JPH0693104A - Phosphorylated organopolysiloxane and production thereof - Google Patents

Abstract

PURPOSE:To provide a novel phosphorylated organopolysiloxane containing a trifunctional siloxane unit (T unit) and a phosphorus atom bonded to a silicon atom through an oxyalkylene group; and to provide a method for production thereof. CONSTITUTION:The polymer is represented by the formula (wherein R<1> is a monovalent hydrocarbon group; R<2> is a divalent hydrocarbon group; R<3> is a monovalent hydrocarbon group; a is a positive number; b is 0 or larger; c is a positive number; and x is 0, 1, or 2).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel phosphorus-containing organopolysiloxane and a method for producing the same, more specifically, a phosphorus atom is bonded to a silicon atom via an oxyalkylene group and a trifunctional siloxane unit (T Unit) and a phosphorus-containing organopolysiloxane and a method for producing the same.

[0002]

2. Description of the Related Art In order to improve the chemical and physical properties of organopolysiloxane, many functional group-containing organopolysiloxanes prepared by introducing various functional groups into a silicon atom have been proposed. Such functional group-containing organopolysiloxanes are used as fiber treatment agents, paint additives,
It is used as a resin modifier, antistatic agent, water and oil repellent, etc. The functional group-containing organopolysiloxane, particularly the phosphorus-containing organopolysiloxane, has the general formula:

[Chemical 2] (In the formula, m and n are positive numbers.) Phosphinate ester group-containing dimethylpolysiloxane [Organometallic Chemistry Reviews A (Orga
nometallic Chemistry Reviews A, 3 (1968) 469-496), JP-A-62-292837], general formula:

[Chemical 3] (In the formula, n is a positive number), a phosphonate ester group-containing cyclic siloxane, and a general formula:

[Chemical 4] (In the formula, p and q are positive numbers.) A phosphonate ester group-containing dimethylpolysiloxane (see JP-A-61-278564) has been proposed.

[0003]

[Problems to be Solved by the Invention] Organometallic
Chemistry Review and JP-A-62-292837
The phosphinate ester group-containing dimethylpolysiloxane proposed in JP-A No. 1994-242242 was a linear siloxane in which a phosphorus atom is bonded to a silicon atom via an oxyalkylene group. Further, the phosphonate ester group-containing linear or cyclic siloxane proposed in JP-A-61-278564 is a linear or cyclic siloxane in which a phosphorus atom is bonded to a silicon atom via a divalent hydrocarbon group. .

The present inventor has earnestly studied a phosphorus-containing organopolysiloxane having a phosphorus atom bonded to a silicon atom via an oxyalkylene group and containing a trifunctional siloxane unit (T unit), and a method for producing the same. As a result, the present invention has been reached.

That is, an object of the present invention is to bind a phosphorus atom on a silicon atom through an oxyalkylene group and to contain a trifunctional siloxane unit (T unit), and a phosphorus-containing organopolysiloxane and a method for producing the same. To provide.

[0006]

The present invention has the general formula:

[Chemical 5] (In the formula, R ¹ is a monovalent hydrocarbon group, R ² is a divalent hydrocarbon group, R ³ is a monovalent hydrocarbon group, a is a positive number, and b is 0 or a positive number. Is a number, c is a positive number, and x is 0, 1 or 2, and (A) a general formula: (R ¹ SiO _3/2 ) a (R ¹ ₂ SiO _2/2 ) b (R ¹ R ⁴ SiO
_2/2 ) c (wherein R ¹ is a monovalent hydrocarbon group, R ⁴ is a haloalkyl group, a is a positive number, b is 0 or a positive number, and c is a positive number. And a (B) general formula: R ³ _x (R ³ O) _(3-x) P═O (wherein R ³ is a monovalent hydrocarbon group, x is 0, 1 or 2.), and a phosphorus-containing organic compound represented by (C)
The present invention relates to a method for producing a phosphorus-containing organopolysiloxane, which comprises reacting in the presence of a tertiary amine compound.

First, the phosphorus-containing organopolysiloxane of the present invention will be described in detail.

The phosphorus-containing organopolysiloxane of the present invention has the general formula:

[Chemical 6] Indicated by. In the above formula, R ¹ is a monovalent hydrocarbon group, specifically, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group; a phenyl group, a tolyl group, and a xylyl group. Aryl groups such as; vinyl groups,
Examples thereof include alkenyl groups such as allyl group, butenyl group, pentenyl group and hexenyl group; and monovalent hydrocarbon groups such as aralkyl group such as benzyl group and phenethyl group. R ² is a divalent hydrocarbon group, and specific examples thereof include alkylene groups such as methylene group, ethylene group, propylene group and butylene group; and divalent hydrocarbon groups such as phenylene group. Also, R
³ is a monovalent hydrocarbon group, specifically, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group; an aryl group such as a phenyl group, a tolyl group, and a xylyl group; Examples thereof include alkenyl groups such as vinyl group, allyl group, butenyl group, pentenyl group and hexenyl group; and monovalent hydrocarbon groups such as aralkyl group such as benzyl group and phenethyl group.

In the above formula, a is a positive number indicating the number of trifunctional siloxane units (T units) represented by the formula: R ¹ SiO _3/2 , and b is the formula: R ¹ ₂ is 0 or a positive number indicating the number of units of difunctional siloxane units (D units) represented by SiO _2/2, c has the formula: R ¹ R ² two represented by SiO _2/2 monofunctional siloxane units ( It is a positive number indicating the number of units (D unit). Further, x is 0, 1 or 2, and when x is 0, the phosphorus-containing organopolysiloxane of the present invention is a phosphate ester group (phosphate ester group) -containing organopolysiloxane, and x is 1
When the phosphorus-containing organopolysiloxane of the present invention is a phosphonate ester group (phosphonate ester group) -containing organopolysiloxane, and when x is 2, the phosphorus-containing organopolysiloxane of the present invention is a phosphonate. Innate ester group (phosphinic acid ester group)
The contained organopolysiloxane.

Next, the method for producing the phosphorus-containing organopolysiloxane of the present invention will be described in detail.

In the production method of the present invention, the haloalkyl group-containing organopolysiloxane as the component (A) is a main raw material and has the general formula: (R ¹ SiO _3/2 ) a (R ¹ ₂ SiO _2/2 ) b ( R ¹ R ⁴ SiO
_2/2 ) c. In the above formula, R ¹ is a monovalent hydrocarbon group, specifically, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group; a phenyl group, a tolyl group, and a xylyl group. Aryl groups such as; vinyl groups,
Examples thereof include alkenyl groups such as allyl group, butenyl group, pentenyl group and hexenyl group; and monovalent hydrocarbon groups such as aralkyl group such as benzyl group and phenethyl group. R ⁴ is a haloalkyl group, and specific examples thereof include a haloalkyl group such as a chloromethyl group, a chloroethyl group and a chloropropyl group. In the above formula, a is a positive number indicating the number of units of the trifunctional siloxane unit (T unit) represented by the formula: R ¹ SiO _3/2 , and b is the formula: R ¹ ₂ SiO _{2 /} is 0 or a positive number indicating the number of units of difunctional siloxane units (D units) represented by _2, c has the formula: R ¹ R ⁴ difunctional siloxane units (D units) represented by SiO _2/2 Is a positive number indicating the number of units of.

The haloalkyl group-containing organopolysiloxane as the component (A) is produced by various methods. As a method for producing such component (A), for example,
A method of co-hydrolyzing a trihalosilane having a monovalent hydrocarbon group and a dichlorosilane having a monovalent hydrocarbon group, and then reacting this with a dialkoxysilane having a haloalkyl group; A method of co-hydrolyzing an alkoxysilane and a dialkoxysilane having a monovalent hydrocarbon group and then reacting this with a dialkoxysilane having a haloalkyl group; a trialkoxysilane having a monovalent hydrocarbon group and a monovalent hydrocarbon. Examples thereof include a method of co-hydrolyzing a dialkoxysilane having a group and a dialkoxysilane having a haloalkyl group. Specific examples of the dialkoxysilane having a haloalkyl group used in the method for producing the component (A) include 3-chloropropyl (methyl) dimethoxysilane, 3-chloropropyl (ethyl) dimethoxysilane, 3-bromopropyl ( Methyl) dimethoxysilane, 3-bromopropyl (ethyl) dimethoxysilane, 3-chloropropyl (methyl) diethoxysilane, 3-chloropropyl (ethyl) diethoxysilane, 3-bromopropyl (methyl)
Examples include diethoxysilane, 3-bromopropyl (ethyl) diethoxysilane, chloromethyl (methyl) dimethoxysilane, 2-chloroethyl (methyl) dimethoxysilane, bromomethyl (methyl) dimethoxysilane, and 2-bromoethyl (methyl) dimethoxysilane. To be done.

In the production method of the present invention, the phosphorus-containing organic compound as the component (B) is a component for introducing a phosphorus atom into the phosphorus-containing organopolysiloxane of the present invention and has the general formula: R ³ _x (R ³ O) _(3-x) P = O. In the above formula, R ³ is a monovalent hydrocarbon group, specifically, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group; a phenyl group, a tolyl group, a xylyl group. Aryl groups such as; vinyl groups,
Examples thereof include alkenyl groups such as allyl group, butenyl group, pentenyl group and hexenyl group; and monovalent hydrocarbon groups such as aralkyl group such as benzyl group and phenethyl group. Further, in the above formula, x is 0, 1 or 2, and when x is 0, the phosphorus-containing organic compound of the component (B) is a phosphate ester compound (phosphate ester compound), and x is When it is 1, the phosphorus-containing organic compound of the component (B) is a phosphonate ester compound (phosphonate ester compound), and when x is 2, the phosphorus-containing organic compound of the component (B) is a phosphinate. It is an ester compound (phosphinic acid ester compound). As such a phosphorus-containing organic compound as the component (B), specifically, dimethyl-methylphosphonate, diethyl-methylphosphonate, dimethyl-phenylphosphonate, dimethyl-benzylphosphonate, diethyl-benzylphosphonate, phenyl-dimethylphosphonate, Examples include methyl-dimethylphosphinate, ethyl-dimethylphosphinate, methyl-methylphenylphosphinate, methyl-methylbenzylphosphinate, phenyl-dimethylphosphinate, phenyl-diethylphosphinate, trimethylphosphate, triethylphosphate and the like.

In the production method of the present invention, the tertiary amine compound as the component (C) is used for promoting the reaction between the haloalkyl group-containing organopolysiloxane as the component (A) and the phosphorus-containing organic compound as the component (B). It is an ingredient. The tertiary amine compound as the component (C) is not particularly limited, and specifically, trimethylamine, triethylamine, tri (i-propyl) amine, tri (n-propyl) amine, tri (t-t).
Examples include butyl) amine, tri (n-butyl) amine, dimethylbenzylamine, and the like.

The phosphorus-containing organopolysiloxane of the present invention comprises the component (A) haloalkyl group-containing organopolysiloxane and the component (B) phosphorus-containing organic compound in the presence of the component (C) tertiary amine compound. Although the reaction temperature is not particularly limited, the reaction can be carried out at room temperature to 250 ° C., for example. Further, in the production method of the present invention, an organic solvent can be used. Specific examples of usable organic solvents include aromatic solvents such as toluene and xylene; hexane,
Examples include aliphatic solvents such as heptane and octane; ether solvents such as methyl ethyl ether and tetrahydrofuran; ester solvents such as methyl acetate, ethyl acetate and propyl acetate.

Since the phosphorus-containing organopolysiloxane of the present invention contains a phosphorus atom in the molecule, it is excellent in electrical characteristics such as low resistance, high dielectric loss tangent, negative triboelectrification and the like. Agent that controls the electrical properties of the agent, anti-static coating agent or additive for electric and electronic parts,
Furthermore, it can be used as an antifouling paint.

[0017]

EXAMPLES The present invention will be described with reference to examples. In the examples, the viscosity value is a value measured at 25 ° C.

[0018]

[Reference Example] 100 g of water, 100 g of isopropyl alcohol and 400 g of toluene were put into a 2 liter round bottom flask equipped with a stirrer, a thermometer and a dropping funnel, and 297 g of phenyltrichlorosilane (about 1.
4 mol), 76 g of diphenylodichlorosilane (about 0.3
Mol) and 39 g of dimethyldichlorosilane (about 0.3
Mol) was added dropwise over 1 hour. After the dropping is completed,
The system was heated, heated to reflux for 2 hours and then cooled.
After standing, the lower layer was taken out, 600 g of a 10% aqueous sodium hydrogen carbonate solution was added, and the mixture was stirred for 30 minutes and left standing to take out the lower layer. The pH of the lower layer was 10. In addition, water 6
The operation of adding 00 g and stirring for 30 minutes and then leaving still and removing the lower layer was repeated twice. Toluene and water were distilled off from the obtained toluene solution by an evaporator to adjust the volatile content at 150 ° C. to be 50%. The viscosity of the obtained toluene solution was 6 centipoise.

Next, 25 g of 3-chloropropyl (methyl) dimethoxysilane was added to 500 g of this toluene solution, and the mixture was heated and stirred at the reflux temperature for 5 hours, and the general formula:

[Chemical 7] A toluene solution of a 3-chloropropyl group-containing organopolysiloxane represented by was prepared.

[0020]

Example 1 A 1 l round-bottomed flask equipped with a stirrer, a thermometer and a dropping funnel was charged with 525 g of a toluene solution of the organopolysiloxane containing 3-chloropropyl group prepared in Reference Example, 25 g of dimethylmethylphosphonate and 2 g of triethylamine, and toluene was added. The mixture was heated and stirred at the reflux temperature for 6 hours. After confirming that the generation of methyl chloride was completed from this system, the low boiling point component was distilled off at 150 ° C / 5 mmHg by an evaporator, and immediately after the distillate was no longer produced, a viscous liquid substance was formed in the metal vat. It was taken out and cooled to room temperature. After cooling, a pale yellow transparent solid was obtained. This slightly yellow transparent solid had a softening point of 75 to 85 ° C. and was found by infrared spectroscopy and ¹³ C-nuclear magnetic resonance spectroscopy to be a phosphorus-containing organopolysiloxane having the structure shown below.

[Chemical 8]

[0021]

Example 2 In a 1 liter round bottom flask equipped with a stirrer, a thermometer and a dropping funnel, a toluene solution 525 of 3-chloropropyl group-containing organopolysiloxane prepared in Reference Example was prepared.
g, 35 g of methylphenylmethylphosphonate and 2 g of dimethylbenzylamine were added, and the mixture was heated to the reflux temperature of toluene and stirred with heating for 6 hours. After confirming that the generation of methyl chloride has ended, use an evaporator to
The low boiling point component was distilled off at 0 ° C./5 mmHg, and immediately after no distillate was produced, it was taken out as a viscous liquid substance into a metallic vat and cooled to room temperature. After cooling, a pale yellow transparent solid was obtained. This slightly yellow transparent solid has a softening point of 78 to 88 ° C.
As a result of infrared spectroscopic analysis and ¹³ C-nuclear magnetic resonance spectral analysis, it was found to be a phosphorus-containing organopolysiloxane having the structure of the following formula since it has the same characteristic absorption as in Example 1.

[Chemical 9]

[0022]

INDUSTRIAL APPLICABILITY The organopolysiloxane of the present invention is a novel phosphorus-containing organopolysiloxane having a phosphorus atom bonded to a silicon atom through an oxyalkylene group and containing a trifunctional siloxane unit (T unit). In addition, the production method of the present invention is characterized in that such a novel phosphorus-containing organopolysiloxane can be produced.

[Brief description of drawings]

FIG. 1 is an infrared spectroscopic analysis chart of the phosphorus-containing organopolysiloxane prepared in Example 1.

2 is a ¹³ C-nuclear magnetic resonance spectrum chart of the phosphorus-containing organopolysiloxane prepared in Example 1. FIG.

Claims (2)

[Claims] 1. A general formula: (In the formula, R ¹ is a monovalent hydrocarbon group, R ² is a divalent hydrocarbon group, R ³ is a monovalent hydrocarbon group, a is a positive number, and b is 0 or a positive number. Is a number, c is a positive number, and x is 0, 1 or 2.). 2. (A) General formula: (R ¹ SiO _3/2 ) a (R ¹ ₂ SiO _2/2 ) b (R ¹ R ⁴ SiO
_2/2 ) c (wherein R ¹ is a monovalent hydrocarbon group, R ⁴ is a haloalkyl group, a is a positive number, b is 0 or a positive number, and c is a positive number. And a (B) general formula: R ³ _x (R ³ O) _(3-x) P═O (wherein R ³ is a monovalent hydrocarbon group, x is 0, 1 or 2.), and a phosphorus-containing organic compound represented by (C)
The method for producing a phosphorus-containing organopolysiloxane according to claim 1, wherein the reaction is carried out in the presence of a tertiary amine compound.