JP4485998B2 - Novel polyolefin-containing polysiloxane and uses thereof - Google Patents

Description

The present invention relates to a novel polysiloxane containing a polyolefin having a weight average molecular weight of 400 to 500,000 in a side chain, and use thereof.

  Conventionally known polyolefin-containing polysiloxane, as shown in Patent Document 1, has an average number of carbon atoms of alkyl groups added to the siloxane of 30 or less, a large fraction of silicone part, and a low pour point, so that it is oily. Thus, it cannot be said that the film-forming property and the glossing effect are excellent.

  In addition, when using polyolefin-containing polysiloxane having an average carbon number of 30 or less as a cosmetic, a method of adding silicone oil is known in order to impart good elongation and smoothness. Since the cosmetic obtained by this method has a low surface tension, it spreads on the skin, has poor durability, and has a disadvantage of poor compatibility with other oily components in the cosmetic.

  In order to improve the compatibility, in Patent Document 2, the compatibility was improved by the method of blending a combination of a polyolefin-containing polysiloxane having an average carbon number of 30 or less and silicone oil, but the film-forming property was deteriorated. .

  Furthermore, in Patent Document 3, polysiloxane having an average carbon number of 32 to 70 was used in order to improve the film forming property, but the length of the alkyl group was insufficient, and compatibility with other oily components was improved. The current situation is that it cannot be improved sufficiently, and a method for improving the compatibility with other oily components of cosmetics and the film-forming properties as cosmetics at once is desired.

JP-A-4-126723 Japanese Patent Publication No. 5-53767 JP 2000-198847 A

An object of the present invention is to provide a novel polyolefin-containing polysiloxane having a siloxane skeleton at two positions adjacent to a polymer terminal and a production method. Furthermore, the subject of this invention is providing the cosmetics containing polyolefin containing polysiloxane.

（式中、Ａは炭素数２〜２０のオレフィンの重合体であり、重量平均分子量が４００〜５０００００のものを表し、Ｒは水素原子、炭素数１〜１８のアルキル基を表す。）
を、酸または塩基性触媒存在下、下記一般式（７）で表される環状ポリシロキサン

（式中、Ｒ ^１ およびＲ ^２ 同一でも異なっていても良く、それぞれ水素原子、炭素数１〜１０のアルキル基、アリール基を表し、Ｙは環状に直結していることを表わし、ｑは１〜５０の整数を表す。）と反応させることにより製造された、一般式（２）で表されるポリシロキサン化合物。

（式中、Ａは、炭素数２〜２０のオレフィンの重合体であり、重量平均分子量が４００〜５０００００のものを表し、Ｒは水素原子、炭素数１〜１８のアルキル基を表し、Ｒ^１、Ｒ^２は同一でも異なっていても良く、それぞれ水素原子、炭素数１〜１０のアルキル基、アリール基を表し、ｎは１〜３０００の数を表す。Ｅは水素原子、炭素数１〜５のアルキル基、アルカリ金属または、下記一般式（３）

（式中、Ａは、炭素数２〜２０のオレフィンの重合体であり、重量平均分子量が４００〜５０００００のものを表し、Ｒは水素原子、炭素数１〜１８のアルキル基を表す。）を表す。）
［２］［１］に記載の重合体を含む化粧料
である。 That is, the present invention
[1] α, β-Dihydroxy polymer represented by the following general formula (5)

(In the formula, A is an olefin polymer having 2 to 20 carbon atoms and represents a polymer having a weight average molecular weight of 400 to 500,000, and R represents a hydrogen atom and an alkyl group having 1 to 18 carbon atoms.)
In the presence of an acid or basic catalyst, a cyclic polysiloxane represented by the following general formula (7)

(In the formula, R ¹ and R ² may be the same or different, and each represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group; Y represents a direct bond in a ring; The polysiloxane compound represented by General formula (2) manufactured by making it react with -50 .

(In the formula, A is an olefin polymer having 2 to 20 carbon atoms, and represents a polymer having a weight average molecular weight of 400 to 500,000, R represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, and R ^1. , R ² may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group, n represents a number from 1 to 3000, and E represents a hydrogen atom, 1 to 5 carbon atoms. An alkyl group, an alkali metal, or the following general formula (3)

(In the formula, A is an olefin polymer having 2 to 20 carbon atoms and represents a weight average molecular weight of 400 to 500,000, and R represents a hydrogen atom and an alkyl group having 1 to 18 carbon atoms ). To express. )
[ 2 ] A cosmetic comprising the polymer according to [1 ] .

The polysiloxane of the present invention is a novel polyolefin-containing polysiloxane containing a polyolefin component represented by the general formula ( 2 ).

In the general formula ( 2 ), examples of the olefin having 2 to 20 carbon atoms that form the group represented by A include ethylene, propylene, 1-butene, 3-methyl-1-pentene, 1-hexene, 1-hexene, Examples include octene. One or more of these are used. Of these, ethylene, propylene, and 1-butene are particularly preferable.

In the general formula ( 2 ), the weight average molecular weight (Mw) measured by gel permeation chromatography (hereinafter abbreviated as GPC) of the group represented by A is 400 to 500,000, preferably 800 to 200,000, more preferably. Is 1000 to 100,000.

（式中、Ａ、Ｒは一般式（２）で定義した通り）で表されるα,β−ジヒドロキシ重合体を、酸または塩基性触媒存在下、下記一般式（７）で表される環状ポリシロキサン

（一般式（７）中、Ｒ^１およびＲ^２は一般式（２）で定義した通り。Ｙは環状に直結していることを表わし、ｑは１〜５０の整数を表す。）を反応させることにより製造することができる。
Ａで表される基の重量平均分子量は該末端エポキシ基含有重合体の重量平均分子量から、エポキシ基の分子量４２とＲで表される基の分子量を差し引いた値として求めることができる。 Polyolefin-containing polysiloxane of the present invention will following general formula the corresponding (5)

(Wherein, A, R is formula (as defined in 2)) represented by alpha, a β- dihydroxy polymer, an acid or basic catalyst presence, is represented by the SL one general formula (7) Cyclic polysiloxane

(In general formula ( 7), R ¹ and R ² are as defined in general formula (2). Y represents that they are directly connected in a ring, and q represents an integer of 1 to 50). Can be manufactured.
The weight average molecular weight of the group represented by A can be obtained as a value obtained by subtracting the molecular weight of the epoxy group and the molecular weight of the group represented by R from the weight average molecular weight of the terminal epoxy group-containing polymer.

In the general formula ( 2 ), the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by GPC of the group represented by A, that is, the molecular weight distribution (Mw / Mn) is 1.0 to 4.0. Is preferable, more preferably 1.1 to 3.0, and still more preferably 1.2 to 2.5.

  The weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) were measured as follows using GPC-150 manufactured by Millipore. That is, the separation column was TSK GNH HT, and the column size was 7.5 mm in diameter and 300 mm in length. The column temperature was 140 ° C., orthodichlorobenzene (Wako Pure Chemical Industries) was used as the mobile phase, and 0.025% by mass of BHT (Takeda Pharmaceutical) was used as the antioxidant, and the mobile phase was moved at 1.0 ml / min. The sample concentration was 0.1% by mass, and the sample injection amount was 500 microliters. A differential refractometer was used as a detector. Standard polystyrene used was manufactured by Tosoh Corporation.

In the general formula ( 2 ) of the present invention, R is a substituent bonded to the double bond of the olefin constituting A. For example, hydrogen, an alkyl group having 1 to 18 carbon atoms, such as hydrogen, a methyl group, an ethyl group, and a propyl group.

Further, in the general formula (2) Contact and (7), the alkyl group having 1 to 10 carbon atoms of ^{R 1} and ^{R 2,} a methyl group, an ethyl group, a propyl group, a vinyl group, butyl group, pentyl group, hexyl Group, cyclohexyl group and the like. The aryl group having 1 to 10 carbon atoms of ^{R 1} and ^{R 2,} a phenyl group, a naphthyl group. Among these, a methyl group and a phenyl group are particularly preferable.

  In the general formula (2), examples of the alkyl group having 1 to 5 carbon atoms of E include a methyl group, an ethyl group, a propyl group, and a butyl group. Examples of the alkali metal include lithium, sodium, potassium, rubidium, and cesium.

< Method for Producing α , β-Dihydroxy Polymer>
Polyolefin-containing polysiloxane of the present invention, alpha shown by a the corresponding general formula (5) can be prepared from β- dihydroxy polymer.

（式中、ＡおよびＲは一般式（２）で定義した通り。）で示される片方の末端に二重結合を有するポリオレフィンをエポキシ化することにより得ることができ、また、α,β−ジヒドロキシ重合体は、対応する末端エポキシ含有重合体を経由して製造することができる。 The terminal epoxy group-containing polymer has the following general formula (8)

(Wherein A and R are as defined in the general formula ( 2 )), and can be obtained by epoxidizing a polyolefin having a double bond at one end, and α, β-dihydroxy The polymer can be produced via the corresponding terminal epoxy-containing polymer.

The terminal double bond-containing polyolefin represented by the general formula (8) can be produced by the following method.
(1) A transition metal compound having a salicylaldoimine ligand as shown in JP-A Nos. 2000-239312, 2001-27331, 2003-73412, etc. is used as a polymerization catalyst. Polymerization method.
(2) A polymerization method using a titanium catalyst comprising a titanium compound and an organoaluminum compound.
(3) A polymerization method using a vanadium catalyst comprising a vanadium compound and an organoaluminum compound.
(4) A polymerization method using a Ziegler-type catalyst comprising a metallocene compound such as zirconocene and an organoaluminum oxy compound (aluminoxane).

  Among the above methods (1) to (4), particularly according to the method (1), the polyolefin can be produced with high yield. In the method (1), a polyolefin having a double bond at one end is produced by polymerizing or copolymerizing the olefin described above in the presence of the transition metal compound having the salicylaldoimine ligand. Can do.

  The polymerization of the olefin by the method (1) can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization or a gas phase polymerization method. Detailed conditions and the like are already known, and the above-mentioned patent documents can be referred to.

（式中、ＡおよびＲは一般式（２）で定義した通り。）で表されるシス、またはトランス型の二重結合を含む場合もある。これら、シスまたはトランス型二重結合の割合は、重合条件によって変わるが好ましくは全二重結合のうち３０％以下、好ましくは２０％以下である。シス、トランスの割合は任意である。¹Ｈ-ＮＭＲについては、測定サンプル管中で重合体を、ロック溶媒と溶媒を兼ねた重水素化-1,1,2,2-テトラクロロエタンに完全に溶解させた後、１２０℃において測定した。ケミカルシフトは、重水素化-1,1,2,2-テトラクロロエタンのピークを５．９２ｐｐｍとして、他のピークのケミカルシフト値を決定した。 Ratio of vinyl or vinylidene type double bond measured by ¹ H-NMR in the low molecular weight ethylene polymer of the present invention (in the following description, this ratio is referred to as “one-end vinyl group content”) ) Is 50% or more of all the ends, more preferably 70% or more, and still more preferably 80% or more. Further, in the above polymerization method, in addition to the vinyl and vinylidene type double bonds described, the following general formula (9)

(In the formula, A and R are as defined in the general formula ( 2 ).) In some cases, a cis or trans double bond represented by the formula ( 2 ) may be included. The proportion of these cis or trans double bonds varies depending on the polymerization conditions, but is preferably 30% or less, preferably 20% or less of the total double bonds. The ratio of cis and trans is arbitrary. ¹ H-NMR was measured at 120 ° C. after completely dissolving the polymer in deuterated 1,1,2,2-tetrachloroethane serving as a lock solvent and a solvent in a measurement sample tube. . The chemical shift was determined by setting the peak of deuterated-1,1,2,2-tetrachloroethane to 5.92 ppm and determining the chemical shift value of other peaks.

The content of one terminal vinyl group in the low molecular weight polymer consisting only of ethylene is determined by ¹ H-NMR. The peak of each hydrogen of the polymer has a peak for three protons (A) based on the terminal saturated methyl group of 0.65 to 0.85 ppm, and a peak for three protons based on the vinyl group (B) of 4.70. It is observed at ˜5.0 ppm and 5.5 to 5.8 ppm. If each S _A and S _B of the peak area of each peak (A) and (B), the double bond content (U%) is calculated by the following equation.
U (%) = S _B × 200 / (S _A + S _B )
The molecular weight of the polyolefin obtained by the method (1) can be adjusted by allowing hydrogen to be present in the polymerization system, changing the polymerization temperature, or changing the type of catalyst used.

  Next, the polyolefin is epoxidized, that is, the double bond at the terminal of the polyolefin is oxidized to obtain a polymer containing an epoxy group at the terminal represented by the general formula (4).

（式中、ＡおよびＲは一般式（２）で定義した通り。）

(In the formula, A and R are as defined in the general formula ( 2 ).)

The epoxidation method is not particularly limited, and the following methods can be exemplified (Japanese Patent Publication No. 7-91338, US Pat. No. 5,252,677, Japanese Patent Laid-Open No. 2001-27331, Japanese Patent Laid-Open No. 2003-73412). Publication).
(1) Oxidation with peracids such as performic acid, peracetic acid, perbenzoic acid (2) Oxidation with titanosilicate and hydrogen peroxide (3) Oxidation with rhenium oxide catalyst such as methyltrioxorhenium and hydrogen peroxide ( 4) Oxidation with a porphyrin complex catalyst such as manganese porphyrin or iron porphyrin and hydrogen peroxide or hypochlorite (5) Salen complex such as manganese Salen and oxidation with hydrogen peroxide or hypochlorite (6) Manganese- Oxidation with a TACN complex such as a triazacyclononane (TACN) complex and hydrogen peroxide (7) Oxidation with hydrogen peroxide in the presence of a group VI transition metal catalyst such as a tungsten compound and a phase transfer catalyst

  Among the methods (1) to (7), the methods (1) and (7) are particularly preferable in terms of the active surface.

The epoxy content in all the terminals of the terminal epoxy group-containing polymer is determined by ¹ H-NMR. For example, in the case of a terminal epoxy group-containing polymer obtained by epoxidizing a single-end double bond-containing polymer consisting only of ethylene, the peak (C) for the three protons of the methyl group at the saturated terminal is 0.65 to 0. The peak (D) corresponding to 3 protons at the root of the epoxy group is observed at 2.3 to 2.4 ppm, 2.6 to 2.7 ppm, and 2.8 to 2.9 ppm for each proton. When the epoxy modification is not sufficient, a peak (E) corresponding to 3 protons of the terminal double bond is observed at 2 protons at 4.70 to 5.0 ppm and 1 proton at 5.5 to 5.8 ppm. Each peak (C), if each _S C, _{S D} and _{S E} peak areas of (D) and (E), epoxy group content (Ep (%)) is calculated by the following equation.
_{Ep (%) = S D ×} 200 / (S C + S D + S E)

  The α, β-dihydroxy polymer represented by the general formula (5) can be obtained by reacting a terminal epoxy group-containing polymer with water.

<Method for producing polyolefin-containing polysiloxane>
Material and ing alpha, beta-dihydroxy polymer, an acid or base catalyst presence, the general formula (7) is reacted with a siloxane represented by can be obtained polyolefin-containing polysiloxane.

  Examples of the acid catalyst include mineral acids such as hydrochloric acid, sulfuric acid and phosphoric acid, sulfonic acids such as p-toluenesulfonic acid, solid acids such as Amberlyst-15 (registered trademark), boron trifluoride ether complex, boron trichloride. And Lewis acids such as boron tribromide, aluminum trichloride, aluminum tribromide, tin tetrachloride, and zinc dichloride.

  Examples of the base catalyst include alkali metal hydroxides such as lithium, sodium, potassium, and cesium, carbonates, hydrogen carbonates, alkali earth metal hydroxides such as magnesium and calcium, carbonates, hydrogen carbonates, Examples thereof include organic amines such as pyridine, 4-dimethylaminopyridine and triethylamine, and weakly basic ion exchange resins such as Amberlyst-21 (registered trademark) and Amberlyst-93 (registered trademark).

The amount of the acid or base catalyst used is preferably 0.001 to 10 times by mass, more preferably 0.01 to 5 times by mass, and most preferably 0.05 to 2 masses with respect to the α 1 , β-dihydroxy polymer. Is double. These acid or base catalysts may be used alone or in combination of two or more.

As the reaction solvent, aliphatic hydrocarbons such as example if n- hexane, alicyclic hydrocarbons such as cyclohexane, toluene, aromatic hydrocarbons such as xylene, esters such as ethyl acetate, acetone, methyl ethyl ketone, Examples thereof include ketones such as methyl isobutyl ketone, diethyl ketone and methyl propyl ketone, ethers such as tetrahydrofuran and 1,4-dioxane, and halogenated hydrocarbons such as chloroform, dichloroethane, trichloroethane and perchloroethane . Toluene, aromatic hydrocarbons such as xylene preferred. The amount of the solvent used affects the solubility of the raw material, but it is preferably 0.8 to 100 times by mass, more preferably 1 to 50 times by mass, and still more preferably 2 to 20 masses with respect to the terminal epoxy group-containing polymer. Is double.

  Examples of the cyclic siloxane of the general formula (7) include decamethylcyclopentasiloxane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, octaphenylcyclotetra Siloxane, hexaethylcyclotrisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, dodecamethylcyclohexasiloxane, 1,3,5,7,9-penta Methylcyclopentasiloxane, 1,3,5,7,9-pentamethyl-1,3,5,7,9-pentavinylcyclopentasiloxane, 1,3,5-trimethyl-1,3,5-triphenylcyclo Trisiloxane, 1,3,5-trimethyl-1,3,5-trivinylcyclotri Loxane, 1,3,5,7,9,11-hexamethylcyclohexasiloxane, 1,3,5,7,9-pentamethylcyclopentasiloxane, 1,3,5,7-tetramethyl-1,3 , 5,7-tetravinylcyclotetrasiloxane and the like.

The reaction can be performed, for example, as follows. The reactor, alpha, beta-dihydroxy polymer, cyclic polysiloxane, mixed put acid or base catalyst, the temperature is raised to be uniformly dissolved. Here, the polysiloxane may be used in advance as an alkali metal or alkaline earth metal salt . Anti応温degree is preferably from 25 to 300 ° C., more preferably 50 to 250 ° C., more preferably from 80 to 200 ° C.. Depending on the compound and solvent used, the reaction temperature may exceed the boiling point, so an appropriate reactor such as an autoclave is selected. The reaction time varies depending on the reaction conditions such as the amount of catalyst used, the reaction temperature, and the reactivity of the polymers, but is usually from several minutes to 50 hours.

In the production method of the present invention, the production of by-products is small, and after the reaction, the excess catalyst, polysiloxane, and reaction solvent are removed by a simple operation such as crystallization operation and washing to obtain the desired polyolefin-containing polysiloxane. Obtainable. In the above reaction, the above reaction can also be carried out without isolation and purification from the production process of the raw α , β-dihydroxy polymer.

The number of siloxane units contained in the polysiloxane of the present invention can be measured by ¹ H-NMR. For example, in the case of a polyolefin-containing polysiloxane obtained by modifying a terminal epoxy group-containing polymer consisting only of ethylene with dimethylsiloxane, the number of siloxane units is a peak for 3 protons of methyl group (0.9 ppm) at one end of polyethylene, Alternatively, it is calculated from the ratio of the peak of one proton at the base of the hydroxyl group generated by siloxane modification (3.3 ppm) and the peak of 6 protons per unit of dimethylsiloxane (0.1 ppm), that is, dimethylsiloxane. be able to.

<Uses of polyolefin-containing polysiloxane>
The polyolefin-containing polysiloxane according to the present invention is suitable as a cosmetic additive and imparts good usability as a cosmetic. Specifically, it has makeup, improves the elongation, and is excellent in compatibility with other oil components. The weight average molecular weight of the group represented by A in the general formula ( 2 ) is preferably in the range of 500 to 5,000, more preferably in the range of 800 to 3,000 in terms of excellent makeup. Further, In terms of excellent good elongation, it is preferable that ^{R 1} and ^{R 2} are methyl groups, n in the general formula (2) preferably is 1 to 3000, 10 to 1000 is more preferable. The polyolefin-containing polysiloxane of the present invention is used together with the silicone oil (a) and the oil component (b). The blending amount of the polyolefin-containing polysiloxane of the present invention is preferably 0.1 to 80% by weight, more preferably 0.5 to 20% by weight.

Silicone oil of the above (a) is not a particular limitation, for example, methyl polysiloxane, methylphenyl polysiloxane, octamethyl cyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, methyl cyclopolysiloxane , Octamethyltrisiloxane, decamethyltrisiloxane, highly polymerized methylpolysiloxane, and the like. These silicone oils may be blended singly or in combination of a plurality of them in arbitrary amounts.

  The blending amount of the silicone oil (a) is preferably 0.1 to 80% by weight, and more preferably 0.2 to 30% by weight.

  The oily component (b) is not particularly limited as long as it is generally blended in cosmetics. For example, carnauba wax, ozokerite, glyceryl tribenate, beeswax, candelilla wax, paraffin , Babel wax, lanolin, microcrystalline, montan wax, rice wax, aliphatic alcohol having 12 to 36 carbon atoms, aliphatic alcohol ester having 12 to 36 carbon atoms, and the like. These may be blended alone or in any combination of a plurality of them.

  The blending amount of the oil component (b) is preferably 0.1 to 80% by weight, and more preferably 0.2 to 30% by weight.

  In addition to the above components, the cosmetics of the present invention can be generally blended with cosmetics in general, in the range not impairing the object of the invention, and generally include oils, dyes, powders, surfactants, perfumes, and antioxidants. Preservatives, thickeners, cosmetic ingredients, water and the like can be blended.

These cosmetics can be used in any form such as liquid, solid, gel, paste, and emulsified liquid.

  EXAMPLES Hereinafter, although an Example etc. demonstrate this invention further more concretely, the scope of the present invention is not limited to these Examples etc.

  In addition, the weight average molecular weight Mw and Mw / Mn were measured by the method described in the text using GPC. The melting point (Tm) was a peak top temperature obtained by measurement using DSC.

(Synthesis Example 1)
[Synthesis of single-end double bond-containing ethylene polymer (P-1)]
The compound (10) used as the catalyst was synthesized according to Synthesis Example 6 of JP-A-2003-73412, and the single-end double bond-containing polyethylene was synthesized according to Example 9 of the same publication.

A stainless steel autoclave with an internal volume of 2000 ml sufficiently purged with nitrogen was charged with 1000 ml of heptane at room temperature, and the temperature was raised to 150 ° C. Subsequently, 30 kg / cm ² G was pressurized with ethylene in the autoclave to maintain the temperature. A hexane solution (1.00 mmol / ml in terms of aluminum atom) of MMAO (manufactured by Tosoh Finechem) was injected with 0.5 ml (0.5 mmol), and then a toluene solution (0.0002 mmol / ml) of the following compound (10) 0. 5 ml (0.0001 mmol) was injected to initiate the polymerization. After carrying out the polymerization at 150 ° C. for 30 minutes in an ethylene gas atmosphere, the polymerization was stopped by press-fitting a small amount of methanol. The obtained polymer solution was added to 3 liters of methanol containing a small amount of hydrochloric acid to precipitate a polymer. After washing with methanol, it was dried under reduced pressure at 80 ° C. for 10 hours.

（１０）

(10)

The obtained polymer was homopolyethylene, and ¹ H-NMR measurement was performed on this one-end double bond-containing ethylene-based polymer. As a result, the integral value S _A = From 3.49, the integrated value S _B of the vinyl group = 3.00, the one-end vinyl group content (U) was 92%. The ¹ H-NMR measurement results and physical properties of this one-end double bond-containing ethylene-based polymer (P-1) (unit) were as follows.
¹ H-NMR: δ (C ₆ D ₆ ) 0.81 (t, 3H, J = 6.9 Hz), 1.10-1.45 (m), 1.93 (m, 2H), 4.80 (dd, 1H, J = 9.2, 1.6 Hz ), 4.86 (dd, 1H, J = 17.2, 1.6 Hz), 5.60-5.72 (m, 1H)
Melting point (Tm) 123 ° C
Mw = 1900, Mw / Mn = 2.24 (GPC)

(Synthesis Example 3)
[Production of α, β-dihydroxy polymer (D-1)]
(As Mn 850, vinyl group 108 mmol) 1000 ml separable flask obtained in Synthesis Example 1 one terminal double bond-containing polymer (P-1) 100 g, toluene _{300g, Na 2 WO 4 · 2H} 2 O 1.79g (5.4 mmol), CH ₃ (nC ₈ H ₁₇ ) ₃ NHSO ₄ (1.27 g, 2.7 mmol), and 85% phosphoric acid (0.23 g, 2.7 mmol) were charged and heated to reflux with stirring for 30 minutes. It was completely dissolved. After the internal temperature was set to 90 ° C., 37 g (326 mmol) of 30% hydrogen peroxide solution was added dropwise over 3 hours, followed by stirring at an internal temperature of 90 to 92 ° C. for 3 hours. By measuring the reaction mixture by ¹ H-NMR, it was confirmed that the terminal olefin was 100% modified with an epoxy group. Thereafter, 34.4 g (54.4 mmol) of 25% aqueous sodium thiosulfate solution was added while maintaining the temperature at 85 ° C., and the mixture was stirred for 30 minutes. The peroxide test paper confirmed that the peroxide in the reaction system was completely decomposed. After cooling to an internal temperature of 80 ° C., 2-propanol was slowly added over 30 minutes to crystallize the product, and the slurry was stirred at 65 ° C. for 1 hour, then the solid was collected by filtration and washed with 2-propanol. did. The obtained solid was stirred at room temperature in a 50% aqueous methanol solution, and the solid was collected by filtration and washed with methanol. The solid was further stirred in 400 g of methanol, collected by filtration and washed with methanol. The white solid 106.6g of (alpha), (beta) -dihydroxy polymer (D-1) was obtained by drying under reduced pressure of 60 degreeC and 1-2 hPa (yield 99%, single terminal double bond containing polymer conversion rate) 100%). The physical properties are as follows.
¹ H-NMR: δ (C ₂ D ₂ Cl ₄ ) 0.89 (t, 3H, J = 6.9 Hz), 1.05-1.84 (m), 3.41 (dd, 2H, J = 5.9, 9.9 Hz), 3.57- 3.63 (m, 1H)
Melting point (Tm) 122 ° C
Hardness (Penetration) 0mm
Melt viscosity 214cp (140 ° C)
Softening point 129 ° C
5% weight loss temperature 297 ° C (TGA)

(Synthesis Example 4)
[Synthesis of single-end double bond-containing ethylene polymer (P-2)]
A 100 ml reactor thoroughly dried and purged with nitrogen was charged with 15.4 g (56.1 mmol) of 5-chloro-3-cumylsalicylaldehyde, 60 ml of toluene and 4.42 g of methylamine (40% methanol solution, 56.9 mmol) at room temperature. For 5 hours. The reaction solution was concentrated under reduced pressure to obtain 16.0 g (yield 99%) of a reddish brown oil represented by the following formula (11).
¹ H-NMRδ (CDCl ₃ ) 1.71 (s, 6H), 3.33 (s, 3H), 7.10-7.44 (m, 7H), 8.16 (s, 1H), 13.8 (s, 1H)

（１１）

(11)

A 500 ml reactor thoroughly dried and purged with argon was charged with 12.1 g (42.0 mmol) of compound (11) and 150 ml of diethyl ether, cooled to -78 ° C and stirred. To this, 27.8 ml of n-butyllithium (n-hexane solution, 1.57M, 43.7 mmol) was added dropwise over 30 minutes, and the mixture was stirred at the same temperature for 2 hours. Stir for hours to adjust the lithium salt. This solution was added dropwise to 150 ml of a tetrahydrofuran solution containing 4.84 g (20.8 mol) of a ZrCl ₄ (THF) ₂ complex cooled to −78 ° C. After completion of the dropping, stirring was continued while slowly raising the temperature to room temperature. After further stirring for 12 hours at room temperature, the solvent of the reaction solution was distilled off. The obtained solid was dissolved in 200 ml of methylene chloride, and insoluble matters were removed with a glass filter. The filtrate was concentrated under reduced pressure, and the precipitated solid was reprecipitated with 80 ml of diethyl ether and 150 ml of n-hexane and dried under reduced pressure to obtain 11.4 g (yield 75%) of a yellow powder compound represented by the following formula (12). Obtained.
¹ H-NMR: δ (CDCl ₃ ) 1.67 (s, 6H), 1.92 (s, 6H), 2.30 (s, 6H), 7.00-7.60 (m, 12H), 7.70 (s, 2H), 7.79 (s , 2H)
FD-mass spectrometry: 734

（１２）

(12)

450 ml of heptane was charged into a stainless steel autoclave with an internal volume of 1000 ml sufficiently purged with nitrogen, and propylene was circulated at room temperature for 15 minutes at room temperature to saturate the liquid phase and the gas phase. Subsequently, the temperature was raised to 80 ° C., and then the pressure of propylene was increased to 4 kg / cm ² G to maintain the temperature. Further, ethylene was introduced to 8 kg / cm ² G to maintain the temperature. 0.25 ml (0.25 mmol) of MMAO (manufactured by Tosoh Finechem) in hexane (1.00 mmol / ml of aluminum atom equivalent) was injected, and then 1.0 ml (0.0003 mmol) of a toluene solution of compound (12) (0.0003 mmol / ml) was added. Injected to initiate polymerization. The pressure was maintained while continuously supplying ethylene gas, polymerization was carried out at 80 ° C. for 15 minutes, and then the polymerization was stopped by injecting 5 ml of methanol. The product was obtained by distilling off the solvent from the resulting polymer slurry. By drying under reduced pressure at 80 ° C. for 10 hours, 38.86 g of a copolymer was obtained. The polymerization activity was 518 kg / mmol-Zr · h, and the ^one -end vinyl group content measured by ¹ H-NMR was 99 mol%. The physical properties are as follows.
¹ H-NMR: δ (C ₆ D ₆ ) 0.81 (t, 3H, J = 6.9 Hz), 1.10-1.45 (m), 1.95 (m, 2H), 4.84 (dd, 1H, J = 9.2, 1.6 Hz ), 4.91 (dd, 1H, J = 17.2, 1.6 Hz), 5.67-5.78 (m, 1H)
Melting point (Tm) 116 ° C
Mw = 1490, Mw / Mn = 2.5 (GPC)
Single-end vinyl group content = 99% (calculated from ¹ H-NMR).

(Synthesis Example 6)
[Production of α, β-dihydroxy polymer (D-2)]
As in Synthesis Example 3, except that the raw material single-end double bond-containing ethylene polymer (P-1) was changed to the single-end double bond-containing ethylene polymer (P-2) obtained in Synthesis Example 4. Reaction was performed and the alpha, beta-dihydroxy polymer (D-2) was obtained.
¹ H-NMR: δ (C ₂ D ₂ Cl ₄ ) 0.88 (t, 3H, J = 6.9 Hz), 1.13-1.70 (m), 3.41 (dd, 2H, J = 6.9, 10.9 Hz), 3.57-3.63 (m, 1H)
Melting point (Tm) 119 ° C
Hardness (Penetration) 0.1mm
Softening point 125.5 ° C
Melt viscosity 84cp (140 ° C)
5% weight loss temperature 366.4 ° C (TGA)

(Synthesis Example 7)
[Synthesis of single-end double bond-containing ethylene polymer (P-3)]
[Preparation of solid component (A)]
After suspending 30 g of silica (SiO ₂ ) dried at 150 ° C. for 5 hours under nitrogen flow in 466 mL of toluene, 134.3 mL of methylalumoxane in toluene (3.08 mmol / mL in terms of Al atom) was added at 25 ° C. For 30 minutes. After completion of dropping, the temperature was raised to 114 ° C. over 30 minutes, and the reaction was carried out at that temperature for 4 hours. Thereafter, the temperature was lowered to 60 ° C., and the supernatant was removed by decantation. The solid component thus obtained was washed three times with toluene, and then toluene was added to prepare a toluene slurry of the solid component (A). A part of the obtained solid component (A) was collected and examined for concentration. As a result, the slurry concentration was 0.150 g / mL and the Al concentration was 1.179 mmol / mL.

[Preparation of solid catalyst component (B)]
150 mL of toluene was put into a 300 mL glass flask purged with nitrogen, and the toluene slurry of the solid component (A) prepared above (1.91 g in terms of solid part) was charged with stirring. Next, 50.0 mL of a toluene solution of compound (10) (0.0012 mmol / mL in terms of Zr atom) was added dropwise over 15 minutes, and the mixture was reacted at room temperature for 1 hour. Thereafter, the supernatant was removed by decantation, washed 3 times with heptane, and 100 mL of heptane was added to prepare a heptane slurry of the solid catalyst component (B). A portion of the resulting heptane slurry of the solid catalyst component (B) was collected to examine the concentration. As a result, the Zr concentration was 0.058 mmol / mL and the Al concentration was 14.8 mmol / mL.

450 ml of heptane was charged into a stainless steel autoclave with an internal volume of 1000 ml sufficiently purged with nitrogen, and 100 liter / hr of ethylene was circulated at room temperature for 15 minutes to saturate the liquid phase and the gas phase. Subsequently, 23 NL of propylene was introduced, the temperature was raised to 80 ° C., and then the pressure was increased to 8 kg / cm ² G with ethylene to maintain the temperature. 0.5 ml (0.5 mmol) of a decane solution of triisobutylaluminum (aluminum atom conversion: 1.00 mmol / ml) was injected, and then the solid catalyst component (B) was injected as 0.0001 mmol in terms of Zr atoms. Polymerization was started. The pressure was maintained while continuously supplying ethylene gas, and the polymerization was carried out at 80 ° C. for 60 minutes. Then, the polymerization was stopped by press-fitting 5 ml of methanol, and the monomer was depressurized after the temperature was lowered. The obtained polymer slurry was mixed with 2 L of methanol and stirred and then filtered. The obtained product was dried under reduced pressure at 80 ° C. for 10 hours to obtain 53.2 g of a terminal double bond-containing polymer (P-3) which is an ethylene-propylene copolymer. The product had Mw = 1730, Mw / Mn = 1.68, melting point 108 ° C., vinyl group / vinylene group / vinylidene group = 78.4 / 17.6 / 3.9 measured by ¹ H-NMR. .

(Synthesis Example 9)
[Synthesis of single-end double bond-containing ethylene polymer (P-4)]
Polymerization was carried out in the same manner as in Synthesis Example 7 except that the amount of propylene introduced was changed to 28 NL, to obtain 41.4 g of a terminal double bond-containing polymer (P-4) which was an ethylene-propylene copolymer. The product was Mw = 1310, Mw / Mn = 1.66, melting point 97.5 ° C., vinyl group / vinylene group / vinylidene group = 70.6 / 24.6 / 4.8 measured by ¹ H-NMR. there were.

Example 1
The raw material α, β-dihydroxy polymer (D-1) synthesized in Synthesis Example 3 was used.

In a 25 ml eggplant flask, α, β-dihydroxy polymer (D-1), 1.0 g (0.91 mmol as Mn1100), 4.18 g (11.3 mmol) decamethylcyclopentasiloxane, 3.0 g octane, CsOH 0 .10 g (0.67 mmol) was charged and heated to a temperature of 120 ° C. and stirred for 20 hours. Then, a small amount of 85% phosphoric acid was added to stop the reaction, and after cooling, acetone was added to crystallize the reaction product, and then left to stand for about 30 minutes to precipitate a solid, and the supernatant was removed by decantation. It was. This operation was repeated several times, and the obtained solid was dried under reduced pressure to obtain a polyolefin-containing polysiloxane having an epoxy conversion rate of 100% and an average number of siloxane segments (m) = 80 (in the general formula (2), A: ethylene Group formed by polymerization of (Mw = 2015), R: hydrogen atom R ¹ , R ² : methyl group, E: group represented by general formula (3) (A: group formed by polymerization of ethylene ( Mw = 2015), R: hydrogen atom), m: 80), 1.3 g of a pale yellow solid was obtained. The physical properties are as follows.
¹ H-NMR: δ (C ₂ D ₂ Cl ₄ ) 0.07 (s, 480H), 0.89 (t, 6H, J = 6.9 Hz), 1.00-1.85 (m), 3.30 (dd, 2H, J = 5.6, 9.6 Hz), 3.58 (m, 4H)
²⁹ Si-NMR: δ (C ₂ D ₂ Cl ₄ ) -22 ppm
Melting point (Tm) 120 ° C.

(Example 2 )
In Example 1, alpha, beta-dihydroxy polymer (D-1) in place, alpha obtained in Synthesis Example 6, beta-dihydroxy polymer (D-2) The same as in Example 1, except that the catalyst The reaction is carried out by a method, and a polyolefin-containing polysiloxane having a conversion rate of 100% and an average number of siloxane segments (m) = 117 (in formula (2), A: group formed by polymerization of ethylene (Mw = 1540), R : Hydrogen atom, R ¹ , R ² : methyl group, E: group represented by general formula (3) (A: group formed by polymerization of ethylene (Mw = 1540), R: hydrogen atom), m: 117) was obtained. The physical properties are as follows.
¹ H-NMR: δ (C ₂ D ₂ Cl ₄ ) 0.07 (s, 704H), 0.89 (t, 6H, J = 6.9 Hz), 1.00-1.85 (m), 3.30 (dd, 2H, J = 6.9, 10.6 Hz), 3.58 (m, 4H)
Melting point (Tm) 119 ° C

  The polyolefin-containing polysiloxane of the present invention has, for example, a makeup that is more conventional than conventional materials, improves compatibility with oil components, is excellent in use feeling as a cosmetic, and is particularly useful as a makeup cosmetic additive.

Claims (2)

Α, β-dihydroxy polymer represented by the following general formula (5)

(In the formula, A is an olefin polymer having 2 to 20 carbon atoms and represents a polymer having a weight average molecular weight of 400 to 500,000, and R represents a hydrogen atom and an alkyl group having 1 to 18 carbon atoms.)
In the presence of an acid or basic catalyst, a cyclic polysiloxane represented by the following general formula (7)

(In the formula, R ¹ and R ² may be the same or different, and each represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group; Y represents a direct bond in a ring; The polysiloxane compound represented by General formula (2) manufactured by making it react with -50 .

(In the formula, A is an olefin polymer having 2 to 20 carbon atoms, and represents a polymer having a weight average molecular weight of 400 to 500,000, R represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, and R ^1. , R ² may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group, n represents a number from 1 to 3000, and E represents a hydrogen atom, 1 to 5 carbon atoms. An alkyl group, an alkali metal, or the following general formula (3)

(In the formula, A is an olefin polymer having 2 to 20 carbon atoms and represents a weight average molecular weight of 400 to 500,000, and R represents a hydrogen atom and an alkyl group having 1 to 18 carbon atoms ). To express. ) A cosmetic comprising the polymer according to claim 1 .