U.S. patent application number 14/163215 was filed with the patent office on 2014-07-31 for method for preparing a polyorganosiloxane and a polyorganosiloxane.
This patent application is currently assigned to Shin-Etsu Chemical Co., LTD.. The applicant listed for this patent is Shin-Etsu Chemical Co., LTD.. Invention is credited to Tsutomu KASHIWAGI, Takayuki KUSUNOKI.
Application Number | 20140213809 14/163215 |
Document ID | / |
Family ID | 51223633 |
Filed Date | 2014-07-31 |
United States Patent
Application |
20140213809 |
Kind Code |
A1 |
KUSUNOKI; Takayuki ; et
al. |
July 31, 2014 |
METHOD FOR PREPARING A POLYORGANOSILOXANE AND A
POLYORGANOSILOXANE
Abstract
A method for preparing a polyorganosiloxane represented by the
following general formula (1):
(R.sub.3SiO.sub.1/2).sub.l(R.sub.2SiO.sub.2/2).sub.m(RSiO.sub.3/2).sub.n(-
SiO.sub.4/2).sub.o (1) wherein the method includes a step of
condensation reacting at least one organic silicon compound having
at least one hydrogen atom and at least one --OX' group in the
molecule, wherein X' is a hydrogen atom, an alkyl group having 1 to
10 carbon atoms or an alkoxyalkyl group having 2 to 10 carbon
atoms, in the presence of a catalyst, wherein the catalyst is at
least one selected from the group consisting of hydroxides of
elements in Group 2 of the periodic table, hydrates of hydroxides
of elements in Group 2 of the periodic table, oxides of elements in
Group 2 of the periodic table, and hydroxides and oxides of metal
elements in Groups 3-15 of the periodic table.
Inventors: |
KUSUNOKI; Takayuki;
(Annaka-shi, JP) ; KASHIWAGI; Tsutomu;
(Annaka-shi, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Shin-Etsu Chemical Co., LTD. |
Tokyo |
|
JP |
|
|
Assignee: |
Shin-Etsu Chemical Co.,
LTD.
Tokyo
JP
|
Family ID: |
51223633 |
Appl. No.: |
14/163215 |
Filed: |
January 24, 2014 |
Current U.S.
Class: |
556/451 |
Current CPC
Class: |
C07F 7/188 20130101;
C08G 77/12 20130101; C07F 7/025 20130101; C08G 77/045 20130101;
C08G 77/80 20130101; C07F 7/1804 20130101 |
Class at
Publication: |
556/451 |
International
Class: |
C07F 7/18 20060101
C07F007/18 |
Foreign Application Data
Date |
Code |
Application Number |
Jan 29, 2013 |
JP |
2013-014750 |
Dec 9, 2013 |
JP |
2013-253999 |
Claims
1. A method for preparing a polyorganosiloxane represented by the
following general formula (1):
(R.sub.3SiO.sub.1/2).sub.l(R.sub.2SiO.sub.2/2).sub.m(RSiO.sub.3/2).sub.n(-
SiO.sub.4/2).sub.o (1) wherein R is, independently of each other, a
hydrogen atom or a monovalent hydrocarbon group having 1 to 18
carbon atoms, and optionally having an oxygen, halogen, nitrogen or
sulfur atom; l, m, n, and o are, independently of each other, an
integer of from 0 to 10,000, and a total of 1, m and n is from 2 to
30,000; and at least one R is a hydrogen atom and at least one R is
an --OX group in the molecule, wherein X is an alkyl group having 1
to 10 carbon atoms or an alkoxyalkyl group having 2 to 10 carbon
atoms, wherein the method comprises a step of condensation reacting
at least one organic silicon compound having at least one hydrogen
atom and at least one --OX' group in the molecule, wherein X' is a
hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an
alkoxyalkyl group having 2 to 10 carbon atoms, in the presence of a
catalyst, wherein the catalyst is at least one selected from the
group consisting of hydroxides of elements in Group 2 of the
periodic table, hydrates of hydroxides of elements in Group 2 of
the periodic table, oxides of elements in Group 2 of the periodic
table, and hydroxides and oxides of metal elements in Groups 3-15
of the periodic table.
2. The method according to claim 1, wherein the polyorganosiloxane
has, on at least one silicon atom, both of at least one hydrogen
atom and at least one --OX group, wherein X is an alkyl group
having 1 to 10 carbon atoms or an alkoxyalkyl group having 2 to 10
carbon atoms.
3. The method according to claim 1, wherein an amount of the
catalyst is 0.0001 to 20 mol %, relative to a total molar amount of
the organic silicon compound subjected to the condensation
reaction.
4. The method according to claim 1, wherein the organic silicon
compound as the raw material is represented by the following
general formula (2):
(HR.sup.1.sub.aSiO.sub.(4-a-b)/2(OX').sub.b).sub.n (2) wherein
R.sup.1 is, independently of each other, a hydrogen atom or a
monovalent hydrocarbon group having 1 to 18 carbon atoms, and
optionally having an oxygen, halogen, nitrogen or sulfur atom, X'
is as defined above, a and b are independent among the
parenthesized repeating units, a is an integer of from 0 to 2 and b
is an integer of from 1 to 3, provided that a total of a and b is
from 0 to 3, and n is an integer of from 1 to 10,000.
5. The method according to claim 1, wherein the condensation
reaction is carried out in the presence of at least one
solvent.
6. The method according to claim 5, wherein the solvent is at least
one selected from the group consisting of hydrocarbons, aromatic
hydrocarbons, water, alcohols, alcohol esters, ketones, ethers,
esters, cyano group-substituted hydrocarbons, amines, amides,
halogenated hydrocarbons and sulfur-containing compounds.
7. The method according to claim 1, wherein the method comprises a
step of surface treating the catalyst with a silane coupling agent
before used in the condensation reaction.
8. The method according to claim 1, wherein the --OX group accounts
for 0.2% or more, in number, of R.
9. A polyorganosiloxane resin represented by the following general
formula (5):
(R.sub.3SiO.sub.1/2).sub.l'(R.sub.2SiO.sub.2/2).sub.m'(RSiO.sub.3/2).sub.-
n'(SiO.sub.4/2).sub.o' (5) wherein R is, independently of each
other, a hydrogen atom or a monovalent hydrocarbon group having 1
to 18 carbon atoms, and optionally having an oxygen, halogen,
nitrogen or sulfur atom; l', m' and o' are, independently of each
other, an integer of from 0 to 10,000; n' is an integer of from 1
to 10,000; a total of l', m' and n' is from 2 to 30,000; and at
least one R is a hydrogen atom and at least one R is an --OX group
in the molecule, wherein X is an alkyl group having 1 to 10 carbon
atoms or an alkoxyalkyl group having 2 to 10 carbon atoms; and at
least one hydrogen atom and at least one --OX group bond to one and
the same silicon atom.
10. The polyorganosiloxane resin according to claim 9, wherein the
--OX group accounts for 0.2% or more, in number, of R.
11. A polyorganosiloxane represented by the following formula (6):
##STR00032## wherein R.sup.1 is, independently of each other, a
monovalent hydrocarbon group having 1 to 18 carbon atoms, and
optionally having an oxygen, halogen, nitrogen or sulfur atom;
R.sup.2 is, independently of each other, a hydrogen atom or
R.sup.1; R.sup.3 is, independently of each other, R.sup.1 or an
--OX group; X is, independently of each other, an alkyl group
having 1 to 10 carbon atoms or an alkoxyalkyl group having 2 to 10
carbon atoms; e is 0 or 1; when e is 0, d is an integer of from 4
to 20 and d' is 0; when e is 1, d is an integer of from 1 to 20 and
d' is d; p is an integer of 1 or more; and the siloxane units in
the square brackets may form a block structure or a random
structure.
12. A polyorganosiloxane represented by the following formula (7):
##STR00033## wherein R.sup.1 is, independently of each other, a
monovalent hydrocarbon group having 1 to 18 carbon atoms, and
optionally having an oxygen, halogen, nitrogen or sulfur atom,
R.sup.2 is, independently of each other, a hydrogen atom or
R.sup.1; R.sup.3 is, independently of each other, R.sup.1 or an
--OX group; Q is, independently of each other, R.sup.1, an --OX
group or a group represented by the following (8): ##STR00034##
provided that at least one of Q is the group represented by the
aforesaid (8); X is, independently of each other, an alkyl group
having 1 to 10 carbon atoms or an alkoxyalkyl group having 2 to 10
carbon atoms; d.sup.1 and d.sup.2 are, independently of each other,
an integer of from 1 to 20; e.sup.1 is 1; e.sup.2 is 0 or 1;
d.sup.3 is d.sup.1; p and p' are, independently of each other, an
integer of 1 or more; and the siloxane units in the square brackets
may form a block structure or a random structure.
13. A polyorganosiloxane represented by the following formula (9):
##STR00035## wherein R.sup.1 is, independently of each other, a
monovalent hydrocarbon group having 1 to 18 carbon atoms, and
optionally having an oxygen, halogen, nitrogen or sulfur atom;
R.sup.2 is, independently of each other, a hydrogen atom or
R.sup.1; R.sup.3 is, independently of each other, R.sup.1 or an
--OX group; R.sup.5 is, independently of each other, a hydrogen
atom, an alkenyl group having 2 to 10 carbon atoms, or
3-glycidyloxypropyl group, provided that, when at least one R.sup.3
bonding to the silicon atom at the end is an --OX group, R.sup.5
bonding to this silicon atom is not a hydrogen atom; X is,
independently of each other, an alkyl group having 1 to 10 carbon
atoms or an alkoxyalkyl group having 2 to 10 carbon atoms; t is 0
or 1; s is an integer of from 1 to 20; when t is 0, s' is 0; when t
is 1, s' is s; q is an integer of 1 or more; and the siloxane units
in the square brackets may form a block structure or a random
structure.
14. The polyorganosiloxane according claim 11, wherein R.sup.1 is a
monovalent aromatic hydrocarbon group having 6 to 18 carbon
atoms.
15. The polyorganosiloxane according to claim 11, wherein e is 0
and p is 1 in said formula (6).
16. The polyorganosiloxane according to claim 12, wherein p and p'
are 1 in said formulas (7) and (8).
17. The polyorganosiloxane according to claim 13, wherein t is 0
and q is 1 in said formula (9).
18. The polyorganosiloxane according to claim 14, wherein R.sup.1
and R.sup.2 are, independently of each other, a group selected from
phenyl, benzyl, 2-phenylethyl, 2-phenylpropyl and tolyl groups.
19. The polyorganosiloxane according to claim 9, wherein said --OX
group is selected from methoxy, ethoxy, isopropoxy, t-butoxy and
phenoxy groups.
20. The polyorganosiloxane according to claim 11, selected from
compounds represented by the following formulas: ##STR00036##
wherein d is an integer of from 4 to 20, ##STR00037## wherein d is
an integer of from 4 to 20, ##STR00038## wherein d is an integer of
from 4 to 20, ##STR00039## wherein d is an integer of from 1 to 20,
d' is d, and p is an integer of 1 or more, and ##STR00040## wherein
d is an integer of from 1 to 20, d' is d, and p is an integer of 1
or more.
21. The polyorganosiloxane according to claim 12, represented by
the following formula: ##STR00041##
22. The polyorganosiloxane according to claim 13, represented by
the following formula, ##STR00042##
Description
CROSS REFERENCE
[0001] This application claims the benefits of Japanese Patent
application No. 2013-014750 filed on Jan. 29, 2013 and Japanese
Patent application No. 2013-253999 filed on Dec. 9, 2013, the
contents of which are incorporated by reference.
[0002] The present invention relates to a method for preparing a
polyorganosiloxane, specifically a polyorganosiloxane having one or
more hydrosilyl groups, i.e., SiH group and, one or more
alkoxysilyl groups, i.e., SiOR group, in a molecule by subjecting
one or more organic silicon compounds having a silanol group, i.e.,
--SiOH, and/or an alkoxysilyl group, i.e., --SiOR, to a
condensation reaction with each other. Further, the present
invention relates to a polyorganosiloxane thus obtained.
BACKGROUND OF THE INVENTION
[0003] Recently, polyorganosiloxanes are attracting attention as a
material having good light permeability, good heat resistance, low
gas permeability and good chemical stability. Polyorganosiloxanes
having various properties are produced by changing types of
siloxane monomers, their ratio and reaction conditions in the
production process and, accordingly, have been put to practical use
in the various fields.
[0004] It is known that a polyoraganosiloxane having one or more
alkoxysilyl groups and one or more hydrosilyl groups in the
molecule has various applications and is very useful as an adhesion
improving agent for a silicone elastomer adhesive composition, as
described in Japanese Patent Application Laid-Open No. H05-194930,
an adhesive component in a primer, as described in Japanese Patent
Application Laid-Open No. H11-100550, and an intermediate of a
polyorganosiloxane modified with various organic groups, as
described in Japanese Patent Application Laid-Open No. H10-106511,
as the hydrosilyl group may undergo a hydrosilation and the alkoxyl
group may undergo a hydrolytic condensation reaction.
[0005] Polyorganosiloxanes are generally prepared by a hydrolysis
and condensation reaction of chlorosilane and/or an alkoxysilane in
contact with a stoichiometric amount of water in an organic solvent
and in the presence of an acid or base catalyst. However, in a case
where the polyorganosiloxane having a hydrosilyl group is prepared
in this method, the hydrosilyl group is also hydrolyzed. Therefore,
this method is not suitable.
[0006] Examples of the other general methods for preparing a
polyorganosiloxane include a method where an organic silicon
compound having a silanol group, i.e., --SiOH, condensation reacts
with each other; a method where an organic silicon compound having
a silanol group, i.e., --SiOH, condensation reacts with an organic
silicon compound having an alkoxysilyl group, i.e., --SiOR; and a
method where an organic silicon compound having an alkoxysilyl
group, i.e., --SiOR, condensation reacts with each other, wherein R
represents an alkyl group or an alkoxyalkyl group. In the aforesaid
condensation reactions, an amount of a silanol group remaining in
the polyorganosiloxane obtained is small. However, these methods
need chemically intense catalysts to cause condensation reaction,
such as, for instance, strong acids such as sulfuric acid and
hydrochloric acid; strong bases such as sodium hydroxide, potassium
hydroxide and tetramethylammonium hydroxide; and Lewis acids. If
the aforesaid catalysts are used, a siloxane bond (Si--O--Si) is
cut to cause rearrangement during the reaction and, therefore, the
polyorganosiloxane obtained has random structures. Further, this
method causes hydrolysis of the hydrosilyl group. Further, it is
difficult to control the amount of an alkoxysilyl group in the
polyorganosiloxane to leave some alkoxysilyl groups in the
polyorganosiloxane.
[0007] Japanese Patent Application Laid-Open No. H02-235933, Patent
Literature 4, describes that a silanol-containing siloxanes is
condensated in the presence of sodium or potassium borate or
phosphate as a catalyst to prepare an organosilicone condensate.
Japanese Patent Application Laid-Open No. H03-197486, Patent
Literature 5, describes that a silanol-containing siloxane is
condensated in the presence of a catalyst selected from the group
consisting of hydroxides, chlorides, oxides and basic metal salts
of an alkali metal or an alkaline earth metal to prepare a
polyorganosiloxane. Japanese National Phase Publication No.
2006-508216, Patent Literature 6, describes that even hydroxides of
magnesium or calcium can work as a catalyst in condition of the
presence of a protonic solvent to promote a condensation reaction
between a silanol-containing siloxane and an alkoxysilane. Japanese
National Phase Publication No. 2010-506982, Patent Literature 7,
describes that a silicon-containing compound having a silanol group
and/or an alkoxysilyl group reacts in the presence of a catalyst
selected from the group consisting of strontium oxide, barium
oxide, strontium hydroxide, barium hydroxide and a mixture thereof
to prepare an organosilicone condensate.
[0008] In the methods described in the afore-mentioned Patent
Literatures 4 to 7, rearrangement of the polyorganosiloxane chain
is minimized and, thus, a polyorganosiloxane having a controlled
structure is obtained. Further, these methods have an advantage
that the catalyst is easily separated from the obtained
polyorganosiloxane by filtration because these catalysts are solid.
These advantages are favorable particularly in fields where
accurate control on materials is required and any remaining
impurity is untolerable, for instance, the fields of optical
materials, electronic materials and medical materials.
PRIOR LITERATURES
Patent Literatures
[0009] [Paten Literature 1] Japanese Patent Application Laid-Open
No. H05-194930 [0010] [Paten Literature 2] Japanese Patent
Application Laid-Open No. H11-100550 [0011] [Paten Literature 3]
Japanese Patent Application Laid-Open No. H10-106511 [0012] [Paten
Literature 4] Japanese Patent Application Laid-Open No. H02-235933
[0013] [Paten Literature 5] Japanese Patent Application Laid-Open
No. H03-197486 [0014] [Paten Literature 6] Japanese National Phase
Publication No. 2006-508216 [0015] [Paten Literature 7] Japanese
National Phase Publication No. 2010-506982
SUMMARY OF THE INVENTION
[0016] As described above, a polyorganosiloxane has useful
properties and is used in the various fields. However, in the field
of encapsulation of semiconductor devices and sealing, the
adhesiveness is low, so that peeling from a subject material occurs
often. In order to solve this problem, a
hydrogenpolyorganosiloxanes having various substituent groups and
reactivities are researched and developed. As stated above, the
hydrosilyl group is hydrolyzed to dehydrogenate in the presence of
the catalyst such as a strong alkali and, therefore, the synthesis
method of the polyorganosiloxane having a hydrosilyl group is
limited and a desired polyorganosiloxane has been not obtained
yet.
[0017] One object of the present invention is to prepare a desired
hydrogenpolyoraganosiloxane having an alkoxysilyl group and a
hydrosilyl group in the molecule by condensation reacting one or
more organic silicon compounds having a silanol group, i.e.,
--SiOH, and/or an alkoxysilyl group, i.e., --SiOR, with each
other.
[0018] To solve the aforesaid problems, the present inventors have
made research and found that one or more organic silicon compounds
having a silanol group, i.e., --SiOH, and/or an alkoxysilyl group,
i.e., --SiOX, condensation reacts with each other in the presence
of the specific catalyst to effectively give a desired
hydrogenpolyorganosiloxane without dehydrogenating a hydrosilyl
group during the reaction.
[0019] Thus, the present invention is a method for preparing a
polyorganosiloxane represented by the following general formula
(1):
(R.sub.3SiO.sub.1/2).sub.l(R.sub.2SiO.sub.2/2).sub.m(RSiO.sub.3/2).sub.n-
(SiO.sub.4/2).sub.o (1)
wherein R is, independently of each other, a hydrogen atom or a
monovalent hydrocarbon group having 1 to 18 carbon atoms, and
optionally having an oxygen, halogen, nitrogen or sulfur atom; l,
m, n, and o are, independently of each other, an integer of from 0
to 10,000, and a total of 1, m and n is from 2 to 30,000; and at
least one R is a hydrogen atom and at least one R is an --OX group
in the molecule, wherein X is an alkyl group having 1 to 10 carbon
atoms or an alkoxyalkyl group having 2 to 10 carbon atoms,
[0020] wherein the method comprises a step of condensation reacting
at least one organic silicon compound having at least one hydrogen
atom and at least one --OX' group in the molecule, wherein X' is a
hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an
alkoxyalkyl group having 2 to 10 carbon atoms, in the presence of a
catalyst (D), wherein said catalyst (D) is at least one selected
from the group consisting of hydroxides of elements in Group 2 of
the periodic table, hydrates of hydroxides of elements in Group 2
of the periodic table, oxides of elements in Group 2 of the
periodic table, and hydroxides and oxides of metal elements in
Groups 3-15 of the periodic table.
[0021] The present method provides an organic silicon compound
having one or more hydrosilyl groups, i.e., Si--H, and one or more
alkoxysilyl groups, i.e., Si--OX in the molecule, preferably on one
and the same silicon atom, wherein X is an alkyl group having 1 to
10 carbon atoms or an alkoxyalkyl group having 2 to 10 carbon
atoms.
[0022] Further, the present invention provides a novel organic
silicon compound obtained in the aforesaid method. The present
organic silicon compound is characterized in that at least one
hydrogen atom and at least one --OX group bond on one and the same
silicon atom.
[0023] A first embodiment of the present organic silicon compound
is a polyorganosiloxane resin represented by the following general
formula (5):
(R.sub.3SiO.sub.1/2).sub.l'(R.sub.2SiO.sub.2/2).sub.m'(RSiO.sub.3/2).sub-
.n'(SiO.sub.4/2).sub.o' (5)
wherein R is, independently of each other, a hydrogen atom or a
monovalent hydrocarbon group having 1 to 18 carbon atoms, and
optionally having an oxygen, halogen, nitrogen or sulfur atom; l',
m' and o' are, independently of each other, an integer of from 0 to
10,000; n' is an integer of from 1 to 10,000; a total of I', m' and
n' is from 2 to 30,000; and at least one R is a hydrogen atom and
at least one R is an --OX group in the molecule, wherein X is an
alkyl group having 1 to 10 carbon atoms or an alkoxyalkyl, group
having 2 to 10 carbon atoms; and at least one hydrogen atom and at
least one --OX group bond to one and the same silicon atom.
[0024] A second embodiment of the present organic silicon compound
is a polyorganosiloxane represented by the following formula
(6):
##STR00001##
wherein R.sup.1 is, independently of each other, a monovalent
hydrocarbon group having 1 to 18 carbon atoms, and optionally
having an oxygen, halogen, nitrogen or sulfur atom; R.sup.2 is,
independently of each other, a hydrogen atom or R.sup.1; R.sup.3
is, independently of each other, R.sup.1 or an --OX group; X is,
independently of each other, an alkyl group having 1 to 10 carbon
atoms or an alkoxyalkyl group having 2 to 10 carbon atoms; e is 0
or 1; when e is 0, d is an integer of from 4 to 20 and d' is 0;
when e is 1, d is an integer of from 1 to 20 and d' is d; p is an
integer of 1 or more; and the siloxane units in the square brackets
may form a block structure or a random structure.
[0025] A third embodiment of the present organic silicon compound
is a polyorganosiloxane represented by the following formula
(7):
##STR00002##
wherein R.sup.1 is, independently of each other, a monovalent
hydrocarbon group having 1 to 18 carbon atoms, and optionally
having an oxygen, halogen, nitrogen or sulfur atom, R.sup.2 is,
independently of each other, a hydrogen atom or R.sup.1; R.sup.3
is, independently of each other, R.sup.1 or an --OX group; Q is,
independently of each other, R.sup.1, an --OX group or a group
represented by the following (8):
##STR00003##
provided that at least one of Q is the group represented by the
aforesaid (8); X is, independently of each other, an alkyl group
having 1 to 10 carbon atoms or an alkoxyalkyl group having 2 to 10
carbon atoms; d.sup.1 and d.sup.2 are, independently of each other,
an integer of from 1 to 20; e.sup.1 is 1; e.sup.2 is 0 or 1;
d.sup.3 is d.sup.1; p and p' are, independently of each other, an
integer of 1 or more; and the siloxane units in the square brackets
may form a block structure or a random structure.
[0026] A fourth embodiment of the present organic silicon compound
is a polyorganosiloxane represented by the following formula
(9):
##STR00004##
wherein R.sup.1 is, independently of each other, a monovalent
hydrocarbon group having 1 to 18 carbon atoms, and optionally
having an oxygen, halogen, nitrogen or sulfur atom; R.sup.2 is,
independently of each other, a hydrogen atom or R.sup.1; R.sup.3
is, independently of each other, R.sup.1 or an --OX group; R.sup.5
is, independently of each other, a hydrogen atom, an alkenyl group
having 2 to 10 carbon atoms, or 3-glycidyloxypropyl group, provided
that, when at least one R.sup.3 bonding to the silicon atom at the
end is an --OX group, R.sup.5 bonding to this silicon atom is not a
hydrogen atom; X is, independently of each other, an alkyl group
having 1 to 10 carbon atoms or an alkoxyalkyl group having 2 to 10
carbon atoms; t is 0 or 1; s is an integer of from 1 to 20; when t
is 0, s' is 0; when t is 1, s' is s; q is an integer of 1 or more;
and the siloxane units in the square brackets may form a block
structure or a random structure.
[0027] According to the present method, an organic silicon compound
having at least one hydrosilyl group and at least one alkoxysilyl
group in the molecule is provided. In particular, a
hydrogenpolyoraganosiloxane having a hydrogen atom and an alkoxy
group on one and the same silicon atom can be provided. The
hydrogenpolyoraganosiloxane having a hydrosilyl group and an
alkoxysilyl group in the molecule is useful in the field of
industry as an adhesion improving agent, a primer and an
intermediate of a polyorganosiloxane modified by various organic
groups. Further, the present invention provides a
polyorganosiloxane having a controlled structure, so that may be
used in various fields such as medical or pharmaceutical
materials.
BRIEF EXPLANATION OF THE DRAWINGS
[0028] FIG. 1 is a .sup.1H-NMR spectrum of the product obtained in
Example 1.
[0029] FIG. 2 is a GPC chart of the product obtained in Example
1.
[0030] FIG. 3 is a chart indicating a possible reaction mechanism
in the present method.
DETAILED DESCRIPTION OF THE INVENTION
[0031] The present invention will be described below in detail.
[0032] The present invention provides a method for preparing a
polyorganosiloxane represented by the following formula (1):
(RSiO.sub.1/2).sub.l(R.sub.2SiO.sub.2/2).sub.m(RSiO.sub.3/2).sub.n(SiO.s-
ub.4/2).sub.o (1)
wherein R is, independently of each other, a hydrogen atom or a
monovalent hydrocarbon group having 1 to 18 carbon atoms, and
optionally having an oxygen, halogen, nitrogen or sulfur atom; 1,
m, n, and o are, independently of each other, an integer of from 0
to 10,000, and a total of l, m and n is from 2 to 30,000; and at
least one R is a hydrogen atom and at least one R is an --OX group
in the molecule, wherein X is an alkyl group having 1 to 10 carbon
atoms or an alkoxyalkyl group having 2 to 10 carbon atoms.
[0033] The aforesaid polyorganosiloxane preferably has at least one
silicon atom having at least one hydrogen atom and at least one
--OX group on one and the same silicon atom, wherein X is an alkyl
group having 1 to 10 carbon atoms or an alkoxyalkyl group having 2
to 10 carbon atoms. The --OX group accounts for preferably 0.2% or
more, further preferably 1 to 85%, more preferably 2 to 70%, in
number, of R.
[0034] The present method will be described below in further
detail.
[0035] The method for preparing a polyorganosiloxane comprises a
step of subjecting one or more organic silicon compounds having at
least one --OX' group in the molecule to a condensation reaction in
the presence of the specific catalyst (D), wherein X' is a hydrogen
atom, an alkyl group having 1 to 10 carbon atoms or an alkoxyalkyl
group having 2 to 10 carbon atoms.
[0036] The organic silicon compound as the raw material is
preferably represented by the following general formula (2):
(HR.sup.1.sub.aSiO.sub.(4-a-b)/2(OX').sub.b).sub.n (2)
wherein R.sup.1 is, independently of each other, a hydrogen atom or
a monovalent hydrocarbon group having 1 to 18 carbon atoms, and
optionally having an oxygen, halogen, nitrogen or sulfur atom, X'
is as defined above, a and b are independent among the
parenthesized repeating units, a is an integer of from 0 to 2 and b
is an integer of from 1 to 3, provided that a total of a and b is
from 0 to 3, and n is an integer of from 1 to 10,000.
[0037] In a first embodiment of the present method, the following
(A) and (B1) are reacted in the presence of the specific catalyst
(D):
(A) at least one organic silicon compound having at least one
silanol group in the molecule and (B1) at least one organic silicon
compound having at least one --OX' group bonded to a silicon atom
in the molecule, wherein X' is a hydrogen atom, an alkyl group
having 1 to 10 carbon atoms or an alkoxyalkyl group having 2 to 10
carbon atoms, provided that at least one organic silicon compound
selected from the group consisting of the components (A) and (81)
has a hydrosilyl group.
[0038] In the second embodiment of the present method, the
following (B2) is reacted in the presence of the specific catalyst
(D):
(B2) one or more organic silicon compounds having at least one --OX
group bonded to a silicon atom in the molecule, wherein X is an
alkyl group having 1 to 10 carbon atoms or an alkoxyalkyl group
having 2 to 10 carbon atoms, provided that at least one organic
silicon compound selected from the group consisting of the
component (B2) has a hydrosilyl group.
[0039] The embodiments will be explained below in detail.
First Embodiment of the Present Method
[0040] In the first embodiment of the present method, the component
(A) is at least one organic silicon compound having at least one
silanol group in the molecule and the component (B1) is at least
one organic silicon compound having at least one --OX' group bonded
to a silicon atom in the molecule, wherein X' is a hydrogen atom,
an alkyl group having 1 to 10 carbon atoms or an alkoxyalkyl group
having 2 to 10 carbon atoms. The organic silicon compound may be a
monomer, dimer, oligomer or polymer. When the organic silicon
compound is an oligomer or a polymer, its structure may be linear,
branched or linear with a branched part. Particularly, a linear
structure is preferred. In a case where a condensate having a high
molecular weight is desired, it is preferred that the
polyorganosiloxane has two or more silanol or --OX groups in each
molecule. When X' in the component (B1) is a hydrogen atom, the
component (A) may be same as the component (B1).
[0041] The component (A) may be represented by the following
general formula (3)
(R.sup.1.sub.aSiO.sub.(4-a-b)/2(OH).sub.b).sub.n (3)
wherein, R.sup.1 is as will be defined below, a and b are
independent among the parenthesized repeating units, and a is an
integer of from 0 to 3 and b is an integer of from 0 to 4, provided
that a total of a and b is from 0 to 4. n is an integer of from 1
to 10,000, preferably 1 to 1,000, provided that the compound (A),
organic silicon compound, has at least one --OH group bonded to a
silicon atom in the molecule.
[0042] The component (B1) may be represented by the following
general formula (4):
(R.sup.1.sub.aSiO.sub.(4-a-b)/2(OH).sub.b(OR.sup.2).sub.c).sub.n
(4)
wherein, R.sup.1 and X are as will be defined below, a, b and c are
independent among the parenthesized repeating units, and a is an
integer of from 0 to 3, b is an integer of from 0 to 4, and c is an
integer of from 0 to 3, provided that a total of a, b and c is from
0 to 4. n is an integer of from 1 to 10,000, preferably 1 to 1,000,
provided that the compound (B1), organic silicon compound, has at
least one --OH group bonded to a silicon atom or --OX group bonded
to a silicon atom in the molecule.
[0043] In the formulas (3) and (4), R.sup.1 is, independently of
each other, a hydrogen atom or a monovalent hydrocarbon group
having 1 to 18, preferably 1 to 10 carbon atoms, and optionally
having an oxygen, halogen, nitrogen or sulfur atom. Examples of
R.sup.1 include alkyl groups such as methyl, ethyl, propyl, butyl
and octyl groups; cycloalkyl groups such as cyclopentyl and
cyclohexyl groups; alkenyl groups such as vinyl and allyl groups;
aryl groups such as phenyl, tolyl and naphthyl groups; and aralkyl
groups such as benzyl, phenylethyl and phenylpropyl groups; and
these groups where a part or the whole of their hydrogen atoms
bonding to carbon atoms are replaced with a halogen atom(s), such
as fluorine, bromine and chlorine atoms, or with a cyano group,
such as, for instance, halogen-substituted monovalent hydrocarbon
groups such as trifluoropropyl and chloropropyl groups; a
cyanoalkyl groups such as a .beta.-cyanoethyl and
.gamma.-cyanopropyl groups; 3-methacryloxypropyl group,
3-glycidyloxypropyl group, 3-mercaptopropyl group and 3-aminopropyl
group. Among these, methyl group and phenyl are preferred.
[0044] In the aforesaid formula (4), X is, independently of each
other, an alkyl group having 1 to 10, preferably 1 to 8 carbon
atoms or an alkoxyalkyl group having 2 to 10, preferably 2 to 8
carbon atoms. Examples of X include alkyl groups such as methyl,
ethyl, propyl, butyl and octyl groups; and alkoxyalkyl group such
as methoxymethyl, methoxyethyl and ethoxymethyl groups. Among
these, a methyl group is preferred.
[0045] As described above, the organic silicon compound represented
by the formula (3) or (4) may be a monomer (i.e., n is 1), dimer
(i.e., n is 2), oligomers (e.g., n is 3 to 100) or polymer (e.g., n
is 100 to 10,000). In particular, a monomer (i.e., n is 1) and a
dimer (i.e., n is 2) are preferred.
[0046] The component (A) is more preferably an organic silicon
compound represented by the following formula (I):
##STR00005##
wherein R' is --OH or R.sup.1, m is n-1, and R.sup.1 and n are as
defined above.
[0047] Examples of the organic silicon compound represented by the
formula (I) includes 1,1,3,3-trimethyldisiloxane-1,3-diol,
1,1,3,3-tetramethyldisiloxane-1,3-diol,
1,1,3,3,5,5-hexamethyltrisiloxane-1,5-diol,
1,1,3,5,5-pentamethyltrisiloxane-1,3,5-triol,
3-glycidyloxypropylmethylsilanetriol,
3-methacryloxypropylsilanetriol, 3-aminopropylsilanetriol,
3-mercaptpropylsilanetriol, 3-chloropropylsilanetriol, silicic
acid, phenylsilanediol, phenylmethylsilanediol, diphenylsilanediol,
distyrylsilanediol and dipentafluorophenylsilanediol; and an
oligomer or a polymer thereof. Among these, diphenylsilanediol is
preferred as it is easily available.
[0048] The component (B1) is more preferably an organic silicon
compound represented by the following formula (II) or (III):
##STR00006##
wherein R'' is --OH, --OX or R.sup.1, preferably --OX or R.sup.1, m
is n-1, and R.sup.1, X and n are as defined above.
##STR00007##
wherein R'' is --OH, --OX or R.sup.1, preferably --OX or R.sup.1,
at least one R'' is --OX, m is n-1, and R.sup.1, X and n are as
defined above.
[0049] Examples of the organic silicon compound represented by the
formula (II) include tetramethoxysilane, tetraethoxysilane,
trimethoxysilane, triethoxysilane, methyltrimethoxysilane,
decyltrimethoxysilane, vinyltrimethoxysilane,
phenyltrimethoxysilane, styryltrimethoxysilane,
3,3,3-trifluoropropyltrimethoxysilane,
3-glicydyloxypropyltrimethoxymethylsilane,
3-methacryloxypropyltrimethoxysilane,
3-aminopropyltrimethoxysilane, 3-mercaptpropyltrimethoxysilane,
3-chloropropyltrimethoxysilane, methyldimethoxysilane,
methyldiethoxysilane, dimethyldimethoxysilane,
dimethyldiethoxysilane, phenyldimethoxysilane,
phenyldiethoxysilane, phenylmethyldimethoxysilane,
diphenyldimethoxysilane, distyryldimethoxysilane,
dipentafluorophenyldimethoxysilane, trimethoxysilanol,
triethoxysilanol, dimethoxysilanol, diethoxysilanol,
methyldimethoxysilanol, decyldimethoxysilanol,
vinyldimethoxysilanol, phenyldimethoxysilanol,
styryldimethoxysilanol, 3,3,3-trifluoropropyldimethoxysilanol,
3-glicydyloxypropyldimethoxysilanol,
3-methacryloxypropyldimethoxysilanol,
3-aminopropyldimethoxysilanol, 3-mercaptpropyldimethoxysilanol,
3-chloropropyldimethoxysilanol and an oligomer and a polymer of the
organic silicon compounds represented by the aforesaid formulas (I)
and (II). Tetramethoxysilane and trimethoxysilane are preferred in
view of the reactivity.
[0050] Examples of the organic silicon compound represented by the
formula (III) include dimethoxysilanediol, diethoxysilanediol,
methoxysilanediol, ethoxysilanediol, methylmethoxysilanediol,
decylmethoxysilanediol, vinylmethoxysilanediol,
phenylmethoxysilanediol, styrylmethoxysilanediol,
3,3,3-trifluoropropylmethoxysilanediol,
3-glicydyloxypropylmethoxysilanediol,
3-methacryloxypropylmethoxysilanediol,
3-aminopropylmethoxysilanediol, 3-mercaptpropylmethoxysilanediol,
3-chloropropylmethoxysilanediol and an oligomer and a polymer of
the organic silicon compounds represented by the aforesaid formulas
(I) to (III).
[0051] The raw material monomer which has a hydrosilyl group and is
used in the present method for preparing an organic silicon
compound having at least one hydrosilyl group and at least one
alkoxysilyl group in the molecule is preferably at least one
organic silicon compound having a hydrosilyl group selected from
the compounds of the formula (II) described above. For instance,
trimethoxysilane, triethoxysilane, methyldimethoxysilane and
methyldiethoxysilane are preferred.
[0052] A blend ratio of the components (A) to (B1) may be decided
properly, depending on a desired structure of a product, organic
silicon compound. In particular, the number of the --OX group in
the component (B1) is larger than the number of the silanol group
in the component (A) so as to leave an alkoxysilyl group in the
organic silicon compound obtained. Thus, it is preferred that the
ratio of the number of the silanol group in the component (A)
relative to the number of --OX group in the component (B1) is 0.001
to 0.999, in particular 0.01 to 0.999, further 0.1 to 0.9.
Second Embodiment of the Present Method
[0053] In the second embodiment of the present method, the
component (B2) is one or more organic silicon compounds having at
least one --OX group bonded to a silicon atom in the molecule,
wherein X is an alkyl group having 1 to 10 carbon atoms or an
alkoxyalkyl group having 2 to 10 carbon atoms. The organic silicon
compound may be a monomer, dimer, oligomer and polymer. When the
organic silicon compound is an oligomer or a polymer, its structure
may be linear, branched or linear with a branched part.
Particularly, a linear structure is preferred. In a case where a
condensate having a high molecular weight is desired, the
polyorganosiloxane preferably has two or more --OX groups in the
molecule.
[0054] The component (B2) may be represented by the following
general formula:
(R.sup.1.sub.aSiO.sub.(4-a-c)/2(OX).sub.c).sub.n
wherein, R.sup.1 is, independently of each other, a hydrogen atom
or a monovalent hydrocarbon group having 1 to 18, preferably 1 to
10 carbon atoms, and optionally having an oxygen, halogen, nitrogen
or sulfur atom. Examples of R.sup.1 are as described for the
formulas (3) and (4) above. X is, independently of each other, an
alkyl group having 1 to 10, preferably 1 to 8 carbon atoms or an
alkoxyalkyl group having 2 to 10, preferably 2 to 8 carbon atoms.
Examples of X are as described for the formula (4) above.
[0055] In the formula, a and c are independent among the
parenthesized repeating units, a is an integer of from 0 to 3 and c
is an integer of from 0 to 4, provided that a total of a and c is
from 0 to 4, provided that the organic silicon compound of formula
has at least one --OX group in the molecule.
[0056] In the formula, n is an integer of from 1 to 10,000,
preferably 1 to 1,000. As described above, the organic silicon
compound represented by the formula may be a monomer (i.e., n is
1), dimer (i.e., n is 2), oligomer (e.g., n is 3 to 100) or polymer
(e.g., n is 100 to 10,000). In particular, a monomer (i.e., n is 1)
and a dimer (i.e., n is 2) are preferred.
[0057] The component (32) is more preferably an organic silicon
compound represented by the following formula (IV):
##STR00008##
wherein R''' is --OX or R.sup.1, m is n-1, and R.sup.1, X and n are
as defined above.
[0058] Examples of the organic silicon compound represented by the
aforesaid formula (IV) includes tetramethoxysilane,
tetraethoxysilane, trimethoxysilane, triethoxysilane,
methyltrimethoxysilane, decyltrimethoxysilane,
vinyltrimethoxysilane, phenyltrimethoxysilane,
styryltrimethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane,
3-glicydyloxypropyldimethoxymethylsilane,
3-methacryloxypropyltrimethoxysilane,
3-aminopropyltrimethoxysilane, 3-mercaptpropyltrimethoxysilane,
3-chloropropyltrimethoxysilane, methyldimethoxysilane,
methyldiethoxysilane, dimethyldimethoxysilane,
dimethyldiethoxysilane, phenyldimethoxysilane,
phenylmethyldimethoxysilane, diphenyldimethoxysilane,
distyryldimethoxysilane and dipentafluorophenyldimethoxysilane.
Tetramethoxysilane and trimethoxysilane are preferred in view of
the reactivity.
[0059] The raw material monomer which has a hydrosilyl group and is
used in the present method for preparing an organic silicon
compound having at least one hydrosilyl group and at least one
alkoxysilyl group in the molecule is preferably at least one
organic silicon compound having a hydrosilyl group selected from
the compounds of the formula (IV) described above. For instance,
trimethoxysilane, triethoxysilane, methyldimethoxysilane and
methyldiethoxysilane are preferred.
[0060] Ina case where two or more kinds of the organic silicon
compounds are condensation reacted with each other, a mixing ratio
of the compounds may be decided properly, depending on a structure
of a desired organic silicon compound.
[0061] The possible reaction mechanism is shown in the FIG. 3.
[0062] The catalyst (D) used in the condensation reaction is at
least one selected from the group consisting of hydroxides of
elements in Group 2 of the periodic table, hydrates of hydroxides
of elements in Group 2 of the periodic table, oxides of elements in
Group 2 of the periodic table, and hydroxides or oxides of metal
elements in Groups 3-15 of the periodic table (hereinafter,
referred to as "metal compound"). The metal compound has a
catalytic function for a condensation reaction of an organic
silicon compound having a silanol group (--SiOH) and/or an
alkoxysilyl group (--SiOX). In view of reactivity or availability,
at least one selected from the group consisting of hydroxides of
elements in Group 2 of the periodic table, hydrates of hydroxides
of elements in Group 2 of the periodic table, oxides of elements in
Group 2 of the periodic table, and hydroxides or oxides of elements
in Groups 3, 8, 10, 11 and 13 is preferred. Examples of the
compound include radium hydroxide, barium hydroxide, strontium
hydroxide, calcium hydroxide, magnesium hydroxide, beryllium
hydroxide, barium hydroxide octahydrate, barium hydroxide
monohydrate, strontium hydroxide octahydrate, barium oxide,
strontium oxide, calcium oxide, magnesium oxide, beryllium oxide,
lanthanum (III) hydroxide, cerium (IV) hydroxide, zirconium (IV)
hydroxide, iron (II) hydroxide, iron (III) hydroxide, cobalt (II)
hydroxide, nickel (II) hydroxide, copper (II) hydroxide, gold (III)
hydroxide, zinc (II) hydroxide, cadmium (II) hydroxide, aluminum
(III) hydroxide, indium (III) hydroxide, thallium (I) hydroxide,
lead (II) hydroxide, bismuth (III) hydroxide, manganese (IV) oxide,
iron (II) oxide and copper (II) oxide. Among these, barium
hydroxide, calcium hydroxide, magnesium hydroxide, strontium
hydroxide, lanthanum (III) hydroxide, aluminum (III) hydroxide,
iron (II) hydroxide, iron (III) hydroxide and copper (II) hydroxide
are preferred in view of availability.
[0063] The present method preferably includes a step of surface
treating the catalyst (D) with a silane coupling agent (D2) before
used in the condensation reaction. On account of the surface
treatment of the catalyst, aggregation of the catalyst is prevented
and the catalyst is homogeneously dispersed in a reaction solvent,
so that the effective surface area as a catalyst is larger.
Therefore, the reaction rate is faster and, that is, the catalytic
activity is higher.
[0064] As the silane coupling agent (D2), any known silane coupling
agent may be used. Particularly, in view of the dispersibility of
the catalyst, a preferred silane coupling agent has a chemical
structure similar to an organic silicon compound which causes a
condensation reaction, particularly similar to an organic silicon
compound having an alkoxy group. Examples of the silane coupling
agent include trimethoxysilane, triethoxysilane,
methyltrimethoxysilane, decyltrimethoxysilane,
vinyltrimethoxysilane, phenyltrimethoxysilane,
styryltrimethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane,
3-glicydyloxypropyldimethoxymethylsilane,
3-glicydyloxypropyltrimethoxysilane,
3-methacryloxypropyltrimethoxysilane,
3-aminopropyltrimethoxysilane, 3-mercaptpropyltrimethoxysilane,
3-chloropropyltrimethoxysilane,
1,1,3,3,5,5-hexamethoxy-1,3,5-trimethyltrisiloxane,
1,1,5,5-tetramethoxy-1,3,5-trimethyltrisiloxane-3-ol,
dimethyldimethoxysilane, dimethyldiethoxysilane,
phenylmethyldimethoxysilane, diphenyldimethoxysilane,
distyryldimethoxysilane, dipentafluorophenyldimethoxysilane and
hexamethyldisilazane. Among these, trimethoxysilane,
vinyltrimethoxysilane, methyltrimethoxysilane and
3-glicydyloxypropyltrimethoxysilane are preferred.
[0065] The surface treatment of the metal compound (D) with the
silane coupling agent (D2) may be conducted in a conventional
manner. For instance, a wet process and a dry process are
utilizable. A mixing ratio of the metal compound (D) to the silane
coupling agent (02) is not limited to particular one. In order not
to lose the catalyst activity, the amount of the silane coupling
agent (D2) is 0.001 to 100 parts by mass, further preferably 0.01
to 10 parts by mass, per 100 parts by mass of the metal compound
(D).
[0066] An amount of the catalyst (D) used in the present method, as
the amount of the compound before the surface treatment with a
silane coupling agent, is 0.0001 to 20 mol %, preferably 0.01 to 10
mol %, more preferably 0.1 to 5 mol %, relative to a total molar
amount of the organic silicone compound to be subjected to a
condensation reaction. When the amount of the catalyst (D) is in
the afore-mentioned range, a sufficient catalytic effect for the
condensation reaction is attained. Further, in a step of removing
the catalyst by filtration after the condensation reaction, a
desired condensate is recovered effectively without clogging a
filter.
[0067] The condensation reaction in the present invention may be
carried out in the presence of at least one solvent (E). The
solvent is used to control a rate and a conversion of the reaction,
or used as a diluent for a condensate obtained. The solvent may be
one or more selected from non-polar solvents and polar solvents.
Examples of the non-polar solvents include hydrocarbons such as
n-hexane, n-heptane and isooctane; aromatic hydrocarbons such as
toluene and xylene. Examples of the polar solvents include water;
alcohols such as methanol, ethanol and isopropanol; alcohol esters;
ketones such as acetone, methylethylketone and cyclohexanone;
ethers such as diethyl ether and dibutyl ether; esters such as
ethyl acetate, isopropyl acetate and butyl acetate; cyano
group-substituted hydrocarbons such as acetonitrile; amines; amides
such as acetamide; halogenated hydrocarbons such as methylene
chloride, chloroform and hexafluoromethaxylene; and
sulfur-containing compounds such as dimethylsulfoxide. An amount of
the solvent is not limited to particular one. Generally, the amount
is such that a concentration of the organic silicon compounds to be
subjected to the condensation reaction is 5 to 95 mass %,
preferably 20 to 80 mass %. The condensation reaction in the
present invention may also be conducted without any solvent.
[0068] In the present condensation reaction, any other components
may also be added as long as such does not obstruct the progress of
the condensation reaction. For instance, a neutral surfactant may
be added so as to improve dispersion of a solid catalyst. When the
group represented by R.sup.1 in the formulas is reactive, a
reaction inhibitor may be added. The afore-mentioned components may
be used alone or in combination of two or more of them. Further, an
amount of the component may be decided properly so that the effects
of the present invention are not obstructed.
[0069] The condensation reaction in the present invention may be
conducted under heating. A temperature is preferably 0 to 150
degrees C., more preferably 60 to 100 degrees C.
[0070] The present method preferably further comprises a step of
filtering a catalyst after the condensation reaction. In the
present method, the catalyst is easily removed from a reaction
product in this step. In the filtration, the afore-mentioned
solvent (E) may be added in order to control a viscosity of the
reaction mixture obtained.
[0071] Further, the present method may comprise a step of
purification in order to remove an unreacted monomer from the
reaction mixture by any known method such as water washing, vacuum
strip and treatment with activated carbon.
[0072] According to the present method, a hydrogenpolyorganosioxane
is provided, which has controlled structure and a desired amount of
an alkoxysilyl group and a hydrosilyl group in the molecule.
[0073] The present invention further provides a novel organic
silicon compound in the aforesaid method. The novel organic silicon
compound is characterized in that at least one hydrogen atom and at
least one --Ox group bond on one and the same silicon atom.
[0074] A first embodiment of the present organic silicon compound
is a polyorganosiloxane resin represented by the following general
formula (5):
(R.sub.3SiO.sub.1/2).sub.l'(R.sub.2SiO.sub.2/2).sub.m'(RSiO.sub.3/2).sub-
.n'(SiO.sub.4/2).sub.o' (5)
wherein R is, independently of each other, a hydrogen atom or a
monovalent hydrocarbon group having 1 to 18 carbon atoms, and
optionally having an oxygen, halogen, nitrogen or sulfur atom; l',
m' and o' are, independently of each other, an integer of from 0 to
10,000; n' is an integer of from 1 to 10,000; a total of l', m' and
n' is from 2 to 30,000; and at least one R is a hydrogen atom and
at least one R is an --OX group in the molecule, wherein X is an
alkyl group having 1 to 10 carbon atoms or an alkoxyalkyl group
having 2 to 10 carbon atoms; and at least one hydrogen atom and at
least one --OX group bond to one and the same silicon atom. In
preferred, 0.2% or more, further preferably 1 to 85%, more
preferably 2 to 70%, of R is --OX group.
[0075] R is, independently of each other, a hydrogen atom or a
monovalent hydrocarbon group having 1 to 18, preferably 1 to 10
carbon atoms, and optionally having an oxygen, halogen, nitrogen or
sulfur atom. Examples of R include alkyl groups such as methyl,
ethyl, propyl, butyl and octyl groups; cycloalkyl groups such as
cyclopentyl and cyclohexyl groups; alkenyl groups such as vinyl and
allyl groups; aryl groups such as phenyl, tolyl and naphthyl
groups; and aralkyl groups such as benzyl, phenylethyl and
phenylpropyl groups; and these groups where a part or the whole of
their hydrogen atoms bonding to carbon atoms are replaced with a
halogen atom(s), such as fluorine, bromine and chlorine atoms, or
with a cyano group, such as, for instance, halogen-substituted
monovalent hydrocarbon groups such as trifluoropropyl and
chloropropyl groups; a cyanoalkyl groups such as a
.beta.-cyanoethyl and .gamma.-cyanopropyl groups;
3-methacryloxypropyl group, 3-glycidyloxypropyl group,
3-mercaptopropyl group and 3-aminopropyl group. Among these, methyl
group and phenyl are preferred.
[0076] A second embodiment of the present organic silicon compound
is a polyorganosiloxane represented by the following general
formula (6):
##STR00009##
wherein R.sup.1 is, independently of each other, a monovalent
hydrocarbon group having 1 to 18 carbon atoms, and optionally
having an oxygen, halogen, nitrogen or sulfur atom; R.sup.2 is,
independently of each other, a hydrogen atom or R.sup.1; R.sup.3
is, independently of each other, R.sup.1 or an --OX group; X is,
independently of each other, an alkyl group having 1 to 10 carbon
atoms or an alkoxyalkyl group having 2 to 10 carbon atoms; e is 0
or 1; when e is 0, d is an integer of from 4 to 20 and d' is 0;
when e is 1, d is an integer of from 1 to 20 and d' is d; p is an
integer of 1 or more; and the siloxane units in the square brackets
may form a block structure or a random structure.
[0077] A third embodiment of the present organic silicon compound
is a polyorganosiloxane represented by the following general
formula (7):
##STR00010##
wherein R.sup.1 is, independently of each other, a monovalent
hydrocarbon group having 1 to 18 carbon atoms, and optionally
having an oxygen, halogen, nitrogen or sulfur atom, R.sup.2 is,
independently of each other, a hydrogen atom or R.sup.1; R.sup.3
is, independently of each other, R.sup.1 or an --OX group; Q is,
independently of each other, R.sup.1, an --OX group or a group
represented by the following (8):
##STR00011##
provided that at least one of Q is the group represented by the
aforesaid (8); X is, independently of each other, an alkyl group
having 1 to 10 carbon atoms or an alkoxyalkyl group having 2 to 10
carbon atoms; d.sup.1 and d.sup.2 are, independently of each other,
an integer of from 1 to 20; e.sup.1 is 1; e.sup.2 is 0 or 1;
d.sup.3 is d.sup.1; p and p' are, independently of each other, an
integer of 1 or more, preferably 1 to 10, further preferably 1 to
5, in particular preferably both p and p' are 1; and the siloxane
units in the square brackets may form a block structure or a random
structure.
[0078] A fourth embodiment of the present organic silicon compound
is a polyorganosiloxane represented by the following general
formula (9):
##STR00012##
wherein R.sup.1 is, independently of each other, a monovalent
hydrocarbon group having 1 to 18 carbon atoms, and optionally
having an oxygen, halogen, nitrogen or sulfur atom; R.sup.2 is,
independently of each other, a hydrogen atom or R.sup.1; R.sup.3
is, independently of each other, R.sup.1 or an --OX group; R.sup.5
is, independently of each other, a hydrogen atom, an alkenyl group
having 2 to 10 carbon atoms, or 3-glycidyloxypropyl group, provided
that, when at least one R.sup.3 bonding to the silicon atom at the
end is an --OX group, R.sup.5 bonding to this silicon atom is not a
hydrogen atom; X is, independently of each other, an alkyl group
having 1 to 10 carbon atoms or an alkoxyalkyl group having 2 to 10
carbon atoms; t is 0 or 1; s is an integer of from 1 to 20; when t
is 0, s' is 0; when t is 1, s' is s; q is an integer of 1 or more,
preferably 1 to 10, further preferably 1 to 5, in particular
preferably t is 0 and q is 1; and the siloxane units in the square
brackets may form a block structure or a random structure.
[0079] In the formulas (6) to (9), R.sup.1 is, independently of
each other, a monovalent hydrocarbon group having 1 to 18,
preferably 1 to 12, carbon atoms; and optionally having an oxygen,
halogen, nitrogen or sulfur atom. R.sup.2 is, independently of each
other, a hydrogen atom or R.sup.1. R.sup.3 is, independently of
each other, R.sup.1 or a group represented by --OX. Q is,
independently of each other, R.sup.1, an --OX group, or a group
represented by the aforesaid formula (8). Examples of R.sup.1
include the same groups as described for the aforesaid formulas (2)
to (4). In particular, R.sup.1 is a monovalent aromatic hydrocarbon
group having 6 to 18, preferably 6 to 12 carbon atoms. The
preferred monovalent aromatic hydrocarbon group is phenyl, benzyl,
2-phenylethyl, 2-phenylpropyl, tolyl, xylyl, mesityl,
4-ethylphenyl, naphthyl and biphenyl groups. Among these, phenyl,
benzyl, 2-phenylethyl, 2-phenylpropyl and tolyl groups are
preferred. In particular, it is preferred that both R.sup.1 and
R.sup.2 are phenyl, benzyl, 2-phenylethyl, 2-phenylpropyl or tolyl
group.
[0080] In the formulas (6) to (9), X is, independently of each
other, an alkyl group having 1 to 10, preferably 1 to 8 carbon
atoms or an alkoxyalkyl group having 2 to 10, preferably 2 to 8
carbon atoms. Examples of X include alkyl groups such as methyl,
ethyl, propyl, butyl and octyl groups; and alkoxyalkyl group such
as methoxymethyl, methoxyethyl and ethoxymethyl groups. Among
these, --OX group is preferably a group selected from methoxy,
ethoxy, isopropoxy, t-butoxy and phenoxy groups. In particular, a
methoxy group is preferred.
[0081] In the formula (9), R.sup.5 is, independently of each other,
a hydrogen atom, alkenyl group having 2 to 10 carbon atoms, or
3-glycidyloxypropyl, provided that when at least one R.sup.3
bonding to the silicon atom at the end is an --OX group, R.sup.5
bonded to this silicon atom is not a hydrogen atom.
[0082] Examples of the compound represented by the formula (6)
include the following compounds.
##STR00013##
wherein d is an integer of from 4 to 20.
##STR00014##
wherein d is an integer of from 4 to 20.
##STR00015##
wherein d is an integer of from 4 to 20.
##STR00016##
wherein a is an integer of from 1 to 20, d'=d, and p is an integer
of 1 or more.
##STR00017##
wherein d is an integer of from 1 to 20, d'=d, and p is an integer
of 1 or more.
[0083] Examples of the compound represented by the formula (7)
include the following compound.
##STR00018##
[0084] Examples of the compound represented by the formula (9)
include the following compound.
##STR00019##
[0085] The novel organic silicon compound obtained in the present
method is characterized in that at least one hydrogen atom and at
least one --OX group bond on one and the same silicon atom. The
organic silicon compound is useful as an intermediate of various
reactive polyorganosiloxanes. Further, the present organic silicon
compound is added in a silicone elastomer or applied on a substrate
to provide adhesiveness to the silicone elastomer or the substrate.
Therefore, the organic silicon compound is useful as an adhesion
improving agent.
EXAMPLES
[0086] The present invention will be explained below in further
detail with reference to a series of the Examples, though the
present invention is in no way limited by these Examples. In the
following descriptions, the term "part" refers to "part by
mass".
[0087] The weight average molecular weight (Mw) described in the
Examples was determined by a gel permeation chromatography, GPC,
and reduced to polystyrene. Conditions in GPC were as follows.
[GPC Conditions]
Solvent: Tetrahydrofuran
[0088] Flow rate: 0.6 mL/min. Columns, all provided by TOSOH
Cop.:
TSK Guardcolumn SuperH-L
[0089] TSKgel SuperH4000 (6.0 mmI.D..times.15 cm.times.1) TSKgel
SuperH3000 (6.0 mmI.D..times.15 cm.times.1) TSKgel SuperH2000 (6.0
mmI.D..times.15 cm.times.2) Column Temperature: 40 degrees C.
Injection Volume: 20 .mu.l of a 0.5% by weight solution in THF.
Detector: Differential refractive index detector (RI)
[0090] 0.2 g of the product obtained in the Examples was dissolved
in 15 g of 1-butanol and, then, 20 g of an aqueous 20 wt % sodium
hydroxide solution were added at 25 degrees C. with stirring. The
amount of a generated hydrogen gas, V.sub.H [dm.sup.3], was applied
on the following equation of gas state to obtain an amount of the
Si--H group.
Amount of the Si--H group [mol/100 g]=1/{(0.2 [g]).times.0.0821
[atmdm.sup.3mol.sup.-1K.sup.-1].times.(25+273 [K])/(1
[atm]).times.V.sub.B [dm.sup.3]}
[0091] The amount of the alkoxy group, mol/100 g, in the following
Example was obtained by determining the .sup.1H-NMR spectrum at 400
MHz of the product and calculating an integral value for hydrogen
atoms, based on dimethylsulfoxide as an internal standard.
[0092] The compounds used in the Examples are as follows.
##STR00020## ##STR00021##
Example 1
[0093] 216.31 g (1.0 mol) of diphenyl silane diol (DPS), 484.77 g
(4.0 mols) of trimethoxysilane (TMS), 200 g of toluene and 60 g of
methanol were mixed, and heated to 30 degrees C. with stirring.
Then, 0.02 mol of Mg(OH).sub.2 was added to the mixture and heated
at 30 degrees C. for 8 hours to react. Mg(OH).sub.2 was removed by
filtration, and toluene, methanol and the unreacted TMS were
distilled off under a reduced pressure to obtain a
polyorganosiloxane mainly comprising a compound represented by the
following formula (10):
##STR00022##
Its Mw was 507, an amount of the Si--H group was 0.50 mol/100 g,
and an amount of the alkoxy group was 0.99 mol/100 g. The
.sup.1H-NMR spectrum and GPC chart of the product obtained are as
shown in FIGS. 1 and 2. The ratios of the integration values of the
functional groups obtained by analyzing the .sup.1H-NMR spectrum
are as follows. --OCH.sub.3:6.0 (3.3 to 3.8 ppm) --SiH:1.0 (4.3 to
4.6 ppm) --C.sub.6H.sub.5:5.1 (7.2 to 8.0 ppm)
Example 2
[0094] 216.31 g (1.0 mol) of diphenyl silane diol (DPS), 424.80 g
(4.0 mols) of dimethoxymethylsilane (DMS), 200 g of toluene and 60
g of methanol were mixed, and heated to 30 degrees C. with
stirring. Then, 0.02 mol of Mg(OH).sub.2 was added to the mixture
and heated at 30 degrees C. for 16 hours to react. The Mg(OH).sub.2
was removed by filtration, and toluene, methanol and the unreacted
DMS were distilled off under a reduced pressure to obtain a
polyorganosiloxane mainly comprising a compound represented by the
following formula (11):
##STR00023##
Its Mw was 462, an amount of the Si--H group was 0.55 mol/100 g,
and an amount of the alkoxy group was 0.55 mol/100 g. The ratios of
the integration values of the functional groups obtained by
analyzing the .sup.1H-NMR spectrum are as follows. --CH.sub.3:3.0
(-0.3 to 0.3 ppm) --OCH.sub.3:3.0 (3.3 to 3.8 ppm) --SiH:1.0 (4.3
to 4.6 ppm) --C.sub.6H.sub.5: 5.0 (7.2 to 8.0 ppm)
Example 3
[0095] 259.57 g (1.0 mol) of diphenyl silane diol (DPS), 200 g of
toluene and 60 g of tetrahydrofuran were mixed, and heated to 30
degrees C. with stirring. Then, 0.02 mol of Ca(OH).sub.2 was added
to the mixture and heated at 30 degrees C. for 16 hours to react.
The mixture was cooled to 10 degrees C., 242.38 g (2.0 mols) of
trimethoxysilane (TMS) was added thereto and reacted at 10 degrees
C. for 8 hours. The Ca(OH).sub.2 was removed by filtration, and
toluene, tetrahydrofuran and the unreacted TMS were distilled off
under a reduced pressure to obtain a polyorganosiloxane mainly
comprising a compound represented by the following formula
(12).
##STR00024##
Its Mw was 916, an amount of the Si--H group was 0.33 mol/100 g,
and an amount of the alkoxy group was 0.65 mol/100 g. The ratios of
the integration values of the functional groups obtained by
analyzing the .sup.1H-NMR spectrum are as follows. --OCH.sub.3:5.9
(3.3 to 3.8 ppm) --SiH:1.0 (4.3 to 4.6 ppm) --C.sub.6H.sub.5:15.2
(7.2 to 8.0 ppm)
Example 4
[0096] 259.57 g (1.2 mols) of diphenyl silane diol (DPS), 104.23 g
(0.86 mol) of trimethoxysilane (TMS) and 100 g of toluene were
mixed, and heated to 30 degrees C. with stirring. Then, 0.01 mol of
Ca(OH).sub.2 was added to the mixture and heated at 30 degrees C.
for 4 hours to react. Subsequently, 100 g of toluene were added to
the reaction mixture, Ca (OH).sub.2 was removed by filtration, and
toluene was distilled off under a reduced pressure to obtain a
polyorganosiloxane. Its Mw was 5008, an amount of the Si--H group
was 0.33 mol/100 g, and an amount of the alkoxy group was 0.02
mol/100 g. The ratios of the integration values of the functional
groups obtained by analyzing the .sup.1H-NMR spectrum are as
follows.
--OCH.sub.3:0.18 (3.3 to 3.8 ppm) --SiH:1.0 (4.3 to 4.6 ppm)
--C.sub.6H.sub.5:14.0 (7.2 to 8.0 ppm)
Example 5
[0097] 166.33 g (1.0 mol) of 1,1,3,3-tetramethyldisiloxane-1,3-diol
(TDS), 484.77 g (4.0 mols) of trimethoxysilane (TMS) and 60 g of
methanol were mixed, and cooled to 0 degrees C. with stirring.
Then, 0.01 mol of Sr(OH).sub.2 was added to the mixture and reacted
at 0 degrees C. for 8 hours. Sr(OH).sub.2 was removed by
filtration. 10 g of a cation exchange resin, Diaion WK-40, ex.
Mitsubishi Chemical Corporation, was added to the mixture, which
was shaken for 30 minutes and, then, the cation exchange resin was
removed by filtration. Methanol and the unreacted TMS were
distilled off under a reduced pressure to obtain a
polyorganosiloxane mainly comprising a compound represented by the
following formula (13).
##STR00025##
Its Mw was 392, an amount of the Si--H group was 0.57 mol/100 g,
and an amount of the alkoxy group was 1.13 mol/100 g. The ratios of
the integration values of the functional groups obtained by
analyzing the .sup.1H-NMR spectrum are as follows. --CH.sub.3:6.1
(-0.3 to 0.3 ppm) --OCH.sub.3:5.95 (3.3 to 3.8 ppm) --SiH:1.0 (4.3
to 4.6 ppm)
Example 6
[0098] 240 g of linear dimethylsilicone oil having OH groups at the
both terminals, Mw 2400, and 242.38 g (2.0 mols) of
trimethoxysilane (TMS) were mixed, and heated to 60 degrees C. with
stirring. Then, 0.005 mol of Ba(OH).sub.2 was added to the mixture
and reacted at 0 degrees C. for 8 hours. Ba(OH).sub.2 was removed
by filtration. 10 g of a cation exchange resin, Diaion WK-40, ex.
Mitsubishi Chemical Corporation, was added to the mixture, which
was shaken for 30 minutes and, then, the cation exchange resin was
removed by filtration. The unreacted TMS was distilled off under a
reduced pressure to obtain a polyorganosiloxane. Its Mw was 2695,
an amount of the Si--H group was 0.08 mol/100 g, and an amount of
the alkoxy group was 0.17 mol/100 g. The ratios of the integration
values of the functional groups obtained by analyzing the
.sup.1H-NMR spectrum are as follows.
--CH.sub.3:102.2 (-0.3 to 0.3 ppm) --OCH.sub.3:6.4 (3.3 to 3.8 ppm)
--SiH:1.0 (4.3 to 4.6 ppm)
Example 7
[0099] 389.36 g (1.5 mols) of diphenyl silane diol (DPS), 118.17 g
(0.5 mol) of 3-glycidyloxypropyltrimethoxysilane (GTS) and 400 g of
toluene were mixed, and heated to 80 degrees C. with stirring.
Then, 1.0 mol of Al(OH).sub.3 was added to the mixture and reacted
at 80 degrees C. for 24 hours. After the reaction, the mixture was
cooled to 30 degrees C., 363.58 g (3.0 mols) of trimethoxysilane
(TMS) and 0.04 mol of Mg(OH).sub.2 were added and, then, reacted at
30 degrees C. for 16 hours. The Al(OH).sub.3 and Mg(OH).sub.2 were
removed by filtration, and toluene and the unreacted TMS were
distilled off under a reduced pressure to obtain a
polyorganosiloxane.
Its Mw was 1175, an amount of the Si--H group was 0.26 mol/100 g,
and an amount of the alkoxy group was 0.51 mol/100 g. The ratios of
the integration values of the functional groups obtained by
analyzing the .sup.1H-NMR spectrum are as follows.
--C.sub.3H.sub.6OCH.sub.2CH(O)CH.sub.2: 3-Glycidyloxypropyl
group:3.8 (0.3 to 3.3 ppm) --OCH.sub.3:5.9 (3.3 to 3.8 ppm)
--SiH:1.0 (4.3 to 4.6 ppm) --C.sub.6H.sub.5:10.3 (7.2 to 8.0
ppm)
Example 8
[0100] 389.36 g (1.5 mols) of diphenyl silane diol (DPS), 74.12 g
(0.5 mol) of vinyltrimethoxysilane (VTS) and 400 g of toluene were
mixed, and heated to 80 degrees C. with stirring. Then, 0.5 mol of
Fe(OH).sub.3 was added to the mixture and reacted at 80 degrees C.
for 12 hours. After the reaction, the mixture was cooled to 30
degrees C., 484.77 g (4.0 mols) of trimethoxysilane (TMS) and 0.04
mol of Mg(OH).sub.2 were added and, then, reacted at 30 degrees C.
for 16 hours. The Fe(OH).sub.3 and Mg(OH).sub.2 were removed by
filtration, and toluene and the unreacted TMS were distilled off
under a reduced pressure to obtain a polyorganosiloxane. Its Mw was
1090, an amount of the Si--H group was 0.26 mol/100 g, and an
amount of the alkoxy group was 0.48 mol/100 g. The ratios of the
integration values of the functional groups obtained by analyzing
the .sup.1H-NMR spectrum are as follows.
--OCH.sub.3:5.5 (3.3 to 3.8 ppm) --SiH:1.0 (4.3 to 4.6 ppm)
--SiCH.dbd.CH.sub.2:3.2 (5.5 to 6.5 ppm) --C.sub.6H.sub.5:10.7 (7.2
to 8.0 ppm)
Example 9
[0101] 49.90 g (0.3 mol) of 1,1,3,3-tetramethyldisiloxane-1,3-diol
(TDS) and 15.22 g (0.1 mol) of tetramethoxysilane (TMOS) were
mixed, and heated to 80 degrees C. with stirring. Then, 0.01 mol of
Mg(OH).sub.2 was added to the mixture and reacted for 8 hours,
while distilling off methanol. After the reaction, the mixture was
cooled to 30 degrees C., 48.48 g (0.4 mol) of trimethoxysilane
(TMS) were added thereto and, then, reacted at 30 degrees C. for 8
hours. The Mg(OH).sub.2 was removed by filtration, and the
unreacted TMS was distilled off under a reduced pressure to obtain
a polyorganosiloxane. Its Mw was 989, an amount of the Si--H group
was 0.24 mol/100 g, and an amount of the alkoxy group was 0.60
mol/100 g. The ratios of the integration values of the functional
groups obtained by analyzing the .sup.1H-NMR spectrum are as
follows.
--CH.sub.3:14.8 (-0.3 to 0.3 ppm) --OCH.sub.3:7.5 (3.3 to 3.8 ppm)
--SiH:1.0 (4.3 to 4.6 ppm)
Example 10
[0102] 166.33 g (1.0 mol) of 1,1,3,3-tetramethyldisiloxane-1,3-diol
(TDS), 122.05 g (1.05 mols) of dimethylmethoxyvinylsilane (DVS) and
200 g of tetrahydrofuran were mixed, and heated to 30 degrees C.
with stirring. Then, 0.02 mol of Ca(OH).sub.2 was added to the
mixture and heated at 30 degrees for 8 hours to react. Ca(OH).sub.2
was removed by filtration. 10 g of a cation exchange resin, Diaion
WK-40, ex. Mitsubishi Chemical Corporation, was added to the
mixture, which was shaken for 30 minutes and, then, the cation
exchange resin was removed by filtration. The unreacted DVS were
distilled off under a reduced pressure and, then, 242.38 g (2 mols)
of trimethoxysilane (TMS) and 0.02 mol of Mg(OH).sub.2 were added
thereto and heated at 30 degrees for 8 hours with stirring to
react. The Mg(OH).sub.2 was removed by filtration, and the
unreacted TMS was distilled off under a reduced pressure to obtain
a polyorganosiloxane mainly comprising a compound represented by
the following formula (14).
##STR00026##
Its Mw was 412, an amount of the Si--H group was 0.25 mol/100 g,
and an amount of the alkoxy group was 0.48 mol/100 g. The ratios of
the integration values of the functional groups obtained by
analyzing the .sup.1H-NMR spectrum are as follows. --CH.sub.3:18.1
(-0.3 to 0.3 ppm) --OCH.sub.3:5.8 (3.3 to 3.8 ppm) --SiH:1.0 (4.3
to 4.6 ppm) --SiCH.dbd.CH.sub.2:3.0 (5.5 to 6.5 ppm)
Example 11
[0103] 216.31 g (1.0 mol) of diphenyl silane diol (DPS) and 195.49
g (0.8 mol) of dimethoxydiphenylsilane (DMPS) were mixed, and
heated to 80 degrees C. with stirring. Then, 0.02 mol of
Ca(OH).sub.2 was added to the mixture and reacted for 16 hours,
while distilling off methanol. The mixture was cooled to 10 degrees
C., 96.95 g (0.8 mol) of trimethoxysilane (TMS) was added thereto
and, then, reacted at 10 degrees C. for 16 hours. The Ca(OH).sub.2
was removed by filtration, and the unreacted TMS was distilled off
under a reduced pressure to obtain a polyorganosiloxane mainly
comprising a compound represented by the following formula
(15).
##STR00027##
Its Mw was 2521, an amount of the Si--H group was 0.08 mol/100 g,
and an amount of the alkoxy group was 0.17 mol/100 g. The ratios of
the integration values of the functional groups obtained by
analyzing the .sup.1H-NMR spectrum are as follows. --OCH.sub.3:6.3
(3.3 to 3.8 ppm) --SiH:1.0 (4.3 to 4.6 ppm) --C.sub.6H.sub.5:57.2
(7.2 to 8.0 ppm)
Example 12
[0104] 324.46 g (1.5 mols) of diphenyl silane diol (DPS), 212.4 g
(2.0 mols) of dimethoxymethylsilane (DMS) and 100 g of toluene were
mixed, and heated to 60 degrees C. with stirring. Then, 0.05 mol of
Mg(OH).sub.2 was added to the mixture and reacted at 60 degrees C.
for 40 hours. The Mg(OH).sub.2 was removed by filtration, and
toluene and the unreacted DMS were distilled off under a reduced
pressure to obtain a polyorganosiloxane mainly comprising a
compound represented by the following formula (16).
##STR00028##
Its Mw was 811, an amount of the Si--H group was 0.40 mol/100 g,
and an amount of the alkoxy group was 0.24 mol/100 g. The ratios of
the integration values of the functional groups obtained by
analyzing the .sup.1H-NMR spectrum are as follows. --CH.sub.3:3.0
(-0.3 to 0.3 ppm) --OCH.sub.3:1.8 (3.3 to 3.8 ppm) --SiH:1.0 (4.3
to 4.6 ppm) --C.sub.6H.sub.5:7.1 (7.2 to 8.0 ppm)
Example 13
[0105] 244.36 g (1.0=1) of di-o-tolylsilanediol (DTS), 484.77 g
(4.0 mols) of trimethoxysilane (TMS), 200 g of toluene and 60 g of
methanol were mixed, and heated to 30 degrees C. with stirring.
Then, 0.02 mol of Mg(OH).sub.2 was added to the mixture and reacted
at 30 degrees C. for 8 hours. The Mg(OH).sub.2 was removed by
filtration, and toluene, methanol and the unreacted TMS were
distilled off under a reduced pressure to obtain a
polyorganosiloxane mainly comprising a compound represented by the
following formula (17).
##STR00029##
Its Mw was 540, an amount of the Si--H group was 0.47 mol/100 g,
and an amount of the alkoxy group was 0.94 mol/100 g. The ratios of
the integration values of the functional groups obtained by
analyzing the .sup.1H-NMR spectrum are as follows.
--C.sub.6H.sub.4--CH.sub.3:3.0 (2.0 to 3.0 ppm) --OCH.sub.3:6.0
(3.3 to 3.8 ppm) --SiH:1.0 (4.3 to 4.6 ppm)
--C.sub.6H.sub.4--CH.sub.3:4.1 (7.2 to 8.0 ppm)
Example 14
[0106] 300.46 g (1.0 mol) of di-2-phenylethylsilanediol (DPES),
484.77 g (4.0 mols) of trimethoxysilane (TMS), 300 g of toluene and
100 g of methanol were mixed, and cooled to 0 degrees C. with
stirring. Then, 0.01 mol of Mg(OH).sub.2 was added to the mixture
and reacted at 0 degrees C. for 8 hours. The Mg(OH).sub.2 was
removed by filtration, and toluene, methanol and the unreacted TMS
were distilled off under a reduced pressure to obtain a
polyorganosiloxane mainly comprising a compound represented by the
following formula (18).
##STR00030##
Its Mw was 540, an amount of the Si--H group was 0.44 mol/100 g,
and an amount of the alkoxy group was 0.86 mol/100 g. The ratios of
the integration values of the functional groups obtained by
analyzing the .sup.1H-NMR spectrum are as follows.
--CH.sub.2CH.sub.2--C.sub.6H.sub.5:4.0 (0.3 to 2.5 ppm)
--OCH.sub.3:6.0 (3.3 to 3.8 ppm) --SiH:1.0 (4.3 to 4.6 ppm)
--C.sub.6H.sub.5:5.0 (7.2 to 8.0 ppm)
Example 15
[0107] 64.89 g (0.3 mol) of diphenylsilanediol (DPS) and 12.72 g
(0.105 mol) of trimethoxysilane (TMS) were mixed, and cooled to 0
degrees C. with stirring. Then, 0.5 mol of Mg(OH).sub.2 was added
to the mixture, reacted at 0 degrees C. for 4 hours and, then,
heated at 60 degrees C. for 4 hours to react. Further, 72.72 g
(0.6=1) of trimethoxysilane (TMS) was added to the reaction mixture
and heated at 60 degrees for 8 hours to react. The Mg(OH).sub.2 was
removed by filtration, and the unreacted TMS was distilled off
under a reduced pressure to obtain a polyorganosiloxane mainly
comprising a compound represented by the following formula
(19).
##STR00031##
Its Mw was 1193, an amount of the Si--H group was 0.44 mol/100 g,
and an amount of the alkoxy group was 0.62 mol/100 g. The ratios of
the integration values of the functional groups obtained by
analyzing the .sup.1H-NMR spectrum are as follows. --OCH.sub.3:4.2
(3.3 to 3.8 ppm) --SiH:1.0 (4.3 to 4.6 ppm) --C.sub.6H.sub.5:7.9
(7.2 to 8.0 ppm)
[0108] As shown in the aforesaid Examples, a polyorganosiloxane
having a hydrosilyl group, i.e., --SiH, and an alkoxysilyl group,
i.e., --SiOX, in the molecule are prepared by condensation reacting
an organic silicon compound having a silanol group, i.e., --SiOH,
and/or an alkoxysilyl group, i.e., --SiOX, with each other in the
presence of a metal compound catalyst with less dehydrogenation of
the hydrosilyl group during the reaction.
INDUSTRIAL APPLICABILITY
[0109] According to the present invention, a polyorganosiloxane
having a hydrosilyl group, i.e., --SiH, and an alkoxysilyl group,
i.e., --SiOX, in the molecule are prepared. The polyorganosiloxane
has a hydrosilyl group which may undergo a hydrosilation and an
alkoxysilyl group which may undergo a hydrolytic condensation
reaction and, therefore, the polyorganosiloxane has various
applications and is very useful as an adhesion improving agent for
a silicone elastomer adhesive composition, an adhesive component in
a primer and an intermediate of a polyorganosiloxane modified with
various organic groups.
* * * * *