JP3198827B2 - Isocyanate group-containing silicon compound and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel silicon compound having an isocyanate group and a method for producing the same, and this silicon compound is used as a polymer modifier or a surface treatment agent for various substrates, It is useful as a raw material for synthesizing polymers, particularly as a raw material for synthesizing reactive polymers having only one isocyanate group in the molecule.

[0002]

2. Description of the Related Art A siloxane compound having an isocyanate group is easily formed under neutral and mild conditions with various polymers and substrates having a functional group such as a hydroxyl group, an amino group and a carboxyl group. Is a useful compound that can modify polymers and substrates in response to
For use as a modifier, it is necessary to have only one isocyanate group in the molecule in order to avoid cross-linking between polymers. However, when a low molecular weight isocyanate group-containing silicon compound that can be purified by distillation is used,
The content of the siloxane unit introduced into the polymer or the base material is reduced, and sufficient modification cannot be often performed. Also,
It is difficult to introduce only one isocyanate group into a high-molecular-weight silicon compound such as a long-chain polysiloxane, and therefore it is difficult to obtain a long-chain silicon compound containing an isocyanate group useful as a modifier. Met.

Therefore, development of a method for introducing only one isocyanate group into a polymer such as a long-chain polysiloxane has been demanded.

The present invention meets the above-mentioned demands, and is used as a raw material for synthesizing a long-chain polysiloxane having only one isocyanate group in a molecule, a polymer modifier or a surface treating agent for various substrates. It is an object of the present invention to provide a silicon compound having an isocyanate group, which is useful as a compound, and a method for producing the same.

[0005]

Means for Solving the Problems The present inventors have conducted various studies to achieve the above object, and as a result, have found that a halogenoalkyl group-containing compound represented by the following general formula (2) and a compound represented by the following general formula (2) By reacting with a cyanate represented by 3) or by thermally decomposing a carbamate represented by the following general formula (4) in the presence of a trialkylchlorosilane and an acid scavenger, It has been found that an isocyanate group-containing silicon compound represented by the formula (1) can be obtained. The silicon compound of the formula (1) has one isocyanate group and one vinyl group, which are reactive functional groups, and the vinyl group is transitioned to the vinyl group using, for example, one end hydrogen polysiloxane. By performing the hydrosilylation reaction in the presence of a metal catalyst or the like, a polysiloxane having only one isocyanate group in the molecule can be easily obtained, and synthesis of a polymer such as an isocyanate group-containing long-chain polysiloxane, The present inventors have found that they are useful for modifying polymers based on the reactivity of isocyanate groups and for surface treatment of various substrates, and have accomplished the present invention.

[0006]

Embedded image (In the formula, R ¹ represents a divalent hydrocarbon group having 1 to 10 carbon atoms, and R ² , R ³ , R ⁴ and R ⁵ may be the same or different, and each may be a monovalent hydrocarbon group having 1 to 10 carbon atoms. Is a hydrocarbon group of
n represents the integer of 0-5. X is a halogen atom, M
Represents a metal ion or a quaternary ammonium ion, m represents a valence of M, and R represents a monovalent hydrocarbon group. )

Accordingly, the present invention provides the following general formula (1a)
A method for producing a silicon compound of the formula (1), which comprises reacting a halogenoalkyl group-containing compound of the formula (2) with a cyanate of the formula (3), and a formula (4) To provide a method for producing a silicon compound of the formula (1) wherein the carbamic acid ester of the formula (1) is thermally decomposed in the presence of a trialkylchlorosilane and an acid scavenger.

Now, the present invention will be described in more detail. The novel isocyanate group-containing silicon compound of the present invention is represented by the following general formula (1a) contained in the following general formula (1).

[0009]

Embedded image

Here, R ¹ is a divalent hydrocarbon group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 3 carbon atoms. Further, R ^{2 to} R ⁵ are the same or different monovalent hydrocarbon groups having 1 to 10 carbon atoms, preferably an alkyl group, particularly an alkyl group having 1 to 6 carbon atoms. k is an integer of 1 to 5, and n is an integer of 0 to 5.

The compounds represented by the formula (1) include, for example, the following. Isocyanatomethyldimethylvinylsilane, isocyanatoethyldimethylvinylsilane, isocyanatopropyldimethylvinylsilane, 1-isocyanatomethyl-1,1,3,3-tetramethyl-3-vinyldisiloxane, 1-isocyanatoethyl-1,1 , 3,3-Tetramethyl-3-vinyldisiloxane, 1-isocyanatopropyl-1,1,
3,3-tetramethyl-3-vinyldisiloxane, 1-
Ethyl-1-isocyanatopropyl-1,3,3-trimethyl-3-vinyldisiloxane, 3-ethyl-1-
Isocyanatopropyl-1,1,3-trimethyl-3
-Vinyldisiloxane, 1,3-diethyl-1-isocyanatopropyl-1,3-dimethyl-3-vinyldisiloxane, 1-n-propyl-1-isocyanatopropyl-1,3,3-trimethyl-3 -Vinyldisiloxane, 1-i-propyl-1-isocyanatopropyl-
1,3,3-trimethyl-3-vinyldisiloxane, 1
-N-butyl-1-isocyanatopropyl-1,3,
3-trimethyl-3-vinyldisiloxane, 1-i-butyl-1-isocyanatopropyl-1,3,3-trimethyl-3-vinyldisiloxane, 1-s-butyl-1
-Isocyanatopropyl-1,3,3-trimethyl-
3-vinyldisiloxane, 1-n-pentyl-1-isocyanatopropyl-1,3,3-trimethyl-3-vinyldisiloxane, 1-cyclopentyl-1-isocyanatopropyl-1,3,3-trimethyl- 3-vinyldisiloxane, 1-n-hexyl-1-isocyanatopropyl-1,3,3-trimethyl-3-vinyldisiloxane, 1-cyclohexyl-1-isocyanatopropyl-1,3,3-trimethyl- 3-vinyldisiloxane, 1-isocyanatomethyl-1,1,3,3,5
5-hexamethyl-5-vinyltrisiloxane, 1-isocyanatomethyl-1,1,3,3,5,5,7,7
-Octamethyl-7-vinyltetrasiloxane, 1-isocyanatomethyl-1,1,3,3,5,5,7,
7,9,9-decamethyl-9-vinylpentasiloxane.

The silicon compound of the formula (1) can be produced, for example, by the following method. That is, the following equation (2)
Wherein a halogenoalkyl group-containing silicon compound represented by the following formula is reacted with a cyanate represented by the following formula (3). In this case, the amount of the cyanate used is preferably 1 to 1.2 mol per 1 mol of the halogenoalkyl group-containing silicon compound.

[0013]

Embedded image (Wherein, R ^{1 to} R ⁵ and n have the same meanings as in formula (1), and X represents a halogen atom), and a halogenoalkyl group-containing compound represented by the following general formula (3): M (OCN) ) _m ... (3) (wherein, M represents a metal ion or a quaternary ammonium ion, m represents the valence of the metal ion or a quaternary ammonium ion.)

When M is a metal ion in the cyanate of the formula (3), it is generally difficult to dissolve in an organic solvent. Therefore, it is preferable to add a phase transfer catalyst to promote the reaction. Examples of the phase transfer catalyst used include quaternary ammonium salts such as tetraethylammonium chloride, tetrabutylammonium chloride, tetraethylammonium bromide, tetrabutylammonium bromide, tetraethylammonium iodide, tetrabutylammonium iodide, hexadecylpyridinium chloride, hexadecyl Pyridinium bromide,
Pyridinium salts such as dodecylpyridinium iodide; phosphonium salts such as benzyltriphenylphosphonium chloride, hexyltriphenylphosphonium bromide and methyltriphenylphosphonium iodide; and crown ethers such as 15-crown-5 and 18-crown-6. Can be

The amount of the phase transfer catalyst to be added is usually 0.1 to 20 mol% based on the halogenoalkyl group-containing silicon compound of the formula (2). At the time of the reaction, it is desirable to use an organic solvent that does not participate in the reaction, and particularly preferred is an aprotic polar solvent such as dimethylformamide. The solvent may be used in such an amount that the whole reaction solution is sufficiently stirred in the presence of the insoluble salt. The reaction temperature varies depending on the reaction substrate and the boiling point of the solvent, but is usually from 20 to 150 ° C, and preferably from 80 to 120 ° C in order to obtain a product efficiently.

After completion of the reaction, the compound of the formula (1) can be obtained by removing the by-produced salt and distilling the mixture under reduced pressure.

The compound of the formula (1) can also be produced by the following method. That is, the following formula obtained by a method such as reacting an aminoalkyl-containing silicon compound represented by the following formula (5) with a halogenoformate represented by the following formula (6) in the presence of an acid scavenger: The compound of the formula (1) can be obtained by thermally decomposing the carbamic acid ester represented by the formula (4) in the presence of a trialkylchlorosilane represented by the following formula (7) and an acid scavenger.

[0018]

Embedded image (In the formula, R ^{1 to} R ⁵ and n have the same meaning as in formula (1).)

[0019]

Embedded image (In the formula, R represents a monovalent hydrocarbon group, and X represents a halogen atom.)

[0020]

Embedded image (Wherein, R ^{1 to} R ⁵ and n have the same meaning as in formula (1), and R represents a monovalent hydrocarbon group.) R ⁶ R ⁷ R ⁸ SiCl (7) R ⁶ , R ⁷ and R ⁸ represent a monovalent hydrocarbon group having 1 to 4 carbon atoms which may be the same or different.)

Here, examples of the monovalent hydrocarbon group for R include those having 1 to 10 carbon atoms, for example, an alkyl group and an aryl group. Examples of the halogenoformate represented by the formula (6) include: Examples include phenyl chloroformate, 4-nitrophenyl chloroformate, 2-naphthyl chloroformate, ethyl chloroformate, and butyl chloroformate. The amount used is preferably from 1 to 1.2 mol per 1 mol of the aminoalkyl group-containing silicon compound of the formula (5).

In the reaction of the aminoalkyl group-containing silicon compound of the formula (5) with the halogenoformate of the formula (6), the reaction temperature is preferably from 0 to 50 ° C. It is preferable to use a hydrocarbon-based solvent such as hexane, heptane, isooctane, toluene, and xylene in that the solvent is easily removed. Examples of the type of the acid scavenger to be used include tertiary amines such as triethylamine, tributylamine, diisopropylethylamine and N-methylmorpholine, and nitrogen-containing heterocyclic compounds such as pyridine and quinoline. 1) to 1.3 equivalents based on the aminoalkyl group-containing silicon compound of (1).

On the other hand, during the thermal decomposition of the carbamic acid ester of the formula (4), a trialkylchlorosilane of the formula (7) is added to make the reaction proceed irreversibly. The amount used is 1 to 1 mol of the carbamate of the formula (4).
~ 1.3 mol is preferred. As a scavenger for the generated hydrochloric acid, the above-mentioned tertiary amine or nitrogen-containing heterocyclic compound is used in an amount of 1 to 1 mol based on the trialkylchlorosilane of the formula (7).
It is necessary to add 1.2 mol. Reaction temperature is 60 ~
150 ° C. is preferable, and as a solvent to be used, hydrocarbon solvents such as isooctane, toluene and xylene, ether solvents such as dibutyl ether, monoglyme and diglyme, dimethylformamide, dimethylacetamide
Aprotic polar solvents such as dimethylsulfoxide, dimethylimidazolidone, and tetramethylurea.

After completion of the reaction, the salt is removed from the reaction solution by filtration and washing with water, followed by distillation under reduced pressure to obtain the compound of the formula (1).

As another method for producing the compound of the formula (1), an aminoalkyl group-containing silicon compound of the formula (6) is reacted with an equimolar amount of phosgene in the presence of an acid scavenger such as a tertiary amine. Although there is a method of causing phosgene, which is highly toxic, it is not preferable.

The compound of the formula (1) has an isocyanate group and a vinyl group in one molecule. Therefore, SiH
Hydrosilylation in the presence of a polymer such as a long-chain organohydrogenpolysiloxane having one group per molecule and a hydrosilylation catalyst such as a platinum-based catalyst results in one isocyanate group per molecule. Polymers such as long-chain organopolysiloxanes can be obtained.

The compound of the formula (1) can modify a polymer or a substrate having a reactive group with an isocyanate group such as a hydroxyl group, an amino group or a carboxyl group by the reactivity of the isocyanate group. Can be.

[0028]

The isocyanate group-containing silicon compound of the present invention is useful as a polymer modifier or a surface treating agent for various substrates, and is particularly useful as a raw material for synthesizing a polymer having only one isocyanate group. Compound.
Further, according to the production method of the present invention, such an isocyanate group-containing silicon compound can be produced at a high yield.

[0029]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited to the following Examples.

Example 1 Synthesis of Isocyanate Methyldimethylvinylsilane A 500-ml three-necked flask equipped with a stirrer, a reflux condenser, and a thermometer was purged with nitrogen, and 56.5 g of iodomethyldimethylvinylsilane was added to the flask. 0.25 mol),
4.6 g of tetrabutylammonium iodide (1
2.5 mmol) and 63 ml of dimethylformamide, and 24.3 g (0.30 mol) of potassium cyanate.
And heated to 100 ° C. with vigorous stirring, and stirring was continued for 5 hours. After cooling, it was confirmed by gas chromatography that iodomethyldimethylvinylsilane had disappeared. Then, 250 ml of hexane was added, and the mixture was stirred at room temperature for 1 hour. The upper layer of the contents of the flask separated into two layers was taken, and the solvent was distilled off under normal pressure, followed by distillation under reduced pressure to give a boiling point of 74.
23.1 g of a colorless and transparent liquid of -75 ° C / 50 mmHg was obtained. When the mass spectrum, nuclear magnetic resonance spectrum and infrared absorption spectrum of this compound were measured, it was confirmed that the product was isocyanatomethyldimethylvinylsilane. The yield was 65.3%. The measurement results of various spectra are shown below. Mass spectrum (EI method) m / z: 126 ([M-CH ₃ ] ⁺ ), 85 ([M-CH
₂ NCO] ⁺ )

[0031]

[Table 1] Infrared absorption spectrum (NaCl) is shown in FIG.

Example 2 Synthesis of 1-isocyanatopropyl-1,1,3,3-tetramethyl-3-vinyldisiloxane 5 equipped with a stirrer, a reflux condenser, a thermometer and a dropping funnel.
The inside of a 00 ml four-necked flask was replaced with nitrogen, and 65.3 g (0.30 mol) of 1-aminopropyl-1,1,3,3-tetramethyl-3-vinyldisiloxane was added to the flask.
l), 33.4 g of triethylamine (0.33 mol
l), 90 ml of o-xylene was charged, and the flask was cooled to 10 ° C in an ice water bath. While stirring the inside of the flask, 49.3 g (0.31 g) of phenyl chloroformate was dropped from the dropping funnel.
5 mol) was added dropwise. At this time, the dripping was performed over 2 hours at a rate such that the temperature of the contents did not exceed 40 ° C. After stirring at room temperature for 1 hour, triethylamine was added.
5 g (0.39 mol) were added and the contents were heated to 80 ° C. Replace the dropping funnel with a new one, and add 39.1 g (0.36 mol) of chlorotrimethylsilane to 80-1.
The mixture was dropped from the dropping funnel over 1 hour at 00 ° C. The reaction mixture was stirred at 100 ° C. for 2 hours and at 120 ° C. for 8 hours, and the disappearance of the carbamate was confirmed by gas chromatography. After cooling, the precipitated triethylamine hydrochloride was separated by filtration, and the filtrate was washed with 100 ml of water and dried over anhydrous sodium sulfate. The obtained solution was distilled under reduced pressure to obtain 60.2 g of a colorless transparent liquid having a boiling point of 90 ° C./6 mmHg. From the measurement results of mass spectrum, nuclear magnetic resonance spectrum and infrared absorption spectrum, the obtained product was identified as 1-isocyanatopropyl-1,1,3,3-
It was confirmed to be tetramethyl-3-vinyldisiloxane. The yield was 82.5%. The measurement results of various spectra are shown below. Mass spectrum (EI method) m / z: 228 ([M-CH ₃ ] ⁺ ), 216 ([M-C
₂ H _3] ⁺⁾

[0033]

[Table 2] Infrared absorption spectrum (NaCl) is shown in FIG.

[Brief description of the drawings]

FIG. 1 is an infrared absorption spectrum of a compound obtained in Example 1 of the present invention.

FIG. 2 is an infrared absorption spectrum of the compound obtained in Example 2 of the present invention.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Akira Yamamoto 28-1 Nishifukushima, Kushiro-mura, Nakakushijo-gun, Niigata Shin-Etsu Chemical Industry Co., Ltd. Synthetic Technology Research Institute (72) Inventor Mikio Endo Kushiro-mura, Nakakubi-jo, Niigata 28-1 Nishifukushima Shin-Etsu Chemical Co., Ltd. Synthetic Technology Laboratory (56) References JP-A-62-238294 (JP, A) JP-A-62-226988 (JP, A) JP-A-62-209112 (JP) JP-A-8-157728 (JP, A) JP-A-9-31155 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 77/20 C08G 77/26 CA (STN) REGISTRY (STN)

Claims (3)

(57) [Claims] 1. The following general formula (1a): (Wherein, R ¹ represents a divalent hydrocarbon group having 1 to 10 carbon atoms, and R ² , R ³ , R ^4, and R ⁵ may be the same or different, and each may be a monovalent C 1-10 hydrocarbon group.) And k represents an integer of 1 to 5.). 2. The following general formula (2): (Wherein, R ¹ represents a divalent hydrocarbon group having 1 to 10 carbon atoms, and R ² , R ³ , R ^4, and R ⁵ may be the same or different, and each may be a monovalent C 1-10 hydrocarbon group.) And n represents an integer of 0 to 5. X represents a halogen atom.) And a halogenoalkyl group-containing compound represented by the following general formula (3): M (OCN) _m (3) (Wherein, M represents a metal ion or a quaternary ammonium ion, and m represents a valence of the metal ion or a quaternary ammonium ion). Formula (1) (Wherein, R ^{1 to} R ⁵ and n have the same meanings as described above). 3. The following general formula (4): (Wherein, R ¹ represents a divalent hydrocarbon group having 1 to 10 carbon atoms, and R ² , R ³ , R ^4, and R ⁵ may be the same or different, and each may be a monovalent C 1-10 hydrocarbon group.) Wherein n represents an integer of 0 to 5 and R represents a monovalent hydrocarbon group.) In the presence of a trialkylchlorosilane and an acid scavenger. The following general formula (1): (Wherein, R ^{1 to} R ⁵ and n have the same meanings as described above).