JPS61167694A - Organosilicon compound - Google Patents

Abstract

NEW MATERIAL:A compound shown by the formula I [R<1>-R<3> are (halogen- substituted) 1-8C monofunctional hydrocarbon]. EXAMPLE:1-Hydroxy-1,3,3,5,5-pentamethylcyclotrisiloxane. USE:A modifier for providing a room temperature curing or low-temperature curing organopolysiloxane of one-pack type or two-pack type. PREPARATION:For example, a compound shown by the formula II (e.g., 1- hydro-1,3,3,5,5-pentamethylcyclotrisiloxane, etc.) is dehydrogenated with water (e.g., buffer solution at 7.6 pH) in the presence of a catalyst (e.g., palladium- carbon) in a polar solvent (e.g., dioxane, etc.) preferably at <=20 deg.C.

Description

[Detailed description of the invention] (Industrial application field) The present invention is a novel organosilicon compound that has not been described in any literature.

In particular, it relates to novel organosilicon compounds that are useful as modifiers for obtaining wavy or two-component room-temperature-curing organopolysiloxanes.

(Structure of the Invention) The organosilicon compound according to the present invention is represented by the following general formula, where R, R, and R'' are methyl group - alkyl group such as ethyl group, propyl group, butyl group, cyclohexyl group - cyclopentyl group, etc. Cyclo-Ci-, J-++++PII
*, An aryl group such as a diyl group, a phenyl group, or a xylyl group in the V hale.

Aralkyl group or r-trifluoropropyl group.

It is the same or different unsubstituted or halogen atom-substituted monovalent hydrocarbon group having 1 to 8 carbon atoms, such as an r-chloropropyl group or an α-chloromethyl group.

Next, the organic silicon compounds of the present invention will be illustrated.

These are all representative examples, and the organosilicon compound of the present invention is not limited thereto. In addition, Me in one example is a methyl group, and vl is a vinyl group.

IPr is an isopropyl group and ph is a phenyl group (same as below).

The organosilicon compound of the present invention has a formula (1, for example, where R, R
, R is the same as above), and can be synthesized by subjecting cyclotrisiloxane having one 5i-H bond to a dehydrogenation reaction with water in the presence of a catalyst. This reaction may be carried out in a polar solvent such as dioxane or tetrahydrofuran at a temperature of 40°C or lower, preferably 20°C or lower, and the catalyst may be an element of Group I of the periodic table or a compound thereof, such as chloroplatinic acid, Alcohol-modified chloroplatinic acid (see U.S. Pat. No. 3,220,972), complexes of chloroplatinic acid and olefins (U.S. Pat. No. 3,159,601-3,159,662)
No. 3,775,452 Osteotomies supported on carriers such as alumina, silica, carbon, rhodium-
Examples include olefin complexes, but these complexes are preferably dissolved in alcohol-based, getone-based, ether-based, or hydrocarbon-based solvents.

The organosilicon compound of the present invention can be used for various purposes, but especially when reacted with a diorganopolysiloxane having silanol groups or reactive functional groups at both ends,
A diorganopolysiloxane with both ends capped with cyclotrisiloxane is obtained, and this diorganopolysiloxane with cyclotrisiloxane bonded to both ends can be heated at room temperature or at low temperature without releasing condensates in the presence of a suitable catalyst. The organosilicon compound provides a solenoid organosiloxane composition, and this curing reaction does not involve the disadvantage of poor curing even in the presence of nitrogen-, sulfur-, and phosphorus-containing compounds. It is said to be useful as a modifying agent for

Note that this organosilicon compound improves the acid resistance and alkali resistance of the conventionally known condensed room-temperature-curing organopolysiloxane composition, so it is suitable for addition to this type of organopolysiloxane composition. It is also said to be useful as a drug.

Next, reference examples and examples of the present invention will be given.

Reference Example 1 (Synthesis of 1-hydro-1,3,3,5,5-pentamethylcyclotrisiloxane) Diethyl ether 1,50011 and triethylamine 2
67I! into a 5t four-ton flask equipped with a stirring bar, two dropping funnels and a condenser, and 1,3-dihydroxy-1,1,3,3-tetramethyldisiloxane/diethyl ether; 2319/600 Mixed solution of !1 and methyldichlorosilane/diethyl ether = 158
．． ! A mixed solution of i+/600 g was added dropwise over 1 hour, stirred for 1 hour, the reaction product was washed with water, and the diethyl ether was distilled off, resulting in xzO,! il (yield 42.
0%) was obtained, and this product was confirmed to be 1-hydro-1,3,3,5,5-pentamethylcyclotrisiloxane from the following analytical values.

IR value Shi5l-H: 2,160α-shi81-0-
81: 1,015crR-boiling point 119-b refractive index 1.3832 (25°C) NMRδ 0.01 (S, 81-Me, 15H
)-δ 5.18 (8,81-H, LH).

Reference Example 2 (Synthesis of l-hydro-1-methyl-3,3,5,5-tetraisopropylcyclotrisiloxane) 1,3-dihydroxy-1,1,3,3-tetraisopropyldisiloxane 17.39 Methyldiisoprobeloxysilane12. OF was placed in a 50m Mitsuro flask equipped with a thermometer, condenser, and nitrogen gas inlet tube, stirred at room temperature for 4 hours, and then distilled under reduced pressure, resulting in a boiling point of 105.
~1 (17°C/7 Hg fraction 10.2.P was obtained,
This product is 1-hydro-1-methyl-
It was confirmed that the product was 3,3,5,5-tetraisopropyl trisiloxane.

IR value ν81-H: 2.155 tan.

νS 1-0-8i: 1,010 cm.

NMRδ o, o 3 (S e Si Me, 3
H).

δ 0.83 (8,0-Me, 24B).

64.76 (S, 51-H, LH).

Refractive index 1.4350 (25°C) Example 1 (Synthesis of 1-hydroxy-1,3,3,5,5-pentamethylcyclotrisiloxane) Equipped with a stirring bar, thermometer, hydrogen exhaust pipe and dropping funnel. 300g of dioxane in a 500WLl four-sided flask,
10 g of a buffer solution (pH 7,6) and 0.5 g of carbon black carrying 5% palladium were added to the mixture under water cooling.
When 30 g of dimethylcyclotrisiloxane was added dropwise in 1 hour, hydrogen was generated at the same time as the first drop was started, and almost no hydrogen was generated in 1 hour after the end of the first drop, so palladium was extracted from this reaction mixture by filtration. When the supported carbon was removed and then distilled under reduced pressure, the boiling point was 55-57.
℃/4ilHg, 12.6 g (yield 39.0%) of a fraction having physical properties of refractive index 1.4220 (25℃) was obtained, but this compound corresponds to IR, Ck0 preform. was confirmed.

IR Figure 1 GO-M8 analysis Parent peak 224 (molecular weight 224.4
).

NMRδ 0.00 (S, 81-Me.

15H).

63.53 (S, 5i-OH, IH)-(solvent aa
t4) Elemental analysis C (%) H (%) Sl (%) Calculated value 26,76 7.19 37.54 Analysis value 26.8 7.0 37.4 (Molecular formula) (1-hydroxy-1-methyl- Synthesis of 3,3,5,5-tetraisopropylcyclotrisiloxane) 501R equipped with a thermometer, hydrogen exhaust pipe and dropping funnel
715.7 g of dioxa-buffer (
pH7,6) Carbon black with 3.4N and 5% Palladium 0.11! and electromagnetic stirring,
1-hydro-1-methyl-3 obtained in Reference Example 2 under water cooling.
6.0 g of 3,5,5-tetraisopropylcyclotrisiloxane was added dropwise to this flask over 1 hour, and the same procedure as in Example 1 was carried out to remove dioxane under reduced pressure.
Boiling point 110-112℃ 15 degrees Hg, refractive index 1.4417
Compound with physical properties of (25°C) 4.89 (yield 76.
2%) was obtained, but this compound was analyzed by IR, Go-MS.

From the results of NMR and elemental analysis, it was confirmed that it corresponds to the following molecular formula.

Go-MS analysis (see IR Figure 2) Parent peak 336 (molecule 1i336.7) NMR δ 0.00 (S, Si-Me, 3H) δ 0.
83 (8,0-Me, 24H).

(Solvent 00L4) Elemental analysis C (%) H (%) Sl (%) Calculated value 46.4 9.6 25.0 Analysis value
46.6 9.4 24.8 (molecular formula)

[Brief explanation of the drawing]

Figure 1 shows 1-hydroxy-1,41 obtained in Example 1.
IR of 3,5,5-pentamethylcyclotrisiloxane
Figure 2 shows 1-hydroxy-1 obtained in Example 2.
-Methyl-3,3,5,5-tetraisopropylcyclotrisiloxane.

Claims (1)

[Claims] 1. General formula ▲ Numerical formula, chemical formula, table, etc. 2. The organosilicon compound according to claim 1, wherein R^1 is a methyl group.