JPH08104755A - Isocyanatosilicon compound and production thereof - Google Patents

Abstract

PURPOSE: To obtain an isocyanatosilicon compd. useful as a material for synthesizing, e.g. a long-chain polysiloxane having only one NCO group in the molecule by selecting a specific isocyanatosilicon compd. CONSTITUTION: An isocyanatosilicon compd. represented by formula I (wherein R<1> is a 1-20C divalent hydrocarbon group; R<2> to R<5> are each a 1-10C monovalent hydrocarbon group; and n is 0-5) is selected. The compd. is pref. prepd. by reacting a halogenoalkyl compd. represented by formula II (wherein X is halogen) with a cyanate represented by the formula: M-(OCN)m (wherein M is a metal ion or a quaternary ammonium ion; and m is the valency of the metal or ammonium ion).

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, which silicon compound is used as a modifier for polymers and as a surface treating agent for various substrates, It is useful as a raw material for synthesizing a polymer, particularly as a raw material for synthesizing a reactive polymer having only one isocyanate group in the molecule.

[0002]

2. Description of the Related Art Siloxane compounds having an isocyanate group are easy to react with various polymers having a functional group such as a hydroxyl group, an amino group or a carboxyl group or a base material under neutral and mild conditions. It is a useful compound capable of modifying a polymer or a substrate by reacting with.
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 siloxane units introduced into a polymer or a base material becomes small, and sufficient modification cannot be performed in many cases. Also,
It is difficult to introduce only one isocyanate group into a high molecular weight silicon compound such as long chain polysiloxane, and thus it is difficult to obtain a long chain silicon compound containing an isocyanate group useful as a modifier. Met.

Therefore, it has been desired to develop a method for introducing only one isocyanate group into a polymer such as long-chain polysiloxane.

The present invention has responded to the above-mentioned demands and is used as a synthetic raw material for a long-chain polysiloxane having a single isocyanate group in a molecule, a polymer modifier, and a surface treatment agent for various substrates. It is an object of the present invention to provide a silicon compound having an isocyanate group and a method for producing the same, which are useful as

[0005]

Means for Solving the Problems As a result of various studies to achieve the above-mentioned object, the present inventors have found that a halogenoalkyl group-containing compound represented by the following general formula (2) and the following general formula ( By reacting with a cyanate represented by 3) or by thermally decomposing the carbamic acid ester represented by the following general formula (4) in the presence of trialkylchlorosilane and an acid scavenger, It has been found that a novel isocyanate group-containing silicon compound represented by the formula (1) can be obtained. The silicon compound of the formula (1) has one reactive functional group, one isocyanate group, and one vinyl group, and transitions to the vinyl group by 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 invention has been completed by finding that it is useful for modifying a polymer based on the reactivity of an isocyanate group and for surface treatment of various base materials.

[0006]

[Chemical 4] (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 is monovalent having 1 to 10 carbon atoms. Is a hydrocarbon group of
n represents an integer of 0 to 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. )

Therefore, the present invention provides a compound of the formula (1) for reacting an isocyanate group-containing silicon compound of the above formula (1), a halogenoalkyl group-containing compound of the formula (2) with a cyanate of the formula (3). Provided are a method for producing a silicon compound and a method for producing a silicon compound of formula (1), which comprises thermally decomposing a carbamic acid ester of formula (4) in the presence of a trialkylchlorosilane and an acid scavenger.

The present invention will be described in more detail below. The novel isocyanate group-containing silicon compound of the present invention is represented by 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. R ^{2 to} R ⁵ are the same or different monovalent hydrocarbon groups having 1 to 10 carbon atoms, preferably alkyl groups, and particularly alkyl groups having 1 to 6 carbon atoms.

Examples of the compound represented by the formula (1) include 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 formula (2)
A halogenated alkyl group-containing silicon compound represented by the formula (3) and a cyanate represented by the following formula (3) are reacted. In this case, the amount of cyanate used is preferably 1 to 1.2 mol per mol of the halogenoalkyl group-containing silicon compound.

[0013]

[Chemical 6] (In the formula, 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 salt of the formula (3), it is usually difficult to dissolve in an organic solvent, so it is preferable to add a phase transfer catalyst in order to accelerate the reaction. As the phase transfer catalyst used, quaternary ammonium salts such as tetraethylammonium chloride, tetrabutylammonium chloride, tetraethylammonium bromide, tetrabutylammonium bromide, tetraethylammonium iodide, tetrabutylammonium iodide, hexadecylpyridinium chloride, hexadecyl Pyridinium bromide,
Examples include pyridinium salts such as dodecylpyridinium iodide, benzyltriphenylphosphonium chloride, hexyltriphenylphosphonium bromide, phosphonium salts such as methyltriphenylphosphonium iodide, crown ethers such as 15-crown-5 and 18-crown-6. To be

The amount of these phase transfer catalysts added is usually 0.1 to 20 mol% with respect to the halogenoalkyl group-containing silicon compound of the formula (2). During the reaction, it is desirable to use an organic solvent that does not participate in the reaction, and an aprotic polar solvent such as dimethylformamide is particularly preferable. The amount of the solvent used may be such that the whole reaction solution is sufficiently stirred in the presence of the insoluble salt. Although the reaction temperature varies depending on the reaction substrate and the boiling point of the solvent, it is usually 20 to 150 ° C., and 80 to 120 ° C. is preferable for efficiently obtaining the product.

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

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

[0018]

[Chemical 7] (In the formula, R ^{1 to} R ⁵ and n have the same meanings as in formula (1).)

[0019]

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

[0020]

[Chemical 9] (In the formula, R ^{1 to} R ⁵ and n have the same meanings as in formula (1), and R represents a monovalent hydrocarbon group.) R ⁶ R ⁷ R ⁸ SiCl (7) (wherein, R ⁶ , R ⁷ and R ⁸ represent the same or different monovalent hydrocarbon groups having 1 to 4 carbon atoms.)

Here, examples of the monovalent hydrocarbon group of R include those having 1 to 10 carbon atoms, such as an alkyl group and an aryl group. Examples of the halogenoformic acid ester represented by the formula (6) include: Examples thereof include phenyl chloroformate, 4-nitrophenyl chloroformate, 2-naphthyl chloroformate, ethyl chloroformate and butyl chloroformate. The amount used is preferably 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) and the halogenoformic acid ester of the formula (6), the reaction temperature is preferably 0 to 50 ° C., and the reaction solvent is a by-produced salt. It is preferable to use a hydrocarbon-based solvent such as hexane, heptane, isooctane, toluene, xylene, etc. from the viewpoint of easy removal. Examples of the type of acid scavenger 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 carbamate of the formula (4), the trialkylchlorosilane of the formula (7) is added in order to cause the reaction to proceed irreversibly. The amount used is 1 with respect to 1 mol of the carbamate of the formula (4).
~ 1.3 moles are preferred. Further, as a scavenger of generated hydrochloric acid, the above-mentioned tertiary amine or nitrogen-containing heterocyclic compound is used in an amount of 1 to 1 mol of the trialkylchlorosilane of the formula (7).
It is necessary to add 1.2 moles. Reaction temperature is 60 ~
150 ° C. is preferred, and as the solvent to be used, hydrocarbon solvents such as isooctane, toluene and xylene, ether solvents such as dibutyl ether, monoglyme and diglyme, dimethylformamide and dimethylacetamide,
Aprotic polar solvents such as dimethyl sulfoxide, dimethyl imidazolidone, tetramethyl urea and the like can be mentioned.

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

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

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

Further, the compound of the formula (1) is obtained by modifying a polymer or a base material having a reactive group with an isocyanate group such as a hydroxyl group, an amino group and a carboxyl group due to the reactivity of the isocyanate group. You can

[0028]

INDUSTRIAL APPLICABILITY The isocyanate group-containing silicon compound of the present invention is useful as a modifier for polymers and as a surface treating agent for various substrates, and is particularly useful as a raw material for synthesizing polymers having only one isocyanate group. It is a compound.
Further, according to the production method of the present invention, such an isocyanate group-containing silicon compound can be produced in good yield.

[0029]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples.

Example 1 Synthesis of Isocyanatomethyldimethylvinylsilane 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 placed in the flask. 0.25 mol),
Tetrabutylammonium iodide 4.6 g (1
2.5 mmol) and 63 ml of dimethylformamide were charged, and potassium cyanate 24.3 g (0.30 mol)
Was added 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, 250 ml of hexane was added, and the mixture was stirred at room temperature for 1 hour. Take the upper layer of the flask contents separated into two layers, distill off the solvent under normal pressure, and then distill 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. The mass spectrum, nuclear magnetic resonance spectrum and infrared absorption spectrum of this compound were measured, and it was confirmed that the product was isocyanate methyldimethylvinylsilane. 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 stirrer, reflux condenser, thermometer and dropping funnel
The inside of a 00 ml four-necked flask was replaced with nitrogen, and 65.3 g (0.30 mo) of 1-aminopropyl-1,1,3,3-tetramethyl-3-vinyldisiloxane was placed in the flask.
l), 33.4 g of triethylamine (0.33 mo
1) and 90 ml of o-xylene were charged, and the flask was cooled to 10 ° C in an ice water bath. While stirring the inside of the flask, phenyl chloroformate 49.3 g (0.31
5 mol) was added dropwise. At this time, the dropping was performed for 2 hours at a speed such that the temperature of the contents did not exceed 40 ° C. Then, after stirring at room temperature for 1 hour, triethylamine 39.
5 g (0.39 mol) was added and the contents were heated to 80 ° C. The dropping funnel was replaced with a new one, and 39.1 g (0.36 mol) of chlorotrimethylsilane was added to 80-1.
It dripped from the dropping funnel at 00 degreeC over 1 hour. The reaction mixture was stirred at 100 ° C. for 2 hours and at 120 ° C. for 8 hours, and it was confirmed by gas chromatography that the carbamate was disappeared. After cooling, the precipitated triethylamine hydrochloride was filtered off, the filtrate was washed with 100 ml of water, and dried over anhydrous sodium sulfate. By distilling the obtained solution under reduced pressure, 60.2 g of a colorless transparent liquid having a boiling point of 90 ° C./6 mmHg was obtained. From the measurement results of mass spectrum, nuclear magnetic resonance spectrum, and infrared absorption spectrum, the obtained product was 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) Shown in FIG.

[Brief description of drawings]

FIG. 1 is an infrared absorption spectrum of the 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.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Mikio Endo 28-1 Nishifukushima, Kubiki Village, Nakakubiki-gun, Niigata Prefecture Shin-Etsu Chemical Co., Ltd.

Claims (3)

[Claims] 1. The following general formula (1): (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 is monovalent having 1 to 10 carbon atoms. Is a hydrocarbon group of
n represents an integer of 0 to 5. ) Isocyanate group-containing silicon compound represented by. 2. The following general formula (2): (In the formula, 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 is the reaction of a cyanate represented by representative.) the valence of the metal ion or a quaternary ammonium ion The method for producing an isocyanato group-containing silicon compound according to claim 1. 3. The following general formula (4): (In the formula, R ^{1 to} R ⁵ and n have the same meanings as in the formula (1), and R represents a monovalent hydrocarbon group.), A carbamate represented by trialkylchlorosilane and an acid scavenger The method for producing an isocyanate group-containing silicon compound according to claim 1, which is characterized by thermally decomposing in the presence of