more than 10 carbon atoms; R
2
represents a divalent organic group of 1 to 20 carbon atoms which contains in a side chain or at a terminus of its molecule at least one atomic species selected from the group consisting of hydrogen, oxygen and nitrogen as its constituent atom or atoms) or the general formula (2):
HC(R
1
)═CH—R
2
—O— (2)
(wherein R
1
represents a hydrocarbon group of not more than 10 carbon atoms; R
2
represents a divalent organic group of 1 to 20 carbon atoms which contains at least one atomic species selected from the group consisting of hydrogen, oxygen and nitrogen as its constituent atom or atoms). with (b) a reactive silicon group-containing compound, (c) in the presence of a Group VIII transition metal catalyst to thereby introduce the reactive silicon group into said oligomer (a).
The present invention, in a further aspect, relates to a reactive silicon group-containing polyether oligomer characterized in that a reactive silicon group of the following general formula (6):
—OR
2
C(R
1
)HCH
2
(Si(R
3
2−b
)(X
b
)O)
m
Si(R
4
3−a
)X
a
(6)
(wherein R
1
represents a hydrocarbon group of not more than 10 carbon atoms; R
2
represents a divalent organic group of 1 to 20 carbon atoms which contains at least one atomic species selected from the group consisting of hydrogen, oxygen and nitrogen as its constituent atom or atoms; R
3
and R
4
are the same or different and each represents an alkyl group of 1 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, an aralkyl group of 7 to 20 carbon atoms, or a triorganosiloxy group of the formula (R′)
3
SiO—; when two or more R
3
or R
4
groups are present, they are the same or different; R′ represents a monovalent hydrocarbon group of 1 to 20 carbon atoms and the three R′ groups are the same or different; X represents a hydroxyl group or a hydrolyzable group and when two or more X groups are present, they are the same or different; a represents 0, 1, 2 or 3; b represents 0, 1, or 2; and m represents an integer of 0 to 19; b in m repeats of the —Si(R
3
2−b
)(X
b
)—O— group are the same or different over the repeats, provided that the condition of a+&Sgr;b≧1 is satisfied) or general formula (7):
—OR
2
CH
2
CH(R
1
)(Si(R
3
2−b
)(X
b
)O)
m
Si(R
4
3−a
)Xa (7)
(wherein R
1
represents a hydrocarbon group of not more than 10 carbon atoms; R
2
represents a divalent organic group of 1 to 20 carbon atoms which contains at least one atomic species selected from the group consisting of hydrogen, oxygen and nitrogen as its constituent atom or atoms; R
3
and R
4
are the same or different and each represents an alkyl group of 1 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, an aralkyl group of 7 to 20 carbon atoms, or a triorganosiloxy group of the formula (R′)
3
SiO— and when two or more R
3
or R
4
groups are present, they are the same or different; R′ represents a monovalent hydrocarbon group of 1 to 20 carbon atoms and the three R′ groups are the same or different; X represents a hydroxyl group or a hydrolyzable group and when two or more X groups are present, they are the same or different; a represents 0, 1, 2 or 3; b represents 0, 1 or 2; m represents an integer of 0 to 19; b in m repeats of the —Si(R
3
2−b
)(X
b
)—O— group are the same or different over the repeats; provided the condition of a+&Sgr;b≧1 is satisfied) is introduced into the terminus of its molecular chain at a rate of not less than 85% on the average by the above process.
DETAILED DESCRIPTION OF THE INVENTION
The present invention is now described in detail. The polyether oligomer having an unsaturated group for use as the component (a) of the present invention may be any polyether oligomer having a polyether backbone chain and containing in a side chain or at a terminus of the molecule at least one unsaturated group of the general formula (1):
H
Ando Hiroshi
Ito Hiroshi
Iwakiri Hiroshi
Jyono Hideharu
Kawakubo Fumio
Dawson Robert
Kaneka Corporation
Zimmer Marc S.
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