JPH1077346A - Organopolysiloxane having cyclic ether group - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new organopolysiloxane useful as a material for hydrophilic silicones applicable to cosmetic oils, ion-conductive materials, antifouling sealants, etc., by containing hydrophilic 1,4-dioxanil, which is a cyclic ether, in its molecule. SOLUTION: This new orgaopolysiloxane, a compound of the formula of R<1> a R<2> b SiO4-(a+b)/2 (R<1> is substituted or unsubstituted monovalent 1-10C hydrocarbon or hydroxyl group; R<2> is a cyclic ether group of the formula; (a) and (b) are positive numbers that satisfy a+b=1.95-2.4), is obtained by a reaction of, for example, pentamethylcyclotrisiloxane with 2-allyloxymethyl-1,4-dioxane in the presence of chloroplatinic acid to form 3-[(1,4-dioxane-2-yl) methoxy]propyl}pentamethylcyclotrisiloxane, and subsequent ring-opening polymerization of this compound by using such a catalyst as n-butyl lithium.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an organopolysiloxane having a cyclic ether group, which is useful as a basic raw material for a hydrophilic silicone.

[0002]

2. Description of the Related Art
As the hydrophilic silicone rubber, for example, JP-A-53-
Although the main chain described in Japanese Patent No. 129247 is a polyether, and one having a hydrolyzable silicon at a molecular chain terminal is known, this kind of hydrophilic silicone rubber has a polyether portion of the main chain which is weather-resistant. However, there was a problem that the properties were poor.

Recently, a silicon compound having a cyclic ether group has been disclosed in US Pat. No. 5,414,093.
And a siloxane polymer having a linear ether group introduced into the side chain (Japanese Patent Application Laid-Open No. 7-150046).
Publication), but an organopolysiloxane having a 1,4-dioxanyl group, which is a six-membered cyclic ether having two oxygen atoms in the molecule, has not yet been reported.

[0004]

Means for Solving the Problems and Embodiments of the Invention In view of the demand for hydrophilic silicone products, the present inventors have conducted intensive research on novel organosilicon compounds that provide hydrophilic silicones. As a result, it has been found that a novel organopolysiloxane having a cyclic ether group of the formula (2) represented by the following formula (1), that is, a 1,4-dioxanyl group, can be synthesized in a high yield by the method described below. And, the organopolysiloxane of the formula (1) is, because of the hydrophilicity of the 1,4-dioxanyl group,
It can be used as a raw material for hydrophilic silicone oils, silicone rubbers, silicone resins, etc., and is useful as a base material for various silicone products used in cosmetic oils, ion conductive materials, paintable surface paints, antifouling sealants, etc. It has been found that the present invention has been accomplished.

[0005] ^{_{R 1 a R 2 b SiO 4-}} (a + b) / 2 ... (1) ( wherein one of R ¹ is from 1 to 10 carbon atoms may also be substituted or unsubstituted be the same or different from each other R ² is a cyclic ether group represented by the following formula (2), a and b are each a positive number, and a + b =
1.95 to 2.40 is satisfied. )

[0006]

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Accordingly, the present invention provides an organopolysiloxane represented by the above general formula (1).

Hereinafter, the present invention will be described in more detail. The organopolysiloxane having a cyclic ether group of the present invention is represented by the following general formula (1).

[0009] ^{_{R 1 a R 2 b SiO 4-}} (a + b) / 2 ... (1) Here, the formula (1) Medium R ¹ is the number of carbon atoms also may substituted or unsubstituted be the same or different from each other 1-10 monovalent hydrocarbon groups or hydroxyl groups, preferably having 1 carbon atom
~ 8 monovalent hydrocarbon groups. Specific examples of these groups include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and an octyl group; an alkenyl group such as a vinyl group; an aryl group such as a phenyl group and a tolyl group; A group in which part or all of the hydrogen atoms in the hydrocarbon group is substituted with a halogen atom, a cyano group, or the like, such as a 3,3,3-trifluoropropyl group or a cyanoethyl group. Group, vinyl group and phenyl group.

R ² is a cyclic ether group represented by the following formula (2).

[0011]

Embedded image

Further, a and b are positive numbers, and a + b =
1.95 to 2.40, preferably a is 0.95 to
2.39, especially a positive number of 1 to 2.2, b is 0.01 to 1,
Particularly, it is a positive number of 0.05 to 1, and a preferable range of a + b is 2 to 2.2.

The organopolysiloxane of the present invention usually has a viscosity at 25 ° C. of 10 to 100,000,000.
cp, in particular, having a viscosity of 100 to 10,000,000 cp, and a degree of polymerization of 10 to 100,000.
0, especially 100 to 10,000 oily or raw rubber.

The organopolysiloxane of the present invention has a polymerization degree of 10 to 100,000, especially 100 to 10
Those having the following structural formula (1a) having 000 are preferred.

[0015]

Embedded image (In the formula, R ¹ and R ² are the same as described above, but when the right end of the compound of the formula (1a) is a hydroxyl group, the formula (1)
R ¹ in the right end in a) is not a hydroxyl group, a hydrogen atom. n is an integer of 0 or more, m is an integer of 2 or more, m + n
Is a number that gives the above degree of polymerization. )

The organopolysiloxane having a cyclic ether group of the present invention can be obtained, for example, by the following polymerization method, but is not limited to the following method.

[0017] 1. Cyclic siloxa having cyclic ether group
This method involves ring-opening polymerization of cyclotrisiloxane and cyclotetrasiloxane having a cyclic ether group using a catalyst such as lithium, sodium, potassium, and tetramethylammonium hydroxide. .

Specifically, [3-{(1,4-dioxan-2-yl) methoxy} propyl] pentamethylcyclotrisiloxane is used as a raw material, and lithium siliconate is used as a polymerization catalyst in a catalytic amount. By performing the polymerization, it is possible to obtain a siloxane in which the ratio of a silicon atom in which a cyclic ether group and a methyl group are bonded to a silicon atom in which two methyl groups are bonded is 1: 2. In this case, a cyclic siloxane having no cyclic ether group such as hexamethylcyclotrisiloxane is used in combination with [3-{(1,4-dioxan-2-yl) methoxy} propyl] pentamethylcyclotrisiloxane to form a cyclic ether group. The content can also be controlled.

Further, [3-１ ， (1,4-dioxane-2)
-Yl) methoxy {propyl] heptamethylcyclotetrasiloxane, a catalytic amount of potassium siliconate may be added as a polymerization catalyst. In this case, a cyclic siloxane having no cyclic ether group such as octamethylcyclotetrasiloxane may be used. It can also be obtained in combination.

A cyclic siloxane having a vinyl group,
For example, 1,3,5,7-tetravinyl-1,3,5,7
It is also possible to polymerize using a combination of -tetramethyltetrasiloxane to introduce a vinyl group into the polymer.

As described above, the cyclic siloxane having the group (R ² ) of the above formula (2) bonded to at least one silicon atom alone or in combination with the cyclic siloxane having no such group is opened according to a conventional method. The organopolysiloxane of the present invention can be obtained by ring polymerization. In this case, the degree of polymerization of the cyclic siloxane is 3 to 10, especially 3 to 6
It is preferred that Further, the organic group bonded to the silicon atom other than R ² is the one represented by R ¹ .

It is to be noted that hexamethyldisiloxane and 1,3-divinyl-1,1, which become polymer terminals at the time of the above polymerization,
3,3-tetramethyl disiloxane, organic groups bonded to the silicon atom such as hexamethylene vinyl disiloxane was added disiloxane is R ^1, a trimethylsilyl group the polymer terminal, dimethyl vinyl silyl group, with trivinylsilyl group Not only can it be blocked, but also the degree of polymerization can be controlled.

After the completion of the above polymerization, trimethylchlorosilane, vinyldimethylchlorosilane, hexamethyldisilazane, 1,3-divinyl-1,1,3,3-
By performing treatment with tetramethyldisilazane, diethylaminotrimethoxysilane, or the like, the polymer ends are treated with trialkylsilyl groups such as trimethylsilyl and vinyldimethylsilyl, vinyldialkylsilyl, divinylalkylsilyl, and trivinylsilyl. A stopped polymer can be obtained.

[0024] 2. Alkoxy groups having a cyclic ether group
Method for hydrolyzing oxane and then performing polymerization This method is based on the following method: [3-{(1,4-dioxan-2-yl) methoxy} propyl] methyldimethoxysilane is converted to hydrochloric acid, sulfuric acid, nitric acid, acetic acid, and a cation exchange resin. Such as an acidic catalyst, or cesium hydroxide, potassium hydroxide, sodium hydroxide, tetramethylammonium hydroxide, tetrabutylphosphonium hydroxide, after hydrolysis with a basic catalyst such as an anion exchange resin according to a conventional method, The chain length is extended by an ordinary method to obtain an organopolysiloxane.

For example, [3-{(1,4-dioxane-
2-yl) methoxy {propyl] methyldimethoxysilane is hydrolyzed by adding tetramethylammonium hydroxide as a catalyst, followed by removal of methanol by-produced by the reaction, followed by heating in the presence of water. The resulting silanol groups condense to give an oily polymer having an OH group at the end of the molecular chain.

In this case, if necessary, the same cyclic siloxane as described in the above 1, such as octamethylcyclotetrasiloxane and 1,3,5,7-tetramethylcyclotetrasiloxane, may be added together for synthesis. A polymer can be obtained, and a polymer in which a cyclic ether group is introduced at an arbitrary ratio can be obtained by changing the amount of these used.

[0027] 3. Organohigh having Si-H in side chain
2-allyloxymethyl-drogenpolysiloxane
1,4-dioxane is added in the presence of a catalyst such as platinum.
In this method, at least one or more Si atoms are present in a molecule.
An organohydrogenpolysiloxane having an —H group and the other organic group bonded to the silicon atom represented by R ¹ is a cyclic ether having an unsaturated group, ie, 2-allyloxymethyl-1,4-dioxane. Chloroplatinic acid, alcohol-treated chloroplatinic acid, cyclopropane complex of platinum, complex of tetrabutylammonium hydride and rhodium chloride, etc. The reaction is carried out in the presence of a catalytic amount of an addition reaction catalyst such as a rhodium complex. After the completion of the reaction, unreacted 2-allyloxymethyl-1,4-dioxane is removed under reduced pressure to obtain the desired organopolysiloxane having a cyclic ether group.

In this case, a method for polymerizing a polymer having a Si—H group includes, for example, equilibrium polymerization of 1,3,5,7-tetramethylcyclotetrasiloxane and octamethylcyclotetrasiloxane with sulfuric acid, and the like. It can be obtained by a conventional method.

In the addition reaction, aromatic compounds such as toluene and xylene, aliphatic compounds such as hexane and pentane, tetrahydrofuran, dioxane,
The reaction can be carried out in the presence of an ether solvent such as dibutyl ether or diethyl ether, but it is preferable to carry out the reaction without a solvent in view of economic efficiency.

[0030]

Since the organopolysiloxane having a cyclic ether group of the present invention has a 1,4-dioxanyl group in the molecule, the organopolysiloxane has a 1,4-dioxanyl group in the molecule by an addition reaction or the like.
A silicone oil having a 4-dioxanyl group, a silicone rubber, a silicone resin, or the like can be provided. The hydrophilicity of the 1,4-dioxanyl group is useful as a raw material of a hydrophilic siloxane polymer. Since such a siloxane polymer is hydrophilic, it can be applied as a cosmetic oil, an ion conductive material, a paintable surface paint or a stain-resistant sealant.

[0031]

The present invention will be described below in more detail with reference to Examples, but the present invention is not limited to the following Examples. In the following examples, the viscosity is a value at 25 ° C.

Example 1 Thermometer, stirrer, and 100
pentamethylcyclotrisiloxane (100.0 ml) was placed in a 300 ml flask equipped with a dropping funnel and purged with nitrogen.
g (0.480 mol) and 0.10 g of chloroplatinic acid were introduced. At room temperature, 79.6 g (0.5037 mo) of 2-allyloxymethyl-1,4-dioxane was dropped from the dropping funnel.
l) was added dropwise over 2 hours, and after completion of the addition, the mixture was stirred for 1 hour and distilled to obtain [3-{(1,4-dioxan-2-yl) methoxy} propyl] pentamethylcyclotrisiloxane 157. 0.3 g (0.429 mol,
Yield 89.4%).

Next, 100 m equipped with a thermometer and a stirrer
30.0 g (0.0818 mol) of the obtained [3-{(1,4-dioxan-2-yl) methoxy} propyl] pentamethylcyclotrisiloxane
And 20.0 g of tetrahydrofuran, and 1.05
mol / l-n-butyllithium hexane solution 0.0
70 ml was further added, and polymerization was carried out at 80 ° C. for 3 hours.

After the completion of the polymerization reaction, 0.50 g of acetic acid was added, and the mixture was stirred for 1 hour. After removing by-product tetrahydrofuran and an excess amount of acetic acid under reduced pressure, the following colorless transparent oily product was obtained. Was.

Viscosity 1450 cp Molecular weight determined by GPC 5800 1H-NMR analysis revealed that one end was OH
The other end of the group was a butyldimethylsilyl group, and it was confirmed that the polymer was represented by the following average composition formula and structural formula. Me _1.67 R ² _0.32 (OH) _0.02 SiO (where R ² is a group represented by the following formula.
Same. )

[0036]

Embedded image (M is a number that satisfies the above viscosity and molecular weight.)

[0037]

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Example 2 Thermometer, stirrer, and 100
100 ml of heptamethylcyclotetrasiloxane in a 300 ml flask equipped with a dropping funnel and purged with nitrogen.
0 g (0.480 mol) and 0.10 g of chloroplatinic acid were introduced. At room temperature, 79.6 g of 2-allyloxymethyl-1,4-dioxane (0.5037 m
ol) was added dropwise over 2 hours, and after completion of the addition, the mixture was stirred for 1 hour and distilled to obtain [3-{(1,4-dioxan-2-yl) methoxy} propyl] heptamethylcyclotetrasiloxane 157. 0.3g (0.429mo
1, yield 89.4%).

Next, 100 m equipped with a thermometer and a stirrer
Then, 20.0 g of the obtained [3-{(1,4-dioxan-2-yl) methoxy} propyl] heptamethylcyclotetrasiloxane and a 15% aqueous solution of tetramethylammonium hydroxide were introduced into 1 flask, 8
After polymerization at 0 ° C. for 4 hours, acetic acid was added to neutralize.

The obtained polymer was dissolved in toluene, washed three times with 100 ml of saturated saline, and then the organic phase was stripped to remove toluene. The following colorless and transparent oily product was obtained. Obtained.

The viscosity was analyzed by 890 cp GPC with a molecular weight of 1200 H-NMR.
The other end of the group was a butyldimethylsilyl group, and it was confirmed that the polymer was represented by the following average composition formula and structural formula. Me _1.76 R ² _0.24 (OH) _0.18 SiO _0.91

[0042]

Embedded image (M is a number that satisfies the above viscosity and molecular weight.)

Example 3 Thermometer, stirrer, and 100
50.0 g of [3-{(1,4-dioxan-2-yl) methoxy} propyl] methyldimethoxysilane was placed in a 300-ml flask equipped with a dropping funnel and purged with nitrogen.
(0.189 mol) and 10 g of water were introduced, and 0.143 g of tetramethylammonium hydroxide pentahydrate was added thereto. Stirring at room temperature for 2 minutes resulted in a homogeneous solution, which was further reacted at room temperature for 48 minutes.

Next, methanol by-produced under reduced pressure,
Excess water was removed, and stirring was continued at 80 ° C. for 2 hours to obtain a colorless transparent oily product.

A thermometer, a stirrer and a nitrogen purged 1
In a 00 ml flask, 8.0 g of a colorless and transparent oily product obtained by the above reaction, 51.6 g of octamethylcyclotetrasiloxane, 1,3,5,7-tetravinyl-
1,3,5,7-tetramethyltetrasiloxane 0.6
3 g and 0.10 g of tetramethylammonium hydroxide pentahydrate were added, and the mixture was stirred at 80 ° C. for 4 hours. After cooling to 30 ° C., 2.0 g of acetic acid was added, and the mixture was stirred for 1 hour. The product was obtained.

Next, the obtained pale yellow oily product was dissolved in toluene, and the washing was repeated until the aqueous phase became neutral. The toluene phase was separated, and toluene was removed at 80 ° C. under reduced pressure to obtain the following colorless and transparent oily polymer.

Viscosity 15,000 cp Molecular weight determined by GPC 32800 1H-NMR analysis revealed that one end was OH
The other end of the group was a butyldimethylsilyl group, and it was confirmed that the polymer was represented by the following average composition formula and structural formula. Vi _0.001 Me _1.95 R ² _0.05 (OH) _0.005 SiO

[0048]

Embedded image (O, p, and q are numbers that satisfy the above viscosity, molecular weight, and average composition.)

Example 4 Colorless and Transparent Oily Product 1
5.0 g, octamethylcyclotetrasiloxane 45.
8g, 1,3,5,7-tetravinyl-1,3,5,7
Polymerization was carried out in the same manner as in Example 3 except that 0.59 g of -tetramethyltetrasiloxane was used, whereby a colorless and transparent oily polymer having the following physical properties was obtained.

The viscosity was determined by 23500 cp GPC. The molecular weight was 35,000. Analysis by 1H-NMR confirmed that the polymer had OH groups at both ends and was represented by the following average composition formula and structural formula. Vi _0.001 Me _1.90 R ² _0.1 SiO

[0051]

Embedded image (O, p, and q are numbers that satisfy the above viscosity, molecular weight, and average composition.)

Example 5 Colorless and Transparent Oily Product 2
0.0 g, octamethylcyclotetrasiloxane 27.
2g, 1,3,5,7-tetravinyl-1,3,5,7
Polymerization was carried out in the same manner as in Example 3 except that 0.39 g of -tetramethyltetrasiloxane was used, whereby a colorless and transparent oily polymer having the following physical properties was obtained.

The viscosity was 4950 cp. The molecular weight was determined by GPC. The analysis by 1H-NMR revealed that the polymer was a polymer represented by the following average composition formula and structural formula at both ends with OH groups. Vi _0.001 Me _1.80 R ² _0.20 (OH) _0.010 SiO

[0054]

Embedded image (O, p, and q are numbers that satisfy the above viscosity, molecular weight, and average composition.)

Example 6 Colorless and Transparent Oily Product 1
7.8 g, octamethylcyclotetrasiloxane 6.1
g, 1,3,5,7-tetravinyl-1,3,5,7-
Polymerization was carried out in the same manner as in Example 3 except that 0.14 g of tetramethyltetrasiloxane was used. As a result, a colorless and transparent oily polymer having the following physical properties was obtained.

Analysis by viscosity 3840 cp GPC determined molecular weight 6900 1H-NMR confirmed that the polymer had OH groups at both ends and was represented by the following average composition formula and structural formula. Vi _0.001 Me _1.50 R ² _0.50 (OH) _0.042 SiO _0.98

[0057]

Embedded image (O, p, and q are numbers that satisfy the above viscosity, molecular weight, and average composition.)

Example 7 A 100 ml flask equipped with a thermometer and a stirrer and purged with nitrogen was charged with a siloxane polymer having a Si—H group in the molecule and an OH group at the molecular chain terminal (average composition formula Me _1.95). H _0.11 SiO _0.97 ) 30.0 g,
2-allyloxymethyl-1,4-dioxane 10.6
g, 0.03 g of chloroplatinic acid and 50 g of toluene,
After reacting at 80 ° C. for 3 hours, stripping was performed under the conditions of 80 ° C./4 mmHg to obtain a polymer.

Analysis by 1H-NMR with a molecular weight of 8500 determined by GPC with a viscosity of 4010 cp confirmed that the polymer was an OH group at both ends and represented by the following average composition formula and structural formula. Me _1.95 R ² _0.12 SiO _0.96

[0060]

Embedded image (M is a number that satisfies the above viscosity and molecular weight.)

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Norio Shinohara 1-10 Hitomi, Matsuida-cho, Usui-gun, Gunma Prefecture Inside Silicone Electronic Materials Technology Laboratory, Shin-Etsu Chemical Co., Ltd.

Claims (1)

[Claims] 1. An organopolysiloxane having a cyclic ether group represented by the following general formula (1). R ¹ _a R ² _b SiO _{4- (a + b) / 2} (1) (wherein, R ¹ may be the same or different and each is a substituted or unsubstituted monovalent hydrocarbon having 1 to 10 carbon atoms.) R ² is a cyclic ether group represented by the following formula (2), a and b are each a positive number, and a + b =
1.95 to 2.40 is satisfied. )