JPH0551461A - Fluoroorganopolysiloxane and its production - Google Patents

Abstract

PURPOSE:To obtain a new fluoroorganopolysiloxane useful as a skin-protecting agent having durability because of excellent water repellency and oil repellency. CONSTITUTION:The objective polymer containing a substituent group shown by formula I P<f> is 1-12C perfluoroalkyl; Y is spacer group comprising main chain contain hetero atom; R<1> is H or methyl) at the end and/or side chain of organopolysiloxane chain. The polymer is obtained by reacting a hydrosilyl- containing organopolysiloxane with a fluorine-containing unsaturated compound shown by formula II in the presence of a metal of the group VH of the periodic table or its metal compound (preferably chloroplatinic acid) preferably at 20-100 deg.C for 1-24 hours. A compound shown by formula III is preferable as the raw material organopolysiloxane. The raw material organopolysiloxane, for example, is obtained by subjecting octamethylcyclotetrasiloxane and tetramethylhydrogen tetrasiloxane to ring-opening equilibration polymerization.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a novel fluoroorganopolysiloxane, more specifically excellent in water repellency and oil repellency,
TECHNICAL FIELD The present invention relates to a fluoroorganopolysiloxane useful as a long-lasting skin protectant and a method for producing the same.

[0002]

2. Description of the Related Art Organopolysiloxane has low surface tension and low refractive index, and has low friction, heat resistance, cold resistance, electrical insulation, water repellency, releasability, defoaming property, chemical resistance, etc. Due to its excellent properties, it is used in a wide range of industrial fields today. However, with recent technological advances, development of organopolysiloxanes excellent in various properties is required in order to meet higher requirements. And
In order to meet some of these demands, organopolysiloxanes having a fluorine-containing organic group in the molecule have been created, and some production methods thereof have been proposed.

[0003]

However, the organopolysiloxane having a fluorine-containing organic group containing a perfluoroalkyl group can be prepared by a known method, that is, the periodic table.
Using a Group VII metal or a metal compound thereof as a catalyst,
It is known that even if an attempt is made to produce a polysiloxane having a Si-H group and a vinyl perfluoroalkyl group by a hydrosilylation method, a target product cannot be obtained in a high yield because a side reaction occurs. Has been. There is also a method of producing a perfluoroorganopolysiloxane by introducing a perfluoroalkyl group into a cyclopolysiloxane having a Si-H group by using a hydrosilylation method, and then polymerizing it, but this method has a long reaction step. It is known that the yield is not good as well as requiring operations such as distillation [Japanese Patent Publication No. 35-8345].
No. 1,207,294, and No. 2-21982.
No. 9]. Therefore, it has been desired to industrially advantageously manufacture an organopolysiloxane having many functions that meet recent demands.

[0004]

Under such circumstances, the present inventor has conducted diligent research and, as a result, has found that the terminal and / or side chain of the organopolysiloxane chain has a perfluoroalkyl-containing substitution represented by the following formula (1). The present invention has been completed by finding that a novel fluoroorganopolysiloxane having a group has excellent water repellency and oil repellency, and that it can be easily produced by a conventionally known hydrosilylation method.

That is, according to the present invention, at the end and / or side chain of the organopolysiloxane chain, the formula (1)

[0006]

[Chemical 5]

(In the formula, R ^f represents a perfluoroalkyl group having 1 to 12 carbon atoms, Y represents a spacer group whose main chain may contain a hetero atom, and R ¹ represents a hydrogen atom or a methyl group. The present invention provides a fluoroorganopolysiloxane having a substituent represented by the formula) and a method for producing the same.

The fluoroorganopolysiloxane of the present invention can be obtained, for example, by using a compound represented by the general formula (2) in the presence of a metal of Group VII of the periodic table or a metal compound thereof in an organopolysiloxane having a hydrosilyl group in the molecule.

[0009]

[Chemical 6]

It is produced by reacting a fluorine-containing unsaturated compound represented by:

The organopolysiloxane having a hydrosilyl group in the molecule used in the method of the present invention preferably has a molecular weight of 300 to 500,000, and more preferably 800.
More preferably, the number is up to 300,000. When the molecular weight of the starting organopolysiloxane is less than 300, the properties of the produced fluoroorganopolysiloxane as a skin protecting agent are not sufficient, and when the molecular weight is more than 500,000, the viscosity is high and the handleability is poor, which is not preferable. Examples of these starting organopolysiloxanes include compounds represented by the following formulas (3) to (5).

[0012]

[Chemical 7]

Further, particularly preferred specific examples include compounds represented by the following formulas (7) and (8).

[0014]

[Chemical 8]

These starting organopolysiloxanes can be produced by a well-known and generally known method, for example, ring-opening equilibration polymerization of octamethylcyclotetrasiloxane and tetramethylhydrogentetrasiloxane.

The fluorine-containing unsaturated compound used in the present invention is bonded to the ethyl group substituted by the perfluoroalkyl group having 1 to 12 carbon atoms represented by the above formula (2) via the spacer group Y. Although it has an ethylenically unsaturated group, examples of the spacer group Y include the groups shown below.

[0017]

[Chemical 9]

Specific preferred examples of these fluorine-containing unsaturated compounds include 3- [2-methoxy-3- (2
-Perfluorooctyl) ethoxy] propoxy-1-
Propene, 3- [2-perfluoropropoxy-3-
(2-Perfluoropropyl) ethoxy] propoxy-
Examples thereof include 1-propene, trifluorononene, 2-perfluorohexylethyl (meth) acrylate, and 5- (2-perfluorooctyl) ethoxy-1-pentene, but are not limited thereto.

The metal of Group VII of the periodic table of the catalyst is platinum, rhodium, cobalt, nickel and the like, and the metal compound thereof is platinum-asbestos, platinum-carbon,
Chloroplatinic acid and its alcohol solution, and an olefin complex of platinum are preferably used. Although the amount of this catalyst is not particularly limited, it is generally 0.01 to 1000 ppm, especially 0.1 to 100 ppm, based on the weight of the metal, based on the reaction raw material.
Is preferred.

The reaction is carried out at a temperature of 20 to 100 ° C. for 1 to 24
It is preferable to carry out for a long time, and in this case, the target product can be obtained in a high yield. Further, this reaction can be carried out without a solvent, but if the viscosity of the organopolysiloxane as a raw material is high or the compatibility of the fluorine-containing unsaturated compound and the organopolysiloxane is low, lower the viscosity or A solvent such as toluene, trifluorotoluene, tetrahydrofuran or hexane may be used for the purpose of enhancing the solubility.

[0021]

INDUSTRIAL APPLICABILITY The fluoroorganopolysiloxane compound of the present invention can be used in various applications, but since it is particularly excellent in water repellency and oil repellency, it can be used in cosmetics as a durable skin protectant.

[0022]

EXAMPLES Next, examples will be described.

Example 1 A three-necked flask having a capacity of 200 ml was charged with the following formula.

[0024]

[Chemical 10]

Polysiloxane represented by (molecular weight 1
20,000) 20 g and 3- [2-methoxy-3- (2-
After charging 100 g of perfluorooctyl) ethoxy] propoxy-1-propene and drying by flowing dry nitrogen gas, chloroplatinic acid was added in an amount corresponding to 40 ppm in terms of platinum with respect to the whole, and reacted with stirring at 60 ° C. for 5 hours. The target fluoroorganopolysiloxane was obtained in a high yield of 90%.
The end of the reaction was determined by IR spectrum analysis to be S at 2130 cm ^-1 .
It was confirmed by the disappearance of the iH bond peak. The IR spectrum of the obtained product is shown in FIG. 1, and the ¹ H-NMR spectrum is shown in FIG.

Example 2 A three-necked flask having a capacity of 300 ml was charged with 100 g of the same polysiloxane as in Example 1 and 70 g of trifluorononene, dried with a stream of dry nitrogen gas, and chloroplatinic acid was added to the whole platinum. An equivalent amount of 20 ppm was added, and the mixture was stirred and reacted at 60 ° C. for 2 hours to obtain a target fluoroorganopolysiloxane.

Example 3 A three-necked flask having a capacity of 200 ml was charged with the following formula.

[0028]

[Chemical 11]

Polysiloxane represented by (molecular weight 2
6,000) 25 g and 3- [2-perfluoropropoxy-3- (2-perfluoropropyl) ethoxy] propoxy-1-propene 100 g were charged and dried by flowing dry nitrogen gas, and then chloroplatinic acid was totally added. Then, an amount equivalent to 20 ppm in terms of platinum was added and reacted at 60 ° C. for 3 hours with stirring to obtain a target fluoroorganopolysiloxane.

[Brief description of drawings]

FIG. 1 is an IR spectrum of the fluoroorganopolysiloxane obtained in Example 1.

FIG. 2 is a ¹ H-NMR spectrum of the fluoroorganopolysiloxane obtained in Example 1.

Claims (4)

[Claims] 1. An end of an organopolysiloxane chain and / or
Alternatively, the side chain may be represented by the formula (1): (In the formula, R ^f represents a perfluoroalkyl group having 1 to 12 carbon atoms, Y represents a spacer group whose main chain may contain a hetero atom, and R ¹ represents a hydrogen atom or a methyl group.) A fluoroorganopolysiloxane having a substituent represented by: 2. The fluoroorganopolysiloxane according to claim 1, wherein the spacer group Y is selected from the following groups. [Chemical 2] 3. An organopolysiloxane having a hydrosilyl group in the molecule, in the presence of a metal of Group VII of the periodic table or a metal compound thereof, represented by the following general formula (2): (In the formula, R ^f represents a perfluoroalkyl group having 1 to 12 carbon atoms, Y represents a spacer group whose main chain may contain a hetero atom, and R ¹ represents a hydrogen atom or a methyl group.) The method for producing a fluoroorganopolysiloxane according to claim 1, wherein a fluorine-containing unsaturated compound represented by the formula (1) is reacted. 4. The method for producing a fluoroorganopolysiloxane according to claim 3, wherein Y in the general formula (2) is selected from the following groups. [Chemical 4]