JP2004168802A - Amphiphilic methacrylate and its polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a nonfluorine hydrocarbon surfactant having an excellent surface tension-lowering ability by polymerizing a methacrylate having a new structure. <P>SOLUTION: An amphiphilic methacrylate polymer has a structure represented by general formula (2). The polymer is a polymer of a new methacrylate having an acetylene compound having a hydrophilic group and a hydrophobic group in combination as a basic structure. <P>COPYRIGHT: (C)2004,JPO

Description

【０００６】
さらに、本発明は、かかる新規メタクリレートを重合して得られる、下記一般式（２）で表される両親媒性メタクリレート重合体である。
【化４】

【０００７】
【発明の実施の形態】
以下本発明を実施の形態に即して詳細に説明する。
両親媒性メタクリレート
本発明にかかる両親媒性メタクリレートは、一般式（１）で表されるものであることを特徴とする。すなわち、アセチレン基に結合したアルキル基に置換された２つのエチレンオイシド末端の水酸基のうち一方の水酸基のみメタクロイル化された構造を有する。ここで前記アルキル基については特に制限はなく、アセチル基の隣の炭素に水酸基が置換されていればよい。またエチレンオキシドの置換数についても特に制限はなく、両方合計した数が１０以下であればよい。
【化５】

【０００８】
また、かかる両親媒性メタクリレートは、水酸基置換アルキル基で両方の炭素に結合したアセチレン化合物を出発物質とし、まず通常公知の方法によりそれらの水酸基に対し適当な数エチレンオキシド化し、さらに、その一方のエチレンオキシド末端水酸基にメタクロリロイル化することにより得ることができる。
ここで、メタクロリロイル化には、種々の置換基を有する化合物が使用できる。またメタクロリロイル化反応の精製物が、モノメタクロリロイル化物とともに、未反応物や、ジメタクロリロイル化物が共存する場合がある。必要な場合、通常公知のクロマトグライー等の分離手段を用いて、モノメタクロリロイル化物を単分離することも可能である。
【０００９】
かかる両親媒性メタクリレートの構造は、通常公知の化学分析方法により容易に確認できる。例えば、元素分析、赤外線吸収スペクトル、核磁気共鳴スペクトルなどの各スペクトル法、質量分析法などである。また純度についても通常公知の分析用クロマトグライーで確認できる。
【００１０】
両親媒性メタクリレートの重合体
本発明にかかる重合体は、上で説明した本発明の両親媒性メタクリレートを種々の重合条件で重合させて得られた重合体である。また、他のモノマーとの種々の共重合体も含まれる。好ましくは下記一般式（２）で表される両親媒性メタクリレート重合体である。
【化６】

ここで、ｋは特に制限はないが２〜１０００である。
【００１１】
重合条件は、通常のアクリレート系モノマーが重合可能な条件であれば特に制限はなく、種々のラジカル重合反応、アニオン重合反応、カチオン重合反応等が使用可能である。特に適当なラジカル重合開始剤を用いた溶液重合、懸濁重合、エマルジョン重合などが好ましい。
【００１２】
【実施例】
以下本発明の実施例を説明するが、本発明がこれら実施例に限定されるものではない。
（実施例１）モノメタクリレートの合成
撹拌機、温度計、空気導入管及び精留塔を取り付けたフラスコ（２Ｌ）にサーフィノール４６５（エアープロダクツジャパン株式会社製、平均分子量６６６）６６６ｇ、シクロヘキサン７９９．２ｇ、ヒドロキノンモノメチルエーテル５０ｐｐｍを含むメタクリル酸メチル８７．５ｇ（０．８７５モル、モル比０．８７５）、ジエチルヒドロキシルアミン０．３３ｇ、ヒドロキノンモノメチルエーテル０．３３ｇ、ジブチルヒドロキシトルエン０．０２ｇを仕込み、乾燥空気を１０ｍＬ／ｍｉｎの速度で吹き込みながら加熱還流し、系内の水分を除去した。次にオルトチタン酸イソプロピル（テトライソプロピルチタネート）９．９９ｇ（サーフィノール４６５に対して１．５重量％）を加えた。反応中、ヒドロキノンモノメチルエーテル５０ｐｐｍを含むメタクリル酸メチル８７．５ｇ（０．８７５モル、モル比０．８７５）を追加仕込みした。釜温度は８１〜８３℃、塔頂温度５５〜６５℃の範囲になるように還流比を調節してメタノールをメタクリル酸メチルとの共沸物として留去しながら反応を行った。８時間３０分後、反応液をＨＰＬＣ分析したところ反応率は９５．８％となったので反応を終了した。反応液を６０〜７０℃に冷却し、ガレオンアースＶ２（水澤化学工業（株））を０．３７ｇ及びセライト５４５を３．６７ｇ添加し、撹拌下５％第二リン酸ソーダ１９９．８ｇを３０分間で滴下し、１時間３０分攪拌した。次いで釜温度４５〜６５℃で約１５ｈＰａ減圧下３時間低沸物の留去を行ない、濾過することによりサーフィノール４６５モノメタクリレート６４０．２ｇ（収率８７．２％）を得た。製品はＨＰＬＣ分析により原料サーフィノール４６５が２３．７％、モノメタクリレート５０．６％、ジメタクリレート２５．７％の組成である。また、色相はＧａｒｄｎｅｒ色数２であった。
ＩＲ分析：３４８１ｃｍ^−１（ＯＨ由来）、１７２０ｃｍ^−１（エステル由来）
【００１３】
得られたモノメタクリレートをリサイクルＧＰＣで分取・精製した。すなわち、得られたモノメタクリレートをＴＯＦ−ＭＳ、ＧＰＣ及び^１Ｈ−ＮＭＲで分析したところ、ジメタクリレートが混合していることが明らかとなったので、リサイクルＧＰＣを用いて分取精製を試みた。分取フラクションは、モノエステルが主成分（分子量分布の分散度Ｍｗ／Ｍｎ＝１．０）であることを、^１Ｈ−ＮＭＲ及び、ＧＰＣで確認した。
【化７】

【００１４】
（実施例２）重合反応
重合は、溶媒としてベンゼンを用いて、開始剤としてＡＩＢＮを用いた。これらをともに試験管に仕込み、凍結・脱気・窒素置換後、封管して６０℃で３時間重合を行った。モノマー濃度［Ｍ］＝０．１８〜１．８ｍｏｌ／ｌ及び開始剤濃度［ＡＩＢＮ］＝１．８ｍｏｌ／ｌとした。
【００１５】
反応生成物の分析は、主にＴＨＦを溶離液とするＧＰＣ、ＩＲ及び^１Ｈ−ＮＭＲで行なった。両親媒性特性は、表面張力と動的光散乱で検討した。
図１にメタクリレートモノマーのラジカル重合で得られたポリマーＧＰＣ曲線の一例を示した。生成ポリマーは単峰性であり、その分子量特性は、Ｍｎ＝１．７×１０^４、Ｍｗ／Ｍｎ＝１．１であった。モノメタクリレートの重合結果を表１に示す。
【００１６】
【表１】

【００１７】
表１より、仕込みモノマー濃度が１．８Ｍではゲル化した。同一重合条件においの分子量や収率が著しく異なるのはＧＰＣでの分取調製において、分取毎にモノマー中のＥＯ鎖の長さが異なることによると考えられる。また低収率でのＭｗ／Ｍｎ値が１．１と極めて低い値となっているのは、ＧＰＣ測定試料中のポリマーの濃度が低いことによると考えられる。しかしながら、Ｍｗ／Ｍｎ値は収率の増加とともに著しく増加する傾向が認められ、これはジアクリレートモノマーが幾分含まれていることによると考えられる。
【００１８】
生成ポリマーの水分散液による表面張力の濃度依存性を図２に示した。ポリマー及びモノマーどちらの場合も濃度の増加とともに表面張力は著しく低下し、ポリマーで０．４ｇ／Ｌ及びモノマーで２ｇ／Ｌ付近に臨界ミセル濃度（ＣＭＣ）が確認され、その表面張力はポリマーで３０．４ｍＮ／ｍ及びモノマーで３０．５ｍＮ／ｍであった。これらの結果から、本発明のモノメタクリレートは低濃度領域で優れた表面張力低下能を示し、さらにポリマーではモノマーに比べ、より低濃度領域でのＣＭＣを示すことが分かる。それらの表面張力低下能は、フッ素系界面活性剤に匹敵するものである。
【００１９】
水分散液中に形成される分子会合体の平均粒径を図３に示した。ポリマー及びモノマーどちらの場合も分子会合体の粒径は濃度の増加とともに大きくなるが、ＣＭＣ以降はほぼ一定の値を示し、その平均粒径はモノマーで約１８０ｎｍ及びポリマーで約２００ｎｍであった。このように、ポリマー化によりさらに高次会合しミセルのサイズが大きくなることが示唆される。これらの分子会合体はアセチレン基の強い疎水性相互作用により多分子膜構造を形成したと考えられる。
【００２０】
さらに、図４には水分散液による１ｇ／ｌの粒径分布（２５℃）の測定結果を示した。
【００２１】
【発明の効果】
本発明のかかる、さらにかかる新規構造を有するメタクリレートを重合することにより表面張力低下能に優れた非フッ素系炭化水素界面活性剤を得る。
【図面の簡単な説明】
【図１】メタクリレートモノマーのラジカル重合で得られたポリマーＧＰＣ曲線の一例を示す。
【図２】生成ポリマーの水分散液による表面張力の濃度依存性（２５℃）を示す。
【図３】水分散液中に形成される分子会合体の平均粒径の濃度依存性（２５℃）を示す。
【図４】水分散液による１ｇ／ｌの粒径分布（２５℃）の測定結果を示す。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to amphiphilic methacrylates and polymers thereof.
[0002]
[Prior art]
Conventionally, several compounds exhibiting amphiphilic properties having a hydrophilic group and a hydrophobic group in a molecule are known.For example, a fluorine compound is a typical substance having a low surface free energy, and a surfactant is used. Widely applied to such as.
[0003]
[Problems to be solved by the invention]
The present invention provides a novel methacrylate having, as a basic structure, an acetylene compound having both a hydrophilic group and a hydrophobic group, and a polymer thereof.
[0004]
[Means for Solving the Problems]
The present inventor has conducted intensive research with the aim of developing an inexpensive and high-performance non-fluorinated hydrocarbon surfactant and its application, and has developed an acetylene compound having both a hydrophilic group and a hydrophobic group as a novel chemical structure as a side chain. Has come to find polymethacrylate.
More specifically, as such a novel chemical structure, in recent years, a novel methacrylate is obtained by using, as a starting material, an acetylene compound having both a hydrophilic group and a hydrophobic group (for example, a compound referred to as Surfynol series of Air Products, USA). By polymerizing such methacrylate, a non-fluorinated hydrocarbon surfactant excellent in surface tension lowering ability was successfully obtained.
[0005]
More specifically, the novel methacrylate according to the present invention is an amphiphilic methacrylate represented by the following general formula (1).
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[0006]
Further, the present invention is an amphiphilic methacrylate polymer represented by the following general formula (2), which is obtained by polymerizing such a novel methacrylate.
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[0007]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described in detail with reference to embodiments.
Amphiphilic methacrylate The amphiphilic methacrylate according to the present invention is characterized by being represented by the general formula (1). That is, it has a structure in which only one hydroxyl group among two hydroxyl groups at the terminal of ethylene oiside substituted with an alkyl group bonded to an acetylene group is methacryloylated. Here, the alkyl group is not particularly limited as long as the carbon adjacent to the acetyl group is substituted with a hydroxyl group. There is no particular limitation on the number of substitutions of ethylene oxide, and the total number of both may be 10 or less.
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[0008]
Further, such an amphiphilic methacrylate is obtained by starting from an acetylene compound bonded to both carbons with a hydroxyl-substituted alkyl group as a starting material, first converting a suitable number of ethylene oxides to those hydroxyl groups by a generally known method, and further converting one of the ethylene oxides. It can be obtained by subjecting the terminal hydroxyl group to metachlorylylation.
Here, compounds having various substituents can be used for the metachlorilylation. In addition, the purified product of the metachlorilloylation reaction may include an unreacted product or a dimethacryloylated product together with the monomethacryloylated product. If necessary, it is also possible to simply separate the monometachlorylylated product using a known separation means such as chromatography.
[0009]
The structure of such an amphiphilic methacrylate can be easily confirmed by a generally known chemical analysis method. For example, there are various spectral methods such as elemental analysis, infrared absorption spectrum, nuclear magnetic resonance spectrum, etc., and mass spectrometry. In addition, the purity can also be confirmed by generally known analytical chromatography.
[0010]
Polymer of amphiphilic methacrylate The polymer according to the present invention is a polymer obtained by polymerizing the above-described amphiphilic methacrylate of the present invention under various polymerization conditions. Also, various copolymers with other monomers are included. Preferred is an amphiphilic methacrylate polymer represented by the following general formula (2).
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Here, k is not particularly limited but is 2 to 1000.
[0011]
The polymerization conditions are not particularly limited as long as ordinary acrylate-based monomers can be polymerized, and various radical polymerization reactions, anion polymerization reactions, cation polymerization reactions, and the like can be used. Particularly preferred are solution polymerization, suspension polymerization, emulsion polymerization and the like using an appropriate radical polymerization initiator.
[0012]
【Example】
Hereinafter, examples of the present invention will be described, but the present invention is not limited to these examples.
(Example 1) Monomethacrylate synthesis In a flask (2 L) equipped with a stirrer, a thermometer, an air introduction tube and a rectification tower, 666 g of Surfynol 465 (manufactured by Air Products Japan, average molecular weight 666), Cyclohexane 799. 2 g, 87.5 g (0.875 mol, molar ratio 0.875) of methyl methacrylate containing 50 ppm of hydroquinone monomethyl ether, 0.33 g of diethylhydroxylamine, 0.33 g of hydroquinone monomethyl ether, and 0.02 g of dibutylhydroxytoluene were charged. Heating and refluxing was performed while blowing dry air at a rate of 10 mL / min to remove water in the system. Next, 9.99 g of isopropyl orthotitanate (tetraisopropyl titanate) (1.5% by weight based on Surfinol 465) was added. During the reaction, 87.5 g (0.875 mol, molar ratio 0.875) of methyl methacrylate containing 50 ppm of hydroquinone monomethyl ether was additionally charged. The reaction was carried out while adjusting the reflux ratio so that the kettle temperature was in the range of 81 to 83 ° C and the tower top temperature in the range of 55 to 65 ° C, and distilling off methanol as an azeotrope with methyl methacrylate. After 8 hours and 30 minutes, the reaction solution was analyzed by HPLC, and the reaction rate was 95.8%, thus terminating the reaction. The reaction solution was cooled to 60 to 70 ° C., 0.37 g of Galleon Earth V2 (Mizusawa Chemical Industry Co., Ltd.) and 3.67 g of Celite 545 were added, and 199.8 g of 5% sodium phosphate 2% was added with stirring to 30. And the mixture was stirred for 1 hour and 30 minutes. Then, low-boiling substances were distilled off under a reduced pressure of about 15 hPa for 3 hours at a pot temperature of 45 to 65 ° C., and 640.2 g (yield: 87.2%) of surfynol 465 monomethacrylate was obtained by filtration. The product has a composition of 23.7% of raw material Surfynol 465, 50.6% of monomethacrylate, and 25.7% of dimethacrylate by HPLC analysis. The hue was Gardner color number 2.
IR analysis: 3481 cm ^-1 (derived from OH), 1720 cm ^-1 (derived from ester)
[0013]
The obtained monomethacrylate was fractionated and purified by recycling GPC. That is, when the obtained monomethacrylate was analyzed by TOF-MS, GPC and ¹ H-NMR, it was clarified that dimethacrylate was mixed. Therefore, preparative purification was attempted using recycled GPC. The fractionation fraction was confirmed by ¹ H-NMR and GPC that the monoester was the main component (dispersion degree Mw / Mn = 1.0 of molecular weight distribution).
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[0014]
(Example 2) Polymerization Reaction In the polymerization, benzene was used as a solvent and AIBN was used as an initiator. These were all charged in a test tube, frozen, degassed, and replaced with nitrogen, sealed, and polymerized at 60 ° C. for 3 hours. The monomer concentration [M] was set to 0.18 to 1.8 mol / l and the initiator concentration [AIBN] was set to 1.8 mol / l.
[0015]
The analysis of the reaction product was mainly performed by GPC, IR and ¹ H-NMR using THF as an eluent. Amphiphilic properties were studied by surface tension and dynamic light scattering.
FIG. 1 shows an example of a polymer GPC curve obtained by radical polymerization of a methacrylate monomer. The resulting polymer was monomodal and had molecular weight characteristics of Mn = 1.7 × 10 ⁴ and Mw / Mn = 1.1. Table 1 shows the polymerization results of the monomethacrylate.
[0016]
[Table 1]

[0017]
From Table 1, it was gelled when the charged monomer concentration was 1.8 M. The remarkable difference in the molecular weight and the yield under the same polymerization conditions is considered to be due to the fact that the length of the EO chain in the monomer differs for each fractionation in the fractionation preparation by GPC. The reason why the Mw / Mn value at a low yield is as extremely low as 1.1 is considered to be due to the low concentration of the polymer in the GPC measurement sample. However, the Mw / Mn values tended to increase significantly with increasing yield, presumably because some diacrylate monomer was included.
[0018]
FIG. 2 shows the concentration dependency of the surface tension due to the aqueous dispersion of the produced polymer. In the case of both the polymer and the monomer, the surface tension decreased significantly with increasing concentration, and a critical micelle concentration (CMC) was confirmed at around 0.4 g / L for the polymer and around 2 g / L for the monomer. 0.4 mN / m and 30.5 mN / m for the monomer. From these results, it can be seen that the monomethacrylate of the present invention exhibits excellent surface tension lowering ability in a low concentration region, and that the polymer exhibits CMC in a lower concentration region as compared with the monomer. Their surface tension lowering ability is comparable to fluorosurfactants.
[0019]
FIG. 3 shows the average particle size of the molecular aggregate formed in the aqueous dispersion. In both cases of the polymer and the monomer, the particle size of the molecular aggregate increased with an increase in the concentration, but showed a substantially constant value after CMC, and the average particle size was about 180 nm for the monomer and about 200 nm for the polymer. Thus, it is suggested that polymerization leads to higher-order association and an increase in the size of micelles. It is considered that these molecular aggregates formed a multimolecular film structure by strong hydrophobic interaction of acetylene groups.
[0020]
Further, FIG. 4 shows the measurement result of the particle size distribution of 1 g / l (25 ° C.) using the aqueous dispersion.
[0021]
【The invention's effect】
By polymerizing the methacrylate having the novel structure according to the present invention, a non-fluorinated hydrocarbon surfactant excellent in surface tension lowering ability can be obtained.
[Brief description of the drawings]
FIG. 1 shows an example of a polymer GPC curve obtained by radical polymerization of a methacrylate monomer.
FIG. 2 shows the concentration dependence (25 ° C.) of the surface tension of a produced polymer with an aqueous dispersion.
FIG. 3 shows the concentration dependency (25 ° C.) of the average particle size of a molecular aggregate formed in an aqueous dispersion.
FIG. 4 shows a measurement result of a particle size distribution (25 ° C.) of 1 g / l by an aqueous dispersion.

Claims (2)

An amphiphilic methacrylate represented by the following general formula (1).

An amphiphilic methacrylate polymer represented by the following general formula (2).

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