JPH07206875A - Bis(silyl)alkane and its production - Google Patents

Abstract

PURPOSE: To provide a bissilylalkane useful as a coupling agent for coupling an org. matter such as plastic or the like and an inorg. matter used as a filler.

CONSTITUTION: This compd. is represented by formula I (wherein R¹ is H or phenyl; R² is -CH₂CH₂R³ or cyclohexyl; R³ is phenyl, -CH₂Cl, -(CH₂)MCH₃ or the like; (m) is 0-15; (n) is 1-4; and X is Cl or 1-4C alkoxy), for example, 1,1,1,3,3,6-hexachloro-1,3-disilahexane and is obtained by adding bissilylalkane represented by formula II and a compd. having a double bond represented by the formula, CH₂=CH-R³ or cylohexene by hydrosilylation reaction using a catalyst selected from platinic chloride, platinum supported on silica, tributylamine and other compd. of Pd, Rh, Ni or the like. Further, if necessary, an alcohol can be reacted with it, to thereby convert the Cl bonded to silicon to an alkoxy.

COPYRIGHT: (C)1995,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to various organic group-substituted bissilylalkanes useful as a substance for binding between an organic substance such as plastic and an inorganic substance used as a filler, and a method for producing the same. Regarding

[0002]

2. Description of the Related Art Organosilicon-containing coupling agents are important substances widely used in the production of composite materials for plastics. They are well compatible with inorganic fillers having different physical properties and organic plastics, and have good bonding strength. To improve. It is possible to impart desired physical properties to plastics and maximize economic efficiency. A general molecular structure of a coupling agent is represented as (RO) ₃ Si-A-Y. Here, the -Si (OR) ₃ portion of the alkoxysilane becomes -Si (OH) ₃ when hydrolyzed. This silanol is unstable and self-bonds to itself, or reacts with the metal hydroxyl group of the metal oxide on the surface of the filler which is an inorganic substance, and chemically bonds to enhance the reinforcing property of the filler. Y represents an organic functional group capable of reacting with plastic or resin,
A is an organic group connecting the organic functional group and silicon, and is a methylene group, an ethylene group or a propylene group.

The most common coupling agent is γ-chloropropyltrimethoxysilane. In the method for producing the binder, as shown in the following reaction formula, a compound having an unsaturated bond is added to trichlorosilane by a hydrosilylation reaction to introduce various organic groups. Since the chloro atom bonded to silicon is hydrolyzed to generate hydrogen chloride having a strong corrosive property, it is reacted with alcohol to substitute it with an alkoxy group.

[0004]

[Chemical 4]

This hydrosilylation reaction requires a catalyst, and metal platinum or a noble metal compound such as chloroplatinic acid is used as the catalyst. The most common and most used catalyst is chloroplatinic acid. It is used by dissolving it in isopropanol. In addition, depending on the nature of the unsaturated compound added to the trichlorosilane, other catalysts may be advantageous over using the platinum compound as the catalyst. As the catalyst used for the hydrosilylation reaction, compounds such as nickel, rhodium, ruthenium, copper and lead can be used in addition to precious metals such as platinum and palladium. It is known that an organic compound as well as a metal or an inorganic substance can be used as a catalyst. Examples of organic compounds that can be used for the catalyst include triethylamine,
Triphenylphosphine, dimethylformamide and the like are known to have catalytic activity. (EY Lukevites a
nd MG Voronkov, "Organic Inscrtion Reactions of
Group IV Elements ", Consultants Bureau, New York 1
966).

The most general method for producing γ-chloropropyltrialkoxysilane as a coupling agent is as follows:
First, trichlorosilane is reacted with allyl chloride to produce γ
-Chloropropyltrichlorosilane is obtained and then reacted with alcohol to give γ-chloropropyltrialkoxysilane. The reaction of adding allyl chloride to trichlorosilane requires a reaction time of 4 to 10 hours at 100 ° C. in the presence of a chloroplatinic acid catalyst, and a reaction time of 50 to 300 psi.
It is reported that it is better to apply the pressure. In this reaction, chlorine of allyl chloride and hydrogen of silicon are exchanged in the side reaction, tetrachlorosilane and propylene are produced as by-products, and propylene is further reacted with trichlorosilane to produce propyltrichlorosilane (FP Mackay,
OW Steward and PG Campbell, J. Am. Chem. Soc.,
79, 2764 (1957); JL Speier, JA Webstre and S.
W. Barnes, J. Am. Chem. Soc., 79, 974 (1957)).

When γ-chloropropyltrichlorosilane is reacted with alcohol, hydrogen chloride is generated and it becomes an alkoxy compound. The amount of alcohol used in this reaction is
It is preferable to use a minimum of 3 mol or more per 1 mol of γ-chloropropyltrichlorosilane. When an inert organic solvent is used, the reaction is fast and the amount of hydrogen chloride produced is small, so that the side reaction in which hydrogen chloride and alcohol react to produce water is reduced. As alcohols that can be used in this reaction, not only aliphatic alcohols such as methanol, ethanol and propanol but also aromatic alcohols such as phenol can be used.

Hydrocarbons having unsaturated bonds generally react readily with trichlorosilane. A compound having an unsaturated bond at the end of the molecule is more reactive than a compound having an intermediate bond, and a linear compound is more reactive than a cyclic compound. A compound having an aromatic ring such as styrene easily reacts. However, when it has a cyano group such as acrylonitrile, it is known that the catalyst of the noble metal has weak activity and it is better to use an organic amine, nickel or iron compound as the catalyst (W. Noll, "Chemistry.
and Technology of Silicones ", Academic Press, New
York, 1968).

As described above, instead of first reacting trichlorosilane with an organic substance having an unsaturated bond such as allyl chloride and then reacting with alcohol to convert it into alkoxysilane, first react trichlorosilane with alcohol. It is also possible to obtain a trialkoxysilane and then carry out an addition reaction with the unsaturated compound. Although it may be inevitable to use such a reaction sequence, there are cases where the organic group introduced in the hydrosilylation reaction reacts with an acid. An example is the case of having an ester group such as glycidyl ether having an epoxy group or allyl methacrylate. The epoxy or ester group must be first converted to an alkoxy and then hydrosilylated in order to be hydrolyzed by an acid or to react with an alcohol. Prudman and his collaborators hydrolyzed vinyl acrylate or allyl methacrylate with trialkoxysilanes to produce acrylate-substituted coupling agents in US Pat. No. 3,258,477, The product is reported to be obtained in good yield. The catalyst used in this reaction was reported to be chloroplatinic acid. Moreover, they
In order to synthesize a coupling agent substituted with a glycidoxypropyl group, it was reported that it was synthesized by adding trialkoxysilane to allyl glycidyl ether (EP
Ptueddemann and G Fanger, J. Am. Chem. Soc., 81,
2632 (1959).

We have mixed various silanes having a chloromethyl group with hydrogen chloride or an organic chloride such as t-butyl chloride which can decompose at the reaction temperature to generate hydrogen chloride, It was found that a bissilylalkane having a silicon-hydrogen bond can be obtained by reacting with metal silicon (Korean Patent Application No. 24243 (1991.1)).
2.24). In the same manner, if methylene chloride or α, α-dichlorotoluene, α, ω-dichloroalkane or the like is used instead of using a silane having a chloromethyl group, chlorobissilylmethane having a silicon-hydrogen bond is obtained. It has been found that chlorobissilylphenylmethane and chlorobissilylalkane can be obtained (Korean Patent Application No. 935 (1992.23)).

[0011]

[Chemical 5]

[0012]

In the present invention, a compound of the general formula (I) synthesized as mentioned above is used as a starting material, and two silyl groups having a hydrolyzable chloro atom or an alkoxy group are used. It has been found that it is possible to produce a coupling agent having The coupling agent produced from such a compound having two silyl groups as a starting material has more hydrolyzable chloro atoms or alkoxy groups than existing coupling agents. It is expected that the binding property with the inorganic substance will be increased, and therefore, the property as a coupling agent will be improved.

[0013]

DISCLOSURE OF THE INVENTION The present inventors have found that bissilylalkane of the general formula (I) and a compound having a double bond of the general formula (II) or cyclohexene are chloroplatinic acid, platinum supported on silica, Tributylamine, other Pd, R
It was possible to obtain the bissilylalkane of the general formula (III) obtained by the addition of a compound such as h or Ni as a catalyst in the hydrosilylation reaction.

[0014]

[Chemical 6]

(In the formula, n represents a positive number of 1-4, R ¹ represents a hydrogen atom or a phenyl group, X represents a chlorine atom or C ₁
An alkoxy group -C _4).

CH ₂ = CH-R ³ (II)

(Where

[Chemical 7] Represents).

[0018]

[Chemical 8]

(In the formula, n, R ¹ and X are represented by the general formula (I)
R ² is the same as defined in the above, and R ² is —CH ₂ CH ₂ R ³
(R ³ is the same as above) or represents a cyclohexyl group)

Further, if necessary, the product of the hydrosilylation reaction is reacted with alcohol to convert the chlorine atom bonded to the silicon atom into an alkoxy group.

The hydrosilylation reaction for the addition of bissilylalkanes to various organic compounds having unsaturated bonds in order to prepare the coupling agents having two silicons according to the invention is usually used in the laboratory. Glassware may be used or commercialized reaction vessels may be used. The reactor must have a device capable of gradually injecting the raw materials in an inert gas, and must have a stirrer and a device capable of applying heat or cooling. Unlike the case of producing a coupling agent using trichlorosilane, since the boiling point of bissilylalkane is not low, it is not necessary to apply pressure to the reaction tank, but as with allyl chloride, a gaseous by-product is generated. If it does, pressure must be applied. However, this reaction step does not differ depending on the apparatus and reaction pressure. A solvent may be used in this reaction, but in most cases it is possible to use no solvent.

In a typical synthetic process, a chlorobissilylalkane (I) and a catalyst are placed in a reaction vessel in an inert gas, and a compound (II) having an unsaturated bond is gradually injected. In some cases, the injection order of the chlorobissilylalkane (I) and the organic compound (II) may be changed. Since a certain reaction is a considerable exothermic reaction, it can be refluxed without external heating by adjusting the injection rate of chlorobissilylalkane. Chlorobissilyl alkane (I)
After completion of the injection, the stirring is continued for a certain period of time to complete the reaction. When the reaction is completed, the solution is fractionally distilled to remove the product.

[0023]

The following examples serve to illustrate the invention in more detail and the invention is not restricted thereby.

Example 1. A two-neck flask with a capacity of 1.500 ml was equipped with a condenser and a mechanical stirrer, and dry nitrogen was passed through the end of the condenser, and the whole equipment was maintained under a nitrogen atmosphere. It was to so. 100 g (0.40 mole) of 1,1,1,3,3-pentachloro-1,3-disilapropane and 37.0 g (0.48 mole) of allyl chloride were placed in a flask, and 156 μl of 1% chloroplatinic acid catalyst solution was injected. .
While maintaining the reactor at about 45 to 50 ° C., the mixture was vigorously stirred with a stirrer and reacted for 3 hours. At this time, the consumption of the starting material can be confirmed by gas chromatography, and the addition reaction product 1,1, 1,
77.5 g (yield: 59.6%) of 1,3,3,6-hexachloro-1,3-disilahexane was obtained. The obtained product is δ 1,59ppm as a result of 60MHz hydrogen nuclear magnetic resonance analysis.
(s, 2H, Si-CH ₂ -Si), 1.42ppm (t, 2H, Si-CH ₂ -C), 2.10
Peaks were confirmed at ppm (m, 2H, C-CH ₂ -C), 3.60ppm (t, 2H, C-CH ₂ -Cl).

Table 1 shows the results of the hydrosilylation reaction of various unsaturated compounds in the presence of a chloroplatinic acid catalyst by such a method.

[0026]

[Table 1]

Example 2. Table 2 shows the results of the hydrosilylation reaction of various unsaturated compounds by the method of Example 1 using various catalysts other than chloroplatinic acid.

[0028]

[Table 2]

Example 3. Table 3 shows the results of hydrosilylation reaction of various unsaturated silane compounds in the presence of a chloroplatinic acid catalyst by the method of Example 1.

[0030]

[Table 3]

Example 4. Using the method of Example 1, 1,1,
Table 4 shows the results of hydrosilylation reaction of various unsaturated compounds in the presence of a chloroplatinic acid catalyst using 1,3,3-pentachloro-2-phenyl-1,3-disilapropane.

[0032]

[Table 4]

Example 5. Table 5 shows the results of hydrosilylation reaction of various unsaturated compounds by the method of Example 4 using various catalysts other than chloroplatinic acid.

[0034]

[Table 5]

Example 6. Table 6 shows the results of hydrosilylation reaction of various unsaturated silane compounds in the presence of a chloroplatinic acid catalyst by the method of Example 4.

[0036]

[Table 6]

Example 7. Using the method of Example 1, 1,1,
Table 7 shows the results of hydrosilylation reaction of various unsaturated compounds using 1,4,4-pentachloro-1,4-disilabutane and various catalysts such as chloroplatinic acid.

[0038]

[Table 7]

Example 8. Using the method of Example 1, 1,1,
Table 8 shows the results of hydrosilylation reaction of various unsaturated compounds using 1,5,5-pentachloro-1,5-disilapentane and various catalysts such as chloroplatinic acid.

[0040]

[Table 8]

Example 9. Using the method of Example 1, 1,1,
Table 9 shows the results of the hydrosilylation reaction of 1,6,6-pentachloro-1,6-disilahexane with various unsaturated compounds using various catalysts such as chloroplatinic acid.

[0042]

[Table 9]

Example 1 A 0.1 L three-necked flask was equipped with a condenser, a stirrer and a dropping funnel, and dry nitrogen was allowed to pass through the end of the condenser. To be able to maintain. 50 g (0.15 mole) of 1,1,1,3,3,6-hexachloro-1,3-disilahexane produced by the hydrosilylation reaction in Example 1
Was added to a flask, and 48 g (1.5 mole) of methyl alcohol was gradually added dropwise using a dropping funnel while vigorously stirring with a stirrer. The product 1,1,1,3,3-pentamethoxy-6-chloro-1,3-disilahexane was obtained from the reaction product at a yield rate of 85.2%. The obtained product was analyzed by hydrogen nuclear magnetic resonance analysis at 60MHz δ: 1.59ppm (s, 2H, Si-CH ₂ -Si), 1.4
2ppm (t, 2H, Si-CH ₂ -C), 2.10ppm (m, 2H, C-CH ₂ -C), 3.
60 ppm (t, 2H, C-CH ₂ -Cl) and 3.50 ppm (s, 15H, Si-OCH ₃ ) were confirmed.

The results obtained by reacting the products obtained by the hydrosilylation reaction of Examples 1 to 9 with methyl alcohol by the above method are shown in Tables 10-1 to 10-5.

[0045]

[Table 10]

[0046]

[Table 11]

[0047]

[Table 12]

[0048]

[Table 13]

[0049]

[Table 14]

[0050]

[Table 15]

[0051]

[Table 16]

Example 11. Table 11 shows the results obtained by reacting a part of the products obtained by the hydrosilylation reaction of Examples 1 to 9 with ethyl alcohol by the method of Example 10.
1 to 3.

[0053]

[Table 17]

[0054]

[Table 18]

[0055]

[Table 19]

Example 12 Table 12 shows the results obtained by reacting a part of the products obtained by the hydrosilylation reaction of Examples 1 to 9 with propyl alcohol by the method of Example 10.

[0057]

[Table 20]

Example 13 Table 13 shows the results obtained by reacting a part of the products obtained by the hydrosilylation reaction of Examples 1 to 9 with butyl alcohol by the method of Example 10.

[0059]

[Table 21]

 ─────────────────────────────────────────────────── ───Continued from the front page (72) Inventor, Ms. Ishi, 519-559, Sujeon-dong, Dobong-gu, Seoul, Korea Sansho apartment 101-506

Claims (3)

[Claims] 1. A bissilylalkane of the general formula (III). [Chemical 1] In the formula, R ¹ represents a hydrogen atom or a phenyl group, and R ² is-.
CH ₂ CH ₂ R ³ or a cyclohexyl group is represented by: And n represents a positive number of 1 to 4, and X represents a chlorine atom or a C _{1 to} C ₄ alkoxy group. 2. A bissilylalkane of the general formula (I) is reacted with a compound having a double bond of the general formula (II) or cyclohexene in the presence of a catalyst and, if necessary, the above-mentioned hydrosilylation reaction is formed. The method for producing a bissilylalkane of the general formula (III) according to claim 1, wherein the chlorine atom bonded to the silicon atom is converted into an alkoxy group by reacting the substance with alcohol. [Chemical 3] (In the formula, n, R ¹ , R ² , R ³ and X are the same as above) 3. A catalyst comprising chloroplatinic acid, platinum supported on silica, platinum supported on alumina, platinum supported on carbon,
The method according to claim 2, which is at least one selected from platinum black, rhodium black, palladium black, ruthenium black, nickel, tributylamine, and 3-chloropaoxybenzoic acid.