U.S. patent application number 10/634859 was filed with the patent office on 2004-02-12 for production process for silsesquioxane derivative and silsesquioxane derivative.
Invention is credited to Ito, Kenya, Morimoto, Yoshitaka, Oikawa, Hisaoi, Ootake, Nobumasa, Watanabe, Kenichi, Yamahiro, Mikio.
Application Number | 20040030084 10/634859 |
Document ID | / |
Family ID | 31497645 |
Filed Date | 2004-02-12 |
United States Patent
Application |
20040030084 |
Kind Code |
A1 |
Morimoto, Yoshitaka ; et
al. |
February 12, 2004 |
Production process for silsesquioxane derivative and silsesquioxane
derivative
Abstract
If chlorosilane is used in order to introduce a functional group
into a silsesquioxane derivative having Si--OH, by-produced
hydrogen chloride has to be treated. However, if alkoxysilane is
substituted for chlorosilane, the long reaction time is required. A
production process for a silsesquioxane derivative represented by
Formula (2) characterized by using a compound represented by
Formula (1), has been developed in order to solve such problems of
conventional techniques. 1 In Formula (1) and Formula (2), R is
hydrogen, an alkyl, an aryl, or an arylalkyl; M is an alkaline
metal atom; and X is hydrogen, chlorine, a functional group, or a
group having a functional group.
Inventors: |
Morimoto, Yoshitaka;
(Yokohama, JP) ; Ito, Kenya; (Yokohama, JP)
; Oikawa, Hisaoi; (Yokohama, JP) ; Yamahiro,
Mikio; (Yokohama, JP) ; Watanabe, Kenichi;
(Yokohama, JP) ; Ootake, Nobumasa; (Yokohama,
JP) |
Correspondence
Address: |
WENDEROTH, LIND & PONACK, L.L.P.
2033 K STREET N. W.
SUITE 800
WASHINGTON
DC
20006-1021
US
|
Family ID: |
31497645 |
Appl. No.: |
10/634859 |
Filed: |
August 6, 2003 |
Current U.S.
Class: |
528/10 |
Current CPC
Class: |
C08G 77/04 20130101 |
Class at
Publication: |
528/10 |
International
Class: |
C08G 077/00 |
Foreign Application Data
Date |
Code |
Application Number |
Aug 7, 2002 |
JP |
2002-228914 |
May 7, 2003 |
JP |
2003-129349 |
Claims
1. A production process for a silsesquioxane derivative represented
by Formula (2), characterized by using a silicon compound
represented by Formula (1): 32wherein in Formula (1), each of R's
is a group selected independently from hydrogen, the group of
alkyls having 1 to 45 carbon atoms, the group of substituted or
non-substituted arylalkyls; in the alkyl having 1 to 45 carbon
atoms, optional hydrogen may be replaced by fluorine, and optional
--CH.sub.2-- may be replaced by --O--, --CH.dbd.CH--, cycloalkylene
or cycloalkenylene; in alkylene of the substituted or
non-substituted arylalkyl, optional hydrogen may be replaced by
fluorine, and optional --CH.sub.2-- may be replaced by --O--,
--CH.dbd.CH-- or cycloalkylene; and M is a monovalent alkaline
metal atom; in Formula (2), R has the same meaning as that of R in
Formula (1); and X is hydrogen, chlorine, a functional group or a
group having a functional group; provided that X is not any of a
group having a hydroxy group which is not bonded directly to Si, a
group having alkanoyloxy, a group having halogenated sulfonyl and a
group having an .alpha.-haloester group.
2. The production process according to claim 1, wherein each of R's
in Formula (1) is a group selected independently from hydrogen, the
group of alkyls in which the number of carbon atoms is 1 to 20,
optional hydrogen may be replaced by fluorine and optional
--CH.sub.2-- may be replaced by --O-- or cycloalkylene, the group
of alkenyls in which the number of carbon atoms is 2 to 20,
optional hydrogen may be replaced by fluorine and optional
--CH.sub.2-- may be replaced by --O-- or cycloalkylene, the group
of alkyls in which the number of carbon atoms is 1 to 10 and at
least one --CH.sub.2-- is replaced by cycloalkenylene, the group of
phenyls in which optional hydrogen on the benzene ring may be
replaced by halogen or alkyl having 1 to 10 carbon atoms, the group
of phenylalkyls in which optional hydrogen on the benzene ring may
be replaced by halogen or alkyl having 1 to 10 carbon atoms, and
naphthyl; in the alkyl having 1 to 10 carbon atoms which is a
substituent on the benzene ring, optional hydrogen may be replaced
by fluorine, and optional --CH.sub.2-- may be replaced by --O--,
--CH.dbd.CH--, cycloalkylene or phenylene; and in alkylene of the
phenylalkyl, the number of carbon atoms is 1 to 12 , optional
hydrogen may be replaced by fluorine, and optional --CH.sub.2-- may
be replaced by --O--, --CH.dbd.CH-- or cycloalkylene.
3. The production process according to claim 1, wherein each of R's
in Formula (1) is a group selected independently from the group of
alkyls in which the number of carbon atoms is 1 to 10, optional
hydrogen may be replaced by fluorine and optional --CH.sub.2-- may
be replaced by --O-- or cycloalkylene, the group of phenyls in
which optional hydrogen on the benzene ring may be replaced by
halogen, methyl or methoxy, the group of phenylalkyls in which
optional hydrogen on the benzene ring may be replaced by fluorine,
alkyl having 1 to 4 carbon atoms, vinyl or methoxy, and naphthyl;
and in alkylene of the phenylalkyl, the number of carbon atoms is 1
to 8, and optional --CH.sub.2-- may be replaced by --O--,
--CH.dbd.CH-- or cycloalkylene.
4. The production process according to claim 1, wherein all of R's
in Formula (1) are the same group selected from the group of alkyls
in which the number of carbon atoms is 1 to 10, optional hydrogen
may be replaced by fluorine and optional --CH.sub.2-- may be
replaced by --O-- or cycloalkylene, the group of phenyls in which
optional hydrogen on the benzene ring may be replaced by halogen,
methyl or methoxy, the group of phenylalkyls in which optional
hydrogen on the benzene ring may be replaced by fluorine, alkyl
having 1 to 4 carbon atoms, vinyl or methoxy, and naphthyl; and in
alkylene of the phenylalkyl, the number of carbon atoms is 1 to 8,
and optional --CH.sub.2-- may be replaced by --O--, --CH.dbd.CH--
or cycloalkylene.
5. The production process according to any one of claims 1 to 4,
wherein M in Formula (1) defined in claim 1 is Na.
6. The production process according to any one of claims 1 to 4,
wherein M in Formula (1) defined in claim 1 is Na, and a step for
reacting the silicon compound represented by Formula (1) with a
silicon compound represented by Formula (3) is included therein:
33wherein X has the same meaning as that of X in Formula (2)
defined claim 1.
7. The production process according to claim 6, wherein X is
hydrogen, chlorine, alkenyl or a group having any of halogen,
alkenyl, cycloalkenyl, cyano, alkoxy, phenoxy, acryloyloxy,
methacryloyloxy and glycidyloxy; provided that a group having
halogenated sulfonyl and a group having an .alpha.-haloester group
are not included in the group having halogen.
8. A silsesquioxane derivative represented by Formula (2):
34wherein each of R's is a group selected independently from the
group of alkyls in which the number of carbon atoms is 1 to 20, at
least one hydrogen is replaced by fluorine and optional
--CH.sub.2-- may be replaced by --O--, the group of phenyls in
which optional hydrogen on the benzene ring may be replaced by
halogen or alkyl having 1 to 10 carbon atoms, the group of
phenylalkyls in which optional hydrogen on the benzene ring may be
replaced by halogen or alkyl having 1 to 10 carbon atoms, and
naphthyl; in the alkyl having 1 to 10 carbon atoms which is a
substituent on the benzene ring, optional hydrogen may be replaced
by fluorine, and optional --CH.sub.2-- may be replaced by --O--,
--CH.dbd.CH--, cycloalkylene or phenylene; in alkylene of the
phenylalkyl, the number of carbon atoms is 1 to 12, optional
hydrogen may be replaced by fluorine, and optional --CH.sub.2-- may
be replaced by --O--, --CH.dbd.CH-- or cycloalkylene; and X is
hydrogen, chlorine, a functional group or a group having a
functional group; provided that X is not any of a group having a
hydroxy group which is not bonded directly to Si, a group having
alkanoyloxy, a group having halogenated sulfonyl and a group having
an .alpha.-haloester group.
9. The silsesquioxane derivative according to claim 8, wherein each
of R's in Formula (2) is a group selected independently from the
group of alkyls in which the number of carbon atoms is 1 to 10, at
least one hydrogen is replaced by fluorine and optional
--CH.sub.2-- may be replaced by --O--, the group of phenyls in
which optional hydrogen on the benzene ring may be replaced by
halogen, methyl or methoxy, the group of phenylalkyls in which
optional hydrogen on the benzene ring may be replaced by fluorine,
alkyl having 1 to 4 carbon atoms, vinyl or methoxy, and naphthyl;
and in alkylene of the phenylalkyl, the number of carbon atoms is 1
to 8, and optional --CH.sub.2-- may be replaced by --O--,
--CH.dbd.CH-- or cycloalkylene.
10. The silsesquioxane derivative according to claim 8, wherein all
of R's are the same group selected from the group of alkyls in
which the number of carbon atoms is 1 to 10, at least one hydrogen
is replaced by fluorine and optional --CH.sub.2-- may be replaced
by --O--, the group of phenyls in which optional hydrogen on the
benzene ring may be replaced by halogen, methyl or methoxy, the
group of phenylalkyls in which optional hydrogen on the benzene
ring may be replaced by fluorine, alkyl having 1 to 4 carbon atoms,
vinyl or methoxy, and naphthyl; and in alkylene of the phenylalkyl,
the number of carbon atoms is 1 to 8, and optional --CH.sub.2-- may
be replaced by --O--, --CH.dbd.CH-- or cycloalkylene.
11. The silsesquioxane derivative according to claim 8, wherein all
of R's are the same alkyl in which the number of carbon atoms is 1
to 10, at least one hydrogen is replaced by fluorine, and one
--CH.sub.2-- may be replaced by --O--.
12. The silsesquioxane derivative according to claim 8, wherein all
of R's in Formula (2) are phenyl.
13. The silsesquioxane derivative according to claim 8, wherein all
of R's in Formula (2) are trifluoropropyl.
14. The silsesquioxane derivative according to claim 8, wherein all
of R's in Formula (2) are
tridecafluoro-1,1,2,2-tetrahydrooctyl.
15. The silsesquioxane derivative according to any one of claims 8
to 14, wherein X in Formula (2) defined in claim 8 is hydrogen,
chlorine, a hydroxy group, alkenyl, or a group having any of
halogen, alkoxy, phenoxy, polyalkyleneoxy, --COOH,
2-oxapropane-1,3-dioyl, alkoxycarbonyl, alkenyloxycarbonyl,
oxiranyl, 3,4-epoxycyclohexyl, oxetanyl, oxetanylene, --NH--,
--NH.sub.2, --CN, --NCO, alkenyl, alkynyl, cycloalkenyl,
acryloyloxy, methacryloyloxy, --SH and --PH.sub.2, provided that X
is not any of a group having a hydroxy group which is not bonded
directly to Si, a group having alkanoyloxy, a group having
halogenated sulfonyl and a group having an .alpha.-haloester
group.
16. A silsesquioxane derivative represented by Formula (5):
35wherein Ph is phenyl.
17. A silsesquioxane derivative represented by Formula (6):
36wherein Ph is phenyl.
18. A silsesquioxane derivative represented by Formula (1-2):
37wherein F.sup.3 is --CH.sub.2CH.sub.2CF.sub.3.
19. A silsesquioxane derivative represented by Formula (14):
38wherein F.sup.3 is --CH.sub.2CH.sub.2CF.sub.3.
20. A silsesquioxane derivative represented by Formula (1-5):
39wherein F.sup.13 is --CH.sub.2CH.sub.2(CF.sub.2).sub.5CF.sub.3.
Description
FIELD OF THE INVENTION
[0001] The present invention relates to a production process for a
silsesquioxane derivative having a functional group and a
silsesquioxane derivative obtained by this production process.
BACKGROUND OF THE INVENTION
[0002] A silsesquioxane derivative has an excellent heat resistance
and weatherability, and therefore it is expected to be applied to a
modifier for a thermoplastic resin, a interlayer dielectric, a
sealing material, a flame retardant and an additive for a coating
material. It has so far been tried to introduce various functional
groups into silsesquioxane. Disclosed in Literature 1 is, for
example, a process in which a compound having Si--OH shown below is
synthesized and in which various functional groups are then
introduced by reacting the compound with chlorosilanes. Disclosed
in Literature 4 is a process in which a small amount of a basic
compound is added when a compound having Si--OH shown below is
reacted with trialkoxysilane in an organic solvent. 2
[0003] A in Formula (a) is the same group selected from hydrogen,
methyl, ethyl, 2-methylpropyl, cyclohexyl, cyclopentyl, phenyl and
vinylhexyl.
[0004] The compound represented by Formula (a) can be synthesized
by hydrolyzing chlorosilane and further ripening the mixture.
Disclosed by Frank J. Feher et al. in California University is, for
example, a process in which cyclopentyltrichlorosilane is reacted
at a room temperature or a refluxing temperature in a water-acetone
mixed solvent and in which the reaction mixture is further ripened
for 2 weeks (Literature 2 and Literature 3).
[0005] Literature 1: U.S. Pat. No. 5,484,867
[0006] Literature 2: Organometallics, 10, 2526-2528 (1991)
[0007] Literature 3: Chem. Eur. J, 3, No. 6, 900-903 (1997)
[0008] Literature 4: U.S. patent application Ser. No. 2003/0055193
A1
[0009] However, in order to industrially utilize them, the compound
represented by Formula (a) can preferably be produced at a higher
yield for shorter time with less by-products than those of such
publicly known techniques. The process in which a functional group
is introduced by reacting the compound represented by Formula (a)
with chlorosilane has the industrial difficulty that by-produced
hydrogen chloride has to be treated. Hydrogen chloride is not
by-produced in the process of Literature 4, but it requires a very
long reacting time. An object of the present invention is to
provide a novel synthetic process for a functional group-containing
silsesquioxane derivative and a novel compound obtained by this
process in order to solve these problems.
SUMMARY OF THE INVENTION
[0010] First, a term used in the present invention shall be
explained. The term "optional" shows that not only the position but
also the number is optional. When the number is plural, they may be
replaced by different groups respectively. For example, when two of
--CH.sub.2-- are replaced by --O-- or --CH.dbd.CH-- in alkyl,
alkoxyalkenyl and alkenyloxyalkyl are included in the alkyl. Alkyl
and alkylene may be linear groups or branched groups in any cases.
This shall apply when optional hydrogen is replaced by halogen or a
cyclic group in these groups or when optional --CH.sub.2-- is
replaced by --O--, --CH.dbd.CH--, cycloalkylene or cycloalkenylene.
Any group of alkoxy, alkenylene, alkenyl and alkylene may be either
a linear group or a branched group in such case. It is not
preferred in the present invention either that a plurality of
adjacent --CH.sub.2-- is replaced by --O-- or that --CH.sub.2--
bonded to a silicon atom is replaced by --O--.
[0011] The present inventors have found a novel silicon compound
represented by Formula (1) described later as an intermediate which
can be used in order to achieve the object described above. The
production process of the present invention is characterized by
using the silicon compound represented by Formula (1) as the
intermediate. According to this process, the reactivity is high,
and less by-products are produced as compared with publicly known
techniques. A novel silsesquioxane derivative is provided by the
production process of the present invention. The silicon compound
represented by Formula (1) can not be synthesized by the process of
Feher described above. An example in which the compound represented
by Formula (1) is used to synthesize a silicon compound represented
by Formula (2) is not known as well. The present invention relates
to a novel process in which the compound represented by Formula (1)
is used to efficiently synthesize the compound represented by
Formula (2).
[0012] The present invention comprises the following
structures.
[0013] {1} A production process for a silsesquioxane derivative
represented by Formula (2), characterized by using a silicon
compound represented by Formula (1): 3
[0014] wherein in Formula (1), each of R's is a group selected
independently from hydrogen, the group of alkyls having 1 to 45
carbon atoms, the group of substituted or non-substituted aryls and
the group of substituted or non-substituted arylalkyls; in the
alkyl having 1 to 45 carbon atoms, optional hydrogen may be
replaced by fluorine, and optional --CH.sub.2-- may be replaced by
--O--, --CH.dbd.CH--, cycloalkylene or cycloalkenylene; in alkylene
of the substituted or non-substituted arylalkyl, optional hydrogen
may be replaced by fluorine, and optional --CH.sub.2-- may be
replaced by --O--, --CH.dbd.CH-- or cycloalkylene; and M is a
monovalent alkaline metal atom;
[0015] in Formula (2), R has the same meaning as that of R in
Formula (1); and X is hydrogen, chlorine, a functional group or a
group having a functional group;
[0016] provided that X is not any of a group having a hydroxy group
which is not bonded directly to Si, a group having alkanoyloxy, a
group having halogenated sulfonyl and a group having an
.alpha.-haloester group.
[0017] {2} The production process as-described in the item {1},
wherein each of R's in Formula (1) is a group selected
independently from hydrogen, the group of alkyls in which the
number of carbon atoms is 1 to 20, optional hydrogen may be
replaced by fluorine and optional --CH.sub.2-- may be replaced by
--O-- or cycloalkylene, the group of alkenyls in which the number
of carbon atoms is 2 to 20, optional hydrogen may be replaced by
fluorine and optional --CH.sub.2-- may be replaced by --O-- or
cycloalkylene, the group of alkyls in which the number of carbon
atoms is 1 to 10 and at least one --CH.sub.2-- is replaced by
cycloalkenylene, the group of phenyls in which optional hydrogen on
the benzene ring may be replaced by halogen or alkyl having 1 to 10
carbon atoms, the group of phenylalkyls in which optional hydrogen
on the benzene ring may be replaced by halogen or alkyl having 1 to
10 carbon atoms, and naphthyl; in the alkyl having 1 to 10 carbon
atoms which is a substituent on the benzene ring, optional hydrogen
may be replaced by fluorine, and optional --CH.sub.2-- may be
replaced by --O--, --CH.dbd.CH--, cycloalkylene or phenylene; and
in alkylene of the phenylalkyl, the number of carbon atoms is 1 to
12 optional hydrogen may be replaced by fluorine, and optional
--CH.sub.2-- may be replaced by --O--, --CH.dbd.CH-- or
cycloalkylene.
[0018] {3} The production process as described in the item {1},
wherein each of R's in Formula (1) is a group selected
independently from the group of alkyls in which the number of
carbon atoms is 1 to 10, optional hydrogen may be replaced by
fluorine and optional --CH.sub.2-- may be replaced by --O-- or
cycloalkylene, the group of phenyls in which optional hydrogen on
the benzene ring may be replaced by halogen, methyl or methoxy, the
group of phenylalkyls in which optional hydrogen on the benzene
ring may be replaced by fluorine, alkyl having 1 to 4 carbon atoms,
vinyl or methoxy, and naphthyl; and in alkylene of the phenylalkyl,
the number of carbon atoms is 1 to 8, and optional --CH.sub.2-- may
be replaced by --O--, --CH.dbd.CH-- or cycloalkylene.
[0019] {4} The production process as described in the item 1,
wherein all of R's in Formula (1) are the same group selected from
the group of alkyls in which the number of carbon atoms is 1 to 10,
optional hydrogen may be replaced by fluorine and optional
--CH.sub.2-- may be replaced by --O-- or cycloalkylene, the group
of phenyls in which optional hydrogen on the benzene ring may be
replaced by halogen, methyl or methoxy, the group of phenylalkyls
in which optional hydrogen on the benzene ring may be replaced by
fluorine, alkyl having 1 to 4 carbon atoms, vinyl or methoxy, and
naphthyl; and in alkylene of the phenylalkyl, the number of carbon
atoms is 1 to 8, and optional --CH.sub.2-- may be replaced by
--O--, --CH.dbd.CH-- or cycloalkylene.
[0020] {5} The production process as described in any one of the
items {1} to (4), wherein M in Formula (1) as described in the item
{1} is Na.
[0021] {6} The production process as described in any one of the
items {1} to {4}, wherein M in Formula (1) as described in the item
{1} is Na, and a step for reacting the silicon compound represented
by Formula (1) with a silicon compound represented by Formula (3)
is included therein: 4
[0022] wherein X has the same meaning as that of X in Formula (2)
as described in the item {1}.
[0023] {7} The production process as described in the item {6},
wherein X is hydrogen, chlorine, alkenyl or a group having any of
halogen, alkenyl, cycloalkenyl, cyano, alkoxy, phenoxy,
acryloyloxy, methacryloyloxy and glycidyloxy;
[0024] provided that a group having halogenated sulfonyl and a
group having an .alpha.-haloester group are not included in the
group having halogen.
[0025] {8} A silsesquioxane derivative represented by Formula (2):
5
[0026] wherein each of R's is a group selected independently from
the group of alkyls in which the number of carbon atoms is 1 to 20,
at least one hydrogen is replaced by fluorine and optional
--CH.sub.2-- may be replaced by --O--, the group of phenyls in
which optional hydrogen on the benzene ring may be replaced by
halogen or alkyl having 1 to 10 carbon atoms, the group of
phenylalkyls in which optional hydrogen on the benzene ring may be
replaced by halogen or alkyl having 1 to 10 carbon atoms, and
naphthyl; in the alkyl having 1 to 10 carbon atoms which is a
substituent on the benzene ring, optional hydrogen may be replaced
by fluorine, and optional --CH.sub.2-- may be replaced by --O--,
--CH.dbd.CH--, cycloalkylene or phenylene; in alkylene of the
phenylalkyl, the number of carbon atoms is 1 to 12, optional
hydrogen may be replaced by fluorine, and optional --CH.sub.2-- may
be replaced by --O--, --CH.dbd.CH-- or cycloalkylene; and X is
hydrogen, chlorine, a functional group or a group having a
functional group;
[0027] provided that X is not any of a group having a hydroxy group
which is not bonded directly to Si, a group having alkanoyloxy, a
group having halogenated sulfonyl and a group having an
.alpha.-haloester group.
[0028] {9} The silsesquioxane derivative described in the item {8},
wherein each of R's in Formula (2) is a group selected
independently from the group of alkyls in which the number of
carbon atoms is 1 to 10, at least one hydrogen is replaced by
fluorine and optional --CH.sub.2-- may be replaced by --O--, the
group of phenyls in which optional hydrogen on the benzene ring may
be replaced by halogen, methyl or methoxy, the group of
phenylalkyls in which optional hydrogen on the benzene ring may be
replaced by fluorine, alkyl having 1 to 4 carbon atoms, vinyl or
methoxy, and naphthyl; and in alkylene of the phenylalkyl, the
number of carbon atoms is 1 to 8, and optional --CH.sub.2-- may be
replaced by --O--, --CH.dbd.CH-- or cycloalkylene.
[0029] {10} The silsesquioxane derivative as described in the item
{8}, wherein all of R's are the same group selected from the group
of alkyls in which the number of carbon atoms is 1 to 10, at least
one hydrogen is replaced by fluorine and optional --CH.sub.2-- may
be replaced by --O--, the group of phenyls in which optional
hydrogen on the benzene ring may be replaced by halogen, methyl or
methoxy, the group of phenylalkyls in which optional hydrogen on
the benzene ring may be replaced by fluorine, alkyl having 1 to 4
carbon atoms, vinyl or methoxy, and naphthyl; and in alkylene of
the phenylalkyl, the number of carbon atoms is 1 to 8, and optional
--CH.sub.2-- may be replaced by --O--, --CH.dbd.CH-- or
cycloalkylene.
[0030] {11} The silsesquioxane derivative as described in the item
{8}, wherein all of R's are the same alkyl in which the number of
carbon atoms is 1 to 10, at least one hydrogen is replaced by
fluorine, and one --CH.sub.2-- may be replaced by --O--.
[0031] {12} The silsesquioxane derivative as described in the item
{8}, wherein all of R's in Formula (2) are phenyl.
[0032] {13} The silsesquioxane derivative as described in the item
{8}, wherein all of R's in Formula (2) are trifluoropropyl.
[0033] {14} The silsesquioxane derivative as described in the item
{8}, wherein all of R's in Formula (2) are
tridecafluoro-1,1,2,2-tetrahydrooct- yl.
[0034] {15} The silsesquioxane derivative as described in any one
of the items {8} to {14}, wherein X in Formula (2) as described in
the item {8} is hydrogen, chlorine, a hydroxy group, alkenyl, or a
group having any of halogen, alkoxy, phenoxy, polyalkyleneoxy,
--COOH, 2-oxapropane-1,3-dioyl, alkoxycarbonyl, alkenyloxycarbonyl,
oxiranyl, 3,4-epoxycyclohexyl, oxetanyl, oxetanylene, --NH--,
--NH.sub.2, --CN, --NCO, alkenyl, alkynyl, cycloalkenyl,
acryloyloxy, methacryloyloxy, --SH and --PH.sub.2,
[0035] provided that X is not any of a group having a hydroxy group
which is not bonded directly to Si, a group having alkanoyloxy, a
group having halogenated sulfonyl and a group having an
.alpha.-haloester group.
[0036] {16} A silsesquioxane derivative represented by Formula (5):
6
[0037] wherein Ph is phenyl.
[0038] {17} A silsesquioxane derivative represented by Formula (6):
7
[0039] wherein Ph is phenyl.
[0040] {18} A silsesquioxane derivative represented by Formula
(1-2): 8
[0041] wherein F.sup.3 is --CH.sub.2CH.sub.2CF.sub.3.
[0042] {19} A silsesquioxane derivative represented by Formula
(14): 9
[0043] wherein F.sup.3 is --CH.sub.2CH.sub.2CF.sub.3.
[0044] {20} A silsesquioxane derivative represented by 10
[0045] wherein F.sup.13 is
--CH.sub.2CH.sub.2(CF.sub.2).sub.5CF.sub.3.
DETAILED DESCRIPTION OF THE INVENTION
[0046] The silicon compound represented by Formula (1) shall be
denoted by the compound (1) in the following explanation. The
silicon compound represented by Formula (2) shall be denoted by the
compound (2). The same shall be applied to the compounds
represented by the other formulas.
[0047] The production process of the present invention for the
compound (2) is characterized by using the compound (1): 11
[0048] The compound (1) can readily be produced at a good yield by
hydrolyzing a silicon compound having three hydrolyzable groups in
an oxygen-containing organic solvent such as alcohol and ether in
the presence of an alkaline metal hydroxide such as sodium
hydroxide, and subjecting it to polycondensation. Success in
synthesizing this compound (1) has made it possible to complete the
production process of the present invention. That is, reaction of
the compound (1) with the compound (3) has made it possible to
easily synthesize for short time, the compound (2) into which X in
the compound (3) is introduced. The compound (3) is chloride but
may be other halide. X shall be described later. 12
[0049] An organic solvent is preferably used for the reaction of
the compound (1) with the compound (3). That is, the compound (1)
is mixed with an organic solvent, and the compound (3) is dropwise
added to this mixture, whereby the reaction goes on while
by-producing chloride of alkaline metal. After finishing the
reaction, water is added to dissolve the chloride described above
and hydrolyze the unreacted compound (3). Then, the organic layer
is separated from the mixture, and the solvent is removed by
distillation, whereby the compound (2) can be obtained. The organic
layer is washed with water and dried on a dehydrating agent before
removing the solvent, whereby the compound having a high purity can
be obtained. If the functional group introduced is a group reacting
with water, the unreacted compound (3) and the organic solvent are
advisably removed by distillation after removing the chloride by
filtration. In either case, the purity can be enhanced by carrying
out, if necessary, recrystallization.
[0050] The solvent described above used in the reaction shall not
specifically be restricted as long as it does not retard progress
of the reaction. The preferred solvent includes aliphatic
hydrocarbons (hexane, heptane and the like), aromatic hydrocarbons
(benzene, toluene, xylene and the like), ethers (diethyl ether,
tetrahydrofuran (THF), dioxane and the like), halogenated
hydrocarbons (methylene chloride, carbon tetrachloride and the
like) and esters (ethyl acetate and the like). These solvents may
be used alone or in combination of a plurality thereof. More
preferred solvents are ethers, and THF is most preferred. The
compound (3) is readily reacted with water, and therefore the
solvent having a very small moisture content is preferably
used.
[0051] A preferred proportion of the compound (1) in mixing with
the solvent is 0.05 to 50% by weight based on the weight of the
solvent. If it is 50% by weight or less, a concentration of the
by-produced salts can be controlled so that it is not such high as
retarding progress of the reaction. If it is 0.05% by weight or
more, the volume efficiency can be prevented from being so
deteriorated that an adverse effect is exerted on the cost. More
preferred proportion is 1 to 10% by weight. A use amount of the
compound (3) shall not be restricted as long as it is used in an
equivalent mole or more based on the compound (1), but considering
an after-treatment step, it is not preferably used in an excessive
amount. The reaction temperature may be a room temperature, and
heating may be carried out, if necessary, in order to accelerate
the reaction. Further, cooling may be carried out, if necessary, in
order to control heat generated by the reaction or undesirable
reactions.
[0052] This reaction can readily be accelerated by adding a
compound having an amino group such as triethylamine or an organic
compound showing basicity. To give an example in which
triethylamine is used, a preferred use amount thereof falls in a
range of 0.005 to 10% by weight, more preferably 0.01 to 3% by
weight based on the weight of the solvent. However, an added amount
of triethylamine shall not specifically be basically restricted as
long as the reaction can readily be accelerated. A particularly
excellent point of the production process of the present invention
is a short reaction time. The reaction time after dropwise adding
the compound (3) may be about one hour in almost all cases. The
reaction is finished in about 3 hours at the longest.
[0053] In Formula (1), each of R's is a group selected
independently from hydrogen, alkyl having 1 to 45 carbon atoms,
substituted or non-substituted aryl and substituted or
non-substituted arylalkyl. All of R's are preferably the same one
group, but they may be constituted from two or more different
groups. An example in which R's are constituted from at least two
different groups includes an example in which they are constituted
from two or more alkyls, an example in which they are constituted
from two or more aryls, an example in which they are constituted
from two or more aralkyls, an example in which they are constituted
from hydrogen and at least one aryl, an example in which they are
constituted from at least one alkyl and at least one aryl, an
example in which they are constituted from at least one alkyl and
at least one aralkyl, and an example in which they are constituted
from at least one aryl and at least one aralkyl. They may be
combinations other than these examples. The compound (1) having at
least two different R's can be obtained by using two or more raw
materials in producing it.
[0054] When R is alkyl, it has 1 to 45 carbon atoms, preferably 1
to about 20 carbon atoms. Optional --CH.sub.2-- in this alkyl may
be replaced by --O--, --CH.dbd.CH--, cycloalkylene or
cycloalkenylene. The preferred examples in which R is alkyl or its
related group described above, are alkyl in which the number of
carbon atoms is 1 to 20, optional hydrogen may be replaced by
fluorine and optional --CH.sub.2-- may be replaced by --O-- or
cycloalkylene, alkenyl in which the number of carbon atoms is 2 to
20, optional hydrogen may be replaced by fluorine and optional
--CH.sub.2-- may be replaced by --O-- or cycloalkylene, and alkyl
in which the number of carbon atoms is 1 to 10 and at least one
--CH.sub.2-- is replaced by cycloalkenylene.
[0055] The examples of such groups are alkyl having 1 to 20 carbon
atoms, alkoxyalkyl having 2 to 20 carbon atoms, alkyl in which the
number of carbon atoms is 1 to 10 and at least one --CH.sub.2-- is
replaced by cycloalkylene, alkenyl having 2 to 20 carbon atoms,
alkenyloxyalkyl having 2 to 20 carbon atoms, alkoxyalkenyl having 2
to 20 carbon atoms, alkyl in which the number of carbon atoms is 1
to 10 and at least one --CH.sub.2-- is replaced by cycloalkenylene,
and groups obtained by substituting optional hydrogens with
fluorine in the groups given above. In the cycloalkylene and the
cycloalkenylene, they have preferably 3 to 8 carbon atoms, and two
carbons which are not adjacent to each other may be
cross-linked.
[0056] The examples of the alkyl having 1 to 20 carbon atoms are
methyl, ethyl, propyl, 1-methylethyl, butyl, 2-methylpropyl,
1,1-dimethylethyl, pentyl, hexyl, 1,1,2-trimethylpropyl, heptyl,
octyl, 2,4,4-trimethylpentyl, nonyl, decyl, undecyl, dodecyl,
tetradecyl, hexadecyl, octadecyl, eicocyl and dococyl.
[0057] The examples of the alkoxyalkyl having 2 to 20 carbon atoms
are methyloxypropyl, ethyloxypropyl, propyloxypropyl,
methyloxybutyl, ethyloxybutyl, propyloxybutyl, methyloxyisobutyl,
ethyloxyisobutyl and propyloxyisobutyl.
[0058] The examples of the alkyl in which the number of carbon
atoms is 1 to 10 and one --CH.sub.2-- is replaced by cycloalkylene,
are cyclohexylmethyl, adamantaneethyl, cyclopentyl, cyclohexyl,
2-bicycloheptyl and cyclooctyl. Cyclohexyl is an example in which
--CH.sub.2-- in methyl is replaced by cyclohexylene.
Cyclohexylmethyl is an example in which the 2nd --CH.sub.2-- in
ethyl is replaced by cyclohexylene.
[0059] The examples of the alkenyl having 2 to 20 carbon atoms, are
vinyl, 2-propenyl, 3-butenyl, 5-hexenyl, 7-octenyl, 10-undecenyl
and 21-dococenyl. The example of the alkenyloxyalkyl having 2 to 20
carbon atoms is allyloxyundecyl.
[0060] The examples of the alkyl in which the number of carbon
atoms is 1 to 10 and one --CH.sub.2-- is replaced by
cycloalkenylene, are 2-(3-cyclohexenyl)ethyl,
5-(bicycloheptenyl)ethyl, 2-cyclopentenyl, 3-cyclohexenyl,
5-norbornene-2-yl and 4-cyclooctenyl.
[0061] More preferred example in which R is alkyl or its related
group described above, is alkyl in which the number of carbon atoms
is 1 to 10, at least one hydrogen is replaced by fluorine and one
--CH.sub.2-- may be replaced by --O--. In this case, it is not
preferred that --CH.sub.2-- bonded to Si is replaced by --O--. It
is not preferred as well that --CH.sub.2-- at a terminal is
replaced by --O--.
[0062] The examples of such preferable alkyl are trifluoromethyl,
2-fluoroethyl, 2,2-difluoroethyl, 3,3,3-trifluoropropyl,
hexafluoropropyl, tridecafluoro-1,1,2,2-tetrahydrooctyl,
3,3,4,4,5,5,6,6,6-nonafluorohexyl,
heptadecafluoro-1,1,2,2-tetrahydrodecy- l, 2-fluoroethyloxypropyl,
2,2,2-trifluoroethyloxypropyl,
2-fluoro-1-fluoromethylethyloxypropyl,
2,2,3,3-tetrafluoro-propyloxypropy- l,
2,2,3,3,3-pentafluoropropyloxypropyl, hexafluoroisopropyloxypropyl,
hexafluorobutyloxypropyl, heptafluorobutyloxypropyl,
octafluoroisobutyloxypropyl, octafluoropentyloxypropyl,
2-fluoroethyloxybutyl, 2,2,2-trifluoroethyloxybutyl,
2-fluoro-1-fluoromethylethyloxy-butyl,
2,2,3,3-tetrafluoropropyloxybutyl,
2,2,3,3,3-pentafluoropropyloxybutyl, hexafluoroisopropyloxybutyl,
hexafluorobutyloxybutyl, heptafluorobutyloxybutyl,
octafluoroisobutyloxybutyl, octafluoropentyloxybutyl,
2-fluoroethyloxyisobutyl, 2,2,2-trifluoroethyloxyisobutyl,
2-fluoro-1-fluoromethylethyloxyisobutyl,
2,2,3,3-tetrafluoropropyloxyisob- utyl,
2,2,3,3,3-pentafluoropropyloxyisobutyl,
hexafluoroisopropyloxy-isobu- tyl, hexafluorobutyloxyisobutyl,
heptafluorobutyloxyisobutyl, octafluoroisobutyloxy-isobutyl and
octafluoropentyloxy-isobutyl.
[0063] The preferred examples in which R in Formula (1) is
substituted or non-substituted aryl, are phenyl in which optional
hydrogen may be replaced by halogen or alkyl having 1 to 10 carbon
atoms, and naphthyl. The preferred examples of halogen are
fluorine, chlorine and bromine. In the alkyl having 1 to 10 carbon
atoms which is a substituent for the phenyl, optional hydrogen may
be replaced by fluorine, and optional --CH.sub.2-- may be replaced
by --O--, --CH.dbd.CH-- or phenylene.
[0064] That is, the preferred examples of substituted or
non-substituted aryl are phenyl, naphthyl, halogenated phenyl,
alkylphenyl, alkoxyphenyl, alkenylphenyl, phenyl having alkyl in
which the number of carbon atoms is 1 to 10, at least one
--CH.sub.2-- is replaced by phenylene and optional --CH.sub.2-- may
be replaced by --O-- or --CH.dbd.CH-- as a substituent, and groups
obtained by substituting optional hydrogens with fluorine in the
groups given above. In the present invention, phenyl described
simply unless otherwise defined means non-substituted phenyl. The
same shall apply to naphthyl.
[0065] The examples of the halogenated phenyl are
pentafluorophenyl, 4-chlorophenyl and 4-bromophenyl. The examples
of the alkylphenyl are 4-methylphenyl, 4-ethyl-phenyl,
4-propylphenyl, 4-butylphenyl, 4-pentylphenyl, 4-heptylphenyl,
4-octylphenyl, 4-nonylphenyl, 4-decylphenyl, 2,4-dimethylphenyl,
2,4,6-trimethylphenyl, 2,4,6-triethylphenyl,
4-(1-methylethyl)-phenyl, 4-(1,1-dimethylethyl)phen- yl,
4-(2-ethylhexyl)-phenyl and 2,4,6-tris(1-methylethyl)phenyl.
[0066] The examples of the alkoxyphenyl are 4-methoxy-phenyl,
4-ethoxyphenyl, 4-propoxyphenyl, 4-butoxyphenyl, 4-pentyloxyphenyl,
4-heptyloxyphenyl, 4-decyloxyphenyl, 4-octadecyloxyphenyl,
4-(1-methylethoxy)-phenyl, 4-(2-methylpropoxy)phenyl and
4-(1,1-dimethylethoxy)phenyl.
[0067] The examples of the alkenylphenyl are 4-vinylphenyl,
4-(1-methylvinyl)phenyl and 4-(3-butenyl)phenyl.
[0068] The examples of the phenyl having alkyl in which the number
of carbon atoms is 1 to 10, at least one --CH.sub.2-- is replaced
by phenylene and optional --CH.sub.2-- may be replaced by --O-- or
--CH.dbd.CH-- as a substituent, are 4-(2-phenylvinyl)phenyl,
4-phenoxyphenyl, 3-phenylmethylphenyl, biphenyl and terphenyl.
4-(2-Phenylvinyl)phenyl is an example which in ethylphenyl the 2nd
--CH.sub.2-- of ethyl is replaced by phenylene and another
--CH.sub.2-- is replaced by --CH.dbd.CH--.
[0069] The examples of the phenyl in which at least one hydrogen on
the benzene ring is replaced by halogen and another hydrogen is
replaced by alkyl, alkoxy or alkenyl, are 3-chloro-4-methylphenyl,
2,5-dichloro-4-methylphenyl, 3,5-dichloro-4-methylphenyl,
2,3,5-trichloro-4-methyl-phenyl, 2,3,6-trichloro-4-methylphenyl,
3-bromo-4-methylphenyl, 2,5-dibromo-4-methylphenyl,
3,5-dibromo-4-methylphenyl, 2,3-difluoro-4-methylphenyl,
3-chloro-4-methoxyphenyl, 3-bromo-4-methoxyphenyl,
3,5-dibromo-4-methoxyphenyl, 2,3-difluoro-4-methoxyphenyl,
2,3-difluoro-4-ethoxyphenyl, 2,3-difluoro-4-propoxyphenyl and
4-vinyl-2,3,5,6-tetrafluorophenyl.
[0070] Next, an example in which R is substituted or
non-substituted arylalkyl shall be given. In alkylene of the
arylalkyl, optional hydrogen may be replaced by fluorine, and
optional --CH.sub.2-- may be replaced by --O--, --CH.dbd.CH-- or
cycloalkylene. The preferred example of the arylalkyl is
phenylalkyl. Alkylene in this phenylalkyl has preferably 1 to 12
carbon atoms, more preferably 1 to 8 carbon atoms. The examples of
the unsubstituted phenylalkyl are phenylmethyl, 2-phenylethyl,
3-phenylpropyl, 4-phenyl-butyl, 5-phenylpentyl, 6-phenylhexyl,
11-phenyl-undecyl, 1-phenylethyl, 2-phenylpropyl,
1-methyl-2-phenylethyl, 1-phenylpropyl, 3-phenylbutyl,
1-methyl-3-phenylpropyl, 2-phenylbutyl, 2-methyl-2-phenylpropyl and
1-phenylhexyl.
[0071] In the phenylalkyl, optional hydrogen on the benzene ring
may be replaced by halogen or alkyl having 1 to 10 carbon atoms. In
this alkyl having 1 to 10 carbon atoms, optional hydrogen may be
replaced by fluorine, and optional --CH.sub.2-- may be replaced by
--O--, --CH.dbd.CH--, cyclo-alkylene or phenylene. The examples of
the phenylalkyl in which optional hydrogen on the benzene ring is
replaced by fluorine, are 4-fluorophenylmethyl,
2,3,4,5,6-pentafluorophenylmethyl,
2-(2,3,4,5,6-pentafluorophenyl)ethyl,
3-(2,3,4,5,6-pentafluorophenyl)-pro- pyl, 2-(2-fluorophenyl)propyl
and 2-(4-fluorophenyl)-propyl.
[0072] The examples of the phenylalkyl in which optional hydrogen
on the benzene ring is replaced by chlorine, are
4-chlorophenylmethyl, 2-chlorophenylmethyl,
2,6-dichlorophenylmethyl, 2,4-dichlorophenylmethyl,
2,3,6-trichlorophenylmethyl,
2,4,6-trichlorophenylmethyl,2,4,5-trichlorop- henylmethyl,
2,3,4,6-tetrachlorophenyl-methyl, 2,3,4,5,6-pentachlorophenyl-
methyl, 2-(2-chlorophenyl)ethyl, 2-(4-chlorophenyl)ethyl,
2-(2,4,5-trichlorophenyl)ethyl, 2-(2,3,6-trichlorophenyl)ethyl,
3-(3-chlorophenyl)propyl, 3-(4-chlorophenyl)propyl,
3-(2,4,5-trichlorophenyl)propyl, 3-(2,3,6-trichlorophenyl)-propyl,
4-(2-chlorophenyl)butyl, 4-(3-chlorophenyl)butyl,
4-(4-chlorophenyl)butyl- , 4-(2,3,6-trichlorophenyl)butyl,
4-(2,4,5-trichlorophenyl)butyl, 1-(3-chlorophenyl)ethyl,
1-(4-chlorophenyl)ethyl, 2-(4-chlorophenyl)propy- l,
2-(2-chlorophenyl)propyl and 1-(4-chlorophenyl)butyl.
[0073] The examples of phenylalkyl in which optional hydrogen on
the benzene ring is replaced by bromine, are 2-bromophenylmethyl,
4-bromophenylmethyl, 2,4-dibromophenylmethyl,
2,4,6-tribromophenylmethyl, 2,3,4,5-tetrabromophenylmethyl,
2,3,4,5,6-pentabromophenylmethyl, 2-(4-bromophenyl)ethyl,
3-(4-bromophenyl)propyl, 3-(3-bromophenyl)propyl,
4-(4-bromophenyl)butyl, 1-(4-bromophenyl)ethyl,
2-(2-bromophenyl)propyl and 2-(4-bromophenyl)propyl.
[0074] The examples of the phenylalkyl in which optional hydrogen
on the benzene ring is replaced by alkyl having 1 to 10 carbon
atoms, are 2-methylphenylmethyl, 3-methylphenylmethyl,
4-methylphenylmethyl, 4-dodecylphenylmethyl,
3,5-dimethylphenylmethyl, 2-(4-methylphenyl)ethyl,
2-(3-methylphenyl)ethyl, 2-(2,5-dimethylphenyl)ethyl,
2-(4-ethylphenyl)ethyl, 2-(3-ethylphenyl)ethyl,
1-(4-methylphenyl)ethyl, 1-(3-methylphenyl)ethyl,
1-(2-methylphenyl)ethyl, 2-(4-methylphenyl)propy- l,
2-(2-methylphenyl)propyl, 2-(4-ethylphenyl)propyl,
2-(2-ethylphenyl)propyl, 2-(2,3-dimethylphenyl)propyl,
2-(2,5-dimethylphenyl)propyl, 2-(3,5-dimethylphenyl)propyl,
2-(2,4-dimethylphenyl)propyl, 2-(3,4-dimethylphenyl)propyl,
2-(2,5-dimethylphenyl)butyl, 4-(1-methylethyl)phenylmethyl,
2-(4-(1,1-dimethylethyl)-phenyl)ethyl,
2-(4-(1-methylethyl)phenyl)-propyl and
2-(3-(1-methylethyl)phenyl)propyl.
[0075] The examples of the phenylalkyl in which optional hydrogen
on the benzene ring is replaced by alkyl having 1 to 10 carbon
atoms and at least one hydrogen in this alkyl is replaced by
fluorine, are 3-trifluoromethylphenylmethyl and
2-(4-trifluoromethyl-phenyl)ethyl,
2-(4-nonafluorobutylphenyl)-ethyl,
2-(4-tridecafluorohexylphenyl)ethyl,
2-(4-heptadecafluorooctylphenyl)ethyl,
1-(3-trifluoromethylphenyl)ethyl,
1-(4-trifluoromethylphenyl)-ethyl,
1-(4-nonafluorobutylphenyl)ethyl,
1-(4-tridecafluorohexylphenyl)ethyl,
1-(4-heptadecafluorooctylphenyl)ethy- l,
2-(4-nonafluorobutyl-phenyl)propyl,
1-methyl-1-(4-nonafluorobutylphenyl- )ethyl,
2-(4-tridecafluorohexyl-phenyl)propyl, 1-methyl-1-(4-tridecafluoro-
hexyl-phenyl)ethyl, 2-(4-heptadecafluorooctylphenyl)propyl and
1-methyl-1-(4-heptadecafluorooctylphenyl)ethyl.
[0076] The examples of the phenylalkyl in which optional hydrogen
on the benzene ring is replaced by alkyl having 1 to 10 carbon
atoms and --CH.sub.2-- in this alkyl is replaced by --CH.dbd.CH--,
are 2-(4-vinylphenyl)ethyl, 1-(4-vinylphenyl)ethyl and
1-(2-(2-propenyl)phenyl)ethyl.
[0077] The examples of the phenylalkyl in which optional hydrogen
on the benzene ring is replaced by alkyl having 1 to 10 carbon
atoms and --CH.sub.2-- in this alkyl is replaced by --O--, are
4-methoxyphenylmethyl, 3-methoxyphenylmethyl, 4-ethoxyphenylmethyl,
2-(4-methoxyphenyl)ethyl, 3-(4-methoxyphenyl)propyl,
3-(2-methoxyphenyl)propyl, 3-(3,4-dimethoxyphenyl)propyl,
11-(4-methoxyphenyl)undecyl, 1-(4-methoxyphenyl)ethyl,
(3-methoxymethylphenyl)ethyl and
3-(2-nonadecafluorodecenyloxyphenyl)prop- yl.
[0078] The examples of the phenylalkyl in which optional hydrogen
on the benzene ring is replaced by alkyl having 1 to 10 carbon
atoms and one of --CH.sub.2-- in this alkyl is replaced by
cycloalkylene are, to give the examples thereof including those in
which another --CH.sub.2-- is replaced by --O--,
cyclopentylphenylmethyl, cyclopentyloxyphenylmethyl,
cyclohexylphenylmethyl, cyclohexylphenylethyl,
cyclohexylphenylpropyl and cyclohexyloxyphenylmethyl.
[0079] The examples of the phenylalkyl in which optional hydrogen
on the benzene ring is replaced by alkyl having 1 to 10 carbon
atoms and one of --CH.sub.2-- in this alkyl is replaced by
phenylene are, to give the examples thereof including those in
which another --CH.sub.2-- is replaced by --O--,
2-(4-phenoxyphenyl)ethyl, 2-(4-phenoxyphenyl)propyl,
2-(2-phenoxyphenyl)propyl, 4-biphenylylmethyl, 3-biphenylylethyl,
4-biphenylylethyl, 4-biphenylylpropyl, 2-(2-biphenylyl)propyl and
2-(4-biphenylyl)propyl.
[0080] The examples of the phenylalkyl in which at least two
hydrogen on the benzene ring are replaced by diffrent groups
respectively, are 3-(2,5-dimethoxy-3,4,6-trimethylphenyl)propyl,
3-chloro-2-methylphenylmet- hyl, 4-chloro-2-methylphenylmethyl,
5-chloro-2-methylphenyl-methyl, 6-chloro-2-methylphenylmethyl,
2-chloro-4-methylphenylmethyl, 3-chloro-4-methylphenylmethyl,
2,3-dichloro-4-methylphenylmethyl,
2,5-dichloro-4-methylphenylmethyl,
3,5-dichloro-4-methylphenylmethyl,
2,3,5-trichloro-4-methylphenylmethyl,
2,3,5,6-tetrachloro-4-methylphenylm- ethyl,
2,3,4,6-tetrachloro-5-methylphenylmethyl,
2,3,4,5-tetrachloro-6-met- hylphenyl-methyl,
4-chloro-3,5-dimethylphenylmethyl,
2-chloro-3,5-dimethylphenylmethyl,
2,4-dichloro-3,5-dimethylphenyl-methyl- ,
2,6-dichloro-3,5-dimethylphenylmethyl,
2,4,6-trichloro-3,5-dimethylpheny- lmethyl,
3-bromo-2-methylphenylmethyl, 4-bromo-2-methylphenylmethyl,
5-bromo-2-methylphenylmethyl, 6-bromo-2-methylphenylmethyl,
3-bromo-4-methylphenylmethyl, 2,3-dibromo-4-methylphenyl-methyl,
2,3,5-tribromo-4-methylphenylmethyl,
2,3,5,6-tetrabromo-4-methylphenylmet- hyl and
11-(3-chloro-4-methoxyphenyl)undecyl.
[0081] The most preferred examples of phenyl group in the
phenylalkyl are non-substituted phenyl and phenyl having at least
one of fluorine, alkyl having 1 to 4 carbon atoms, vinyl and
methoxy as a substituent.
[0082] The examples of the phenylalkyl in which --CH.sub.2-- in
alkylene is replaced by --O--, --CH.dbd.CH-- or cycloalkylene, are
3-phenoxypropyl, 1-phenylvinyl, 2-phenylvinyl, 3-phenyl-2-propenyl,
4-phenyl-4-pentenyl, 13-phenyl-12-tridecenyl, phenylcyclohexyl and
phenoxycyclohexyl.
[0083] The examples of the phenylalkenyl in which hydrogen on the
benzene ring is replaced by fluorine or methyl, are
4-fluorophenylvinyl, 2,3-difluorophenylvinyl,
2,3,4,5,6-pentafluorophenylvinyl and 4-methylphenylvinyl.
[0084] Preferred R among the examples described above are the alkyl
in which the number of carbon atoms is 1 to 10, optional hydrogen
may be replaced by fluorine and optional --CH.sub.2-- may be
replaced by --O-- or cycloalkylene, the phenyl in which optional
hydrogen may be replaced by halogen, methyl or methoxy, and the
phenylalkyl in which optional hydrogen on the benzene ring may be
replaced by fluorine, alkyl having 1 to 4 carbon atoms, vinyl or
methoxy. Alkylene in this phenylalkyl has 1 to 8 carbon atoms, and
optional --CH.sub.2-- in this alkylene may be replaced by --O--,
--CH.dbd.CH-- or cycloalkylene. When phenyl has plural substituents
in the preferred examples of R described above, these substituents
may be the same groups or different groups. All of R's in Formula
(1) are preferably the same group selected from these preferred
examples of R.
[0085] More preffered examples of R are 3,3,3-trifluoropropyl,
hexafluoropropyl, tridecafluoro-1,1,2,2-tetrahydrooctyl,
3,3,4,4,5,5,6,6,6-nonafluorohexyl,
heptadecafluoro-1,1,2,2-tetrahydrodecy- l, 2-fluoroethyloxypropyl,
2,2,2-trifluoroethyloxypropyl,
2-fluoro-1-fluoromethylethyloxypropyl,
2,2,3,3-tetrafluoropropyloxypropyl- ,
2,2,3,3,3-pentafluoropropyloxypropyl, hexafluoroisopropyloxypropyl,
hexafluorobutyloxypropyl, heptafluorobutyloxypropyl,
octafluoroisobutyloxypropyl, octafluoropentyloxypropyl, phenyl,
halogenated phenyl, phenyl in which at least one hydrogen on the
benzene ring is replaced by methyl, methoxyphenyl, naphthyl,
phenylmethyl, phenylethyl, phenylbutyl, 2-phenylpropyl,
1-methyl-2-phenylethyl, pentafluorophenylpropyl,
4-ethylphenylethyl, 3-ethylphenylethyl,
4-(1,1-dimethylethyl)phenylethyl, 4-vinylphenylethyl,
1-(4-vinylphenyl)ethyl, 4-methoxyphenylpropyl and
phenoxypropyl.
[0086] The most preffered examples of R are 3,3,3-trifluoropropyl,
tridecafluoro-1,1,2,2-tetrahydrooctyl and phenyl.
[0087] Next, the compound (3) shall be explained. The examples of X
in Formula (3) are hydrogen bonded to Si, chlorine bonded to Si,
alkenyl bonded to Si, and a group having any of halogen, alkenyl,
cycloalkenyl, cyano, alkoxy, phenoxy, acryloyloxy, methacryloyloxy
and glycidyloxy, provided that a group having halogenated sulfonyl
and a group having an .alpha.-haloester group are not included in
the group having halogen.
[0088] The examples of the compound (3) described above are
trichlorosilane, tetrachlorosilane,
3-acryloyloxypropyltrichlorosilane, allyltrichlorosilane,
5-bicycloheptenyltrichlorosilane, 2-bromoethyltrichloro-silane,
bromophenyltrichlorosilane, 3-bromopropyl-trichlorosilane,
11-bromoundecyltrichlorosilane,
2-(methoxycarbonyl)ethyltrichlorosilane,
1-chloroethyl-trichlorosilane, 2-chloroethyltrichlorosilane,
1-chloro-2-methylallyltrichlorosilane,
2-(chloromethyl)allyl-trichlorosilane,
chloromethylphenethyltrichlorosila- ne,
p-chloromethylphenyltrichlorosilane, chloromethyl-trichlorosilane,
chlorophenyltrichlorosilane, 3-chloropropyltrichlorosilane,
3-glycidyloxypropyl-trichlorosilane, 3-cyanobutyltrichlorosilane,
2-cyanoethyltrichlorosilane, 3-cyanopropyltrichlorosilane,
2-(3-cyclohexenyl)ethyltrichlorosilane,
3-cyclohexenyl-trichlorosilane, 4-cyclooctenyltrichlorosilane,
1,2-dibromoethyltrichlorosilane, 1,2-dichloroethyl-trichlorosilane,
dichloromethyltrichlorosilane, dichlorophenyltrichlorosilane,
5-hexenyltrichlorosilane, methacryloyloxypropyltrichlorosilane,
3-(p-methoxyphenyl)propyltrichloros- ilane,
7-octenyltrichloro-silane, 3-phenoxypropyltrichlorosilane,
trichloromethyl-trichlorosilane,
2-[2-(trichlorosilyl)-ethyl]pyridine,
4-[2-(trichlorosilyl)ethyl]pyridine and vinyltrichloro-silane.
[0089] Use of these compounds makes it possible to synthesize
silsesquioxane derivatives into which the respective functional
groups are introduced. The compound (1) is reacted with the
compound (3) to introduce X, and then it can be converted to the
other functional group by making use of a reactivity of X. When X
is hydrogen, very many functional groups can be introduced by
hydrosilylation of a compound having a double bond at a terminal
and a functional group, with the compound (2). If chlorine, bromine
or iodine is included in X in Formula (2), this silsesquioxane
derivative is dissolved in acetone to prepare a dilute solution,
and then silver perchlorate is added thereto, whereby the halogen
described above can be converted to alcohol. After the reaction is
carried out for several hours at a room temperature, silver
chloride is removed by filtration, and then acetone is removed
under reduced pressure, whereby the product can be obtained. When
tetrachlorosilane is used, reactive silyl chloride is introduced.
If two equivalent of phosphineimine is reacted therewith, a Wittig
reaction reagent can be obtained. It can further be converted as
well to the other functional groups by publicly known
techniques.
[0090] Examples other than the functional groups included in the
examples of the compound (3) described above shall be shown below:
13
[0091] In these formulas, X.sup.1 represents independently hydrogen
or a substituent having no reactivity; X.sup.2 represents
independently fluorine, chlorine, bromine or a substituent having
no reactivity; X.sup.3 represents a functional organic silicon
group; and --OH represents a hydroxy group bonded directly to Si.
Specific examples of an oxetane ring (F19) shall be shown below:
14
[0092] That is, the examples of X in the compound (2) are hydrogen
bonded to Si, chlorine bonded to Si, a hydroxy group bonded to Si,
alkenyl bonded to Si, and a group having any of halogen, alkoxy,
phenoxy, polyalkyleneoxy, --COOH, 2-oxapropane-1,3-dioyl,
alkoxycarbonyl, alkenyloxycarbonyl, oxiranyl, 3,4-epoxycyclohexyl,
oxetanyl, oxetanylene, --NH--, --NH.sub.2, --CN, --NCO, alkenyl,
alkynyl, cycloalkenyl, acryloyloxy, methacryloyloxy, --SH and
--PH.sub.2, provided that X is not any of a group having
alkanoyloxy, a group having halogenated sulfonyl and a group having
an .alpha.-haloester bond.
[0093] When the functional group is a polymerizable group, it can
be a homopolymer of the compound (2) or a copolymer with other
conventional monomers. It may be a copolymer of the compounds (2)
themselves. In this case, any of conventional methods can be used
for the polymerizing method.
EXAMPLES
[0094] The present invention shall be explained below with
reference to examples, but the present invention shall not be
restricted to these examples. In chemical formulas in the examples,
Ph is phenyl; TMS is trimethylsilyl; and i-Bu is isobutyl.
Example 1
[0095] <Synthesis of Compound (1-1)>
[0096] A four neck flask having an inner volume of 1 liter equipped
with a reflux condenser, a thermometer and a dropping funnel was
charged with phenyltrimethoxysilane (99 g), sodium hydroxide (10 g)
and 2-propanol (500 ml). Deionized water (11 g) was dropwise added
at a room temperature in about 2 minutes while stirring by means of
a magnetic stirrer. Then, the solution was heated in an oil bath up
to a temperature at which 2-propanol was refluxed. Stirring was
continued for 1.5 hour since refluxing started to complete the
reaction. Then, the flask was pulled up from the oil bath and left
standing still at a room temperature for a night to completely
deposit a product. A pressure filter equipped with a membrane
filter having a pore diameter of 0.1 .mu.m was used to filter the
deposited product. Then, a solid matter thus obtained was washed
once with 2-propanol, and it was dried at 70.degree. C. for 4 hours
in a vacuum dryer to obtain a white powder solid matter of 66
g.
Example 2
[0097] <Confirmation of Structure of Compound (1-1)>
[0098] A four neck flask having an inner volume of 50 ml equipped
with a dropping funnel, a reflux condenser and a thermometer was
charged with the white powder solid matter (1.2 g) described above,
THF (12 g) and triethylamine (1.8 g) and sealed under dry nitrogen.
Chlorotrimethylsilane (2.3 g) was dropwise added at a room
temperature in about one minute while stirring by means of a
magnetic stirrer. After finishing dropwise adding, stirring was
further continued at a room temperature for 3 hours to complete the
reaction. Then, deionized water (10 g) was added thereto to
dissolve by-produced sodium chloride and hydrolyze unreacted
chlorotrimethylsilane. The reaction mixture thus obtained was
transferred to a separating funnel to separate an organic layer
from an aqueous layer, and the resulting organic layer was
repeatedly washed with water until the washing solution was
neutralized. This organic layer was dried on anhydrous magnesium
sulfate and concentrated under reduced pressure by means of a
rotary evaporator to obtain a white powder solid matter of 1.2
g.
[0099] The white powder solid matter thus obtained was used to
carry out structural analysis by means of gel permeation
chromatography (GPC), .sup.1H-NMR, .sup.29Si-NMR and IR analysis.
It was confirmed from the GPC chart that the white powder solid
matter showed monodispersibility and that it had a weight average
molecular weight of 900 in terms of polystyrene and a purity of 98%
by weight. It was confirmed from the .sup.1H-NMR chart that a
phenyl group and a trimethylsilyl group were present in an integral
ratio of 7:3. It was confirmed from the .sup.29Si-NMR chart that
three peaks originating in a T structure having phenyl were present
in a ratio of 1:3:3 and that one peak originating in a
trimethylsilyl group was present in 11.66 ppm. It was confirmed
from the IR spectrum measured by a KBr tablet method that present
in the spectrum of the white powder solid matter obtained above
were absorptions attributed respectively to deformation vibration
of Si--Ph in 1430 and 1590 cm.sup.-1, harmonic vibration of a
substituted benzene ring in 1960 to 1760 cm.sup.-1, stretching
vibration of Si--O--Si in 1200 to 950 cm.sup.-1 and vibration of
Si--CH.sub.3 in 1250 cm.sup.-1, and they supported a structure of
Formula (b). Accordingly, it was judged that the compound before
trimethylsilylated had a structure of Formula (1-1): 15
Example 3
[0100] <Introduction of 3-(methacryloyloxy)propyl Group>
[0101] A three neck flask having an inner volume of 300 ml equipped
with a dropping funnel, a reflux condenser and a thermometer was
charged with Compound (1-1) (10 g) synthesized in Example 1, THF
(200 ml) and triethylamine (1.5 g) and sealed under dry nitrogen.
3-(Methacryloyloxy)propyltrichlorosilane (3.9 g) was dropwise added
at a room temperature while stirring by means of a magnetic
stirrer. After finishing dropwise adding, stirring was further
continued at a room temperature for one hour to complete the
reaction. Then, deionized water (50 g) was added thereto to
dissolve by-produced sodium chloride and hydrolyze unreacted
3-(methacryloyloxy)propyltrichlorosilane. The organic layer
obtained by separating operation was washed with water and dried on
anhydrous magnesium sulfate, and then it was concentrated under
reduced pressure by means of a rotary evaporator to obtain a crude
product. This was recrystallized from ethyl acetate and dried to
obtain a white powder solid matter (6.6 g).
[0102] The white powder solid matter thus obtained was subjected to
structural analysis by means of GPC, .sup.1H-NMR, .sup.29Si-NMR, IR
analysis and mass spectrum, and the following results were
obtained. It was confirmed from the GPC chart that the white powder
solid matter was monodispersed and that it had a weight average
molecular weight of 800 (no correction) in terms of polystyrene and
a purity of 99% by weight. It was confirmed from the .sup.1H-NMR
chart that a phenyl and a terminal double bond of methacryloyloxy
were present in an integral ratio of 35:2. It was confirmed from
the .sup.29Si-NMR chart that three kinds of peaks originating in a
T structure having a 3-(methacryloyloxy)propyl group and a T
structure having phenyl were present in a ratio of 1:4:3. It was
confirmed from the IR spectrum measured by a KBr tablet method that
present in the spectrum of the white powder solid matter obtained
above were absorptions attributed respectively to deformation
vibration of Si--Ph in 1430 and 1590 cm.sup.-1, harmonic vibration
of a substituted benzene ring in 1960 to 1760 cm.sup.-1, stretching
vibration of Si--O--Si in 1200 to 950 cm.sup.-1, vibration of
C.dbd.O in 1720 cm.sup.-1 and vibration of C.dbd.C in 1640 and 1450
cm.sup.-1. A parent ion peak of m/z1082 was confirmed from the mass
spectrum. These data supported a structure represented by Formula
(8): 16
Example 4
[0103] <Introduction of Cyanoethyl Group>
[0104] A three neck flask having an inner volume of 300 ml equipped
with a dropping funnel, a reflux condenser and a thermometer was
charged with Compound (1-1) (10 g) synthesized in Example 1, THF
(200 ml) and triethylamine (1.5 g) and sealed under dry
nitrogen.
[0105] Cyanoethyltrichlorosilane (2.8 g) was dropwise added at a
room temperature while stirring by means of a magnetic stirrer.
After finishing dropwise adding, stirring was further continued at
a room temperature for one hour to complete the reaction. Then,
deionized water (50 g) was added thereto to dissolve by-produced
sodium chloride and hydrolyze unreacted cyanoethyltrichlorosilane.
The organic layer obtained by separating operation was washed with
water and dried on anhydrous magnesium sulfate, and then it was
concentrated under reduced pressure by means of a rotary evaporator
to obtain a crude product. This was washed with methanol and dried
to obtain a white powder solid matter (6.1 g).
[0106] The white powder solid matter thus obtained was subjected to
structural analysis by means of GPC, .sup.1H-NMR, .sup.29Si-NMR and
IR analysis, and the following results were obtained. It was
confirmed from the GPC chart that the white powder solid matter was
monodispersed and that it had a weight average molecular weight of
730 (no correction) in terms of polystyrene and a purity of 99% by
weight. It was confirmed from the .sup.1H-NMR chart that phenyl and
an ethylene group in a cyanoethyl group were present in an integral
ratio of 35:2. It was confirmed from the .sup.29Si-NMR chart that
three kinds of peaks originating in a T structure having a
cyanoethyl group and a T structure having phenyl were present in a
ratio of 1:4:3. These data indicate a structure of Formula (5):
17
Example 5
[0107] <Introduction of Si--H Group>
[0108] A three neck flask having an inner volume of 300 ml equipped
with a dropping funnel, a reflux condenser and a thermometer was
charged with Compound (1-1) (10 g) synthesized in Example 1, THF
(200 ml) and triethylamine (1.5 g) and sealed under dry nitrogen.
Trichlorosilane (2 g) was dropwise added at a room temperature
while stirring by means of a magnetic stirrer. After finishing
dropwise adding, stirring was further continued at a room
temperature for one hour to complete the reaction. Then, deionized
water (50 g) was added thereto to dissolve by-produced sodium
chloride and hydrolyze unreacted trichlorosilane. The organic layer
obtained by separating operation was washed with water and dried on
anhydrous magnesium sulfate, and then it was concentrated under
reduced pressure by means of a rotary evaporator to obtain a crude
product. This was recrystallized from acetone and dried to obtain a
white powder solid matter (5 g).
[0109] The white powder solid matter thus obtained was subjected to
structural analysis by means of GPC, .sup.1H-NMR, .sup.29Si-NMR, IR
analysis and mass spectrum, and the following results were
obtained. It was confirmed from the GPC chart that the white powder
solid matter was monodispersed and that it had a weight average
molecular weight of 750 (no correction) in terms of polystyrene and
a purity of 95% by weight. It was confirmed from the .sup.1H-NMR
chart that phenyl and a hydrogen group were present in an integral
ratio of 35:1. It was confirmed from the .sup.29Si-NMR chart that
three kinds of peaks originating in a T structure having a hydrogen
group and a T structure having phenyl were present in a ratio of
1:4:3. It was confirmed from the IR spectrum measured by a KBr
tablet method that present in the spectrum of the white powder
solid matter obtained above were absorptions attributed
respectively to deformation vibration of Si--Ph in 1430 and 1590
cm.sup.-1, harmonic vibration of a substituted benzene ring in 1960
to 1760 cm.sup.-1, stretching vibration of Si--O--Si in 1200 to 950
cm.sup.-1 and vibration of Si--H in 2260 cm.sup.-1. A parent ion
peak of m/z956 was confirmed from the mass spectrum. These data
indicate a structure of Formula (4): 18
Example 6
[0110] <Introduction of Vinyl Group>
[0111] A three neck flask having an inner volume of 300 ml equipped
with a dropping funnel, a reflux condenser and a thermometer was
charged with Compound (1-1) (10 g) synthesized in Example 1, THF
(200 ml) and triethylamine (1.5 g) and sealed under dry
nitrogen.
[0112] Vinyltrichlorosilane (2.4 g) was dropwise added at a room
temperature while stirring by means of a magnetic stirrer. After
finishing dropwise adding, stirring was further continued at a room
temperature for one hour to complete the reaction. Then, deionized
water (50 g) was added thereto to dissolve by-produced sodium
chloride and hydrolyze unreacted vinyltrichlorosilane. The organic
layer obtained by separating operation was washed with water and
dried on anhydrous magnesium sulfate, and then it was concentrated
under reduced pressure by means of a rotary evaporator to obtain a
crude product. This was recrystallized and then dried to obtain a
white powder solid matter (6 g).
[0113] The white powder solid matter thus obtained was subjected to
structural analysis by means of .sup.1H-NMR, .sup.29Si-NMR, IR
analysis and mass spectrum, and the following results were
obtained. It was confirmed from the .sup.1H-NMR chart that phenyl
and a terminal double bond of a vinyl group were present in an
integral ratio of 35:2. It was confirmed from the .sup.29Si-NMR
chart that three kinds of peaks originating in a T structure having
a vinyl group and a T structure having phenyl were present in a
ratio of 1:4:3. These data indicate a structure of Formula (7):
19
Example 7
[0114] <Introduction of 3-chloropropyl Group>
[0115] A three neck flask having an inner volume of 300 ml equipped
with a dropping funnel, a reflux condenser and a thermometer was
charged with Compound (1-1) (10 g) synthesized in Example 1, THE
(200 ml) and triethylamine (1.5 g) and sealed under dry nitrogen.
3-Chloropropyltrichlorosilane (3.2 g) was dropwise added at a room
temperature while stirring by means of a magnetic stirrer. After
finishing dropwise adding, stirring was further continued at a room
temperature for one hour to complete the reaction. Then, deionized
water (50 g) was added thereto to dissolve by-produced sodium
chloride and hydrolyze unreacted 3-chloropropyltrichlorosilane. The
organic layer obtained by separating operation was washed with
water and dried on anhydrous magnesium sulfate, and then it was
concentrated under reduced pressure by means of a rotary evaporator
to obtain a crude product. This was washed with methanol, then
recrystallized from ethyl acetate and dried to obtain a white
powder solid matter (6.3 g).
[0116] The white powder solid matter thus obtained was subjected to
structural analysis by means of GPC, .sup.1H-NMR and .sup.29Si-NMR,
and the following results were obtained. It was confirmed from the
GPC chart that the white powder solid matter was monodispersed and
that it had a weight average molecular weight of 740 (no
correction) in terms of polystyrene and a purity of 99% by weight.
It was confirmed from the .sup.1H-NMR chart that phenyl and an
ethylene group in a 3-chloropropyl group were present in an
integral ratio of 35:2. It was confirmed from the .sup.29Si-NMR
chart that three kinds of peaks originating in a T structure having
a 3-chloropropyl group and a T structure having phenyl were present
in a ratio of 1:4:3. These data indicate a structure of Formula
(6). 20
Example 8
[0117] <Introduction of 3-cyclohexenylethyl Group>
[0118] The compound (1-1) synthesized in the same manner as in
Example 1 is reacted with 2-(3-cyclohexenyl)ethyltrichlorosilane
according to Example 3, whereby a compound represented by Formula
(9) can be synthesized: 21
Example 9
[0119] <Introduction of 3,4-epoxycyclohexylethyl Group>
[0120] The compound synthesized in Example 8 is used to apply a
method described in J. Polym. Sci. Part A: Polym. Chem, 1997, 35
(3), 407, whereby a compound represented by Formula (10) can be
synthesized: 22
Example 10
[0121] <Introduction of 3,4-dihydroxycyclohexylethyl
Group>
[0122] The compound synthesized in Example 9 is used to apply a
method described in Toxicol. Environ. Chem, 1996, 57 (1-4), 153,
whereby a compound represented by Formula (11) can be synthesized:
23
Example 11
[0123] <Introduction of 3,4-diacryloyoxy-cyclohexylethyl
Group>
[0124] Methylene chloride, acrylic acid and
4-dimethylaminopyrimidine are added to the compound obtained in
Example 10 and stirred at a room temperature. Then,
N,N-dicyclohexylcarbodiimide dissolved in methylene chloride is
added thereto and stirred at a room temperature for 3 days, and
then diethyl ether is added to filter off dicyclohexylurea. A
saturated aqueous salt solution is added to the filtrate and
stirred, and then the solution is subjected to separating operation
to separate an organic layer. This organic layer is washed in order
with hydrochloric acid and a saturated sodium hydrogencarbonate
aqueous solution, and then it is dried on anhydrous sodium sulfate.
The solvent is distilled off from this organic layer under reduced
pressure, whereby a compound represented by Formula (12) can be
synthesized. 24
Example 12
[0125] <Introduction of N-Propyl Group>
[0126] A four neck flask having an inner volume of 100 ml equipped
with a dropping funnel, a reflux condenser and a thermometer was
charged with Compound (1-1) (1.0 g) obtained in Example 1, THF (20
ml) and triethylamine (0.12 g) and sealed under dry nitrogen.
n-Propyltrichlorosilane (0.213 g) was dropwise added while stirring
by means of a magnetic stirrer. After finishing dropwise adding
stirring was further continued at a room temperature for one hour
to complete the reaction. Then, deionized water (20 g) was added
thereto to dissolve by-produced sodium chloride and hydrolyze
unreacted n-propyltrichlorosilane. The organic layer obtained by
separating operation was washed with water and dried on anhydrous
magnesium sulfate, and then it was concentrated under reduced
pressure by means of a rotary evaporator to obtain a crude product.
This was recrystallized from toluene and dried to obtain a white
powder solid matter (0.49 g). The yield calculated from the charged
amount was 49%.
[0127] The white powder solid matter thus obtained was analyzed by
means of GPC and .sup.1H-NMR, and as a result thereof, it was
confirmed from the GPC chart that the weight average molecular
weight was 686 (no correction) in terms of polystyrene and that the
purity was 99% by weight or more. It was confirmed from the
.sup.1H-NMR chart that phenyl and an n-propyl group were present in
a ratio of 7:1. It was confirmed from these data that the white
powder solid matter obtained had a structure represented by Formula
(13): 25
Comparative Example 1
[0128] <Introduction of N-Propyl Group>
[0129] An n-propyl group was tried to introduce by a method
according to Example 12, except that a compound (0.93 g)
represented by Formula (a-1) manufactured by Hybrid Plastics Co,
Ltd. was substituted for the compound (1-1). However, the solid
matter obtained in Example 12 was not obtained. That is, when using
the compound (a-1), an alkaline component for accelerating the
reaction by capturing HCl has to be indispensably present.
Considering this fact and that the compound (1-1) is produced more
easily than the compound (a-1), it is apparent that the process of
the present invention is more excellent: 26
Example 13
[0130] <Production of Compound (1-2)>
[0131] A four neck flask having an inner volume of one liter
equipped with a reflux condenser, a thermometer and a dropping
funnel was charged with trifluoropropyltrimethoxysilane (100 g),
THF (500 ml), deionized water (10.5 g) and sodium hydroxide (7.9
g), and it was heated in an oil bath from a room temperature up to
a temperature at which THF was refluxed while stirring by means of
a magnetic stirrer. Stirring was continued for 5 hours since
refluxing started to complete the reaction. Then, the flask was
pulled up from the oil bath and left standing still at a room
temperature for a night, and then it was set again in the oil bath
to carry out heating and concentrating under atomospheric pressure
until a solid matter was deposited. The deposited product was
separated by means of a pressure filter equipped with a membrane
filter having a pore diameter of 0.5 .mu.m. Then, the solid matter
thus obtained was washed once with THF and dried at 80.degree. C.
for 3 hours in a vacuum dryer to obtain a white powder solid matter
of 74 g.
[0132] <Confirmation of Structure of Compound (1-2)>
[0133] A four neck flask having an inner volume of 50 ml equipped
with a dropping funnel, a reflux condenser and a thermometer was
charged with the white powder solid matter (1.0 g) described above,
THF (10 g) and triethylamine (1.0 g), and sealed under dry
nitrogen. Chlorotrimethylsilane (3.3 g) was dropwise added at a
room temperature in about one minute while stirring by means of a
magnetic stirrer. After finishing dropwise adding, stirring was
further continued at a room temperature for 3 hours to complete the
reaction. Then, the same treatment as in the confirmation of the
structure of Compound (1-1) in Example 2 was carried out to obtain
a white powder solid matter of 0.9 g.
[0134] The white powder solid matter thus obtained was subjected to
structural analysis by means of GPC, .sup.1H-NMR, 29Si-NMR and
.sup.13C-NMR. It was confirmed from the GPC chart that the white
powder solid matter showed monodispersibility and that it had a
weight average molecular weight of 1570 in terms of polystyrene and
a purity of 98% by weight. It was confirmed from the .sup.1H-NMR
chart that a trifluoropropyl group and a trimethylsilyl group were
present in an integral ratio of 7:3. It was confirmed from the
.sup.29Si-NMR chart that three peaks originating in a T structure
having a trifluoropropyl group were present in a ratio of 1:3:3 and
that one peak originating in a trimethylsilyl group was present in
12.11 ppm. It was confirmed from the .sup.13C-NMR chart that peaks
originating in a trifluoropropyl group were present in 131 to 123
ppm, 28 to 27 ppm and 6 to 5 ppm and that a peak originating in a
trimethylsilyl group was present in 1.4 ppm. These values show that
the white powder solid matter which is a target for the structural
analysis has a structure of Formula (c). Accordingly, it is judged
that the compound before subjected to trimethylsilylation has a
structure of Formula (1-2): 27
[0135] F3 in Formula (c) and Formula (1-2) is
--CH.sub.2CH.sub.2CF.sub.3.
Example 14
[0136] <Introduction of 3-(methacryloyloxy)propyl Group>
[0137] A three neck flask having an inner volume of 100 ml equipped
with a reflux condenser and a thermometer was charged with Compound
(1-2) (2.85 g) produced in Example 13, THF (50 g) and triethylamine
(0.4 g), and sealed under dry argon.
3-(Methacryloyloxy)propyltrichlorosilane (1.0 g) was dropwise added
at a room temperature while stirring by means of a magnetic
stirrer. After finishing dropwise adding, stirring was further
continued at a room temperature for 3 hours to complete the
reaction. The reaction mixture was subjected to pressurized
filtration (argon pressure: 0.2 to 0.3 MPa and PTFF-made membrane
filter: 0.1 .mu.m) to thereby remove by-produced sodium chloride,
and then the filtrate was concentrated to one tenth, followed by
adding methanol (150 g) to obtain a deposit. The deposit mixture
was stirred for one hour and then filtrated by means of a suction
filter equipped with a membrane filter having a pore diameter of
0.1 .mu.m. The resulting solid matter component was dried at
80.degree. C. for 3 hours in a vacuum dryer to obtain a white
powder solid matter (1.6 g).
[0138] The white powder solid matter thus obtained was subjected to
structural analysis by means of GPC, .sup.1H-NMR, .sup.29Si-NMR and
.sup.13C-NMR, and the following results were obtained. It was
confirmed from the GPC chart that the white powder solid matter was
monodispersed and that it had a weight average molecular weight of
1430 (no correction) in terms of polystyrene and a purity of 99% by
weight. It was confirmed from the .sup.1H-NMR chart that
trifluoropropyl and a terminal double bond of methacryloyloxy were
present in an integral ratio of 28:2. It was confirmed from the
.sup.29Si-NMR chart that three kinds of peaks originating in a T
structure having a 3-(methacryloyloxy)propyl group and a T
structure having phenyl were present in a ratio of 1:4:3. It was
confirmed from the .sup.13C-NMR chart that peaks originating in a
3-(methacryloyloxy)propyl group were present in 167 to 125 ppm and
68 to 4 ppm and that peaks originating in a trifluoropropyl group
was present in 131 to 123 ppm. A structure represented by Formula
(14) was supported by these data: 28
[0139] F.sup.3 in Formula (14) is --CH.sub.2CH.sub.2CF.sub.3.
Example 15
[0140] <Production (1) of Compound (1-3)>
[0141] A four neck flask having an inner volume of 200 ml equipped
with a reflux condenser, a thermometer and a dropping funnel was
charged with cyclopentyltrimethoxysilane (19.0 g), THF (100 ml),
sodium hydroxide (1.7 g) and deionized water (2.3 g), and it was
heated while stirring by means of a magnetic stirrer. Stirring was
continued for 10 hours since refluxing started at 67.degree. C. to
complete the reaction. Then, the flask was pulled up from the oil
bath and left standing still at a room temperature for a night to
completely deposit a solid matter formed. The deposited solid
matter was separated by filtration and dried under vacuum to obtain
a powder solid matter of 4.2 g.
[0142] <Confirmation of Structure of Compound (1-3)>
[0143] A four neck flask having an inner volume of 100 ml equipped
with a reflux condenser was charged with the powder solid matter
(1.0 g) described above, THF (30 ml), triethylamine (0.5 g) and
trimethylchlorosilane (0.7 g) and stirred at a room temperature for
2 hours while stirring by means of a magnetic stirrer. After
finishing the reaction, the same treatment as in the confirmation
of the structure of Compound (1-1) in Example 2 was carried out to
obtain a powder solid matter of 0.9 g.
[0144] The powder solid matter thus obtained was subjected to
structural analysis by means of .sup.1H-NMR, .sup.29Si-NMR and X
ray crystalline structure analysis. It was confirmed from the
.sup.1H-NMR that a cyclopentyl group and a trimethylsilyl group
were present in an integral ratio of 7:3. Confirmed from the
.sup.29Si-NMR were a peak of 8.43 ppm originating in a
trimethylsilyl group and three kinds of peaks of -66.37 ppm, -67.97
ppm and -67.99 originating in a T structure having a cyclopentyl
group. A ratio of the sum of the peak strengths in -67.97 ppm and
-67.99 to the peak strengths in -66.37 ppm was 6:1. It was
confirmed from these results and the crystalline structure obtained
by the X ray crystalline structure analysis that the powder solid
matter which was a target for the analysis was a silicon compound
represented by Formula (d). Accordingly, it was indicated that the
compound obtained in Example 15 had a structure shown by Formula
(1-3): 29
Example 16
[0145] <Production (2) of Compound (1-3)>
[0146] A separable four neck flask having an inner volume of 100 ml
equipped with a reflux condenser, a thermometer and a dropping
funnel was charged with toluene (10.0 g) and deionized water (5.0
g). Then, a mixed solution of cyclopentyltrimethoxysilane (10.0 g)
and toluene (10.0 g) was dropwise added thereto in 30 minutes while
stirring by means of a magnetic stirrer and further stirred at a
room temperature for 2 hours. Thereafter, a 5.0 weight % aqueous
solution (1.0 ml) of sodium hydroxide was added thereto and heated
up to the refluxing temperature, and the solution was further
stirred for 2 hours to complete the reaction. The solution was
cooled down to a room temperature and then washed with water, and
it was concentrated under reduced pressure to obtain a residue (5.1
g). The residue thus obtained was analyzed by means of GPC to find
that it was a solid matter having a weight average molecular weight
of 1190 in terms of polystyrene.
[0147] A four neck flask having an inner volume of 200 ml equipped
with a reflux condenser and a thermometer was charged with the
residue (2.8 g) described above, THF (50 ml) and sodium hydroxide
(0.4 g), and the mixture was heated under refluxing at 67.degree.
C. while stirring by means of a magnetic stirrer. Stirring was
continued for 17 hours since refluxing started to complete the
reaction. Then, the flask was pulled up from the oil bath and left
standing still at a room temperature for a night. The deposited
solid matter was separated by filtration and dried under vacuum to
obtain a powder solid matter of 0.3 g. This powder solid matter was
subjected to structural analysis, and as a result thereof, it was
estimated that this compound had the structure shown by Formula
(1-3) as with the compound obtained in Example 15.
Example 17
[0148] <Production (3) of Compound (1-3)>
[0149] A four neck flask having an inner volume of 100 ml equipped
with a reflux condenser, a thermometer and a dropping funnel was
charged with cyclopentyltrimethoxysilane (5.0 g), 2-propanol (30
ml), sodium hydroxide (0.7 g) and deionized water (0.6 g), and it
was heated while stirring by means of a magnetic stirrer. Stirring
was continued for 5 hours since refluxing started at 77.degree. C.
to complete the reaction. Then, the solvent was removed under
heating at 80.degree. C. by means of an evaporator to obtain a
powder solid matter of 3.6 g. This powder solid matter was
subjected to structural analysis, and as a result thereof, it was
estimated that this compound had the structure shown by Formula
(1-3) as with the compound obtained in Example 15.
Example 18
[0150] <Production of Compound (1-4)>
[0151] A four neck flask having an inner volume of 200 ml equipped
with a reflux condenser, a thermometer and a dropping funnel was
charged with isobutyltrimethoxysilane (18.7 g), THF (100 ml),
sodium hydroxide (1.8 g) and deionized water (2.4 g), and it was
heated while stirring by means of a magnetic stirrer. Stirring was
continued for 10 hours since refluxing started at 67.degree. C. to
complete the reaction. The reaction solution was concentrated under
atomospheric pressure until a solid matter was deposited, and then
the resulting concentrate was left standing still at a room
temperature for a night to completely deposit a solid matter. This
solid matter was separated by filtration and dried under vacuum to
obtain a powder solid matter of 5.1 g.
[0152] <Confirmation of Structure of Compound (1-4)>
[0153] A four neck flask having an inner volume of 200 ml equipped
with a reflux condenser was charged with the powder solid matter
(1.0 g) described above, THF (20 ml), triethylamine (0.5 g) and
trimethylchlorosilane (0.8 g). And the mixture was stirred by means
of a magnetic stirrer at a room temperature for 2 hours. After
finishing the reaction, the same treatment as in the confirmation
of the structure of Compound (1-1) in Example 2 was carried out to
obtain a powder solid matter of 0.9 g.
[0154] The powder solid matter described above was subjected to
structural analysis by means of .sup.1H-NMR and 29Si-NMR. It was
confirmed from the .sup.1H-NMR chart that an isobutyl group and a
trimethylsilyl group were present in an integral ratio of 7:3. It
was confirmed from the .sup.29Si-NMR chart a peak of 8.72 ppm
originating in a trimethylsilyl group was present and that three
kinds of peaks of -67.38 ppm, -68.01 ppm and -68.37 ppm originating
in a T structure having an isobutyl group were present in a ratio
of 1:3:3. It was confirmed from these results that the powder solid
matter which was a target for the analysis was a silicon compound
represented by Formula (e). Accordingly, it was indicated that the
compound obtained in Example 18 had a structure represented by
Formula (1-4): 30
Example 19
[0155] <Production of Compound (1-5)>
[0156] A four neck flask having an inner volume of 50 ml equipped
with a reflux condenser, a thermometer and a dropping funnel was
charged with tridecafluoro-1,1,2,2-tetrahydrooctyltriethoxysilane
(4.9 g), THF (15 ml), sodium hydroxide (0.2 g) and deionized water
(0.2 g). The mixture was refluxed by heating at 75.degree. C. while
stirring by means of magnetic stirrer. Stirring was continued for 5
hours since refluxing started to complete the reaction. Then, the
flask was pulled up from the oil bath and left standing still at a
room temperature for a night, and then it was set again in the oil
bath to carry out heating and concentrating under atomospheric
pressure until a solid matter was deposited. The deposited product
was separated by means of a pressure filter equipped with a
membrane filter having a pore diameter of 0.5 .mu.m. Then, the
solid matter thus obtained was washed once with THF and dried at
80.degree. C. for 3 hours in a vacuum dryer to obtain a white
powder solid matter of 4.0 g.
[0157] <Confirmation of Structure of Compound (1-5)>
[0158] A three neck flask having an inner volume of 50 ml was
charged with the white powder solid matter (2.6 g) described above,
THF (10 g), triethylamine (1.0 g) and trimethylchlorosilane (3.3
g). And the mixture was stirred by means of a magnetic stirrer at a
room temperature for 3 hours. After finishing the reaction, the
same treatment as in the confirmation of the structure of Compound
(1-1) in Example 2 was carried out to obtain a powder solid matter
of 1.3 g.
[0159] The powder solid matter thus obtained was analyzed by means
of GPC. As the result, it was confirmed that the white powder solid
matter was monodispersed and that it had a weight average molecular
weight of 3650 (no correction) in terms of polystyrene and a purity
of 100% by weight. Synthetically judging this result and the
results obtained in Examples 1, 13, 15 and 18, it was estimated
that the powder solid matter which was a target for the analysis
was a silicon compound represented by Formula (f). Accordingly, it
was judged that the compound obtained in Example 19 had a structure
represented by Formula (1-5): 31
[0160] F.sup.13 in Formula (f) and Formula (1-5) is
--CH.sub.2CH.sub.2(CF.sub.2).sub.5CF.sub.3.
[0161] Use of Compound (1-2), Compound (1-3), Compound (1-4) or
Compound (1-5) makes it possible to derive the respective compounds
into compounds having an Si--H group in the same manner as in
Example 5. The silsesquioxane derivatives having various functional
groups can readily be produced from these compounds having an Si--H
group.
[0162] Industrial applicability
[0163] Provided according to the present invention is a process in
which a functional group-containing silsesquioxane derivative
represented by Formula (2) can readily be produced at a high yield.
Further, the novel functional group-containing silsesquioxane
derivative of the present invention can easily be introduced into
general purpose resins by various methods, and therefore it is very
useful as a reaction intermediate raw material for reforming a heat
resistance, a light fastness, a water resistance, a stretching
characteristic and the like of conventional resins.
* * * * *