JPH04321694A - Methyl-hexyl-dimethoxysilane - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention is a novel methyl-thexyl-dimethoxysilane that has not been described in any literature, and in particular, it has the characteristics of controlled hydrolyzability of the methoxysilyl group and bulky organic group of the thexyl group. It can be used as a water repellent for the surface of buildings such as wood, concrete, and marble, as well as for metals, Mg, and T.
Methyl is useful as an additive for olefin polymerization catalysts because it can easily form coordination compounds with i and Al.
It concerns thexyl-dimethoxysilane.

0002

[Prior Art] Conventionally, organosilanes and organosiloxanes containing a linear hydrocarbon group as a group for expressing water repellency have been known for the purpose of making the surface of various substrates water repellent. It is said that increasing the chain length increases water repellency, and some organosilanes are known to be used as additives for olefin polymerization catalysts. Since it has a hydrogen group, its effectiveness is said to increase.

0003

[Problem to be Solved by the Invention] However, although water repellency improves as the chain length increases, the longer the chain length, the higher the boiling point and melting point. However, there is a limit to the chain length from the viewpoint of use. In addition, silanes for olefin polymerization catalysts also become bulky when the chain length is extended, but the rate of increase in bulk decreases as the chain length increases, so this also has a limit in terms of performance.

0004

[Means for Solving the Problems] The present invention solves the above problems, and is achieved by the following formula (1).

[0005]

[Case 2]

The present invention relates to a novel methyl-thexyl-dimethoxysilane shown in the following, which has not been published in any literature. That is, as a result of various studies by the present inventors to develop an organosilane that is useful as a water repellent for construction and a catalyst for olefin polymerization, methyl-thexyl-dimethoxysilane represented by the above general formula (1) was found. It was discovered that it exhibits excellent properties for this type of use, and this manufacturing method,
The present invention was completed after conducting research on how to use it. This will be explained in further detail below.

[0007]

[Operation] The present invention relates to methyl-thexyl-dimethoxysilane represented by the above formula (1).
This product can be synthesized by the following three-step reaction including hydrosilation.

That is, this first step is to obtain thexyl-methylphenylchlorosilane from methylphenylchlorosilane, which is obtained by adding methylphenylchlorosilane or a hydrocarbon solvent solution having a silane concentration of 0.01 to 10 mol%, 0.001 for this raw material silane
~50 mol% of aluminum trichloride is added, and to this is added 100 to 110 mol% of 2, based on the starting silane.
3-dimethyl-2-butene is added dropwise at -20 to 40°C, preferably 10 to 30°C over a period of 0.1 to 5 hours.
After heating at 0°C for 1 to 5 hours, aluminum trichloride was removed by suction filtration, and the solvent and unreacted substances were removed from the filtrate.
Thexyl-methylphenylchlorosilane can be obtained by vacuum distillation at 3°C/3mmHg.

This second step is to obtain thexyl-methyldichlorosilane from the thus obtained thexyl-methylphenylchlorosilane, which is obtained by adding the thexyl-methylphenylchlorosilane obtained above to a solution of a hydrocarbon solvent, preferably Add benzene to a concentration of 0.01 to 10
Prepare a mol % solvent solution, and add dry hydrogen chloride gas to it at -20 to 40°C.
After bubbling at a rate of 0.1 molar for 0.5 to 5 hours, aluminum trichloride was removed by suction filtration, the solvent and hydrogen chloride were distilled under reduced pressure from the filtrate, and the concentrate was vacuum distilled at 75°C/3 mmHg. Thexyl-methyldichlorosilane can be obtained by distillation.

This third step is to obtain the desired methyl-thexyl-dimethoxysilane from the thexyl-methyldichlorosilane thus obtained, which is different from the thexyl-methylmethyldichlorosilane obtained above. 220 mol% methanol and 220 mol% urea or 1,5-diazabicyclo[5,4,0]unde7-
Methanol concentration containing 5-ene (DBU) is 0.1 ~
A 10 molar hexane solution is heated at 10-45°C, preferably at 2
Dropwise over 0.1 to 3 hours at 0 to 30°C, and 1 hour at 20°C.
After aging for ~5 hours, the lower layer, which is urea hydrochloride, was separated, propylene oxide was added to the upper layer of hexane solution to adjust the pH to 7, and then the hexane was distilled off under normal pressure, and the concentrate was Distillation under reduced pressure at 82° C./3 mmHg is sufficient, and by this method, the desired methyl-hexyl-dimethoxysilane can be obtained.

The hydrocarbon solvent used in the above-mentioned first to third steps is a linear or branched saturated hydrocarbon having 5 to 10 carbon atoms, or any hydrogen atom thereof. It may be a hydrocarbon substituted with a chlorine atom, such as benzene or any hydrogen atom thereof substituted with a saturated hydrocarbon or chlorine. Further, the solvent or aluminum trichloride used in the first and second steps described above may be used as they are in the next reaction without being removed by distillation or suction filtration.

The methyl of the present invention thus obtained
Hexyl-dimethoxysilane is a colorless and transparent liquid.
This product has controlled hydrolyzability of =Si-O-CH3, and this texyl group is a bulky organic group, so it is used as a surface water repellent treatment agent for buildings made of wood, concrete, marble, etc. In addition to being useful as a compound, it is also easy to form coordination compounds with metal Mg, Ti, and Al compounds, so it can be used instead of diphenyl-dimethoxy-silane, which has traditionally been used as an additive for complex catalysts for olefin polymerization. The highly active catalysts prepared thereby virtually eliminate the need for a deashing step and optionally eliminate the purification step to produce isotactic polymers.

[0013]

EXAMPLES Next, examples and application examples of the present invention will be shown. Example 1 12.7 g (0.952 mol) of aluminum trichloride was added to 149 g (0.952 mol) methylphenylchlorosilane.
2,3-dimethyl-2-
85.3 g (1.015 mol) of butene was added dropwise over 1.5 hours while stirring at 20°C, and after aging at 20°C for 5 hours, unreacted methylphenylchlorosilane and 2.
3-dimethyl-2-butene was distilled off under reduced pressure.

Next, 200 c of benzene was added to this concentrate.
．． c. Add 0.005% dry hydrogen chloride gas at 20°C.
Bubbling was carried out at a rate of mol/min for 3 hours, low-boiling compounds were distilled off under reduced pressure at 20°C/100 mmHg, and the residue was mixed with 25 g (0.70 mol) of methanol and 42 g of urea.
g (0.70 mol) and 200 c.g of hexane. c.
It was added dropwise to the mixture at 20°C over 1 hour and aged at 20°C for 3 hours.

After this reaction, urea hydrochloride is separated, 10 g of propylene oxide is added to the obtained hexane solution, the pH of the solution is adjusted to 7 by this operation, the hexane is distilled off under normal pressure, and the concentrate is heated to 82°C. When distilled under reduced pressure at /30 mmHg, 60.3 g of a colorless and transparent liquid was obtained at room temperature.
was obtained in a yield of 33%.

Gas chromatography on this liquid
Analysis of this substance showed that it was a single component, but 1H-NMR analysis of this substance revealed that
The following results were obtained, and Figure 1 was obtained by infrared absorption spectrum analysis.
Since we obtained the result shown in

[0017]

[Chemical formula 3]

It was confirmed that it was as shown in the following.

1H-NMR analysis value (ppmδ: CDCl3) 3.55 (s, 6H, -OCH3) 1.9 to 1
．． 1 (m, 1H, -CH)1.1 -0.8 (
m, 12H, -CH3)0.13 (S, 3H,
-SiCH3)

Application example: 400 ml of dry normal heptane was placed in a 1 liter four-necked flask under a nitrogen atmosphere, and 76.2 g (0.8 mol) of magnesium chloride and 271.9 g (0.8 mol) of tetrabutanoxytitanium were added thereto. In addition, 95℃
The mixture was stirred for 2 hours. After cooling, solid components were collected by filtration at room temperature and washed with dry normal heptane. This was placed in a 1 liter four-necked flask under a nitrogen atmosphere, and 167 ml of n-heptane was added. A normal heptane solution (83 ml) of 226.7 g (1.3 mol) of tetrachlorosilane was added dropwise to this at 25°C over 1 hour, and the mixture was reacted at 95°C for 3 hours. A normal heptane solution (83 ml) containing 10.8 g (0.05 mol) of phthaloyl chloride was added dropwise to this over 0.5 hours, and the mixture was aged for 1 hour. After cooling, solid components were collected by filtration at room temperature and washed with dry normal heptane. This was carried out under a nitrogen atmosphere.
The mixture was placed in a 4-necked flask, and 136 g (0.8 mol) of tetrachlorosilane was added thereto, followed by reaction at 95° C. for 1 hour. After cooling, solid components were collected by filtration at room temperature and washed with dry normal heptane. 10g of this
was placed in a 0.5 liter four-necked flask under a nitrogen atmosphere, and 100 ml of n-heptane was added. 25 for this
1.9 g of thexyl-methyl-dimethoxysilane (
0.01 mol) was added, and the mixture was aged at 25° C. for 2 hours, and solid components were collected by filtration and washed with dry normal heptane.

Next, in a 1 liter stainless steel autoclave, 0.5 liters of normal heptane and 0.25 g of triethylaluminum (2.2 mmol) were placed in a 1 liter stainless steel autoclave.
1) was introduced and reacted for 0.5 hour at 70°C, and 0.2 liters of propylene was introduced thereto. 6 mg of the previously synthesized catalyst component was introduced into this and reacted for 3 hours. The yield of polypropylene per unit catalyst amount varies somewhat depending on the reaction conditions, but it is 13,000 to 14,000 (g・P
P/g・Cat. ), and the amount of soluble components in xylene at 25°C is lower than that of atactic polymers with poor crystallinity.
As an indicator of quantity, this is 0.5 to 1.5 (wt%)
It was extremely low.

[0022]

[Effect of the invention] The present invention relates to a novel methyl-thexyl-dimethoxysilane which has not been described in any literature, and which has the formula

[0023]

[C4]

This is shown as =S
Due to the controlled hydrolyzability of i-O-CH3 and the bulky organic nature of the texyl group, it is useful as a water repellent for the surface of buildings such as wood, concrete, and marble.
g, Ti Also, since it is easy to form a coordination compound with an Al compound, this mixture is said to be useful as an additive for a complex catalyst for olefin polymerization.

[Brief explanation of drawings]

FIG. 1 is an infrared absorption spectrum analysis diagram of thexyl-methyl-dimethoxysilane obtained in Example 1.

Claims (1)

[Claims] [Claim 1] Formula [Chemical formula 1] Methyl-thexyl-dimethoxysilane represented by