JP4271291B2 - Polyethylene wax - Google Patents
Polyethylene wax Download PDFInfo
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- JP4271291B2 JP4271291B2 JP02753299A JP2753299A JP4271291B2 JP 4271291 B2 JP4271291 B2 JP 4271291B2 JP 02753299 A JP02753299 A JP 02753299A JP 2753299 A JP2753299 A JP 2753299A JP 4271291 B2 JP4271291 B2 JP 4271291B2
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- 0 CC*C1CCCC1 Chemical compound CC*C1CCCC1 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/42—Introducing metal atoms or metal-containing groups
Description
【０００１】
【発明の属する技術分野】
本発明は化粧料分野や車用ワックスに有用なポリエチレンワックス及びその製造法に関する。
【０００２】
【従来の技術及び発明が解決しようとする課題】
無機物表面を疎水化し、有機物との親和性を高めようとする試みは、数多く行われており、例えば、シランカップリング剤がある。一般のシランカップリング剤は片方に有機物との反応性官能基を有し、片方に無機物表面と結合を形成するアルコキシシラン部分を有する。
また、化粧品用に用いられる表面処理剤に、粧配規記載のハイドロジェンメチルポリシロキサンがある。これは、反応性の高い水素−ケイ素結合と無機物表面の金属水酸化物部分との脱水素反応により、無機物表面にメチルポリシロキサンを局在化させるものである。
【０００３】
しかし、シランカップリング剤処理は有機物との反応が必要であり、非反応性のものとの相溶化は難しく、ハイドロジェンメチルポリシロキサン処理はシリコーン以外の有機物とは相溶性が乏しいものであった。
そのため、無機物表面と反応性の高いケイ素−水素結合等を有し、非反応性でありながら、汎用有機物との相溶性に富む、長鎖アルキル基等を有する化合物が求められていた。
【０００４】
一方、ワックスに極性基を導入する試みは数多く行われており、酸化反応により、水酸基やカルボキシル基を導入する検討が行われている。しかし、化粧品の毛髪のコンディショニング剤として用いたり、車用の艶出しワックスとして用いる場合、対する毛髪や塗装の表面が陰イオンに帯電しているため、陽イオン性の官能基を有するものが求められていた。
本発明の課題は、化粧料分野や車用ワックスに有用なポリエチレンワックスを提供することにある。
【０００５】
【課題を解決するための手段】
本発明は、式（Ｉ）で表されるポリエチレンワックス（以下ポリエチレンワックス（Ｉ）と略記）及びその製造法を提供する。
【０００６】
【化５】
（式中、R1及びR2は同一又は異なって炭素数１〜10の１価炭化水素基、R3は炭素数１〜６のアルキル基、ｎは平均値が４〜300 の数を示す。）
さらに本発明は、ポリエチレンワックス（Ｉ）を製造中間体として得られる、式(II)
【０００８】
【化６】
（式中、R1, R2，R3及びｎは前記の意味を示し、R4は炭素数１〜10の２価炭化水素基、R5及びR6は同一又は異なって炭素数１〜10の１価炭化水素基を示す。）
で表されるポリエチレンワックス（以下ポリエチレンワックス(II)と略記）及びその製造法を提供する。
【００１０】
【発明の実施の形態】
式（Ｉ）において、R1及びR2はそれぞれ炭素数１〜10の１価炭化水素基であり、好ましくはメチル基あるいはフェニル基である。R3は炭素数１〜６のアルキル基であり、好ましくはｎ−ブチル基あるいは sec−ブチル基である。ｎは平均値が４〜300 の数を示し、配合時の溶媒への溶解性の点で、平均値が14〜50であることが好ましい。
【００１１】
ポリエチレンワックス（Ｉ）は、アルキルリチウムを用いてエチレンを重合し、この重合物と式(III)
【００１２】
【化７】
（式中、R1及びR2は前記の意味を示し、 Xはハロゲン、アルコキシ基等の脱離基を示す。）
で表されるシラン化合物（以下シラン化合物(III) と略記）を反応させることにより得られる。
アルキルリチウムのアルキルとしては、ｎ−ブチル、sec −ブチル、tert−ブチル等が例示される。
【００１４】
エチレンの重合は、ヘキサン、シクロヘキサン等の炭化水素系溶媒中、アルキルリチウムと、活性化剤として、Ｎ，Ｎ，Ｎ',Ｎ’−テトラメチルエチレンジアミン、ジピペリジノエタン等の３級アミンを共存させ、エチレンを導入することにより、円滑に進行する。これらの仕込み量は任意でよいが、生成ポリエチレンの溶解性を考慮して、炭化水素系溶媒はエチレン導入重量の50％以上加えることが好ましい。３級アミンはアルキルリチウムに対して0.1 〜100 モル％使用することが好ましい。アルキルリチウムの添加量は、エチレン１モルに対して0.3 〜25モル％が好ましい。
【００１５】
反応温度は生成ポリエチレンが炭化水素系溶媒に溶解する温度であればよく、０〜150 ℃、エチレンの導入圧力は0.0098〜7.8MPaであり、反応時間はこれらによって左右される。
【００１６】
シラン化合物(III) はポリエチレン溶液に添加してもよいし、逆にシラン化合物(III) にポリエチレン溶液を加えてもよい。本反応の反応条件はエチレン重合条件と同様でよく、１〜24時間程度で反応は完結する。添加するシラン化合物 (III)は溶媒で希釈してもよい。
【００１７】
生成する塩、溶媒、アミンは抽出、吸着等各化合物に適した処理によって除去することもできるが、そのまま用いることもできる用途であれば、中和処理をするだけで製品化することも可能である。このようにして分子末端にケイ素−水素結合を有するポリエチレンワックス（Ｉ）が得られる。
【００１８】
ポリエチレンワックス(II)は、ポリエチレンワックス（Ｉ）と、式(IV)
【００１９】
【化８】
（式中、R4, R5及びR6は前記の意味を示す。）
で表される末端ビニル基含有３級アミン（以下３級アミン(IV)と略記）を反応させることにより得られる。
【００２１】
式（II）において、R4は炭素数１〜10の２価炭化水素基であり、メチレン基、ポリメチレン基あるいは一部にフェニレン基(-C6H4-)を含むポリメチレン基が好ましい。R5及びR6はそれぞれ炭素数１〜10の１価炭化水素基であり、好ましくはメチル基である。
【００２２】
３級アミン(IV)は、ポリエチレンワックス（Ｉ）に添加してもよいし、逆に３級アミン(IV)にポリエチレンワックス（Ｉ）を加えてもよい。本反応の反応条件はエチレン重合条件と同様でよく、１〜24時間程度で反応は完結する。添加する３級アミン(IV)は溶媒で希釈してもよい。
本反応は、ヒドロシリル化反応に用いられる触媒（例えば、白金等の金属錯体）をポリエチレンワックス１モルに対して好ましくは0.01〜１モル％使用する。
【００２３】
【実施例】
実施例１（末端ジメチルシリルポリエチレンの合成）
窒素置換した１Ｌのオートクレーブに乾燥シクロヘキサン400mL 、ジピペリジノエタン4.3mL 、ｎ−ブチルリチウムのシクロヘキサン溶液(1.6mol/Ｌ）12.5mL（0.02モル）を仕込み、反応系の温度を50℃、エチレンガス導入圧力を0.39MPa に保ちながら、エチレンガスを7.62Ｌ導入して重合を行った。
ジメチルクロロシラン5.0mL を前述の重合混合物中に窒素気流下、滴下した。滴下終了後、50℃で１時間反応させた後、反応混合物を冷メタノール２Ｌに投入し、得られた白色固体を濾取した。室温、窒素気流下で乾燥させ、白色粉末状固体を得た。生成物の収量は 9.8ｇ。
【００２４】
得られた生成物の 1Ｈ−ＮＭＲスペクトルを図１に示す。このスペクトルには、0.6ppmにSi-CH2、0.1ppmにSi-CH3、3.8 〜3.9ppmにSi-Hのシグナルが観測された。各シグナルの積分値から、得られた生成物は前記式（Ｉ）において、R1＝R2＝CH3 、R3＝CH3-CH2-CH2-CH2-、ｎ＝平均16、末端シラン導入率95％であることがわかった。
【００２５】
実施例２（末端ジメチルアミノプロピルジメチルシリルポリエチレンの合成）
200mL のフラスコに、乾燥トルエン 4.0ｇ、実施例１で得られた末端ジメチルシリルポリエチレン 1.0ｇ、ジメチルアリルアミン 1.0ｇを入れ、オイルバス上で60℃に加熱し、全ての原料が均一に溶解したことを確認した後、触媒として、塩化白金酸（１％トルエン溶液)0.1ｇを添加した。加熱攪拌を続け、17時間反応を行った。反応混合物を冷メタノール１Ｌに投入し、得られた白色固体を濾取した。室温、窒素気流下で乾燥させ、白色粉末状固体を得た。生成物の収量は 1.0ｇ。
【００２６】
得られた生成物の 1Ｈ−ＮＭＲスペクトルを図２に示す。このスペクトルは、3.8 〜3.9ppmのSi-Hのシグナルが消失し、0.1ppmのSi-CH2に特徴的なシグナルが一重線となったことから、Si-Hが消費されたことがわかり、2.2ppmにN-CH3 のシグナルが観測されたことからアミンが導入されたことがわかった。各シグナルの積分値から、得られた生成物は前記式（II）において、R1＝R2＝R5＝R6＝CH3 、R3＝CH3-CH2-CH2-CH2-、R4＝CH2 、ｎ＝平均16、末端アミン導入率98％であることがわかった。
【００２７】
【発明の効果】
本発明によれば、無機物表面と反応し、有機物との相溶性を向上させる分子末端にケイ素−水素結合を有するポリエチレンワックス、及び毛髪、塗装表面等に親和性が高いワックス被膜を形成できる分子末端に３級アミノ基を有するポリエチレンワックスを収率良く得ることができる。
【図面の簡単な説明】
【図１】 実施例１で得られた末端ジメチルシリルポリエチレンの 1Ｈ−ＮＭＲスペクトルである。
【図２】 実施例２で得られた末端ジメチルアミノプロピルジメチルシリルポリエチレンの 1Ｈ−ＮＭＲスペクトルである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a polyethylene wax useful in the cosmetics field and car wax and a method for producing the same.
[0002]
[Prior art and problems to be solved by the invention]
Many attempts have been made to hydrophobize the surface of inorganic materials and increase the affinity with organic materials, for example, silane coupling agents. A general silane coupling agent has a reactive functional group with an organic substance on one side and an alkoxysilane part that forms a bond with the inorganic surface on one side.
Further, as a surface treatment agent used for cosmetics, there is hydrogenmethylpolysiloxane described in makeup regulations. This localizes methylpolysiloxane on the inorganic surface by a dehydrogenation reaction between a highly reactive hydrogen-silicon bond and a metal hydroxide portion on the inorganic surface.
[0003]
However, the silane coupling agent treatment requires a reaction with an organic substance, and it is difficult to compatibilize with a non-reactive substance, and the hydrogenmethylpolysiloxane treatment has a poor compatibility with organic substances other than silicone. .
Therefore, there has been a demand for a compound having a long-chain alkyl group or the like that has a silicon-hydrogen bond having high reactivity with the inorganic surface, is non-reactive, and is highly compatible with general-purpose organic substances.
[0004]
On the other hand, many attempts have been made to introduce polar groups into wax, and studies have been conducted on introducing hydroxyl groups and carboxyl groups by oxidation reaction. However, when it is used as a hair conditioner for cosmetics or as a polishing wax for cars, the surface of the hair or paint is charged with anions, so that it must have a cationic functional group. It was.
The subject of this invention is providing the polyethylene wax useful for the cosmetics field | area and the wax for vehicles.
[0005]
[Means for Solving the Problems]
The present invention provides a polyethylene wax represented by the formula (I) (hereinafter abbreviated as polyethylene wax (I)) and a method for producing the same.
[0006]
[Chemical formula 5]
(Wherein R 1 and R 2 are the same or different and are monovalent hydrocarbon groups having 1 to 10 carbon atoms, R 3 is an alkyl group having 1 to 6 carbon atoms, and n is a number having an average value of 4 to 300) .)
Furthermore, the present invention relates to a compound of formula (II) obtained by using polyethylene wax (I) as a production intermediate.
[0008]
[Chemical 6]
(Wherein R 1 , R 2 , R 3 and n represent the above meanings, R 4 is a divalent hydrocarbon group having 1 to 10 carbon atoms, and R 5 and R 6 are the same or different and have 1 to 10 represents a monovalent hydrocarbon group.)
And a method for producing the polyethylene wax (hereinafter abbreviated as polyethylene wax (II)).
[0010]
DETAILED DESCRIPTION OF THE INVENTION
In the formula (I), R 1 and R 2 are each a monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably a methyl group or a phenyl group. R 3 is an alkyl group having 1 to 6 carbon atoms, preferably an n-butyl group or a sec-butyl group. n represents a number having an average value of 4 to 300, and the average value is preferably 14 to 50 in terms of solubility in a solvent at the time of blending.
[0011]
Polyethylene wax (I) polymerizes ethylene using alkyllithium, and this polymer and formula (III)
[0012]
[Chemical 7]
(Wherein R 1 and R 2 have the above-mentioned meanings, and X represents a leaving group such as a halogen or an alkoxy group.)
It is obtained by reacting with a silane compound (hereinafter abbreviated as silane compound (III)).
Examples of the alkyl of alkyl lithium include n-butyl, sec-butyl, tert-butyl and the like.
[0014]
The polymerization of ethylene involves alkyllithium in a hydrocarbon solvent such as hexane or cyclohexane, and a tertiary amine such as N, N, N ′, N′-tetramethylethylenediamine or dipiperidinoethane as an activator. Coexist and progress smoothly by introducing ethylene. These charging amounts may be arbitrary, but considering the solubility of the produced polyethylene, the hydrocarbon solvent is preferably added in an amount of 50% or more of the ethylene introduction weight. The tertiary amine is preferably used in an amount of 0.1 to 100 mol% with respect to the alkyl lithium. The amount of alkyllithium added is preferably 0.3 to 25 mol% with respect to 1 mol of ethylene.
[0015]
The reaction temperature may be a temperature at which the produced polyethylene is dissolved in the hydrocarbon solvent, and is 0 to 150 ° C., the introduction pressure of ethylene is 0.0098 to 7.8 MPa, and the reaction time depends on these.
[0016]
The silane compound (III) may be added to the polyethylene solution, or conversely, the polyethylene solution may be added to the silane compound (III). The reaction conditions for this reaction may be the same as the ethylene polymerization conditions, and the reaction is completed in about 1 to 24 hours. The silane compound (III) to be added may be diluted with a solvent.
[0017]
The generated salt, solvent, and amine can be removed by a treatment suitable for each compound such as extraction and adsorption, but if it can be used as it is, it can be commercialized just by neutralization treatment. is there. A polyethylene wax (I) having a silicon-hydrogen bond at the molecular end is thus obtained.
[0018]
Polyethylene wax (II) includes polyethylene wax (I) and formula (IV)
[0019]
[Chemical 8]
(In the formula, R 4 , R 5 and R 6 have the above-mentioned meanings.)
It is obtained by reacting a terminal vinyl group-containing tertiary amine represented by (hereinafter abbreviated as tertiary amine (IV)).
[0021]
In the formula (II), R 4 is a divalent hydrocarbon group having 1 to 10 carbon atoms, preferably a methylene group, a polymethylene group or a polymethylene group partially containing a phenylene group (—C 6 H 4 —). R 5 and R 6 are each a monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably a methyl group.
[0022]
The tertiary amine (IV) may be added to the polyethylene wax (I), or conversely, the polyethylene wax (I) may be added to the tertiary amine (IV). The reaction conditions for this reaction may be the same as the ethylene polymerization conditions, and the reaction is completed in about 1 to 24 hours. The tertiary amine (IV) to be added may be diluted with a solvent.
In this reaction, a catalyst (for example, a metal complex such as platinum) used in the hydrosilylation reaction is preferably used in an amount of 0.01 to 1 mol% with respect to 1 mol of polyethylene wax.
[0023]
【Example】
Example 1 (Synthesis of terminal dimethylsilyl polyethylene)
A 1-liter autoclave purged with nitrogen was charged with 400 mL of dry cyclohexane, 4.3 mL of dipiperidinoethane, and 12.5 mL (0.02 mol) of a cyclohexane solution of n-butyllithium (1.6 mol / L). The temperature of the reaction system was 50 ° C, ethylene While maintaining the gas introduction pressure at 0.39 MPa, 7.62 L of ethylene gas was introduced for polymerization.
Dimethylchlorosilane (5.0 mL) was dropped into the polymerization mixture described above under a nitrogen stream. After completion of the dropwise addition, the mixture was reacted at 50 ° C. for 1 hour, and then the reaction mixture was poured into 2 L of cold methanol, and the resulting white solid was collected by filtration. Drying was performed at room temperature under a nitrogen stream to obtain a white powdery solid. The yield of product is 9.8 g.
[0024]
The 1 H-NMR spectrum of the obtained product is shown in FIG. In this spectrum, signals of Si—CH 2 at 0.6 ppm, Si—CH 3 at 0.1 ppm, and Si—H at 3.8 to 3.9 ppm were observed. From the integral value of each signal, the obtained product was obtained in the formula (I) as follows: R 1 = R 2 = CH 3 , R 3 = CH 3 -CH 2 -CH 2 -CH 2- , n = average 16, It was found that the terminal silane introduction rate was 95%.
[0025]
Example 2 (Synthesis of terminal dimethylaminopropyldimethylsilyl polyethylene)
A 200 mL flask was charged with 4.0 g of dry toluene, 1.0 g of the terminal dimethylsilyl polyethylene obtained in Example 1 and 1.0 g of dimethylallylamine, and heated to 60 ° C. on an oil bath to dissolve all the raw materials uniformly. Then, 0.1 g of chloroplatinic acid (1% toluene solution) was added as a catalyst. The reaction was continued with heating and stirring for 17 hours. The reaction mixture was poured into 1 L of cold methanol, and the resulting white solid was collected by filtration. Drying was performed at room temperature under a nitrogen stream to obtain a white powdery solid. The yield of product is 1.0 g.
[0026]
The 1 H-NMR spectrum of the obtained product is shown in FIG. This spectrum shows that Si-H was consumed because the signal of 3.8 to 3.9 ppm Si-H disappeared and the characteristic signal of 0.1 ppm Si-CH 2 became a single line, The N-CH 3 signal was observed at 2.2 ppm, indicating that amine was introduced. From the integral value of each signal, the obtained product is obtained in the formula (II) as follows: R 1 = R 2 = R 5 = R 6 = CH 3 , R 3 = CH 3 -CH 2 -CH 2 -CH 2- , R 4 = CH 2 , n = average 16, terminal amine introduction rate was found to be 98%.
[0027]
【The invention's effect】
According to the present invention, a polyethylene wax having a silicon-hydrogen bond at a molecular terminal that reacts with an inorganic surface and improves compatibility with an organic substance, and a molecular terminal capable of forming a wax film with high affinity on hair, a painted surface, and the like. A polyethylene wax having a tertiary amino group can be obtained in good yield.
[Brief description of the drawings]
1 is a 1 H-NMR spectrum of a terminal dimethylsilyl polyethylene obtained in Example 1. FIG.
2 is a 1 H-NMR spectrum of terminal dimethylaminopropyldimethylsilyl polyethylene obtained in Example 2. FIG.
Claims (2)
で表されるポリエチレンワックスと、式(IV)
で表される末端ビニル基含有３級アミンを反応させる、請求項１記載のポリエチレンワックスの製造法。 Formula (I)
A polyethylene wax represented by formula (IV)
In reacting a terminal vinyl group-containing tertiary amine represented, the preparation of a polyethylene wax according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02753299A JP4271291B2 (en) | 1999-02-04 | 1999-02-04 | Polyethylene wax |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02753299A JP4271291B2 (en) | 1999-02-04 | 1999-02-04 | Polyethylene wax |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000226411A JP2000226411A (en) | 2000-08-15 |
| JP4271291B2 true JP4271291B2 (en) | 2009-06-03 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP02753299A Expired - Fee Related JP4271291B2 (en) | 1999-02-04 | 1999-02-04 | Polyethylene wax |
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| JP (1) | JP4271291B2 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4548685B2 (en) * | 2000-07-12 | 2010-09-22 | 信越化学工業株式会社 | Solid cosmetics |
| JP4248842B2 (en) * | 2002-10-16 | 2009-04-02 | 三井化学株式会社 | Silicone room temperature solidified composition |
| WO2008004514A1 (en) * | 2006-07-04 | 2008-01-10 | Mitsui Chemicals, Inc. | Polyolefin chain-containing silicon compound and olefin polymer |
| JP5220050B2 (en) * | 2010-03-09 | 2013-06-26 | 新日鐵住金株式会社 | Surface-treated steel sheet with excellent resistance to condensation whitening and corrosion |
| CN103756396B (en) * | 2013-12-14 | 2015-05-20 | 衢州市中通化工有限公司 | Preparation method for mixed wax capable of enhancing smoothness of coating |
| JP7378411B2 (en) * | 2018-03-19 | 2023-11-13 | ダウ シリコーンズ コーポレーション | Polyolefin-polydiorganosiloxane block copolymer and hydrolysis reaction method for its synthesis |
| US20200407512A1 (en) * | 2018-03-19 | 2020-12-31 | Dow Silicones Corporation | Polyolefin-polydiorganosiloxane block copolymer and method for the synthesis thereof |
-
1999
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| Publication number | Publication date |
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| JP2000226411A (en) | 2000-08-15 |
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