JP2000273178A - Chloromethylphenyl group-containing diorganopolysiloxane and method for producing the same - Google Patents

Abstract

(57) [Summary] (Modifications) [PROBLEMS] To provide a diorganopolysiloxane having a highly reactive chloroalkyl group. A compound represented by the following general formula (3) and a compound represented by the following general formula (4) are reacted in the presence of a hydrosilylation reaction catalyst such as platinum, iridium, ruthenium, palladium, molybdenum, and manganese. A diorganopolysiloxane compound having a highly reactive chloromethylphenyl group at both terminals, one terminal, a side chain, and the like, and a method for producing the same.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a chloromethylphenyl group-containing diorganopolysiloxane and a method for producing the same. More specifically, the present invention relates to a chloromethylphenyl group-containing diorganopolysiloxane having an alkyl group containing at least a chloromethylphenyl group and a method for producing the same.

[0002]

2. Description of the Related Art In order to impart properties such as water repellency, releasability, and lubricity to an organic resin, it has been conventionally used to incorporate a diorganopolysiloxane into the organic resin. However, when the diorganopolysiloxane used does not have an organic functional group, the diorganopolysiloxane is removed by washing from the organic resin containing the diorganopolysiloxane, or the diorganopolysiloxane is removed. Since the bleed out of the organic resin occurs due to the low compatibility of the siloxane with the various organic resins, the above-described provision of the properties to the organic resin is temporary and has no permanent property.

On the other hand, when a diorganopolysiloxane having an organic functional group is used, the diorganopolysiloxane is chemically bonded to various organic resins by utilizing the reactivity of the organic functional group. The organic resin serving as a binding partner can be added to a diorganopolysiloxane without deteriorating its inherent properties (water repellency,
Peelability, lubricity, etc.). Since this method is not a mere mixing, there is no bleed-out problem and no deterioration in various characteristics due to cleaning. Therefore, the provision of various characteristics by this method has a permanent effect. Thus, a diorganopolysiloxane having an organic functional group is useful as a modifier for an organic resin.

Examples of the diorganopolysiloxane having an organic functional group include amino-modified diorganopolysiloxane, epoxy-modified diorganopolysiloxane, alcohol-modified diorganopolysiloxane, methacryloxy-modified diorganopolysiloxane, and carboxyl-modified diorganopolysiloxane. It has been known.

When these diorganopolysiloxanes are chemically bonded to an organic resin, the type of the organic functional group on the diorganopolysiloxane side depends on the type of the organic functional group on the organic resin side. That is, the organic functional group on the diorganopolysiloxane side had to be an organic functional group that reacted with the organic functional group on the organic resin side. Therefore, in order to provide organic resins having various organic functional groups with properties unique to diorganopolysiloxane such as water repellency, releasability, lubricity, etc., a new diorganopolyorganic compound having an organic functional group corresponding thereto is required. Development of polysiloxane was necessary.

[0006] A chloroalkyl group, which is one of the organic functional groups, can be reacted with various drugs using a nucleophilic substitution reaction. Examples include the synthesis of ester derivatives by reaction with carboxylic acids, the synthesis of ether derivatives by reaction with alcohols, phenols, and thiophenols; the synthesis of phosphonium salts by reaction with phosphines;
Reaction with a reagent.

[0007]

However, the chloroalkyl groups known so far are not sufficiently reactive with various reagents. It has been desired to develop a diorganopolysiloxane having the same.

[0008]

DISCLOSURE OF THE INVENTION Since the reactivity of a chloroalkyl group depends on a substituent of a carbon having a chloro group, the present inventors have found that a chloromethyl group having a phenyl group, that is, a chloromethyl group, We thought that a diorganopolysiloxane having a methylphenyl group would provide sufficient reactivity, and made intensive studies on the synthesis of a diorganopolysiloxane having a chloromethylphenyl group. As a result, a chloromethylphenyl group-containing diorganopolysiloxane having an alkyl group containing a chloromethylphenyl group at one end, both ends, side chains, etc.
The inventors have found that high reactivity can be obtained, and have completed the present invention based on this finding.

As apparent from the above description, an object of the present invention is to provide a chloromethylphenyl group having at least one alkyl group containing a chloromethylphenyl group at one end, both ends, and side chains of a diorganopolysiloxane. An object of the present invention is to provide a diorganopolysiloxane and a method for producing the same.

Hereinafter, the present invention will be described in detail. A first invention is a chloromethylphenyl group-containing diorganopolysiloxane compound represented by the following general formula (1).

Embedded image (1) wherein R ¹ is a methyl group or a phenyl group, R ² is a linear or branched alkyl group having 1 to 6 carbon atoms or a phenyl group or A, and l is an integer of 0 to 500 , M is 0
N is an integer of 0 to 500, p is an integer of 0 to 2, A is a group represented by the following general formula (2),

Embedded image (2) X is a linear or branched alkylene group having 2 to 20 carbon atoms, at least one of R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ is a chloromethyl group, and the remaining groups Is hydrogen or carbon number 1
To 20 linear or branched alkyl groups.] In addition, the arrangement of each siloxane unit in the polysiloxane skeleton in the general formula (1) may be a random arrangement or a block arrangement. In any case.

When the general formula (1) is a diorganopolysiloxane having a chloromethylphenyl group at one end, R
² is a linear or branched alkyl group or phenyl group having 1 to 6 carbon atoms, and when the general formula (1) is a diorganopolysiloxane containing a chloromethylphenyl group at both terminals, R ² represents A is there.

Further, the number-average molecular weight of the diorganopolysiloxane having a chloromethylphenyl group at one end and the diorganopolysiloxane having a chloromethylphenyl group at both ends is preferably in the range of 500 to 200,000. When the number average molecular weight is 500 or less, various properties imparted to the organic resin tend to be reduced by the incorporation of the diorganopolysiloxane into the organic resin, and when the number average molecular weight is 200,000 or more, it corresponds. It becomes relatively difficult to obtain raw materials.

A second invention is characterized in that a compound represented by the following general formula (3) and a compound represented by the following general formula (4) are reacted in the presence of a hydrosilylation reaction catalyst. This is a method for producing a group-containing siloxane compound.

Embedded image (3) wherein R ¹ is a methyl group or a phenyl group, R ⁸ is a linear or branched alkyl group having 1 to 6 carbon atoms or a phenyl group or hydrogen, and q is an integer of 0 to 1000 , M
Is an integer of 0 to 1000, and p is an integer of 0 to 2]

Embedded image (4) [wherein at least one of R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ is an alkylene group having a carbon-carbon double bond and having 2 to 20 carbon atoms; Number 1
20 to 20 straight-chain or branched-chain alkyl groups.] In addition, the arrangement of each siloxane unit in the polysiloxane skeleton in the general formula (3) may be a random arrangement or a block arrangement. In any case.

In the case of producing a diorganopolysiloxane compound having a chloromethylphenyl group at one end having a number average molecular weight of 500 to 200,000, the compound represented by the general formula (3)
Wherein R ⁸ is a linear or branched alkyl group or phenyl group having 1 to 6 carbon atoms, p is 2, and the number average molecular weight is 500 to 200,000 at one terminal SiH group. The diorganopolysiloxane compound is preferred. When the number average molecular weight is 500 or less,
By adding the diorganopolysiloxane to the organic resin, various properties imparted to the organic resin tend to be reduced. When the number average molecular weight is 200,000 or more, it becomes relatively difficult to obtain a corresponding raw material.

On the other hand, when the number average molecular weight is 500 to 200,0
In the case of producing a diorganopolysiloxane compound having a chloromethylphenyl group at both ends of 00, the compound represented by the general formula (3) is a compound in which R ⁸ is hydrogen, p is 2, and the number average molecular weight is It is preferably a diorganopolysiloxane compound containing 500 to 200,000 SiH groups at both ends. When the number average molecular weight is 500 or less,
By adding the diorganopolysiloxane to the organic resin, various properties imparted to the organic resin tend to be reduced. When the number average molecular weight is 200,000 or more, it becomes relatively difficult to obtain a corresponding raw material.

The SiH group-containing organosilicon compound represented by the general formula (3) is synthesized by a cohydrolysis reaction of chlorosilanes, an equilibration reaction, a living polymerization of a strong base, or the like. In the co-hydrolysis reaction, monochlorosilane represented by the following general formula (8) and dichlorosilane represented by the following general formula (9)
This is a reaction for removing hydrogen chloride using water or a solvent containing water (reaction formula (1)), and the generated hydrogen chloride may be captured by a base as necessary.

Embedded image _{^{R 14 R 1 2 SiCl (8}} ) [ in the formula, R ¹ is a methyl group or a phenyl group, R ¹⁴ is an alkyl group or a phenyl group or a hydrogen, straight-chain or branched-chain having 1 to 6 carbon atoms Is]

R ¹⁵ R ¹ SiCl ₂ (9) wherein R ¹ is a methyl group or a phenyl group, and R ¹⁵ is a linear or branched alkyl group having 1 to 6 carbon atoms, a phenyl group, or hydrogen. Is]

Embedded image 2R ¹⁴ R ¹ ₂ Si chlorine _{^{+ x R 15 R 1 SiCl 2}} + H 2 O → R 14 R 1 2 SiO (R 15 R 1 SiO) xSiR 14 R 1 2 + H chlorine reaction formula (1) [Wherein at least one of R ¹⁴ and R ¹⁵ is hydrogen] By coexisting trichlorosilane as represented by the general formula (10) in the reaction formula (1), a polydialkylsiloxane having a T structure is also produced. be able to.

Embedded image R ¹⁶ SiCl ₃ (10) wherein R ¹⁶ is a methyl group or a phenyl group or hydrogen.

The equilibration reaction is a reaction of polymerizing a disiloxane represented by the following general formula (11) and a cyclopolysiloxane represented by the general formula (12) with an acidic catalyst or a basic catalyst (reaction formula (2)). ).

Embedded image _{^{(R 17 R 1 2 Si)}} 2 0 (11) [ in the formula, R ¹ is a methyl group or a phenyl group, R ¹⁷ is an alkyl group of straight or branched chains of 1 to 6 carbon atoms A phenyl group or hydrogen]

Embedded image (12) wherein R ¹ is a methyl group or a phenyl group, R ¹⁸ is a linear or branched alkyl group having 1 to 6 carbon atoms or a phenyl group or hydrogen, and t is an integer of 0 to 6. And u is an integer from 0 to 6, and t + u is an integer from 3 to 10.

Embedded image Reaction formula (2) [wherein, at least one of R ¹⁷ and R ¹⁸ is hydrogen]

In the strong base living polymerization, an organic alkali metal compound is used as an initiator to polymerize a cyclopolysiloxane represented by the following general formula (13), and then the following general formula (14)
Reaction to seal the end with chlorosilane represented by (reaction formula
(3)).

Embedded image (13) [wherein, R ¹ is a methyl group or a funyl group, R ²⁰ is a linear or branched alkyl group having 1 to 6 carbon atoms, a phenyl group, or hydrogen, and v is 0 to 3. , W is 0-3
And v + w is 3 to 6]

Embedded image _{^{R 21 R 1 2 SiCl (14}} ) [ in the formula, R ¹ is a methyl group or a phenyl group, R ²¹ is an alkyl group or a phenyl group or a hydrogen a linear or branched chain having 6 or less carbon atoms is there. ]

Embedded image Reaction formula (3) [wherein, at least one of R ²⁰ and R ²¹ is hydrogen and Y is an alkali metal atom] A trichlorosilane represented by the general formula (10) coexists in the reaction formula (3). Thereby, a polydialkylsiloxane having a T structure can also be produced.

Examples of the compound represented by the general formula used in the second invention (4), carbon having at least one carbon-carbon double bond of ^{R 9, R 10, R 1} 1, R 12, R 13 An alkylene group having 2 to 20 carbon atoms, and other than that, a hydrogen or a linear or branched alkyl group having 1 to 20 carbon atoms can be used. In particular,

Embedded image And the like.

The above-described manufacturing method according to the second invention of the present application comprises:
This is a hydrosilylation reaction performed in the presence of a catalyst. In this production method, a catalyst generally used for a hydrosilylation reaction can be used. As this catalyst, a transition metal catalyst can be used, and specific examples thereof include platinum, rhodium, iridium, ruthenium, palladium, molybdenum, and manganese. When using these catalysts, the form of a homogeneous catalyst dissolved in a solvent, the form of a supported catalyst supported on carbon, silica, or the like, or the form of a catalyst system using phosphine, amine, potassium acetate, etc. as a co-catalyst are used. Either can be adopted.

A solvent is not necessarily required in the production method, but an appropriate solvent may be used if necessary. Such solvents may be those that do not inhibit the reaction, such as hydrocarbon solvents such as hexane and heptane, aromatic hydrocarbon solvents such as benzene, toluene, and xylene, diethyl ether, THF, and dioxane. Ether solvents,
Examples include halogenated hydrocarbon solvents such as methylene chloride and carbon tetrachloride, alcohol solvents such as methanol, ethanol, and propanol, and water.
These solvents may be used alone or a plurality of solvents may be used in combination.

The reaction temperature in the production method is not particularly limited, but is usually lower than the boiling point when a solvent is generally used. When a solvent is not used in the reaction, the temperature is preferably 0 to 250 ° C, and preferably 20 to 120 ° C in consideration of economy and the like.

The third invention is characterized in that a siloxane compound having a chloromethylphenyl group at both ends represented by the following general formula (5) is reacted with the following general formula (6) in the presence of an acidic catalyst. This is a method for producing a diorganopolysiloxane compound having a chloromethylphenyl group at both ends and having a number average molecular weight of 500 to 200,000 represented by the general formula (7).

Embedded image (5) wherein R ¹ is a methyl group or a phenyl group, and q ′ is 0
An integer of from 1 to 1000, m 'is an integer of from 0 to 1000, and A is the general formula (2)]

Embedded image (6) wherein R ¹ is a methyl group or a phenyl group;
S is an integer of 0 to 6, r + s is 3 to
It is an integer of 10.]

Embedded image (7) wherein R ¹ is a methyl group or a phenyl group;
M is an integer of 0 to 1000, and A is represented by the general formula (2). Where q> = q 'and m> = m'
Note that the arrangement of the siloxane units in the polysiloxane skeleton in the general formulas (5) and (7) may be either a case where they are arranged in a random state or a case where they are arranged in a block state. Is also good.

The above-mentioned manufacturing method according to the third invention of the present application comprises:
This is an equilibration reaction performed in the presence of an acidic catalyst. The compound of the general formula (5) used in the present invention is produced by the second production method of the present application. The compound of the general formula (6) used in the present invention can be obtained as a commercial product, for example, TSL8221 manufactured by Toshiba Silicone Co., Ltd. (R ¹ is methyl and r
Is 5, and s is 0, decamethylcyclopentasiloxane),
TSL8234 (tetramethylcyclotetrasiloxane where R ¹ is methyl, r is 2 and s is 2), TSL824
7 (dimethyl where R ¹ is methyl, r is 1 and s is 3)
cyclotetrasiloxane), TSL8420 (octamethylcyclotetrasil where R ¹ is methyl, r is 4 and s is 0)
oxane), TSL82333 (hexamethylcyclotrisiloxane where R ¹ is methyl, r is 3 and s is 0) and the like correspond to this compound. In the production method, a catalyst generally used for an equilibration reaction can be used.
Specific examples of the catalyst include sulfuric acid, hydrochloric acid, phosphoric acid, activated soil, iron chloride, boric acid, trifluoroacetic acid, and acidic ion-exchange citrus.

A solvent is not necessarily required in the production method, but an appropriate solvent may be used if necessary.
Such a solvent may be one that does not inhibit the reaction, and may be a hydrocarbon solvent such as hexane or heptane, an aromatic hydrocarbon solvent such as benzene, toluene, or xylene,
Examples thereof include ether solvents such as diethyl ether, THF, and dioxane, and halogenated hydrocarbon solvents such as methylene chloride and carbon tetrachloride. These solvents may be used alone or in combination of two or more.

The reaction temperature in the production method is not particularly limited, but is usually lower than the boiling point when a solvent is usually used. When a solvent is not used in the reaction, the temperature is preferably 0 to 250 ° C, and preferably 20 to 120 ° C in consideration of economy and the like.

[0027]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. Note that, in the present example, for the purpose of confirming the reactivity of the chloromethylphenyl group-containing polysiloxane that is the compound of the present invention, as a reference example, the compound obtained in the example and the mercapto agent were used. Attempted a chemical reaction. The viscosity was measured using a Cannon-Fenske viscometer according to JIS Z8803.
(Viscosity measurement method) It measured according to the regulation. The moisture was measured in accordance with JIS K 0068 (method for measuring moisture in chemical products). The specific gravity was measured according to JIS K 0061 (method for measuring density and specific gravity of chemical products). Number average molecular weight and degree of dispersion were measured by gel permeation chromatography (GP
C). The column used was Shodex K
F-804L × 2, column temperature is 40 ° C., detector is R
I, the mobile phase is toluene. Example 1 Production of polysiloxane containing chloromethylphenyl groups at both ends having a number average molecular weight of about 1000 A magnetic stirrer, a cooling tube, a thermometer, and a dropping funnel were attached.
A polydimethylsiloxane having a number average molecular weight of 500 having SiH groups at both ends was placed in a 00 ml four-necked flask.
0 g was put in, and dry air was blown. The temperature of the solution was raised to 60 ° C., 5 μl of a self-gold catalyst was added, and chloromethylstyrene was added.
A uniform solution of 9 g and 0.3 g of t-butylcatechol was added dropwise from a dropping funnel over 2 hours. After aging for 1 hour, the reaction solution was cooled, and unreacted chloromethylstyrene and volatiles were distilled off under reduced pressure by an evaporator to obtain 149 g of a brown transparent liquid. This product has a viscosity of 21 (cSt / 25 ° C.), a water content of 250 ppm, a specific gravity of 1.029 (d ₄ ²⁵ ), and a chlorine content of 8.3 w.
The polystyrene equivalent number average molecular weight Mn was 950, and the dispersion (Mw / Mn) was 1.18. ¹ H-N shown in FIG.
From the MR chart and the IR chart shown in FIG. 7, it was confirmed that this product was a polysiloxane containing chloromethylphenyl groups at both ends.

Example 2 Production of borosiloxane having a chloromethylphenyl group at both ends having a number average molecular weight of about 5,000 A magnetic stirrer, a cooling tube, a thermometer, and a dropping funnel were attached.
In a 00 ml four-necked flask, 1 g of acidic ion exchange resin DIAION RCP160M (manufactured by Mitsubishi Chemical Corporation) and 50.8 g of toluene were placed and azeotropically dehydrated. After allowing to cool to room temperature, 40.7 g of octamethylcyclotetrasiloxane was added.
10 g of a chloromethylphenyl-modified silicone having both ends at the number average molecular weight of 950 obtained in the above was added, and the temperature was raised to 70 ° C.
The reaction was performed for 4 hours. After cooling the reaction solution, the ion exchange resin RCP160M was removed by filtration. The solvent and volatiles were distilled off under reduced pressure using an evaporator to obtain 42.8 g of a pale yellow transparent liquid. This product had a viscosity of 94 (cSt / 25 ° C.), a water content of 300 ppm, a chlorine content of 1.6 wt%, a polystyrene equivalent number average molecular weight (Mn) of 5,700, and a degree of dispersion (Mw / M).
n) was 1.53. From the ¹ H-NMR chart shown in FIG. 2 and the IR chart shown in FIG. 8, it was confirmed that this product was a polysiloxane having a chloromethylphenyl group at both ends.

Example 3 Production of polysiloxane containing chloromethylphenyl groups at both ends having a number average molecular weight of about 10,000 A magnetic stirrer, a cooling tube, a thermometer, and a dropping funnel were attached.
In a 00 ml four-necked flask, 1 g of acidic ion exchange resin DIAION RCP160M and 50 g of toluene were placed and azeotropically dehydrated until the water concentration became 100 ppm or less. After release to room temperature, 45.7 g of octamethylcyclotetrasiloxane
And 5 g of chloromethylphenyl-modified silicone having both ends and having a number average molecular weight of 950 obtained in Example 1 were added thereto, and the temperature was raised to 70 ° C. and reacted for 6 hours. After cooling the reaction solution, the ion exchange resin RCP160M was removed by care. The solvent and volatiles were distilled off under reduced pressure using an evaporator to obtain 43 g of a pale yellow transparent liquid. The viscosity of this product is 265 (cSt
/ 25 ° C), moisture is 300 (ppm), chlorine content is 0.76w
t%, number average molecular weight (Mn) in terms of polystyrene is 10
000 and the degree of dispersion (Mw / Mn) was 1.64. FIG.
From the ¹ H-NMR chart and FIG. 9 IR chart illustrating shown in, it was confirmed this product is chloro-terminated methylphenyl group-containing polysiloxane.

Example 4 Production of a polysiloxane containing a chloromethylphenyl group at one end having a number average molecular weight of about 2,000 A magnetic stirrer, a cooling tube, a thermometer, and a dropping funnel were attached.
In a 00 ml four-necked flask, 100 g of polydimethylsiloxane having a SiH group at one terminal and having a number average molecular weight of 1,000 was placed, and dry air was blown into the flask. The liquid temperature was raised to 60 ° C., 5 ul of a toluene solution containing 5 wt% of a platinum catalyst was added, and a uniform solution of 3.9 g of chloromethylstyrene and 0.2 g of t-butylcatechol was dropped from the dropping funnel over 30 minutes. After aging for 1 hour, the reaction solution was cooled, and 200 g of methanol was added to 120 g of the reaction solution to extract unreacted chloromethylstyrene. This operation was repeated four times. The solvent and volatiles were distilled off from the toluene layer under reduced pressure using an evaporator.
8 g of a pale yellow transparent liquid were obtained. The viscosity of this product is 1
6 (cSt / 25 ° C.), water content 17 ppm, specific gravity 0.97
4 (d ₄ ²⁵ ), chlorine content 2.25 (wt%), polystyrene-equivalent number average molecular weight (Mn) 1900, dispersity (Mw /
Mn) was 1.11. From the ¹ H-NMR chart shown in FIG. 4 and the IR chart shown in FIG. 10, it was confirmed that this product was a polysiloxane having a chloromethylphenyl group at one end.

Example 5 Production of a polysiloxane containing a chloromethylphenyl group at one end having a number average molecular weight of about 6000 A magnetic stirrer, a cooling tube, a thermometer, and a dropping funnel were attached.
In a 00 ml four-necked flask, 100 g of polydimethylsiloxane having a SiH group at one end and having a number average molecular weight of 5,000 was put, and dry air was blown into the flask. The temperature of the solution was raised to 60 ° C., 5 ul of a 5 wt% platinum catalyst in toluene solution was added, and a homogeneous solution of 3.9 g of chloromethylstyrene and 0.2 g of t-butylcatechol was dropped from the dropping funnel over 30 minutes. After aging for 1.5 hours, the reaction solution was cooled, and 200 g of methanol was added to 95 g of the reaction solution to extract unreacted chloromethylstyrene. This operation was repeated four times. The solvent and volatiles were distilled off from the toluene layer under reduced pressure using an evaporator to obtain 78 g of a pale yellow transparent liquid. The viscosity of this product is 69 (c
St / 25 ° C.), water content 200 ppm, specific gravity 0.976 (d
₄ ²⁵ ), chlorine content 0.60 (wt%), polystyrene equivalent number average molecular weight (Mn) 6300, polydispersity (Mw / M
n) was 1.07. From the ¹ H-NMR chart shown in FIG. 5 and the IR chart shown in FIG. 11, it was confirmed that this product was a polysiloxane having one terminal chloromethylphenyl group.

Example 6 Production of borosiloxane having a chloromethylphenyl group at one end having a number average molecular weight of about 9000
In a 00 ml four-necked flask, 100 g of polydimethylsiloxane having a SiH group at one terminal and having a number average molecular weight of 5,000 was put, and dry air was blown into the flask. The liquid temperature was raised to 60 ° C., 5 μl of a 5 wt% platinum catalyst in toluene solution was added, and a homogeneous solution of 3.9 g of chloromethylstyrene and 0.2 g of t-butylcatechol was dropped from the dropping funnel over 30 minutes. After aging for 21 hours, the reaction solution was cooled, and
Unreacted chloromethylstyrene was extracted by adding 200 g of methanol to 3 g. This operation was repeated four times. Solvents and volatiles are decompressed and distilled off from the toluene layer with an evaporator and 9
7.0 g of a pale yellow clear liquid were obtained. The viscosity of the product 117 (cSt / 25 ℃), moisture 180 ppm, specific gravity 0.976 (d ₄ ^25), chlorine is 0.41 (wt%), the number average molecular weight in terms of polystyrene (Mn) of 8,700 and the degree of dispersion (Mw / Mn) was 1.05. ¹ H shown in FIG.
From the NMR chart and the IR chart shown in FIG. 12, it was confirmed that this product was a polysiloxane having one terminal chloromethylphenyl group. Example 7 Production of dimethylpolysiloxane having a number average molecular weight of about 5,000 and having chloromethylphenyl groups at both ends having SiH groups in the main chain A magnetic stirrer, a cooling tube, a thermometer, and a dropping funnel were attached.
In a 00 ml four-necked flask, 2.25 g of an acidic ion exchange resin DIAION RCP 160M, 40 g of octamethylcyclotetrasiloxane, 135 g of hexamethylcyclotetrasiloxane, and the both ends of a chloro resin having a number average molecular weight of about 1000 obtained in Example 1 having a number average molecular weight of about 1000 Add 150 g of methylphenyl group-containing dimethylpolysiloxane, and raise the temperature to 70 ° C.
The reaction was performed for 21 hours. After cooling the reaction solution, the acidic ion exchange resin was removed by filtration. The volatiles were distilled off under reduced pressure using an evaporator to obtain 218 g of a pale yellow transparent liquid. This product has a viscosity of 100 (cSt / 25 ° C.) and a water content of 0.6.
%, Specific gravity 1.002 (d ₄ ^25), chlorine is 1.8 (wt
%), And the number average molecular weight (Mn) in terms of polystyrene is 55.
00 and the degree of dispersion (Mw / Mn) is 2.00. FIG.
It was confirmed from the ¹ H-NMR chart shown in that the product was a polysiloxane containing chloromethylphenyl groups at both ends. Reference Example 1 Production of dimethylpolysiloxane having a mercaptomethylphenyl group at both ends having a number average molecular weight of about 1000 A 500 ml flask equipped with a magnetic stirrer, a cooling tube, and a thermometer was charged with the number average molecular weight obtained in Example 1. About 1000 g of dimethylpolysiloxane containing chloromethylphenyl groups at both ends 50 g, sodium hydrogen sulfide 9.4
g and 150 g of 2-propanol. This mixture was heated to 40 ° C. and heated and stirred for 24 hours. Turbidity generated in the reaction solution was filtered, and 2-propanol was distilled off from the filtrate by an evaporator under reduced pressure. After the distillation was completed, the generated turbidity was filtered to obtain 45.2 g of a reddish yellow transparent liquid. From analysis results such as NMR, IR and GPC, it was confirmed that this product was a polydimethylsiloxane having a mercaptomethylphenyl group at both ends with a number average molecular weight of about 1,000.

[0033]

The chloromethylphenyl group-containing diorganopolysiloxane of the present invention can be easily converted into various substituents due to its high reactivity. By utilizing the good reactivity of the chloromethylphenyl group, it is possible to graft diorganopolysiloxane to various polymers, and to impart the characteristics of diorganopolysiloxane to various polymers. Further, according to the production method of the present invention, a chloromethylphenyl group-containing diorganopolysiloxane having an arbitrary molecular weight can be produced.

[Brief description of the drawings]

FIG. 1 shows a ¹ H-NMR chart of a dimethylpolysiloxane containing chloromethylphenyl groups at both ends according to Example 1 of the present invention.

FIG. 2 shows a ¹ H-NMR chart of a dimethylpolysiloxane containing chloromethylphenyl groups at both ends according to Example 2 of the present invention.

FIG. 3 shows a ¹ H-NMR chart of a dimethylpolysiloxane containing chloromethylphenyl groups at both ends according to Example 3 of the present invention.

FIG. 4 shows a ¹ H-NMR chart of a dimethylpolysiloxane having a chloromethylphenyl group at one end according to Example 4 of the present invention.

FIG. 5 shows a ¹ H-NMR chart of dimethylpolysiloxane having a chloromethylphenyl group at one end according to Example 5 of the present invention.

FIG. 6 shows a ¹ H-NMR chart of dimethylpolysiloxane having a chloromethylphenyl group at one end according to Example 6 of the present invention.

FIG. 7 shows an IR chart of a dimethylpolysiloxane containing chloromethylphenyl groups at both ends according to Example 1 of the present invention.

FIG. 8 shows an IR chart of dimethylpolysiloxane having a chloromethylphenyl group at both ends according to Example 2 of the present invention.

FIG. 9 shows an IR chart of a polysiloxane having a chloromethylphenyl group at both ends according to Example 3 of the present invention.

FIG. 10 shows an IR chart of dimethylpolysiloxane having one terminal chloromethylphenyl group of Example 4 of the present invention.

FIG. 11 shows an IR chart of dimethylpolysiloxane having one terminal chloromethylphenyl group of Example 5 of the present invention.

FIG. 12 shows an IR chart of dimethylpolysiloxane having one terminal chloromethylphenyl group of Example 6 of the present invention.

FIG. 13 shows a ¹ H-NMR chart of a dimethylpolysiloxane having a chloromethylphenyl group at both ends and having a SiH group in the main chain of Example 7 of the present invention.

Claims (5)

[Claims] 1. A chloromethylphenyl group-containing diorganopolysiloxane compound represented by the following general formula (1). Embedded image (1) wherein R ¹ is a methyl group or a phenyl group; R ² is a linear or branched alkyl group having 1 to 6 carbon atoms or a phenyl group or A; , M is 0
N is an integer of 0 to 500, p is an integer of 0 to 2, A is a group represented by the following general formula (2), and (2) X is a linear or branched alkylene group having 2 to 20 carbon atoms, at least one of R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ is a chloromethyl group, and the remaining groups Is hydrogen or carbon number 1
-20 linear or branched alkyl groups] 2. In the general formula (1) according to claim 1, R
² is a linear or branched alkyl group or phenyl group having 1 to 6 carbon atoms, 1 is 0, p is 2, and the number average molecular weight is in the range of 500 to 200,000. A diorganopolysiloxane compound containing one terminal chloromethylphenyl group. 3. The method according to claim 1, wherein R
² is A, 1 is 0, p is 2, and the number-average molecular weight is in the range of 500 to 200,000. A diorganopolysiloxane compound having a chloromethylphenyl group at both ends. [Course 4] A compound represented by the following general formula (3):
A method for producing a chloromethylphenyl group-containing diorganopolysiloxane compound, comprising reacting a compound represented by the following general formula (4) in the presence of a hydrosilylation reaction catalyst. Embedded image (3) wherein R ¹ is a methyl group or a phenyl group, R ⁸ is a linear or branched alkyl group having 1 to 6 carbon atoms or a phenyl group or hydrogen, and q is an integer of 0 to 1000 , M
Is an integer of 0 to 1000, and p is an integer of 0 to 2.] (4) [wherein at least one of R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ is an alkylene group having a carbon-carbon double bond and having 2 to 20 carbon atoms; Numbers 1-20
Is a linear or branched alkyl group of 4. The compound represented by the general formula (3) according to claim 4, wherein R ⁸ is a linear or branched alkyl or phenyl group having 1 to 6 carbon atoms, and p is 2. A method for producing a diorganopolysiloxane compound having a chloromethylphenyl group at one end, wherein a diorganopolysiloxane compound having a one-end SiH group having a number average molecular weight in the range of 500 to 200,000 is used. 5. The compound represented by the general formula (3) according to claim 4, wherein R ⁸ is hydrogen, p is 2, and the number average molecular weight is in the range of 500 to 200,000. Terminal SiH
A method for producing a diorganopolysiloxane compound having chloromethylphenyl groups at both ends, characterized by using a diorganopolysiloxane compound having a group. [Claim 7] A polysiloxane compound having a chloromethylphenyl group at both ends represented by the general formula (5) is reacted with the following general formula (6) in the presence of an acidic catalyst. ) Is 50.
A process for producing a diorganopolysiloxane compound having 0 to 200,000 chloromethylphenyl groups at both ends. Embedded image (5) wherein R ¹ is a methyl group or a phenyl group;
An integer of 1000, m 'is an integer of 0 to 1000, and A is represented by the general formula (2). (6) wherein R ¹ is a methyl group or a phenyl group;
S is an integer of 0 to 6, r + s is 3 to
And an integer of 10.] (7) wherein R ¹ is a methyl group or a phenyl group;
M is an integer of 0 to 1000, A is a group represented by the general formula (2), and X is 2 to 20 carbon atoms.
A linear or branched alkylene group of R ³ , R ⁴ , R ⁵ ,
At least one of R ⁶ and R ⁷ is a chloromethyl group,
The remaining group is hydrogen or a linear or branched alkyl group having 1 to 20 carbon atoms. Where q> = q 'and m> =
m ']