JPH06100574A - Amide group-containing polydiorganosiloxane and its production - Google Patents

Abstract

PURPOSE:To provide a novel compound having a silicon atom-bonded amide group on only one side of the compound. CONSTITUTION:The compound of formula I (R<1>-R<5> are monovalent hydrocarbon; R<6> is H, alkyl, etc.; (n) is 3-1000; (a),(b) are 0-3 and a+b=3). The compound of formula I is obtained by reacting a compound of formula II (X is halogen, H) with a compound of formula III (M is H, alkali metal, trialkylsilyl) in a solvent or in the absence of the solvent preferably at -25 to 150 deg.C. The compound of formula I includes a tetrasiloxane of formula: Vi(Me2SiO)3SiMe2N(Me) COMe.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polydiorganosiloxane containing an amide group bonded to a silicon atom only at one end and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, many compounds and methods for producing polyorganosiloxanes containing amidosilyl groups have been proposed. For example, JP-A-1-125388
The publication discloses a method of synthesizing an amidosilane and an amidosiloxane by reacting a compound having a Si-H group and an organic amide in the presence of a platinum catalyst. Further, US Pat. No. 3,488,371 describes that a diamidosilane can be synthesized by reacting a dihalosilicon compound with an organic amide in the presence of a special tertiary amine.

However, the silicon atom-bonded amide group-containing polysiloxanes reported so far have at least two amide groups in one molecule. Therefore, when these polysiloxanes are reacted with a compound having two or more active hydroxyl groups or water, there is a drawback that gelation or abnormal increase in viscosity occurs. To overcome this drawback, polydiorganosiloxanes having amide groups bonded to silicon atoms on only one end of the molecule are required, but such polymers have not been known to date.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polydiorganosiloxane having a silicon atom-bonded amide group at only one end of the molecule, and a method for producing the same.

[0005]

Means for Solving the Problems As a result of repeated studies to solve the above problems, the present inventors have found that

[0006]

[Chemical 5]

The amide group-containing polydiorganosiloxane represented by the following formula was successfully synthesized. Here, R ^{1 to} R ⁵ are the same or different monovalent hydrocarbon groups, R ⁶ is a hydrogen atom,
It is a group selected from an alkyl group, an alkenyl group and a halogenated hydrocarbon group, n is an integer of 3 to 1000,
a and b are integers of 0 or more and 3 or less, and a + b is 3.

The polydiorganosiloxane according to the present invention is a linear polymer having a structure represented by the formula (1). Here, it is characterized in that the amide group represented by R ¹ CON (R ² ) — is bonded to only one end of the molecule. Due to this structure, when reacted with a compound having two or more active hydroxyl groups or water, gelation or abnormal increase in viscosity does not occur.

In this formula, R ^{1 to} R ⁵ are the same or different monovalent hydrocarbon groups, but are alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group and hexyl group; phenyl group , Aryl groups such as tolyl group, xylyl group and mesityl group; vinyl group, allyl group, propenyl group,
A group selected from an alkenyl group such as butenyl group; and the like, a methyl group or a phenyl group is preferable from the economical viewpoint, and most of these groups are preferable from the viewpoint of easy control of the molecular structure. Is preferably a methyl group.

R ⁶ is a group selected from a hydrogen atom, an alkyl group, an alkenyl group and a halogenated hydrocarbon group,
The above groups are exemplified as the alkyl group and the alkenyl group.
Examples of the halogenated hydrocarbon group include a chloromethyl group, a chloropropyl group and a trifluoropropyl group. From the viewpoint of easiness of synthesis of polysiloxane as a raw material,
R ⁶ is preferably a hydrogen molecule, an alkyl group or an alkenyl group.

[0011] n, which indicates the degree of polymerization of the compound represented by the formula (1), is a number of 3 or more and 1000 or less, but when n is 2 or less, the boiling point is too low to be volatile and pollute the environment. This is because there is a possibility that the molecular weight will be too large and the viscosity will be too high, and handling will be difficult if the value is 1000 or more. n is preferably 3 or more and 500 or less, and more preferably 3 or more and 200 or less.

Further, according to the present invention, there is provided a method for producing the amide group-containing polydiorganosiloxane represented by the formula (1), which comprises the general formula

[Chemical 6]

A polydiorganosiloxane represented by:
formula

[0014]

[Chemical 7]

The compound represented by is reacted.

In the above formulas (2) and (3), R ^{1 to} R ⁶ are as described in detail above. X in the formula (2) is a hydrogen atom or a halogen atom such as chlorine, bromine, iodine or fluorine. M in the formula (3) is a hydrogen atom or an alkali metal such as lithium, sodium or potassium, or a trialkylsilyl group such as a trimethylsilyl group, a triethylsilyl group or a dimethylethylsilyl group. Here, when X is a hydrogen atom, M is preferably a hydrogen atom or a trialkylsilyl group, and when X is a halogen atom, M may be any of those exemplified above.

The method for producing the polydiorganosiloxane represented by the formula (2) is not particularly limited. For example, a method for producing a low molecular weight polydiorganosiloxane having a chlorine atom bonded to a silicon atom only at one end of the molecule is described in Poly.
mer, vol. 30, p. 333 (1989). Further, a method for producing a polydiorganosiloxane having Si-H only on one end of the molecule is described in Polymer.
J. Vol. 19, p. 1091 (1987).

In the reaction of the polydiorganosiloxane of formula (2) with the compound of formula (3), using a suitable catalyst often results in good yields.
For example, when X in the formula (2) is a hydrogen atom and M in the formula (3) is also a hydrogen atom, a transition metal catalyst such as platinum or rhodium may be used. Further, when X is a halogen atom and M is a hydrogen atom, it is recommended to add a tertiary amine or the like for trapping a hydrogen halide produced as a by-product. When M is a trialkylsilyl group, particularly when it is a trimethylsilyl group, trimethylsilane (X is a hydrogen atom) and trimethylchlorosilane (X is a chlorine atom), which are by-products, have a low boiling point and can be easily removed by distillation.

The reaction temperature for these reactions may be room temperature, cooling or heating, and the reaction pressure may be normal pressure, reduced pressure or increased pressure. Regarding the reaction temperature, the reaction is usually performed in the range of -80 ° C to 200 ° C, and preferably in the range of -25 ° C to 150 ° C.
In particular, when the reaction is carried out while removing the by-product compound, it is preferable to carry out the reaction at the boiling point of the by-product compound or higher.

These synthetic reactions can be carried out in a suitable solvent or without solvent. The solvent is not particularly limited as long as it can dissolve the raw material compound and the produced polymer well and does not adversely affect the reaction. Examples of the solvent include the following. Aliphatic hydrocarbons such as pentane, hexane, heptane, octane; Aromatic hydrocarbons such as benzene, toluene, xylene; Ether solvents such as diethyl ether, dibutyl ether, diphenyl ether, dioxane, tetrahydrofuran; Ethyl acetate, butyl acetate, etc. Ester-based solvents; ketone-based solvents such as acetone, methyl ethyl ketone, and methyl butyl ketone; halogenated solvents such as carbon tetrachloride, chloroform, trichloroethane, trichloroethylene, and tetrachloroethylene; dimethylformamide; dimethyl sulfoxide; hexamethyltriamide phosphate.

[0021]

EXAMPLES The present invention will be described below with reference to examples. In the examples, the average molecular weight is a value obtained by gel permeation chromatography (GPC) using standard polydimethylsiloxane. ¹ HNMR means proton nuclear magnetic resonance spectroscopy, ²⁹ SiNMR means silicon 29 nuclear magnetic resonance spectroscopy (both have tetramethylsilane as standard and 0 ppm) . Me is a methyl group, Vi is a vinyl group, and Bu is a butyl group.

Example 1 42 g (0.12 mol) of tetrasiloxane of the formula Vi (Me ₂ SiO) ₃ SiMe ₂ Cl, N-
Trimethylsilyl-N-methylacetamide 22 g
(0.15 mol) was added and the mixture was stirred at room temperature. After the mild exothermic reaction subsided, the reaction mixture was heated with stirring at 60 ° C. for 1 hour. Removal of trimethylchlorosilane by-product and unreacted amide by distillation under reduced pressure gave a transparent liquid.

According to ¹ HNMR analysis, the obtained compound was found to have a vinyl group (6.1 to 5.8 ppm), an N-methylacetamide group (2.7 ppm and 2.0 ppm) and a silicon-bonded methyl group (0 .2 to 0.0 ppm), and ²⁹ Si
According to NMR analysis, a dimethylvinylsilyl group (-3.
8ppm), dimethylsiloxane unit (-20.8pp
m), N-methylacetamide dimethylsilyl group (-
It was found to have 7.2 ppm). Further, from the results of gas chromatography and mass spectrometry, the obtained compound was represented by the formula Vi (Me ₂ SiO) ₃ SiMe ₂ N (Me) COM.
It was found to be a tetrasiloxane represented by e and having an amide group at one end.

Example 2 52 g of hexamethylcyclotrisiloxane in a flask
(0.23 mol) and 52 g of tetrahydrofuran were added, and the mixture was stirred at room temperature. 8.6 ml (0.022 mol) of a hexane solution of butyl lithium (2.6 M) was added to this solution, and the mixture was reacted at room temperature. After 1 hour and 40 minutes, the conversion rate of hexamethylcyclotrisiloxane was 86%.
Therefore, the reaction solution was put into a flask containing 13 g (0.1 mol) of dimethyldichlorosilane and 10 g of tetrahydrofuran over 5 minutes while stirring. The solvent and unreacted materials were removed by vacuum distillation, and lithium chloride was removed by filtration to obtain a transparent liquid. G
PC and ²⁹ Si NMR analysis revealed that the polymer obtained was a polydimethylsiloxane of the average formula Bu (Me ₂ SiO) ₂₇ SiMe ₂ Cl.

30 g of this polydimethylsiloxane (0.
014 mol) and N-trimethylsilyl-N-methylacetamide (4.6 g, 0.03 mol) were added, and the mixture was heated with stirring at 50 ° C. for 2 hours. Removal of trimethylchlorosilane and unreacted amide by-produced by vacuum distillation gave a transparent liquid.

According to ¹ HNMR analysis, the obtained compound had a butyl group (1.3 to 0.5 ppm), an N-methylacetamide group (2.8 ppm and 2.0 ppm) and a silicon-bonded methyl group (0 .3 to 0.0 ppm), and ²⁹ Si
According to NMR analysis, a dimethylbutylsilyl group (7.6
ppm), dimethylsiloxane unit (-21.1 ppm),
N-methylacetamide dimethylsilyl group (-7.2pp
m). Furthermore, from the result of GPC analysis (Mn: 2100, Mw: 2600), the obtained polymer was found to have the formula Bu (Me ₂ SiO) ₂₇ SiMe ₂ N (M
e) It was found to be a polydimethylsiloxane represented by COMe.

Example 3 The average formula Bu which is the intermediate in Example 2 was added to the flask.
(Me₂SiO)₂₇Me ₂Polydimethl represented by SiCl
30 g (0.014 mol) of tyl siloxane
50 g of drofuran, N-methylacetamide of sodium
Add 1.4 g (0.014 mol) of salt for 24 hours.
Fluxed. Remove solvent by distillation and filter
Removal of sodium chloride gave a clear liquid.
¹H,²⁹According to SiNMR and GPC analysis,
The polymer obtained is exactly the same as that obtained in Example 2.
It has been found.

[0028]

As described above, the polydiorganosiloxane represented by the formula (1) is a novel compound, and a reactive polymer such as a hydrophilic compound utilizing the reactivity of the terminal amidosilyl group with the active hydroxyl group. It is very useful as a hydrophobizing agent and a grafting agent of polysiloxane onto a polyol compound. Moreover, the novel polydiorganosiloxane represented by the formula (1) is synthesized by the production method of the present invention.

Claims (4)

[Claims] 1. A general formula: (In the formula, R ¹ , R ² , R ³ , R ⁴ , and R ⁵ are the same or different monovalent hydrocarbon groups, and R ⁶ is a hydrogen atom, an alkyl group, an alkenyl group, or a halogenated hydrocarbon group. It is a group selected, n is an integer of 3 to 1000, a and b are integers of 0 or more and 3 or less, and a + b is 3.)
An amide group-containing polydiorganosiloxane represented by: 2. R ^{1 to} R ⁵ are methyl groups, and R ⁶ is a vinyl group or a butyl group.
An amide group-containing polydiorganosiloxane according to item 1. 3. A general formula: (Wherein R ^{3 to} R ⁶ , n, a, and b have the same meanings as described above, and X is a halogen atom or a hydrogen atom), and a polydiorganosiloxane represented by the formula: (Wherein R ¹ and R ² have the same meanings as described above, and M is a hydrogen atom, an alkali metal or a trialkylsilyl group.) And the compound represented by the general formula: Chemical 4] (In the formula, R ^{1 to} R ⁶ , n, a, and b have the same meanings as described above.) A method for producing an amide group-containing polydiorganosiloxane. 4. The method for producing an amide group-containing polydiorganosiloxane according to claim 3, wherein X is a chlorine atom and M is a trimethylsilyl group or sodium.