JP3192545B2 - Modified polysiloxane and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a modified polysiloxane having an aromatic side chain and a long chain hydrocarbon group at a molecular terminal, a method for producing the same, and a silanol group or a terminal at one terminal of a molecule as a synthetic intermediate thereof. The present invention relates to a modified polyethylene having a silanolate group and a method for producing the same.

[0002]

2. Description of the Related Art Polysiloxanes having a long-chain alkyl group have better lubricity, blocking property and miscibility with hydrocarbon materials than polydimethylsiloxane having only a methyl group as a substituent. Because of its excellent properties, it is widely used in cosmetic raw materials, release agents, lubricants, etc. In addition, polysiloxane having an aromatic hydrocarbon group such as a phenyl group in the side chain is excellent in heat resistance, compatibility with polar solvents, pigments, and the like, and has a high refractive index aromatic hydrocarbon group. It is widely used as a heating medium, a raw material for cosmetics, and the like because it gives gloss and luster to the compound. However, a polysiloxane having a long-chain alkyl group and further having an aromatic hydrocarbon group has not been known so far.

A conventional synthesis method for introducing a long-chain alkyl group into a polysiloxane is a method in which a 1-olefin is reacted with a polysiloxane having a Si—H group under a platinum catalyst. Therefore, it is difficult to synthesize unless the molecular weight of the alkyl group component is low, and it is difficult to increase the melting point.
Many of the synthesizable alkyl groups have no branch and are straight-chain, and it is difficult to control the crystallinity. In addition, in this synthesis method, there is a possibility that the Si-H terminal may remain, but in order to avoid this, it is usual to use an olefin in excess. Moreover, there is a disadvantage that it is difficult to remove the residual olefin, and that the heavy metal catalyst also remains in the product.

[0004] Therefore, a production method for solving these problems, controlling the structure easily and precisely, leaving no raw materials or generating by-products, and further introducing an aromatic hydrocarbon group into the side chain of siloxane. Development was desired. If a polysiloxane having a long-chain alkyl group and an aromatic side chain can be produced with an accurate structure and with reduced generation of raw materials and catalysts and generation of by-products, cosmetic raw materials, release agents, lubrication It can be used for a wide range of applications, such as chemicals and heating media, and can be provided with a plurality of new functions. An object of the present invention is to provide a polysiloxane having such a long-chain alkyl group and having an aromatic side chain, a method for producing the same, and an intermediate thereof.

[0005]

Under such circumstances, the present inventors have made intensive studies and as a result, have found that living siloxane obtained after living polymerization of ethylene is reacted with a cyclic siloxane, and a part or all of the aromatic siloxane is reacted with an aromatic compound. Polymerization of cyclic siloxane with side chain, chain siloxane with hydroxyl group at the end or a mixture of these, in the presence of a catalyst, reproduces modified polysiloxane with a long alkyl group at the end and aromatic side chain The inventors have found that the compounds can be synthesized with good efficiency, and have completed the present invention. That is, the present invention provides a modified polysiloxane having a long-chain hydrocarbon group at the molecular terminal represented by the formula (I) and having an aromatic side chain.

[0006]

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(Wherein, R ₁ and R ₂ represent an alkyl group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, wherein (p + 2) R ₁ and (p + 2) R ₂ may be the same or different, provided that at least one substituent in one molecule is an aromatic hydrocarbon group, and R ₃ has an average carbon number of 16
To 600 linear or branched saturated hydrocarbon groups, and p is a number from 0 to 3000. Further, the present invention provides the following steps (1), (2), (3) and (4), which are performed in this order: a long-chain hydrocarbon group at the molecular terminal represented by the formula (I). And a method for producing a modified polysiloxane having an aromatic side chain.

(1) A step of subjecting ethylene to living anion polymerization using a linear or branched alkyllithium / tertiary diamine initiator having 1 to 6 carbon atoms. (2) The living polyethylene obtained in the above step (1) is reacted with the cyclic siloxane represented by the formula (II), and if necessary, silanolized by acid treatment to obtain a molecular fragment represented by the formula (III). A step of obtaining a modified polyethylene having a silanol group or a silanolate group at a terminal;

[0009]

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(Wherein, R ₁ and R ₂ represent an alkyl group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, wherein q R ₁ and q R ₂ are the same) And q may be a number from 3 to 7.)

[0011]

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(Wherein, R ₁ and R ₂ have the same meaning as in formula (II), s represents a number of 1 to 7. R ₄ is a linear or branched alkyl group having 1 to 6 carbon atoms.) A is hydrogen or lithium, and n is a number from 1 to 300.) (3) The modified polyethylene represented by the formula (III) obtained in the above step (2) and the above-mentioned formula (II) ), At least one type of cyclic siloxane having a hydroxyl group at both ends represented by the following formula (IV) or a mixture thereof is equilibrated in the presence of an acid catalyst or a base catalyst. Process.

[0013]

Embedded image

(Wherein, R ₁ and R ₂ represent an alkyl group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and r R ₁ and r R ₂ are the same. And R ₁ and R ₂ in formula (II) may be the same or different. R is a number of 1 or more.) (4) Obtained in the above step (3) Neutralizing and dehydrating the product.

Further, the present invention relates to a modified polyethylene having a silanol group or a silanolate group at one terminal of the molecule represented by the formula (III), and a method for producing the same, comprising the following steps (1) and (2): It is intended to provide a manufacturing method characterized by performing the steps in order. (1) C1-C6 linear or branched alkyllithium /
A step of subjecting ethylene to living anionic polymerization using a tertiary diamine-based initiator. (2) A step of reacting the living siloxane obtained in the above step (1) with the cyclic siloxane represented by the above formula (II) and, if necessary, converting the living polyethylene into silanol by acid treatment.

Hereinafter, the present invention will be described in more detail. The modified polysiloxane having a long-chain alkyl group at the molecular terminal represented by the formula (I) of the present invention and having an aromatic side chain,
It has a long-chain alkyl group at both ends of the molecule and has an aromatic hydrocarbon group as a side chain of the polysiloxane.

In the formula (I), R ₃ is selected from an average of 16 carbon atoms.
A linear or branched saturated hydrocarbon group of 600 is shown, preferably having an average carbon number of 27 to 300, more preferably an average carbon number.
27-100. If the average carbon number is less than 16, the product becomes oily, and has poor pluggability and poor compatibility with hydrocarbon-based raw materials. On the other hand, if it exceeds 600, the effect of the polysiloxane is not exhibited, and compatibility with the polar base, heat resistance, gloss of the compound, and the like are lost. Examples of the branched saturated hydrocarbon group represented by R ₃ include those having a short-chain branch having 1 to 5 carbon atoms at the fifth carbon atom counted from the end of the long-chain alkyl group. Specific examples of the branch include a 2-methyl group, a 3-methyl group, and a 2,2-dimethyl group. These terminal branched chains have the effect of lowering the melting point of the product when the alkyl group chain length is short, but have no effect on other physical properties.

In the formula (I), R ₁ and R _{2 each} have 1 to 1 carbon atoms.
6 represents an alkyl group or an aromatic hydrocarbon group having 6 to 10 carbon atoms. The (p + 2) R ₁ and the (p + 2) R ₂ may be the same or different, but it is necessary that at least one in one molecule has an aromatic hydrocarbon group. Specific examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n
-Butyl group, sec-butyl group, tert-butyl group and the like, and preferably a methyl group. Carbon number 6
Specific examples of the aromatic hydrocarbon group of ~ 10 include a phenyl group, a methylphenyl group, a naphthyl group and the like,
Preferably it is a phenyl group.

In the formula (I), p is 0 or more and 3000 or less;
Preferably it is a number of 2000 or less. When p exceeds 3000, the effect of the long-chain alkyl group is lost, and lubricity and blocking property are lost. Further, the viscosity at the time of dissolution becomes too high, and the miscibility becomes poor.

The modified polysiloxane represented by the formula (I) of the present invention can be obtained by performing the steps (1), (2), (3) and (4) in this order. In the step (1), the number of carbon atoms is 1
In this step, living anionic polymerization of ethylene is carried out with a linear or branched alkyllithium / tertiary diamine-based initiator. In this living anionic polymerization, an aliphatic hydrocarbon solvent is used. Specific examples of such a solvent include pentane, hexane, heptane, octane, cyclohexane, cyclopentane and the like.

The straight-chain or branched alkyllithium having 1 to 6 carbon atoms includes methyllithium, ethyllithium, n
-Butyl lithium, tert-butyl lithium, sec
-Butyl lithium, isobutyl lithium and the like. As the tertiary diamine, the number of carbon atoms between two nitrogens is 2
Three to three are preferably used, and two are particularly preferred. Specific examples of such a diamine include tetramethylethylenediamine, dipiperidinoethane, dipyrrolidinoethane, sparteine, and the like. These tertiary diamines are usually used in an amount of 0.1 to 10 equivalents to alkyl lithium. If the amount of the amine used is less than 0.1 equivalent, the polymerization becomes very slow, and if it exceeds 10 equivalents, the living terminal is inactivated and the desired molecular weight is not reached.

Living polymerization of ethylene is carried out by introducing ethylene into a solution containing the above-mentioned alkyllithium and tertiary diamine. There is no particular limitation on the pressure for introducing ethylene, but 1 kg / cm ² to 100 kg / cm ² is appropriate. 1kg /
At low pressures below cm ^{2 the} polymerization reaction is too slow and not economic. On the other hand, at a high pressure exceeding 100 kg / cm ² ,
The polymerization is too fast to control the reaction. The polymerization temperature is not particularly limited, but is suitably from 0 ° C to 100 ° C. The temperature is preferably from 20C to 80C. If the temperature is lower than 0 ° C., the polymerization reaction is extremely slow, and the resulting living polyethylene is undesirably precipitated at a low molecular weight. If the temperature exceeds 100 ° C., the terminal of the living room is deactivated, which is not preferable. The polymerization time varies depending on the polymerization temperature, the tertiary diamine concentration, the ethylene introduction pressure and the like, but is generally about 0.1 to 24 hours. However, it is preferable that the time is as short as possible to remove the heat of polymerization from the viewpoint of preventing the deactivation of the living terminal. The average molecular weight of the produced polyethylene can be accurately controlled by changing these polymerization conditions.

In the step (2), the living polyethylene produced in the above step (1) is reacted with the cyclic siloxane represented by the above formula (II), and if necessary, silanolized by acid treatment to give the above formula (III) This is a step of obtaining a modified polyethylene represented by the following formula: The modified polyethylene represented by the formula (III) obtained here is also a novel compound. In addition to the use as a synthetic intermediate of the modified polysiloxane represented by the formula (I) of the present invention, an inorganic material or a polar group may be used. It can also be used as an admixture of a material, a silicone material, and a hydrocarbon solvent, oil, resin, or the like.

In the formulas (II) and (III), R ₁ and R ₂ are an alkyl group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms. The same as in the case (I), preferably a methyl group or a phenyl group. In the formula (III), the terminal A atom of the siloxane is hydrogen or lithium, and a mixture thereof is also included. In the formula (III), the degree of polymerization (n) of ethylene is 1 to
300. If the degree of polymerization exceeds 300, the concentration of the terminal silanol group or silanolate group is too low, which is not preferable. When blended in cosmetics, those having n = 10 to 100 are particularly preferable in the form of oil or wax. Also,
When used as a resin additive, those having n = 10 to 150 are preferable, and if it exceeds 300, a sufficient effect cannot be obtained.

The number of siloxane units (s) varies depending on the cyclic siloxane to be reacted, as described later.
The minimum is 1 unit and the maximum is the number of siloxane units of the cyclic siloxane represented by the formula (II), but it is possible in principle to increase the number to 7 or more by using a macrocyclic one. Further, s may be different for each molecule.

The amount of the cyclic siloxane represented by the formula (II) is not particularly limited as long as the molar amount of the siloxane unit is equal to or greater than the molar amount of the living polyethylene. However, considering the suppression of side reactions, etc., 2
It is preferable to use at least twice the molar amount. The cyclic siloxane represented by the formula (II) may be added to the living polyethylene solution as it is or as a hydrocarbon solution, as long as it is promptly performed with sufficient stirring. However, in order to avoid a side reaction in which two living polyethylenes react with one silicon atom, the living polyethylene solution is gradually added to the cyclic siloxane previously diluted in a hydrocarbon solvent with sufficient stirring. Is particularly preferred.

The reaction temperature is not particularly limited, but is 0 ° C to 1 ° C.
00 ° C is appropriate. The temperature is preferably from 20C to 80C. 0 ° C
If it is less than 100 ° C., living polyethylene precipitates, which is not preferable. If it exceeds 100 ° C., side reactions tend to occur, which is not preferable. Generally, it is carried out at around the polymerization temperature of ethylene.
Since this reaction occurs quickly in the above-mentioned temperature range, a reaction time of about several minutes is sufficient. However, when the product precipitates, several hours may be required. Usually 30 minutes ~
Perform for about 5 hours.

The product thus obtained is a polyethylene modified with a silanolate group at one end where A is lithium in the formula (III). If necessary, the polyethylene is neutralized and modified with a silanol group at one end where A is a hydrogen atom. Polyethylene is obtained. Neutralization is performed by adding an acid equivalent to the amount of the initiator used to the obtained one-end silanolate group-modified polyethylene to make it neutral, and removing salts formed by washing with water. However, when a solid acid is used, it can be removed by filtration. Thus, one-terminal silanol group-modified polyethylene can be synthesized in high yield, but in some cases, purification such as reprecipitation can be performed.

Most of the products of this reaction are silanols or silanolates having 1 to 7 siloxane units at the polyethylene terminals, but depending on the reaction conditions and the like, dehydration coupling products may be produced as by-products. Since this coupling product undergoes the same reaction as silanol in the next step, there is no particular problem in synthesis, but it may be decomposed into two molecules of silanol or silanolate by hydrolysis if necessary. .

In the step (3), the compound of the formula (I) synthesized in the step (2) is used.
A modified polyethylene represented by the formula (II) and a cyclic siloxane represented by the formula (II), a chain siloxane having a hydroxyl group at both terminals represented by the formula (IV), or a mixture thereof is treated with an acid catalyst or This is a step of performing equilibrium polymerization in the presence of a base catalyst. Chlorosilane or alkoxysilane can be used as a raw material for this polymerization, but in this case, it is necessary to form a chain siloxane having hydroxyl groups at both ends by hydrolysis. In the formula (IV), R ₁ and R ₂ are an alkyl group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms. It is the same, preferably a methyl group or a phenyl group. R is not particularly limited as long as it is 1 or more, but is preferably 1 to 30 from the viewpoint of viscosity and solubility in the reaction solvent.
00.

The molecular weight of the produced polysiloxane is not limited, but the modified polyethylene represented by the formula (III) synthesized in the above step (2) and the cyclic siloxane represented by the formula (II) and / or the formula (II) The molecular weight can be arbitrarily determined by the number of moles charged with the linear siloxane having a hydroxyl group at both terminals represented by the formula (IV). As specific examples of the catalyst, an inorganic acid such as sulfuric acid, a sulfonic acid such as methanesulfonic acid, and a solid acid such as an ion exchange resin are preferably used as an acid catalyst. As the base catalyst, a hydroxide of an alkali metal such as potassium hydroxide, a tetraalkylammonium hydroxide, a silanolate prepared from a tetraalkylammonium hydroxide and a cyclic siloxane, and the like are suitably used.
The amount of the catalyst to be added is not particularly limited, but about 0.01 to 1% by mole based on the number of moles of the siloxane unit is sufficient.

In this step, a solvent may be appropriately added in order to increase the solubility of the catalyst or the compatibility between the raw materials. Specific examples of such a solvent include aromatic hydrocarbons such as toluene and aliphatic hydrocarbons such as octane. The reaction temperature is not particularly limited, but is suitably from 20 ° C to 300 ° C. Preferably it is 60 to 200 ° C. If the temperature is lower than 20 ° C., the reaction system becomes non-uniform.
The reaction time varies considerably depending on the reaction conditions such as the amount of the raw materials charged, the temperature and the like, but it is usually carried out for about 8 hours to 7 days.

Step (4) is a step of neutralizing and dehydrating the product obtained in step (3). Up to the above step (3), a polysiloxane having an acid or base catalyst remaining at the terminal is formed. Therefore, neutralization is carried out, and all the remaining terminals of the catalyst are converted into neutral silanol. In this step, a base or an acid calculated from the amount of the catalyst is added to make it neutral. Here, when an insoluble salt is generated, it can be easily removed by washing with water. However, when a solid acid is used, it can be removed by filtration, and when a tetraalkylammonium hydroxide is used as a base, it can be removed by a thermal decomposition treatment. The silanol generated here is heated and dehydrated by a device equipped with a dehydration tube to cause a coupling reaction to obtain a product. The dehydration reaction is performed neat when the polysiloxane has a low molecular weight and low viscosity, but is dehydrated by refluxing in a hydrocarbon solvent such as toluene when the viscosity is high. The product can be obtained by distilling off the solvent. In some cases, purification such as reprecipitation is performed. Thus, a polysiloxane having a long-chain hydrocarbon group at the molecular terminal represented by the formula (I) and having an aromatic side chain is obtained.

[0034]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

Example 1 400 ml of dry cyclohexane, 9 ml of tetramethylethylenediamine were placed in a 1-liter autoclave purged with nitrogen.
n-butyl lithium (1.6 mol / l) 37.5 ml (0.02
Mol), and while maintaining the temperature of the reaction system at 30 ° C. and the pressure for introducing ethylene gas at 2 kg / cm ² , 24.6 g of ethylene gas was added.
One liter was introduced to perform living polymerization. Thereafter, ethylene gas was removed and the atmosphere was replaced with nitrogen. A solution of 35.4 g of octamethylcyclotetrasiloxane and 10 ml of dry cyclohexane was prepared in advance in a 1-liter eggplant flask, and the above-mentioned polymerization mixture was added dropwise under a nitrogen stream. After completion of the dropwise addition, the mixture was reacted at 30 ° C. for 1 hour, 10 ml of water was added, and the reaction mixture was poured into 2 liters of methanol. After stirring for 1 hour, the resulting solid was collected by filtration under reduced pressure and dried in an oven at 50 ° C. under vacuum for 24 hours to obtain a white waxy solid. The yield of the product was 36.0 g, and the number average molecular weight was 610 and the molecular weight distribution was 1.03 as a result of GPC analysis (ortho-dichlorobenzene, manufactured by Waters, 135 ° C., calibrated with a polyethylene standard sample). FIG. 1 shows the results of ¹ H-NMR analysis (manufactured by Bruker, 200 MHz, chloroform-d, 50 ° C., TMS was used as a standard). As is clear from FIG. 1, the methyl group bonded to the silyl group is -0.05 ppm (singlet), the methylene group bonded to the silyl group is 0.4 ppm (triplet), and the starting terminal is 0.8 ppm (triplet). A signal of a methylene group in the main chain was observed at around 1.2 ppm of the methyl group. From the integration ratio of each signal, it was found that the terminal silanol group introduction rate was 99%. The average number of siloxane units introduced was 1.4 per polyethylene terminal.

Examples 2 to 3 The same procedure as in Example 1 was carried out except that the initiator was changed as shown in Table 1. Table 1 shows the synthesis results together with the results of Example 1.

[0037]

[Table 1]

Examples 4 and 5 The amount of ethylene introduced and the polymerization temperature were varied as shown in Table 2. The experimental operation and procedure were performed in the same manner as in Example 1. However, in Example 5, for polymerization of ethylene, a high pressure-resistant stainless steel autoclave was used. Table 2 shows the synthesis results together with the results of Example 1.

[0039]

[Table 2]

Example 6 A 1 liter separable flask equipped with a condenser was charged with 36.0 g of the terminally silanol-modified polyethylene obtained in Example 1, 42 g of octamethylcyclotetrasiloxane,
28 g of octaphenylcyclotetrasiloxane, toluene
100 ml was added and heated on an oil bath until toluene refluxed. When all the raw materials were uniformly dissolved, 0.01 g of potassium hydroxide was added, and reflux was continued for 48 hours.
Thereafter, 0.18 ml of a 1N alcoholic hydrochloric acid solution was added, and the mixture was sufficiently stirred. Water was added, and it was confirmed that the pH was 7, and inorganic salts formed by water were extracted. Washing was carried out three times with heating, a Dean-Stark tube was attached in place of the condenser, and toluene reflux was carried out until complete dehydration. The toluene was distilled off to obtain a waxy white solid. The yield of the product was 95 g. GPC analysis (Waters
As a result, the weight average molecular weight is 18500 and the molecular weight distribution is
2.05. ¹ H-NMR analysis (manufactured by Bruker, 200 MH
z, chloroform-d, 50 ° C., TMS was used as a standard. 2) shows the result. As is clear from FIG.
−0.05 ppm (singlet) methyl group of siloxane side chain, 0.4 ppm (triplet) methylene group bonded to silicon element, 0.8 ppm (triplet) methyl terminal group at start end, methylene group of polyethylene chain near 1.2 ppm A phenyl group of a siloxane side chain was observed at a signal of 7.0 to 7.7 ppm. From the integration ratio of each signal, the weight ratio of the polyethylene portion to the siloxane portion was 30:70, and the weight ratio of the methylsiloxane portion to the phenylsiloxane portion was 60:40.
It turned out to be.

Comparative Example 1 A 1-liter separable flask equipped with a condenser was charged with hydrogen-terminated polydimethyl-diphenylsiloxane (manufactured by Chisso Corporation, PS085, η = 100).
0, diphenylsiloxane content: 4-6 mol%) 96 g and Dialen 30 (Mitsubishi Chemical Co., Ltd.: C ₃₀ or more α- olefin mixture (using an average C ₃₈₎₎ 4.0 g, toluene
Charge 100 ml, add 100 ppm of chloroplatinic acid in terms of platinum, add 8
The reaction was performed at 0 ° C. for 24 hours. After reprecipitation purification, a slightly brown soft wax was obtained. The yield was 96 g, as a result of ¹ H-NMR analysis and IR analysis,
%, And the residual ratio of the olefin was 5%.

Comparative Examples 2 to 4 The same procedure as in Comparative Example 1 was carried out except that the amount of the dialen 30 and the reaction conditions were changed as shown in Table 3. Table 3 shows the synthesis results.

[0043]

[Table 3]

Examples 7 to 8 The same procedure as in Example 6 was carried out except that the terminal silanol-modified polyethylene obtained in Examples 2 and 3 was used instead of the terminal silanol-modified polyethylene obtained in Example 1. . Table 4 shows the synthesis results together with the results of Example 6.

[0045]

[Table 4]

Examples 9 to 10 The same procedure as in Example 6 was carried out except that the total charge of octamethylcyclotetrasiloxane and octaphenylcyclotetrasiloxane was changed as shown in Table 5, except that octamethylsiloxane was used. And octaphenylsiloxane in a weight ratio of 50:50). Table 5 shows the synthesis results together with the results of Example 6.

[0047]

[Table 5]

Examples 11 to 12 The same procedure as in Example 6 was carried out except that the charging ratio of octamethylcyclotetrasiloxane to octaphenylcyclotetrasiloxane was changed as shown in Table 6. Table 6 shows the synthesis results together with the results of Example 6.

[0049]

[Table 6]

Example 13 Example 6 was repeated except that octamethylcyclotetrasiloxane and octaphenylcyclotetrasiloxane were changed to 1,3,5,7-tetramethyl-1,3,5,7-tetraphenylcyclotetrasiloxane. Was performed in the same manner as described above. Table 7 shows the synthesis results together with the results of Example 6.
In Table 7, the molar ratio (* mark) between the methylsiloxane portion and the phenylsiloxane portion was measured by ¹ H-NMR.

[0051]

[Table 7]

Comparative Example 5 The procedure of Example 6 was repeated, except that octaphenylcyclotetrasiloxane was changed to octamethylcyclotetrasiloxane. The refractive index of the product was measured. Compared to the ones. Table 8 shows the results.

[0053]

[Table 8]

[0054]

According to the present invention, a modified polysiloxane having a long-chain alkyl group at a molecular terminal and an aromatic hydrocarbon group on a siloxane side chain can be obtained in a high yield. It has a high rate, and can be given gloss and gloss by being incorporated into cosmetics and the like. In particular, since the modified polysiloxane obtained in the present invention has an alkyl group obtained by anionic polymerization of ethylene, the control of the chain length of the alkyl group is precise, and it is easy to increase the molecular weight. In addition, since a catalyst that is easily removed is used, and the amount of raw materials and intermediates remaining is extremely small, the safety of the product is high. Further, the synthetic intermediate of the present invention, a modified polyethylene having a silanol group or a silanolate group at one end of the molecule, a material having an inorganic material or a polar group, a silicone material, and a hydrocarbon-based solvent, an oil agent, a resin, or the like. It is also useful as an admixture.

[Brief description of the drawings]

FIG. 1 is a ¹ H-NMR spectrum of a terminal silanol-modified polyethylene obtained in Example 1.

[Figure 2] of the polysiloxane obtained in Example 6 ¹ H-
It is an NMR spectrum.

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Claims (4)

(57) [Claims] 1. A modified polysiloxane having a long-chain hydrocarbon group at the molecular terminal represented by the formula (I) and having an aromatic side chain. Embedded image (Wherein, R ₁ and R ₂ represent an alkyl group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and (p + 2)
R ₁ and (p + 2) R ₂ may be the same or different. However, at least one substituent in one molecule is an aromatic hydrocarbon group. R ₃ is a linear or branched saturated hydrocarbon group having an average carbon number of 16 to 600, and p is a number of 0 or more and 3000 or less. ) 2. The method according to claim 1, wherein the following steps (1), (2), (3) and (4) are carried out in this order. A method for producing a modified polysiloxane having a hydrogen group and having an aromatic side chain. (1) C1-C6 linear or branched alkyllithium /
A step of subjecting ethylene to living anionic polymerization using a tertiary diamine-based initiator. (2) The living polyethylene obtained in the above step (1) is reacted with the cyclic siloxane represented by the formula (II), and if necessary, silanolized by acid treatment to obtain a molecular fragment represented by the formula (III). A step of obtaining a modified polyethylene having a silanol group or a silanolate group at a terminal; Embedded image (Wherein, R ₁ and R ₂ represent an alkyl group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and q R ₁ and q R ₂ are the same or different. Q may be 3 to 7
Is the number of ) (Wherein R ₁ and R ₂ have the same meaning as in formula (II), and s is 1
1 to 7 are shown. R ₄ is a linear or branched alkyl group having 1 to 6 carbon atoms, A is hydrogen or lithium, and n is 1
Number of ~ 300. (3) The modified polyethylene represented by the formula (III) obtained in the above step (2), one or more kinds of cyclic siloxanes represented by the aforementioned formula (II), and the cyclic siloxane represented by the following formula (IV) A step of carrying out equilibrium polymerization of one or more chain siloxanes having hydroxyl groups at both ends or a mixture thereof in the presence of an acid catalyst or a base catalyst. Embedded image (Wherein, R ₁ and R ₂ represent an alkyl group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and r R ₁ and r R ₂ are the same or different. Further, R ₁ and R ₂ in the formula (II) may be the same or different. R is a number of 1 or more.) (4) The product obtained in the above step (3) Neutralizing and dehydrating. 3. A modified polyethylene having a silanol group or a silanolate group at one terminal of a molecule represented by the formula (III ′) . Embedded image (Wherein, R ₁ and R ₂ represent an alkyl group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and s R ₁ and s R ₂ are the same or different. Yes, but small
At least one substituent in one molecule is an aromatic hydrocarbon group.
You. s is a number from 1 to 7, R ₄ is a linear or branched alkyl group having 1 to 6 carbon atoms, A is hydrogen or lithium, and n ′ is a number from 10 to 300. ) 4. The modified polyethylene having a silanol group or a silanolate group at one terminal of a molecule represented by the formula (III) according to claim 3, wherein the following steps (1) and (2) are performed in this order. Manufacturing method. (1) C1-C6 linear or branched alkyllithium /
A step of subjecting ethylene to living anionic polymerization using a tertiary diamine-based initiator. (2) A step of reacting the living siloxane obtained in the above step (1) with the cyclic siloxane represented by the above formula (II) and, if necessary, converting the living polyethylene into silanol by acid treatment.