JPS6127992A - Preparation of organosilane compound having aromatic ring - Google Patents

Abstract

NEW MATERIAL:An organosilane compound expressed by formula I (R<1> is OCH2CH2, formula II, etc.; R<2> and R<3> are 1-4C hydrocarbon; X is Cl or Br; Y is O, SO2, CH2, etc; k and n are 0 or 1; l and m are integers 1-4). EXAMPLE:A compound expressed by formula III. USE:A protecting film and functional film for materials, e.g. metal, plastic, wood, etc. PREPARATION:A diallyl compound having an aromatic ring expressed by formula IV is subjected to addition reaction with an alkoxysilane compound, containing hydrogen atoms, and expressed by formula V in the presence of a platinum compound, e.g. platinum black, to afford the aimed compound expressed by formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a novel organosilane compound containing an aromatic ring substituted with an alkoxysilyl group at both ends of the molecule, and a method for producing the same.

[Prior Art] ' Conventionally, A-sl(oR4)s (where .R4 is an alkyl group, and A represents a functional group such as epoxy, amine, or cyano).

), such as 3-aminopropyltriethoxysilane.

2-cyanoethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, etc. are known compounds.
It is known that these compounds can be used as water repellent treatment agents for fiber surfaces and surface hardening treatment agents for plastics. However, these compounds containing a single reactive silicon have poor room temperature crosslinking reactivity and are difficult to form cured products. Therefore, strict conditions are necessary.

Therefore, for example, bis(alkoxysilyl) compounds have been proposed in JP-A-58-219188 and JP-A-58-121292, which are important as they suggest future directions. However, the refractive index of the cured silicon thread obtained here is about 1.5, its physical properties are resin-like with elasticity, and its chemical resistance is not sufficient.

Also, JP-A-5'6-161475, JP-A No. 58-122
No. 971 and No. 58-222160 disclose a composition containing a bis(alkoxysilyl) compound as one component and containing colloidal silica and other silane coupling agents.
JP-A-59-11574 exemplifies bissilyl compounds having an aromatic skeleton. However, among the bissilyl compounds disclosed among these, those with an aromatic ring show improvement in chemical resistance and scratch resistance, but they directly introduce a silyl group into the aromatic ring, resulting in unreacted substances. Many monosubstituted and mono-substituted compounds occur, and the yield of bissilyl compounds is low, making it impractical. Furthermore, among the disclosed examples, bissilyl compounds consisting of linear organic chains are difficult to completely undergo hydrolysis and silanol condensation reactions during the coating process, making it difficult to obtain sufficient durability. is the reality.

On the other hand, there is an increasing demand for organosilicon compounds to be used as protective films or functional films for materials such as metals, plastics, and wood. The scope of use is expanding due to advantages such as surface energy.

〔the purpose〕

An object of the present invention is to provide a novel organic silane compound and a method for producing the same, which are compatible with the new uses described above. In particular, the object of the present invention is to provide a reactive organosilane compound that has sufficient transparency and high refractive index properties useful for optical applications, and at the same time provides strong and chemically resistant functions as a structural material, and a method for producing the same. The purpose is to

〔overview〕

The novel aromatic ring-containing organic silane compound of the present invention is
General formula (to) ÷OR2)s-n (2) (wherein R1 is -0=OR20R2-.

Each R3 independently represents a hydrocarbon group having 1 to 4 carbon atoms. or represents a chlorine or bromine atom, Y represents -01-8021-cH2-, and each independently represents an integer from 1 to 4; n represents 0 or 1; ), and the manufacturing method thereof includes general formulas (I) and (1), (wherein R'', R2, R3, Jr,
n, X and Y are as described above. ) These compounds of the present invention, which are obtained by addition-reacting diallyl compounds represented by the following formula using a platinum-based catalyst in the presence of a suitable solvent, are described in, for example, JP-A-57-147505. Diallyl compound (I), (1) a mono-addition reaction of trialkoxysilane or alkyldialkoxysilane, (2) after addition reaction of halogenated silane such as trichlorosilane or alkyldichlorosilane, and lower alcohol. There are two routes that can be considered: (1) is suitable for carrying out the present invention because it causes fewer side reactions.

Examples of bissilyl compounds obtained in this way include -oaH20H20C○(OH2)! 51cocHs
>s-0OH20H20(OH21)s'51(o
oa3)s-OOH20H20(OH2)s 51(o
Cu,)s+oaa20H2)2000(OH2)s
5i(OCH3)34oam20H2)s O(+0(
OH2)s 5t(ooa,)sl 4oam20H2)20(,0H2)s Si(OCH
3) 34oca2ah2)go(cl(2),sl(
oCu3)s-oog, bHo(aH2)s 5t(
oau, )s, etc.

Further, among these compounds, compounds in which the nuclear substituent is -0+, -5o2-, -0H2- instead of a bromo group, such as compounds having or, or a hydroxide group, etc., can be mentioned. Furthermore, those in which the carbonate group is composed of an ether group are also useful because they can be synthesized by the same reaction.

The platinum compounds used in the present invention are generally useful as catalysts used in hydrosilylation, such as platinum chloride (first and second), hydrates of chloroplatinic acid, alcohol compounds, aldehyde compounds, olefins, phosphine complexes, and platinum Black etc. can be used. In particular, platinum black is suitable for the present invention because it does not cause coloring of reaction products.

Solvents include BTx such as benzene, toluene, and xylene;
Cyclohexane, dimethyl ether, diethyl ether, chloroform, tetracyclic carbon 1. f Solvents such as trahydrofuran can be used.

In addition, the reaction conditions are not particularly limited, but
It varies depending on the type of raw material and catalyst, but in general -2
The reaction is completed in a reaction time of several tens of minutes to 60 minutes at a temperature of 0 to 100°C. Further, although it is preferable to carry out the reaction in nitrogen gas, there is no problem in dry air. Further, the reaction conditions may be carried out under increased pressure or reduced pressure. An example of the reaction is shown in the following reaction formula.

(However, X, Y, R1, R2, R3, f!,
, 9 is as described above ◎) The diallyl compound and silane compound represented by the above formula are both known compounds, and can be used without being limited to the manufacturing method.

Although the reaction is not particularly limited, it is generally preferable to dilute the diallyl compound and the catalyst in the above-mentioned solvent, and then drop an excess amount of the silane compound to cause the reaction. Further, the amount of the catalyst can be used in the range of 10 -5 to 1 mol % of the silane compound, but since it depends on trace amounts of impurities in the raw materials and the type of catalyst, it is necessary to select an appropriate amount depending on the reaction system.

〔Example〕

EXAMPLES In order to explain the present invention more specifically, examples and application examples will be described below, but the present invention is not limited to these examples.

Example 1 A magnetic stirrer was placed in a Pyrex round-bottomed flask equipped with a cooling reflux tube that had been dried by flame treatment under reduced pressure, and the inside was sufficiently purged with nitrogen.

Subsequently, purified and dried 2,2-bis(4-allyl carbonate ethoxy-3゜5-dibrom-phenyl)propane-0OH,0H2000 (IH20H=O horse (hereinafter referred to as T
BO) was added to 32F (40 mwofi), dehydrated toluene was added to 1001 mf, and platinum black was added to 160 mf.
The liquid temperature was set to 40°C without electromagnetic stirring. ・Continuously, while stirring, trimethoxysilane 14.6f' (
A solution of 202 diluted with dehydrated methanol was added dropwise over 1 hour. Subsequently, the reaction was completed by heating under reflux for 4 hours. The catalyst was separated from this reaction mixture, and then filtered through a membrane filter (
The film was made with a pore size of 1 μm (manufactured by Fuji Photo Film Co., Ltd.) in an overloaded manner.

While stirring the r liquid, unreacted trimethoxysilane and a portion of the solvent were recovered under reduced pressure (~2 ossHf). Furthermore, by increasing the degree of vacuum and raising the temperature to ~2 μar) so ~70 °C, the remaining low-boiling components were distilled off, and 41 g of a viscous colorless transparent liquid was obtained. The measurements showed that the absorption at <1660 cm based on the O=a bond observed in TBO disappeared, while the strong absorption at <1100 cm based on 51-0 and 785cm1
, and an absorption at 2975 cm based on O-H were newly generated. In addition, GPC chromatography analysis (column; trade name GL-A110+Al2O manufactured by Hitachi Chemical Co., Ltd.)
The conversion rate was approximately 100%, the bissilyl compound was 96 Area% or more, and the sum of the monosilyl compound and the polymeric compound was A Area% or less (detector: differential refractometer, manufactured by Showa Denko KK). From these results, the first product is 2,2-bis(trimethoxysilylpropyl carbonate ethoxy-3,5-dibromphenyl)propane-0OH,0H2080-(-OH,
)s (hereinafter abbreviated as 5TBO). The crude yield of this 5TBO was 96% based on the TBO used.
Met.

This 5TBO is benzene, toluene, chloroform,
It was soluble in acetone, slightly soluble in alcohol and cellosolves, and insoluble in water.

Examples 2 and 3 In Example 1, instead of using trimethoxysilane 14.61, the compounds shown in Table 1 were used, and the reaction and purification was carried out in the same manner as in Example 1 to obtain the corresponding bissilyl compound. The results are shown in Table 1.

Table 1 Example 4 EITBO10S' obtained in Example 1) Luene 5Q
f, t+-butanol 20? , P-toluenesulfonic acid (0.2 f) was added, and the mixture was heated with stirring. Set the liquid temperature to 70℃
The reaction was continued for 21 hours while gradually distilling off methanol. In this way, methanol was recovered almost quantitatively. Subsequently, 200 cc of cold water was added, and after stirring quickly, the mixture was allowed to stand to separate, and the aqueous layer was removed. After performing this operation twice, 50 cc of four molecular sieves were added to the obtained oil layer, and the mixture was left in the apparatus overnight. By filtering this liquid and distilling off the solvent under reduced pressure, 2,2-bis(triptoxysilylpropyl carbonate ethoxy-6,
5-dibromphenyl)propane (hereinafter abbreviated as BSTBO) was obtained.

Reference Example 1 9 In Example 1, instead of trimethoxysilane,
A reaction was carried out in the same manner as in Example 1 using trichlorosilane 162f and using the silane compound without diluting it with methanol. Subsequently, while bubbling nitrogen into the reaction solution, 30 parts of dry methanol was added and reacted for 30 minutes.Separation and purification was carried out in the same manner as in Example 1. As a result of QPO chromatography analysis, it was found that about 10 Area% of polymer components were produced. This was extracted with a mixed solvent of cyclohexane and methanol, and 5TBe was isolated (16.4 f). The isolated yield was 40%.

Examples 5 to 12 In Example 1, synthesis was performed using the compounds shown in Table 2 instead of TBO, and using platinum black or chloroplatinic acid hexahydrate as a catalyst. This result is the second
Shown in the table. However, when chloroplatinic acid is used as a catalyst, it is filtered and concentrated to obtain a solution with a product concentration of 50%. H20H=OH.

-(-oca2+, a2 chicken 0000H20H=OH.

^ -O(!H2OH2O0H20H=(”H.

-0OH20H2oao+on, +ssi, (-oa
H3) s-oa horse OH, o4am2+3814oam,
)j Application example 1 (Application to surface-curing coating film) 10 g of S'C'EO obtained in Example 1 was dissolved in 602 methyl ethyl ketone, and γ-glycidoxyprobyl trimester was added.
Add Toxysilane 102 and 5 of colloidal silica (trade name "Oscar 1232" solid content concentration 30%, manufactured by Catalyst Kasei Co., Ltd.), and with stirring, 1.5 f of 01N aqueous salt solution.
added. This liquid was aged for a day and night to obtain a coating liquid. This coating liquid was applied to an aluminum plate, a glass plate, a polycarbonate plate, and a diethylene glycol bisallyl carbonate resin plate by the tapping method, respectively, and then cured at 130°C for 2 hours.
The molded product thus obtained was hard, dense, and acidic (1
Normal hydrochloric acid) Alkali (1N sodium hydroxide) Solvent (
While no changes were observed after being immersed in acetone for -1 week, untreated aluminum plates and polycarbonate plates showed surface corrosion or cracks.
The surface gloss of the glass has decreased.

Application example 2 (Application to water-repellent/touch-resistant coating liquid) BSTBO10f obtained in Example 4 was dissolved in 100 tons of toluene, applied to steel plates and wood, and cured at 160°C for 2 hours. . The molded article thus obtained was immersed in 2% saline for one week. As a result, it was found that the weight increased less than the untreated product and had excellent water repellency. In addition, there was no abnormality in appearance and good contact resistance. Application Example 3 (Application to high refractive index resin) TBO was polymerized in a glass mold using a peroxide such as benzoyl peroxide as an initiator. Molded into a plastic lens. The refractive index of this resin was 1.6. As a hard coating agent for this resin, 5TBC2Of, the aforementioned colloidal silica 10f1γ-glycidoxypropyltrimethoxysilane 5f? , methyl ethyl ketone 501
, ammonium perchlorate, o it , 01N hydrochloric acid 11 were mixed and stirred, and the mixture was aged day and night.

Apply it to the previously obtained lens by dipping method,
When heated and cured at 130° C. for 2 hours, a plastic lens with excellent surface hardness, good appearance, and improved practicality was obtained.

For comparison, hard coating agents with compositions that do not contain 5TBO and paints prepared according to various disclosed formulation examples (for example, Japanese Patent Publication No. 57-2735, Japanese Patent Application Laid-open No. 57-139153, etc.) were used. When coated and cured in the same manner as above, reflection interference fringes of light were generated due to the difference between the lens refractive index and the cured film refractive index, resulting in a lack of commercial value. The new organosilane compound is
The basic skeleton is a substituted aromatic ring that is rigid and chemically stable.
It is a reactive compound that has two reactive silyl groups at both ends, and by using this compound as it is or by hydrolyzing it and then condensing it, it has transparency, chemical resistance, scratch resistance, Excellent water resistance and refractive index of 1.55
Resins with high optical densities of ~1.60 can be obtained. It is also a useful compound as a coating agent when used in combination with other silane coupling agents, metal oxide fine powders, metal alcoholades, and condensing monomers.

Utilizing these characteristics, we can produce paint vehicles, scratch-resistant coatings, coatings for forming protective films, transparent high-refractive index coatings, chemical-resistant coatings,
It exhibits its effects when used as a corrosion-resistant coating or coating material. Furthermore, these coated materials can be applied to materials such as glass, metals such as iron, aluminum, and ram, paper, wood, cellulose, and plastics by applying them to the surface in various forms and curing them by heating.

In addition, as high refractive index resins with various functions are expected to spread in the future, especially in the field of plastic lenses, it will be used as a basic material for forming high refractive index hard coat films that match high refractive index resins. Useful. Furthermore,
It has high utility value in the optical field, such as application as a component of a high refractive index transmission layer that is essential for the construction of an antireflection film made only of organic silicone resin.

Claims (1)

[Claims] 1. ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼...[I] (In the formula, R^1 is -OCH_2CH_2-, ▲ Numerical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Also, X is a chlorine or bromine atom, and Y is -
Represents O-, -SO_2-, -CH_2- or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, k is 0 or 1, l
and m each independently represent an integer from 1 to 4. ) and a diallyl compound having an aromatic ring represented by the general formula▲mathematical formula, chemical formula, table, etc.▼・・・・・・[II] ,
Represents a hydrocarbon group having 1 to 4 carbon atoms, where n is 0 or 1
It is. ) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ・・・・・・ [III
] A method for producing an organic silane compound containing an aromatic ring. 2. The method for producing an aromatic ring-containing organic silane compound according to claim 1, wherein the addition reaction is carried out in the presence of a platinum compound catalyst.