JPH07278309A - Modified polysioxane and its production - Google Patents

Abstract

PURPOSE:To obtain the subject polymer having a long-chain hydrocarbon group at molecular ends and having an aromatic hydrocarbon groups at siloxane side chains, having high refractive index, excellent in gloss, heat resistance, lubricity, etc., and useful as a material for cosmetics, a lubricant and a heating medium. CONSTITUTION:This polymer is expressed by formula I [R1 and R2 are each a 1-6C alkyl or a 6-10C aromatic hydrocarbon group and one or more substituent groups in the molecule are 1-6C aromatic hydrocarbon groups; R3 is an average 16-600C straight or branched saturated hydrocarbon group; (p) is 0-3000)]. This polymer of formula I is obtained by subjecting ethylene to anion polymerization using 1-6C alkyl Li.tert-diamine-based catalyst to afford living PE, reacting the living PE with a compound of formula II [(q) is 3-7] to afford a polymer of formula III [A is H or Li; R4 is a 1-6C alkyl; (n) is 1-300; (s) is 1-7] and subjecting the polymer of formula III to equilibration polymerization with a compound of formula II and a compound of formula IV [(r)>=1] in the presence of a base catalyst and neutralizing and dehydrating the resultant product.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a modified polysiloxane having a long-chain hydrocarbon group at the molecular end and an aromatic side chain, a process for producing the same, and a silanol group or a silanol group at the end of the molecule which is a synthetic intermediate. 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 long-chain alkyl groups are more lubricious, occlusive, and miscible with hydrocarbon materials than polydimethylsiloxanes having only methyl groups as substituents. Because of its excellent properties, it is widely used in cosmetic raw materials, mold release agents, lubricants, etc. Further, since the 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, etc., and has a high refractive index aromatic hydrocarbon group. It is widely used as a heat medium, a raw material for cosmetics, etc., because it gives gloss and gloss to the blended product. However, a polysiloxane having a long chain alkyl group and further having an aromatic hydrocarbon group has not been known so far.

The conventional synthetic method of introducing a long-chain alkyl group into polysiloxane is a method of reacting a polysiloxane having a Si--H group with a 1-olefin under a platinum catalyst. Therefore, unless the molecular weight of the alkyl group component is low, it is difficult to synthesize and it is difficult to increase the melting point.
Most of the alkyl groups that can be synthesized are straight-chain ones that have no branching, and it was difficult to control the crystallinity. Further, in this synthetic method, there is a possibility that the Si-H terminal may remain, but in order to avoid it, it is a conventional method to use olefin in excess. Moreover, it is difficult to remove the residual olefin, and further, the heavy metal catalyst remains in the product.

Therefore, a method of solving these problems, in which the structure control is easy and precise, there is no residual raw material or by-products, and an aromatic hydrocarbon group is introduced into the side chain of the siloxane, Development was desired. If polysiloxanes with long-chain alkyl groups and aromatic side chains can be manufactured with an accurate structure and with less residual raw materials, catalysts, etc., and by-products, cosmetic raw materials, release agents, lubricants It can be used in a wide range of applications such as agents and heat media, and it is possible to add 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, as a result of intensive investigations by the present inventors, the living polyethylene obtained after the living polymerization of ethylene was reacted with a cyclic siloxane, and a part or all of the aromatic siloxane was reacted. A modified polysiloxane having a long-chain alkyl group at the end and an aromatic side chain is reproduced by polymerizing a cyclic siloxane having a side chain, a chain siloxane having a hydroxyl group at the terminal, or a mixture thereof in the presence of a catalyst. The present invention has been completed by finding that they can be synthesized with good properties. That is, the present invention provides a modified polysiloxane having a long chain hydrocarbon group at the molecular end represented by the formula (I) and having an aromatic side chain.

[0006]

[Chemical 6]

(In the formula, 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 s} 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. ) In addition, the present invention is characterized in that the following steps (1), (2), (3) and (4) are performed in this order, and a long chain hydrocarbon group is attached to the molecular end represented by the above formula (I). And a method for producing a modified polysiloxane having an aromatic side chain.

(1) A step of carrying out living anion polymerization of ethylene using a linear or branched alkyl lithium / tertiary diamine type 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 silanolized by an acid treatment, if necessary, to obtain the molecular fragment represented by the formula (III). A step of obtaining a modified polyethylene having a silanol group or a silanolate group at the terminal.

[0009]

[Chemical 7]

(In the formula, 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. However, they may be different, and q is a number of 3 to 7.)

[0011]

[Chemical 8]

(In the formula, R ₁ and R ₂ have the same meanings as in the formula (II), s represents a number of 1 to 7. R ₄ represents a linear or branched alkyl group having 1 to 6 carbon atoms. And 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 step (2) and the above-mentioned formula (II ) One or more cyclic siloxanes, one or more chain siloxanes represented by the following formula (IV) having hydroxyl groups at both ends, or a mixture thereof, in the presence of an acid catalyst or a base catalyst for equilibration polymerization. The process of doing.

[0013]

[Chemical 9]

(In the formula, 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 ₁ R ₁ and r 2 R ₂ are the same. Furthermore, R ₁ and R ₂ in formula (II) may be the same or different, and r is a number of 1 or more.) (4) Obtained in the above step (3) The step of neutralizing and dehydrating the product.

The present invention further relates to a modified polyethylene having a silanol group or a silanolate group at the terminal of the molecule represented by the formula (III), and a method for producing the same, which comprises the following steps (1) and (2): The present invention provides a manufacturing method characterized by being carried out in order. (1) Linear or branched alkyllithium having 1 to 6 carbon atoms /
Living anion polymerization of ethylene using a tertiary diamine-based initiator. (2) A step of reacting the living polyethylene obtained in the above step (1) with the cyclic siloxane represented by the above formula (II), and if necessary, silanolization by acid treatment.

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

In the formula (I), R ₃ has an average carbon number of 16
It shows 600 straight or branched saturated hydrocarbon groups, preferably an average carbon number of 27 to 300, more preferably an average carbon number.
27 to 100. When the average carbon number is less than 16, the product becomes oily and has poor clogging properties and poor compatibility with hydrocarbon-based raw materials. On the other hand, when it exceeds 600, the effect of polysiloxane is not exerted, and the compatibility with polar base material, heat resistance, and gloss of the compounded product 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 5th carbon atom counted from the end of the long-chain alkyl group. Specific examples of the branch include 2-methyl group, 3-methyl group, and 2,2-dimethyl group. The branched chains at these ends 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 have 1 to 1 carbon atoms.
It represents an alkyl group having 6 or an aromatic hydrocarbon group having 6 to 10 carbon atoms. The (p + 2) R _{1 s} and the (p + 2) R _{2 s} may be the same or different, but it is necessary that at least one R 1 has an aromatic hydrocarbon group in one molecule. Specific examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n
Examples thereof include a -butyl group, a sec-butyl group and a tert-butyl group, but a methyl group is preferable. Carbon number 6
Specific examples of the aromatic hydrocarbon group of ~ 10 include phenyl group, methylphenyl group, naphthyl group and the like,
A phenyl group is preferred.

In the formula (I), p is 0 or more and 3000 or less,
The number is preferably 2000 or less. When p exceeds 3000, the effect of the long-chain alkyl group is lost, and the lubricity and clogging are lost. Further, the viscosity at the time of dissolution becomes too high, resulting in poor miscibility.

The modified polysiloxane represented by the above formula (I) of the present invention can be obtained by carrying out the steps (1), (2), (3) and (4) in this order. Step (1) has 1 carbon
Is a step of performing living anionic polymerization of ethylene with the linear or branched alkyllithium / tertiary diamine-based initiator of -6. An aliphatic hydrocarbon solvent is used in this living anionic polymerization. Specific examples of such a solvent include pentane, hexane, heptane, octane, cyclohexane and cyclopentane.

Examples of the linear or branched alkyl lithium having 1 to 6 carbon atoms include methyl lithium, ethyl lithium, and n.
-Butyllithium, tert-butyllithium, sec
-Butyl lithium, isobutyl lithium, etc. are mentioned. As a tertiary diamine, the number of carbon atoms between two nitrogens is 2
To 3 are preferably used, and 2 are particularly preferable. Specific examples of such a diamine include tetramethylethylenediamine, dipiperidinoethane, dipyrrolidinoethane, sparteine and the like. These tertiary diamines are usually used in 0.1 to 10 equivalents with respect to alkyl lithium. If the amount of amine used is less than 0.1 equivalent, the polymerization becomes very slow, and if it exceeds 10 equivalents, the living terminal is deactivated and the target molecular weight is not reached.

Living polymerization of ethylene is carried out by introducing ethylene into the solution containing the alkyllithium and the tertiary diamine. The introduction pressure of ethylene is not particularly limited, but 1 kg / cm ² to 100 kg / cm ² is suitable. 1kg /
At a low pressure of less than cm ² , the polymerization reaction is too slow, which is not economical. On the other hand, at high pressure exceeding 100 kg / cm ² ,
The polymerization is too fast and the reaction is difficult to control. The polymerization temperature is not particularly limited, but 0 ° C to 100 ° C is suitable. It is preferably 20 ° C to 80 ° C. If the temperature is lower than 0 ° C, the polymerization reaction will be very slow and the living polyethylene produced will precipitate with a low molecular weight, which is not preferable. If the temperature exceeds 100 ° C, the living end is inactivated, which is not preferable. The polymerization time varies depending on the polymerization temperature, the concentration of tertiary diamine, the ethylene introduction pressure, etc., but is generally about 0.1 to 24 hours. However, it is preferable to be as short as possible to remove the heat of polymerization in order to prevent deactivation of the living end. By changing these polymerization conditions, the average molecular weight of polyethylene produced can be accurately controlled.

In the step (2), the living polyethylene produced in the step (1) is reacted with the cyclic siloxane represented by the formula (II), and if necessary, silanolized by acid treatment to give the formula (III). ) Is a step of obtaining a modified polyethylene. The modified polyethylene represented by the formula (III) obtained here is also a novel compound, and 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 is used. It can also be used as an admixture of a material or silicone material with a hydrocarbon-based solvent, an oil agent, a 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 of (I), preferably a methyl group or a phenyl group. In formula (III), the siloxane terminated A atom is hydrogen or lithium, including mixtures thereof. In the formula (III), the degree of polymerization (n) of ethylene is 1 to
300. Those having a degree of polymerization of more than 300 are not preferable because the concentration of terminal silanol groups or silanolate groups is too low. When blended in cosmetics, it is preferable that n = 10 to 100 is in the form of oil or wax. Also,
When used as a resin additive, n = 10 to 150 is preferable, and when it exceeds 300, a sufficient effect cannot be obtained.

The number of siloxane units (s) depends 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 also possible in principle to use 7 or more by using a macrocyclic one. Further, s may be different for each molecule.

The addition 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 larger than the molar amount of living polyethylene. However, considering the suppression of side reactions, etc.
It is preferable to use a double mole or more. The cyclic siloxane represented by the formula (II) may be added to the living polyethylene solution as it is or as a hydrocarbon solution thereof, as long as it is rapidly carried out with sufficient stirring. However, in order to avoid a side reaction in which one living atom reacts with two living polyethylenes, the living polyethylene solution is gradually added to the cyclic siloxane that has been diluted with a hydrocarbon solvent in advance with sufficient stirring. Is particularly preferable.

The reaction temperature is not particularly limited, but it is 0 ° C to 1
00 ° C is suitable. It is preferably 20 ° C to 80 ° C. 0 ° C
If it is less than 100 ° C., living polyethylene is precipitated, which is not preferable, and if it exceeds 100 ° C., a side reaction is likely to occur, which is not preferable. Generally, it is carried out near the polymerization temperature of ethylene.
Since this reaction takes place rapidly within the above-mentioned temperature range, a reaction time of about several minutes is sufficient. However, when the product precipitates, it may take several hours. Usually 30 minutes ~
Do about 5 hours.

The product thus obtained is a polyethylene having one terminal silanolate group modified in which A is lithium in the formula (III), but is neutralized if necessary, and one terminal silanol group modified where A is a hydrogen atom is modified. Polyethylene is obtained. Neutralization is carried out by adding an equivalent amount of acid to the amount of the initiator used to neutralize the obtained polyethylene having one terminal silanolate group, and removing the salt formed by washing with water. However, when a solid acid is used, it can be removed by filtration. With this, one-terminal silanol group-modified polyethylene can be synthesized with 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 terminal, but depending on the reaction conditions, the dehydrated coupling products may be by-produced. Since this coupling product undergoes the same reaction as silanol in the next step, there is no particular problem in the synthesis, but it may be decomposed into two molecules of silanol or silanolate by hydrolysis if necessary. .

The step (3) includes the formula (I) synthesized in the step (2).
A modified polyethylene represented by II), a cyclic siloxane represented by the formula (II), a chain siloxane represented by the formula (IV) having hydroxyl groups at both ends, or a mixture thereof, an acid catalyst or This is a step of carrying out equilibrium polymerization in the presence of a base catalyst. Chlorosilane or alkoxysilane may be used as a raw material for this polymerization, but in this case, it is necessary to hydrolyze the chain siloxane having hydroxyl groups at both ends. 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. Specifically, as in the case of the above formula (I), The same, and preferably a methyl group or a phenyl group. Also, r is not particularly limited as long as it is a number of 1 or more, but is preferably 1 to 30 in view of viscosity and solubility in a reaction solvent.
00.

The molecular weight of the polysiloxane produced 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 chain siloxane having a hydroxyl group at both ends represented by IV). As specific examples of the catalyst, inorganic acids such as sulfuric acid, sulfonic acids such as methanesulfonic acid, and solid acids such as ion exchange resins are preferably used as the acid catalyst. As the base catalyst, hydroxides of alkali metals such as potassium hydroxide, tetraalkylammonium hydroxide, silanolates prepared from tetraalkylammonium hydroxide and cyclic siloxane, and the like are preferably used.
The amount of the catalyst added is not particularly limited, but 0.01 to 1 mol% is sufficient with respect to the number of moles of the siloxane unit.

Further, in this step, a solvent may be appropriately added in order to improve the solubility of the catalyst or the compatibility of 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 20 ° C to 300 ° C is suitable. It is preferably 60 ° C to 200 ° C. If it is lower than 20 ° C, the reaction system becomes non-uniform, and if it exceeds 300 ° C, by-products such as cyclic siloxane are likely to occur, which is not preferable.
The reaction time varies considerably depending on the reaction conditions such as the amount of raw materials charged and the temperature, but it is usually about 8 hours to 7 days.

Step (4) is a step of neutralizing and dehydrating the product obtained in step (3). Up to the step (3) above, polysiloxane with an acid or base catalyst remaining at the terminal ends. Therefore, neutralization is performed, and all the remaining terminals of the catalyst are converted to neutral silanol. In this step, a base or acid calculated from the catalytic amount is added to make it neutral. Here, when 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 heat decomposition treatment. The silanol generated here is heated and dehydrated by an apparatus equipped with a dehydration tube to cause a coupling reaction to obtain a product. The dehydration reaction is carried out neat when the polysiloxane has a low molecular weight and the viscosity is low, but when the viscosity is high, it is dehydrated by refluxing it in a hydrocarbon solvent such as toluene. The product is obtained by distilling off the solvent, but purification such as reprecipitation is carried out in some cases. In this way, a polysiloxane having a long chain hydrocarbon group at the molecular end 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 the present invention is not limited thereto.

Example 1 400 ml of dry cyclohexane and 9 ml of tetramethylethylenediamine were placed in a 1 liter autoclave purged with nitrogen.
n-Butyllithium (1.6 mol / l) 37.5 ml (0.02
Mol) was added to the reaction system while maintaining the temperature of the reaction system at 30 ° C. and the ethylene gas introduction pressure at 2 kg / cm ² while maintaining the ethylene gas at 24.6%.
Living polymerization was carried out by introducing 1 liter. Then, 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 dropping, the reaction was carried out at 30 ° C. for 1 hour, 10 ml of water was added, and the reaction mixture was put into 2 liters of methanol. After stirring for 1 hour, the solid produced by vacuum filtration was collected and dried under vacuum in an oven at 50 ° C. for 24 hours to obtain a white waxy solid. The yield of the product was 36.0 g. As a result of GPC analysis (Waters, orthodichlorobenzene, 135 ° C., calibrated with polyethylene standard sample), the number average molecular weight was 610 and the molecular weight distribution was 1.03. ^{The result of 1} H-NMR analysis (manufactured by Bruker, 200 MHz, chloroform-d, 50 ° C., TMS was used as a standard) is shown in FIG. 1. As is clear from Fig. 1, a methyl group bonded to the silyl group at -0.05ppm (singlet), a methylene group bonded to the silyl group at 0.4ppm (triplet), and a starting end at 0.8ppm (triplet). A signal of the main chain methylene group was observed at around 1.2 ppm for the methyl group. From the integral 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. The synthesis results are shown in Table 1 together with the results of Example 1.

[0037]

[Table 1]

Examples 4 to 5 The amount of ethylene introduced and the polymerization temperature were changed as shown in Table 2. The experimental operation and procedure were the same as in Example 1. However, in Example 5, ethylene was polymerized in a high pressure resistant stainless steel autoclave. The synthesis results are shown in Table 2 together with the results of Example 1.

[0039]

[Table 2]

Example 6 In a 1-liter separable flask equipped with a condenser, 36.0 g of terminal silanol-modified polyethylene obtained in Example 1, 42 g of octamethylcyclotetrasiloxane,
Octaphenylcyclotetrasiloxane 28g, toluene
100 ml was added and heated on an oil bath until the 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.
Then, 0.18 ml of a 1N alcoholic hydrochloric acid solution was added and sufficiently stirred. Water was added to confirm that the pH was 7, and the inorganic salt produced by water was extracted. Washing with water was repeated three times with heating, a Dean-Stark tube was attached instead of the condenser, and toluene was refluxed until completely dehydrated. Toluene was distilled off to obtain a waxy white solid. The yield of product was 95 g. GPC analysis (Waters
As a result of ortho-dichlorobenzene, 135 ° C, polystyrene conversion), the weight average molecular weight is 18500, and the molecular weight distribution is
It was 2.05. ¹ H-NMR analysis (manufactured by Bruker, 200 MH
z, chloroform-d, 50 ° C., TMS was used as standard. 2) shows the results. As is clear from FIG.
-0.05 ppm (singlet) is a siloxane side chain methyl group, 0.4 ppm (triplet) is a methylene group bonded to a silicon element, 0.8 ppm (triplet) is a starting terminal methyl group, and 1.2 ppm is a polyethylene chain methylene group. The phenyl group of the siloxane side chain was observed at a signal of 7.0 to 7.7 ppm. From the integral ratio of each signal, the weight ratio of polyethylene part and siloxane part was 30:70, and the weight ratio of methylsiloxane part and phenylsiloxane part was 60:40.
I found out.

Comparative Example 1 A 1-liter separable flask equipped with a condenser was charged with hydrogen-modified polydimethyl-diphenylsiloxane at both ends (manufactured by Chisso Corporation, PS085, η = 100).
0, diphenyl siloxane content 4-6 mol%) 96 g, DIAREN 30 (Mitsubishi Kasei Co., Ltd .: C ₃₀ or more α-olefin mixture (using average C ₃₈ )) 4.0 g, toluene
Charge 100 ml, add 100 ppm of chloroplatinic acid in terms of platinum, and add 8
The reaction was carried out at 0 ° C for 24 hours. After purification by reprecipitation, a slightly brown soft wax was obtained. The yield was 96 g. As a result of ¹ H-NMR analysis and IR analysis, the terminal hydrogen residual ratio was 10
%, The residual rate of olefin was 5%.

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

[0043]

[Table 3]

Examples 7 to 8 The procedure of Example 6 was repeated except that the terminal silanol-modified polyethylene obtained in Examples 2 and 3 was used in place of the terminal silanol-modified polyethylene obtained in Example 1. . The synthesis results are shown in Table 4 together with the results of Example 6.

[0045]

[Table 4]

Examples 9 to 10 The procedure of Example 6 was repeated except that the total amount of octamethylcyclotetrasiloxane and octaphenylcyclotetrasiloxane was changed as shown in Table 5 (however, octamethylsiloxane was used). And the weight ratio of octaphenylsiloxane is 50:50). The synthesis results are shown in Table 5 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 and octaphenylcyclotetrasiloxane was changed as shown in Table 6. The synthesis results are shown in Table 6 together with the results of Example 6.

[0049]

[Table 6]

Example 13 Example 6 except that octamethylcyclotetrasiloxane and octaphenylcyclotetrasiloxane were changed to 1,3,5,7-tetramethyl-1,3,5,7-tetraphenylcyclotetrasiloxane. The same method was used. The synthesis results are shown in Table 7 together with the results of Example 6.
In Table 7, the molar ratio (*) of the methyl siloxane portion and the phenyl siloxane 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, and the refractive index of the product was measured. Compared to the one. The results are shown in Table 8.

[0053]

[Table 8]

[0054]

According to the present invention, a modified polysiloxane having a long-chain alkyl group at the molecular end and an aromatic hydrocarbon group at the siloxane side chain can be obtained in a high yield. It has a high rate, and by adding it to cosmetics and the like, gloss and gloss can be imparted. In particular, since the modified polysiloxane obtained in the present invention has an alkyl group obtained by anionic polymerization of ethylene, the chain length of the alkyl group is precisely controlled and the molecular weight is easily increased. In addition, since a catalyst that can be easily removed is used, and the raw materials and intermediates are extremely small remaining, the safety of the product is high. Further, a modified polyethylene having a silanol group or a silanolate group at the end of a molecule, which is a synthetic intermediate of the present invention, is a material containing an inorganic material, a material having a polar group, a silicone material, a hydrocarbon solvent, an oil agent, a resin, It is also useful as an admixture.

[Brief description of drawings]

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

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

Claims (4)

[Claims] 1. A modified polysiloxane having a long chain hydrocarbon group at the molecular end represented by the formula (I) and having an aromatic side chain. [Chemical 1] (In the formula, 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 following steps (1), (2), (3) and (4) are carried out in this order, wherein long-chain carbonization is carried out at the terminal of the molecule represented by formula (I). A method for producing a modified polysiloxane having a hydrogen group and an aromatic side chain. (1) Linear or branched alkyllithium having 1 to 6 carbon atoms /
Living anion polymerization of ethylene 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 silanolized by an acid treatment, if necessary, to obtain the molecular fragment represented by the formula (III). A step of obtaining a modified polyethylene having a silanol group or a silanolate group at the terminal. [Chemical 2] (In the formula, 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. ) [Chemical 3] (In the formula, R ₁ and R ₂ have the same meanings as in formula (II), and s is 1
Indicates a number from ~ 7. R ₄ is a linear or branched alkyl group having 1 to 6 carbon atoms, A is hydrogen or lithium, and n is 1
It is a number from ~ 300. (3) The modified polyethylene represented by the formula (III) obtained in the above step (2), one or more cyclic siloxanes represented by the above formula (II), and the following formula (IV) A step of equilibrating and polymerizing one or more kinds of chain-like siloxane having hydroxyl groups at both ends or a mixture thereof in the presence of an acid catalyst or a base catalyst. [Chemical 4] (In the formula, 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 ₁ R ₁ and r 2 R ₂ are the same or different. Further, R ₁ and R ₂ in formula (II) may be the same or different, and r is a number of 1 or more.) (4) Product obtained in the above step (3) Process of neutralizing and dehydrating. 3. A modified polyethylene having a silanol group or a silanolate group at one end of the molecule represented by the formula (III). [Chemical 5] (In the formula, 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. S is 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 1 to 30.
It is a number of zero. ) 4. The modified polyethylene having a silanol group or a silanolate group at one end of a molecule represented by the formula (III) according to claim 3, characterized in that the following steps (1) and (2) are performed in this order. Manufacturing method. (1) Linear or branched alkyllithium having 1 to 6 carbon atoms /
Living anion polymerization of ethylene using a tertiary diamine-based initiator. (2) A step of reacting the living polyethylene obtained in the above step (1) with the cyclic siloxane represented by the above formula (II), and if necessary, silanolization by acid treatment.