JPH11228701A - Polysiloxane - Google Patents

Abstract

PROBLEM TO BE SOLVED: To well reproducibly obtain a polysiloxane having an alkyl group at the chain end and fluorine-contg. organic group in the side chain, by polymerizing ethylene, thereafter reacting therewith a cyclic siloxane or the like, moreover polymerizing such a polysiloxane or the like as having a fluorine-contg. organic group in the presence of a catalyst. SOLUTION: This polysiloxane is expressed by the formula. In the formula, RF is an organic group contg. at least one fluorine atom; R<1> is a 16-600C alkyl group; R<2> s are same or different, each a 1-30C hydrocarbyl group; (a) is on average 1 or more; and (b) is on average 0 or more. The polysioxane of the formula can be prepared through the following two steps. (1) the 1st step comprises polymerizing ethylene by using an initiator consisting mainly of an organolithium, then reacting therewith one or more kinds of a cyclic polysiloxane, a linear polysiloxane having leaving groups at the both ends, and a silane having two leaving groups, thus giving a modified polyethylene having a molecular end of a silanol group or the like. (2) the 2nd step comprises polymerizing the modified polyethylene and the polysiloxanes or the like as used in the 1st step (at least one kind of which has a fluorine-contg. organic group) in the presence of a catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polysiloxane having a long-chain alkyl group at a molecular terminal and a fluorine-containing organic group at a side chain, and a method for producing the same.

[0002]

BACKGROUND OF THE INVENTION Fluorine-containing compounds generally have a low surface free energy,
It has properties such as water repellency and oil repellency. Utilizing its properties, it has been used to modify the surface properties of any substance.
In particular, with respect to application to cosmetics, application to makeup cosmetics for preventing "make-up loss" by making use of resistance to sweat and sebum (Japanese Patent Laid-Open No. 22182/1993).
9, JP-A-7-53329, JP-A-8-26935, JP-A-8-9
2033, JP-A-8-133930).

[0003] Organic polysiloxanes (silicone) are also poor in oil repellency, but because of their low surface tension, they have water repellency, lubricity and high malleability, so they are used in the same applications as fluorine-containing compounds. Has excellent spreadability and spreadability. However, these compounds have a drawback that they are poorly compatible with raw materials such as oil generally used in cosmetics and the like, solvents and resins used in paints and the like.

[0004] Therefore, it is very effective to introduce a hydrocarbon group such as an alkyl group in order to improve compatibility. However, a conventional synthesis method for introducing a fluorine-containing organic group and an alkyl group into polysiloxane is silicon-based.
Since this is a method in which a polysiloxane having a hydrogen bond is reacted with a metal catalyst, it has been difficult to accurately introduce the polysiloxane into a specific position. Therefore, the composition of the product has a wide distribution, and since each part is arranged at random, there is a disadvantage that only intermediate properties are obtained.

[0005] Accordingly, it has been desired to develop a production method for simultaneously introducing a fluorine-containing organic group and an alkyl group into desired positions of a polysiloxane.

[0006]

Under these circumstances, the present inventors have conducted intensive studies. As a result, after polymerization of ethylene, a cyclic siloxane or the like is reacted, and a polysiloxane having a fluorine-containing organic group is reacted in the presence of a catalyst. It has been found that by polymerization, a polysiloxane having an alkyl group at a terminal and a fluorine-containing organic group in a side chain can be synthesized with good reproducibility. Further, the present inventors have found that a polysiloxane having an alkyl group at a terminal and having a silicon-hydrogen bond in advance, and a similar polysiloxane can be obtained by a method of introducing a fluorine-containing organic group later, and completed the present invention. . That is, the present invention provides a polysiloxane represented by the formula (I) and a method for producing the same.

[0007]

Embedded image

(Wherein, R _F represents an organic group containing at least one fluorine atom. R ¹ represents a linear or branched alkyl group having an average carbon number of 16 to 600. R ² has a substituent. Represents a hydrocarbon group having 1 to 30 carbon atoms, which may be the same or different, and a plurality of R ² may be the same or different a: a number having an average value of 1 or more b: an average value of 0 or more Indicates the number.)

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION In the formula (I), R ¹ represents a linear or branched alkyl group having an average carbon number of 16 to 600. Preferably average carbon number 30 to 600, more preferably average carbon number 4
0 to 300. When the average carbon number is less than 16, the effect of the alkyl group is not obtained, and the compatibility with other components is poor. On the other hand, if it exceeds 600, the effect of fluorine and silicone in the modified polysiloxane portion will not be obtained, dispersibility and solubility in solvents and oils will be poor, and compoundability in products will be poor. When the number of carbon atoms is from 40 to 300, the compatibility with the oil agent and the resin is further improved, and when it is blended in cosmetics, the film forming property is excellent.

R ² has 1 to 5 carbon atoms which may have a substituent.
30 hydrocarbon groups, and a plurality of R ² may be the same or different. The substituent is an ester group, an amide group, an ether group, an amino group, a hydroxyl group or a carboxyl group. The hydrocarbon group is preferably a methyl group or a phenyl group.

In the formula (I), a is a number having an average value of 1 or more, and b is a number having an average value of 0 or more. Preferably both average 3000
The following numbers. When a and b exceed 3,000, the effect of the alkyl group is reduced, the viscosity at the time of dissolution becomes too high, and the miscibility tends to be poor.

[0012] R _F group is an organic group containing a fluorine atom one or more. Specifically, the organic group itself contains a perfluoroalkyl group (preferably having 1 to 10 carbon atoms) such as a trifluoromethyl group and a perfluorooctyl group, and a fluorine-containing group such as a hexafluoropropylene oxide polymer and a trifluoromethyl ethylene oxide polymer. It may be a polyether group or a group partially having a difluoromethylene group, but these exemplified groups may be present as a substituent in the organic group. Preferably, it is represented by the following formula (II).

-(CH ₂ ) _m -O _x- (CH ₂ ) _n (CF ₂ ) _p CF ₃ (II) (where m is a number of 2 to 30, n is a number of 0 to 30, p is The number of 0 to 10, x represents the number of 0 or 1.) The polysiloxane represented by the formula (I) of the present invention is prepared by the following steps:
It is obtained by performing (1) and (2).

In the step (1), ethylene is polymerized by using an organic lithium-based initiator to form a cyclic polysiloxane,
One or more linear polysiloxanes having a leaving group at each end or two or more silanes having two leaving groups are reacted, if necessary, neutralized, and the molecular ends are silanol groups, silanolate groups or the elimination groups. This is a step of obtaining a modified polyethylene which is a silicon atom having a leaving group, and can be carried out by the method described in JP-A-7-278309.

As the organic lithium, an alkyl lithium having 1 to 6 carbon atoms can be used. Tertiary amines, particularly diamines, are preferably used as initiators. Ethylene is introduced into the solution containing the organic lithium and the like to polymerize ethylene. In this case, a hydrocarbon solvent such as hexane is used for the solution. The chain length of the produced polyethylene can be controlled by manipulating the amount of the initiator and the amount of the introduced ethylene. The preferred chain length in the present invention is, as shown by R ¹ in the formula (I), an average carbon number of 16 to
600.

The leaving group of the linear polysiloxane or silane is mainly a hydroxyl group, an alkoxy group, or a halogen. The addition amount of the polysiloxane or silane is preferably such that the molar amount of the siloxane unit is equal to or greater than the molar amount of the living polyethylene in order to suppress a side reaction in which two living polyethylenes react with one silicon atom. The polysiloxane or silane may be added to the polymer solution as it is or after being diluted with a solvent, or a living polyethylene solution may be gradually added to the polysiloxane or silane or a solution thereof in advance.

The thus obtained product is a modified polyethylene having a silicon atom having a silanolate group or a leaving group at one end, and can be used as it is in the next step. One end silanol group-modified polyethylene can also be obtained. Further, if necessary, purification may be performed.

Most of the products of this reaction are silanolates having one or more siloxane units at the polyethylene terminals, but depending on the reaction conditions and the like, coupling products may be by-produced. Since this coupling product has the same reactivity as silanol in the next step,
There is no particular problem.

In the step (2), at least one of the modified polyethylene obtained in the step (1), a cyclic polysiloxane, a chain polysiloxane having a leaving group at both terminals or a silane having two leaving groups ( However, in the step of polymerizing at least one kind of polysiloxane or silane having an organic group containing a fluorine atom) in the presence of a catalyst, performing purification if necessary, and obtaining a polysiloxane represented by the formula (I). is there.

The cyclic polysiloxane, chain polysiloxane and silane used in this step are the same as those used in step (1). In this step, one type of polysiloxane or silane having an organic group containing a fluorine atom is used. Used above. Further, those having a short-chain alkyl group at the position of the leaving group can also be used as a raw material.

The catalyst is not particularly limited as long as it is an acid or a base. Specific examples thereof include hydroxides of alkali metals, tetraalkylammonium hydroxide, inorganic acids, sulfonic acids, carboxylic acids, solid acids, and solid bases. Etc. are preferably used. The catalyst may be removed using water, an organic solvent, an adsorbent, etc.
When a solid catalyst is used, what decomposes by heating or the like by filtration or the like may be removed by a decomposition treatment. When a solvent is used, the product is obtained by distilling off the solvent, but purification may be performed in some cases. Thus, a polysiloxane (I) having a long-chain alkyl group at the molecular terminal and a fluorine-containing organic group at the side chain is obtained.

The polysiloxane (I) of the present invention can
It can also be obtained by performing the following steps (3) and (4) after (1). In step (3), at least one of the modified polyethylene obtained in step (1), a cyclic polysiloxane, a linear polysiloxane having a leaving group at both terminals, or a silane having two leaving groups (at least One type is a step of performing equilibrium polymerization with a polysiloxane or silane having a hydrogen-silicon bond in the presence of an acid catalyst.

The cyclic polysiloxane, chain polysiloxane and silane are the same as those in the step (1), but one or more polysiloxane or silane having a hydrogen-silicon bond is used. Examples of the acid catalyst include those mentioned in the step (2).

In the step (4), a fluorine-containing compound having a carbon-carbon unsaturated bond is bonded to the product obtained in the step (3) in the presence of a metal catalyst.
This is a step of obtaining a polysiloxane represented by (I).

This reaction is a hydrosilylation reaction,
As the metal catalyst, platinum, rhodium, ruthenium, palladium, osmium, iridium and the like, and complexes thereof can be used. The fluorine-containing compound is an organic compound having one or more fluorine atoms, and a compound having a double bond (vinyl group) at a terminal as the carbon-carbon unsaturated bond is preferably used.

[0026]

EXAMPLES Example 1 (Synthesis of polysiloxane having long-chain alkyl groups at both molecular ends and 3,3,3-trifluoropropyl group in side chains) Step 1 (Synthesis of silanol-terminated polyethylene) 300 ml of n-heptane and N, N, N ', N'-tetramethylethylenediamine are placed in a 1 L glass-made pressure-resistant reaction vessel purged with nitrogen.
3.0 ml, 15% n-butyllithium hexane solution (1.6 mol /
L) 100 ml was charged, and while maintaining the temperature of the reaction system at 30 to 80 ° C and the ethylene gas introduction pressure at 4 kg / cm ² , 81.0 L of ethylene gas was introduced to carry out polymerization. 30.0 g of octamethylcyclotetrasiloxane was introduced into the polymerization mixture under a nitrogen stream.
It was dropped. After the completion of the dropping, the reaction was carried out at 80 ° C. for 30 minutes.
10 ml was added, and the reaction mixture was poured into 5 L of methanol.
After stirring for 1 hour, the resulting solid was collected by filtration under reduced pressure,
Drying in a 50 ° C. oven under vacuum for 24 hours gave a white waxy solid. The yield was 108 g.

Step 2 (Synthesis of Polysiloxane) In a 1 L separable flask equipped with a condenser, 60 g of the silanol-terminated polyethylene obtained in Step 1, 100 g of octamethylcyclotetrasiloxane, 1,3,5,7-
Tetrakis (3,3,3-trifluoropropyl) -1,3,5,
50 g of 7-tetramethylcyclotetrasiloxane and 40 ml of n-octane were added and heated on an oil bath at 150 ° C.
After the raw materials were dissolved, 0.1 g of potassium hydroxide was added, a dehydration tube was attached, and heating and stirring were continued. After 150 hours, distilled water was added to perform an extraction operation. This operation was repeated, and after confirming that the aqueous phase was neutral, n-octane was distilled off to obtain a waxy white solid. Product yield 190
g.

As a result of ¹ H-NMR analysis, 0 ppm is a methyl group bonded to silicon, 0.4 ppm is a methylene group at the terminal of an alkyl group bonded to silicon, and 0.7 ppm is a trifluoropropyl bonded to silicon. A signal of a methylene group of the alkyl group and a methylene group of the alkyl group was observed at about 1.2 ppm, and a signal of a methylene group bonded to the trifluoromethyl group was observed at about 2.0 ppm. From the integration ratio of each signal, the average carbon number of the alkyl group (R ¹ ) is 43 and the average number of units of trifluoropropylmethylsiloxane
(a) is 3, average number of dimethylsiloxane units (b) is
It turned out to be 14. FIG. 1 shows the ¹ H-NMR spectrum.

Example 2 (Synthesis of a polysiloxane having a long-chain alkyl group at both molecular terminals and a 3- (2- (perfluorooctyl) ethoxy) propyl group in a side chain) Step 1 (silanol-terminated polyethylene) Using a 50 L stainless steel reactor, a silanol group-terminated polyethylene was synthesized in the same manner as in Example 1. The raw materials used were 19.0 L of n-heptane, N, N, N ',
N'-tetramethylethylenediamine 60 ml, 15% n-butyllithium hexane solution 2.10 kg, ethylene 2471 L,
800 ml of decamethylcyclopentasiloxane was used. The purification was performed with an adsorbent to obtain a white waxy solid.
The product yield was 3.10 kg.

Step 3 (Synthesis of methyl-hydrogenpolysiloxane having long-chain alkyl groups at both ends) In a 1 L separable flask equipped with a condenser, 34 g of the silanol-terminated polyethylene obtained in Step 1 and octamethylcyclohexane 65 g of tetrasiloxane, 20 g of 1,3,5,7-tetramethylcyclotetrasiloxane, n-heptane
40 g and 5 g of activated clay were added and heated on an oil bath.
A Dean-Stark tube was attached, and heating and stirring were continued for 48 hours while dehydrating. After the reaction mixture was purified by filtration under heating, volatile substances such as a solvent were removed by heating under reduced pressure to obtain a wax-like solid. The yield of the product was 105 g.

Step 4 (having a long-chain alkyl group at both ends,
3- (2- (perfluorooctyl) ethoxy) on the side chain
Synthesis of Polysiloxane Having Propyl Group) The methyl-hydrogenpolysiloxane obtained in Step 3 was placed in a 1 L separable flask equipped with a condenser.
20 g and 100 ml of toluene were added and heated on an oil bath. After confirming uniform dissolution, 22.7 g of 2- (perfluorooctyl) ethyl allyl ether and 1 g of a 1% 2-propyl alcohol chloroplatinate solution were added, and stirring was continued at 50 ° C. for 24 hours. After decolorization with activated carbon and filtration, the solvent was distilled off to obtain a waxy white solid.
The product yield was 41 g.

As a result of ¹ H-NMR analysis, a methyl group bonded to silicon was present at 0 ppm, a methylene group bonded to silicon at 0.4 ppm, a methyl group of a long-chain alkyl group at 0.8 ppm, and 1.2 ppm.
A methylene group of a long chain alkyl group at pm, a methylene group at the center of a propyl group at 1.6 ppm, a methylene group bonded to oxygen of a propyl group at 2.3 ppm, a methylene group bonded to oxygen of an ethoxy group at 3.4 ppm, At 3.4 ppm, a signal of a methylene group bonded to a perfluorooctyl group of an ethoxy group was observed.

From the integration ratio of each signal, the average carbon number of the alkyl group (R ¹ ) is 45, the average number of units of the 3- (2- (perfluorooctyl) ethoxy) propylmethylsiloxane moiety (a) is 9.3, The average number of units (b) of the dimethylsiloxane moiety was found to be 43. FIG.
3 shows an MR spectrum.

[Brief description of the drawings]

[1] of the polysiloxane obtained in Example 1 ¹ H-
It is an NMR spectrum.

[Figure 2] of the polysiloxane obtained in Example 2 ¹ H-
It is an NMR spectrum.

Claims (4)

[Claims] 1. A polysiloxane represented by the formula (I). Embedded image (Wherein, R _F represents an organic group containing at least one fluorine atom. R ¹ represents a linear or branched alkyl group having an average carbon number of 16 to 600. R ² has a substituent. Represents a hydrocarbon group having 1 to 30 carbon atoms, and a plurality of R ² may be the same or different from each other: a: a number having an average value of 1 or more b: a number having an average value of 0 or more Shown.) 2. The compound according to claim 1, wherein R ¹ has a linear or branched average carbon number of 30 to
The polysiloxane of claim 1 which has 600 alkyl groups. 3. The method for producing a polysiloxane according to claim 1, wherein the following steps (1) and (2) are performed. Step (1): One kind of cyclic polysiloxane, chain polysiloxane having leaving groups at both ends or silane having two leaving groups is obtained by polymerizing ethylene using an initiator mainly composed of organolithium. Reacting the above to obtain a modified polyethylene having a silanol group, a silanolate group or a silicon atom having the leaving group. Step (2): at least one of the modified polyethylene obtained in the step (1), a cyclic polysiloxane, a chain polysiloxane having a leaving group at both ends, or a silane having two leaving groups (at least One type is a polysiloxane or a silane having an organic group containing a fluorine atom) in the presence of a catalyst,
A step of polymerizing to obtain a polysiloxane represented by the formula (I). 4. The following steps (3) and (4) are performed in place of step 2.
4. The method for producing a polysiloxane according to claim 3, wherein Step (3): at least one of the modified polyethylene obtained in the step (1), a cyclic polysiloxane, a chain polysiloxane having a leaving group at both terminals, or a silane having two leaving groups (at least One type of polysiloxane or silane having a hydrogen-silicon bond) in the presence of an acid catalyst to carry out equilibrium polymerization. Step (4): a step of bonding a fluorine-containing compound having a carbon-carbon unsaturated bond to the product obtained in step (3) in the presence of a metal catalyst to obtain a polysiloxane represented by the formula (I).