JP2012206992A - Polymerizable compound - Google Patents
Polymerizable compound Download PDFInfo
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- JP2012206992A JP2012206992A JP2011074662A JP2011074662A JP2012206992A JP 2012206992 A JP2012206992 A JP 2012206992A JP 2011074662 A JP2011074662 A JP 2011074662A JP 2011074662 A JP2011074662 A JP 2011074662A JP 2012206992 A JP2012206992 A JP 2012206992A
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 66
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 229920001187 thermosetting polymer Polymers 0.000 abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 239000002904 solvent Substances 0.000 description 12
- 238000005160 1H NMR spectroscopy Methods 0.000 description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000000976 ink Substances 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical group CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000012488 sample solution Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- -1 amine compound Chemical class 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 230000008034 disappearance Effects 0.000 description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 3
- 235000019341 magnesium sulphate Nutrition 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000010526 radical polymerization reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000004566 IR spectroscopy Methods 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- DCUFMVPCXCSVNP-UHFFFAOYSA-N methacrylic anhydride Chemical compound CC(=C)C(=O)OC(=O)C(C)=C DCUFMVPCXCSVNP-UHFFFAOYSA-N 0.000 description 2
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000007870 radical polymerization initiator Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 230000035807 sensation Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- 208000034189 Sclerosis Diseases 0.000 description 1
- 210000001015 abdomen Anatomy 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
本発明は、新規な重合性化合物及び当該化合物からなる硬化剤に関する。 The present invention relates to a novel polymerizable compound and a curing agent comprising the compound.
熱や光等のエネルギーを付与することで重合し硬化する化合物は、各種のポリマーや硬化性組成物の原料として、コーティング材、塗料、印刷インク、接着剤、レジスト材等の工業的用途に幅広く利用されている。例えば、熱によって硬化する重合性化合物をインクや塗料に配合し、画像形成後に加熱により当該化合物を重合させ硬化膜を形成することで、画像の耐候性や耐久性を高めることが行われている。
このような硬化は、硬化剤を含有させることによって行うことができる。従来の硬化剤としては、例えば、N,Nメチレンビスアクリルアミド等のアクリルアミド基を含有する重合性化合物があり、しばしば利用されている（非特許文献１参照）。
Compounds that polymerize and cure by applying energy such as heat and light are widely used in various industrial applications such as coating materials, paints, printing inks, adhesives, and resist materials as raw materials for various polymers and curable compositions. It's being used. For example, the weather resistance and durability of an image are improved by blending a polymerizable compound that is cured by heat into an ink or paint, and polymerizing the compound by heating after image formation to form a cured film. .
Such curing can be performed by including a curing agent. Conventional curing agents include, for example, polymerizable compounds containing an acrylamide group such as N, N methylenebisacrylamide and are often used (see Non-Patent Document 1).
本発明は、硬化剤等として有用な重合性化合物、並びに当該化合物からなる硬化剤を提供することを課題とする。 This invention makes it a subject to provide the polymeric compound useful as a hardening | curing agent etc., and the hardening | curing agent which consists of the said compound.
本発明者らは、上記課題に鑑み、高い重合能及び硬化能を有する化合物の開発のため研究を重ねた。その結果、分子内に複数のＣ−Ｃ二重結合を有する新規化合物を見出し、本発明を完成するに至ったものである。 In view of the above problems, the present inventors have conducted research for the development of a compound having high polymerization ability and curing ability. As a result, a novel compound having a plurality of C—C double bonds in the molecule has been found, and the present invention has been completed.
すなわち、上記課題は下記の手段により解決された。
（１）下記一般式（１）で表される化合物。
That is, the said subject was solved by the following means.
(1) A compound represented by the following general formula (1).
（式中、Ｒは水素原子又はメチル基を表し、Ｒは互いに同じでも異なっていてもよい。）
（２）前記（１）項記載の化合物からなる硬化剤。
(In the formula, R represents a hydrogen atom or a methyl group, and R may be the same or different from each other.)
(2) A curing agent comprising the compound described in (1) above.
本発明の前記一般式（１）で表される化合物は、分子内に４個のＣ−Ｃ二重結合を持ち、優れた重合能及び硬化能を有する。当該化合物からなる本発明の硬化剤は、印刷インク、各種塗料、レジスト、接着剤、コーティング材等の用途に用いることができる。より具体的には、例えば、当該化合物の優れた熱硬化反応性を利用して、熱硬化型インク組成物用の硬化剤として用いることができる。 The compound represented by the general formula (1) of the present invention has four C—C double bonds in the molecule, and has excellent polymerization ability and curing ability. The hardening | curing agent of this invention which consists of the said compound can be used for uses, such as printing ink, various coating materials, a resist, an adhesive agent, a coating material. More specifically, for example, it can be used as a curing agent for a thermosetting ink composition by utilizing the excellent thermosetting reactivity of the compound.
本発明の重合性化合物は、下記一般式（１）で表される化合物である。 The polymerizable compound of the present invention is a compound represented by the following general formula (1).
前記一般式（１）中、Ｒは水素原子又はメチル基を表す。本発明において複数のＲは互いに同じでも異なっていてもよい。 In the general formula (1), R represents a hydrogen atom or a methyl group. In the present invention, a plurality of R may be the same or different from each other.
前記一般式（１）で表される化合物は、例えば、下記スキーム１に示す工程により製造することができる。
The compound represented by the general formula (1) can be produced, for example, by the process shown in the following
出発物質（Ａ）としてトリス（ヒドロキシメチル）アミノメタンを用い、トリス（ヒドロキシメチル）アミノメタンの水酸基とアクリロニトリルとを反応させ、アクリロニトリル付加体：中間体（Ｂ）を得る。次に、得られた中間体（Ｂ）を、触媒存在下で水素と反応させ、水素添加反応によりアミン体：中間体（Ｃ）を得る。さらに、得られた中間体（Ｃ）をアクリル酸クロリド又はメタクリル酸クロリドと反応させてアシル化し、目的の化合物（１）を得ることができる。アシル化剤は、酸クロリドに換えてジアクリル酸無水物又はジメタクリル酸無水物を用いてもよい。なお、アシル化工程で、アクリル酸クロリドとメタクリル酸クロリドの両方を用いることで、最終生成物として同一分子内にアクリルアミド基とメタクリルアミド基とを有する化合物（１）を得ることができる。
上記のスキーム１において（Ａ）から（Ｂ）の工程は、０〜６０℃で３０分〜８時間、（Ｂ）から（Ｃ）の工程は、２０〜４５℃で２時間〜１６時間、（Ｃ）から化合物（１）の工程は、０〜３０℃で３０分〜６時間、で行なうのが、それぞれ好ましい。
本発明の化合物は、反応生成液から常法により分離、回収できる。例えば、有機溶媒を用いた抽出操作、貧溶媒を用いた晶析、シリカゲルを用いたカラムクロマトグラフィーなどによって回収できる。
Using tris (hydroxymethyl) aminomethane as the starting material (A), the hydroxyl group of tris (hydroxymethyl) aminomethane and acrylonitrile are reacted to obtain an acrylonitrile adduct: intermediate (B). Next, the obtained intermediate (B) is reacted with hydrogen in the presence of a catalyst, and an amine compound: intermediate (C) is obtained by hydrogenation reaction. Furthermore, the obtained intermediate (C) can be reacted with acrylic acid chloride or methacrylic acid chloride to be acylated to obtain the target compound (1). As the acylating agent, diacrylic anhydride or dimethacrylic anhydride may be used in place of acid chloride. In addition, the compound (1) which has an acrylamide group and a methacrylamide group in the same molecule as a final product can be obtained by using both acrylic acid chloride and methacrylic acid chloride in an acylation process.
In the
The compound of the present invention can be separated and recovered from the reaction product solution by a conventional method. For example, it can be recovered by extraction using an organic solvent, crystallization using a poor solvent, column chromatography using silica gel, and the like.
本発明の化合物は、分子内に重合性基として４つのアクリルアミド基又はメタクリルアミド基を有する多官能モノマーであり、高い重合能及び硬化能を有する。当該化合物は、α線、γ線、Ｘ線、紫外線、可視光線、赤外光線、電子線等の活性放射線や熱などのエネルギーを付与することにより重合して硬化性を示す。本発明の硬化剤は、前記一般式（１）で表される化合物からなる。当該化合物の硬化能により、本発明の硬化剤は優れた硬化性を有し、印刷インク、各種塗料、レジスト、接着剤、コーティング材等の用途に好適に用いられる。本発明の硬化剤は、用途等に応じて、他の硬化剤、重合開始剤、溶媒等を適宜含有してもよい。
特に、本発明の化合物は熱硬化性化合物として好適に用いられる。例えば、本発明の化合物や硬化剤を配合することで、熱硬化性組成物を得ることができる。
The compound of the present invention is a polyfunctional monomer having four acrylamide groups or methacrylamide groups as polymerizable groups in the molecule, and has high polymerization ability and curing ability. The compound is polymerized by applying energy such as actinic radiation such as α rays, γ rays, X rays, ultraviolet rays, visible rays, infrared rays, electron beams, or heat, and exhibits curability. The hardening | curing agent of this invention consists of a compound represented by the said General formula (1). Due to the curing ability of the compound, the curing agent of the present invention has excellent curability and is suitably used for applications such as printing inks, various paints, resists, adhesives and coating materials. The curing agent of the present invention may appropriately contain other curing agents, polymerization initiators, solvents and the like depending on applications.
In particular, the compound of the present invention is suitably used as a thermosetting compound. For example, a thermosetting composition can be obtained by blending the compound of the present invention and a curing agent.
以下、本発明を実施例に基づきさらに詳細に説明するが、本発明はこれらの実施例に限定されるものではない。なお、特に断りのない限り、「部」及び「％」は質量基準である。 EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited to these Examples. Unless otherwise specified, “part” and “%” are based on mass.
実施例１
前記スキーム１にしたがって、化合物（１）のＲが水素原子である化合物（以下、例示化合物（１ａ）という）及びＲがメチル基である化合物（以下、例示化合物（１ｂ）という）を合成した。
Example 1
According to
（１）中間体（Ｂ）の合成
スターラーバーを備えた１Ｌ容の三口フラスコに、トリス（ヒドロキシメチル）アミノメタン（Ａ）（東京化成工業社製）１２１ｇ（１当量）、５０％水酸化カリウム水溶液８４ｍｌ、トルエン４２３ｍｌを加えて攪拌し、水浴下、反応系中を２０〜２５℃で維持し、アクリロニトリル３９７．５ｇ（７．５当量）を２時間かけて滴下した。滴下後、１．５時間攪拌した後、トルエン５４０ｍｌを反応系中に追加し、その反応混合物を分液漏斗へ移し水層を除いた。残った有機層を硫酸マグネシウムで乾燥後、セライトろ過を行い、減圧下溶媒留去することにより中間体（Ｂ）：アクリロニトリル付加体を得た。得られた物質の１Ｈ−ＮＭＲ、ＭＳによる分析結果は既知物と良い一致を示したため、さらに精製することなく次の還元反応に用いた。
(1) Synthesis of intermediate (B) In a 1 L three-necked flask equipped with a stirrer bar, 121 g (1 equivalent) of tris (hydroxymethyl) aminomethane (A) (manufactured by Tokyo Chemical Industry Co., Ltd.), 50% potassium hydroxide 84 ml of an aqueous solution and 423 ml of toluene were added and stirred, and the reaction system was maintained at 20 to 25 ° C. in a water bath, and 397.5 g (7.5 equivalents) of acrylonitrile was added dropwise over 2 hours. After dripping, after stirring for 1.5 hours, 540 ml of toluene was added to the reaction system, the reaction mixture was transferred to a separatory funnel, and the aqueous layer was removed. The remaining organic layer was dried over magnesium sulfate, filtered through Celite, and evaporated under reduced pressure to obtain an intermediate (B): acrylonitrile adduct. Since the analysis result by 1 H-NMR and MS of the obtained substance was in good agreement with the known substance, it was used for the next reduction reaction without further purification.
（２）中間体（Ｃ）の合成
１Ｌ容オートクレーブに先に得られた中間体（Ｂ）を２４ｇ、Ｎｉ触媒４８ｇ（ラネーニッケル２４００、Ｗ．Ｒ．Ｇｒａｃｅ＆Ｃｏ．社製）、２５％アンモニア水：メタノール＝１：１溶液６００ｍｌを入れ懸濁させ反応容器を密閉した。反応容器に１０Ｍｐａの水素を導入し、反応温度を２５℃で１６時間反応させた。
原料の消失を１Ｈ−ＮＭＲにて確認し、反応混合物をセライト濾過し、セライトをメタノールで数回洗浄した。濾液を減圧下溶媒留去することにより中間体（Ｃ）：アミン体を得た。得られた物質はさらに精製することなく次の還元反応に用いた。
(2) Synthesis of intermediate (C) 24 g of intermediate (B) obtained previously in a 1 L autoclave, 48 g of Ni catalyst (Raney
The disappearance of the raw materials was confirmed by 1 H-NMR, the reaction mixture was filtered through Celite, and the Celite was washed several times with methanol. The filtrate was evaporated under reduced pressure to obtain intermediate (C): amine. The obtained material was used for the next reduction reaction without further purification.
（３）例示化合物（１ａ）の合成
攪拌機を備えた２Ｌ容の三口フラスコに先に得られた中間体（Ｃ）３０ｇ、ＮａＨＣＯ３ １２０ｇ（１４当量）、ジクロロメタン１Ｌ、水５０ｍｌを加えて、氷浴下、アクリル酸クロリド９２．８ｇ（１０当量）を３時間かけて滴下し、その後、室温で３時間攪拌した。原料の消失を１Ｈ−ＮＭＲにて確認した後、反応混合物を減圧下溶媒留去し、硫酸マグネシウムで反応混合物を乾燥させ、セライトろ過を行い、減圧下溶媒留去した。最後に、カラムクロマトグラフィー（酢酸エチル／メタノール＝４：１）にて精製することで、常温で黄色の液体（収率４０％）を得た。
(3) Synthesis of Exemplary Compound (1a) 30 g of the intermediate (C) obtained previously, 120 g of NaHCO 3 (14 equivalents), 1 L of dichloromethane and 50 ml of water were added to a 2 L three-necked flask equipped with a stirrer, and iced. Under a bath, 92.8 g (10 equivalents) of acrylic acid chloride was added dropwise over 3 hours, and then stirred at room temperature for 3 hours. After confirming disappearance of the raw material by 1 H-NMR, the solvent was distilled off from the reaction mixture under reduced pressure, the reaction mixture was dried over magnesium sulfate, filtered through celite, and the solvent was distilled off under reduced pressure. Finally, it was purified by column chromatography (ethyl acetate / methanol = 4: 1) to obtain a yellow liquid (yield 40%) at room temperature.
得られた黄色の液体を、下記の測定条件にて、１Ｈ−ＮＭＲ、１３Ｃ−ＮＭＲ、ＩＲ、ＭＳにより同定した。同定データを図１〜４に示す。
１Ｈ−ＮＭＲ 溶媒：重クロロホルム、内部標準：ＴＭＳ
１３Ｃ−ＮＭＲ 溶媒：重クロロホルム、内部標準：ＴＭＳ
ＩＲ 銅箔上に塗布して反射スペクトルを測定し、吸光度に変換した。
ＭＳ 溶媒：ＭｅＯＨ／Ｈ２Ｏ＝９／１、１０ｍＭ ＣＨ３ＣＯＯＮＨ４
The obtained yellow liquid was identified by 1 H-NMR, 13 C-NMR, IR, and MS under the following measurement conditions. Identification data are shown in FIGS.
1 H-NMR Solvent: deuterated chloroform, internal standard: TMS
13 C-NMR Solvent: deuterated chloroform, internal standard: TMS
It was coated on an IR copper foil, the reflection spectrum was measured, and converted to absorbance.
MS solvent: MeOH / H 2 O = 9/1, 10 mM CH 3 COONH 4
図１に示す１Ｈ−ＮＭＲのデータから、３．７５ｐｐｍ付近のシングレットピーク（母骨格由来のピーク）の積分比６に対して、５．６ｐｐｍ付近のアクリル由来の１水素のピークの積分比が４であることから、当該化合物が４つのアクリルアミド基を有することがわかった。図２に示す１３Ｃ−ＮＭＲのデータより、カルボニル基、オレフィンのピークが特徴的な位置に観測され、全炭素数と全ピーク数の一致が確認できることから、例示化合物（１ａ）で示される構造であることがわかった。また、図３に示すＩＲのデータから、アクリルアミドの吸収が存在することがわかった。さらに、図４に示すＭＳのデータから得られる分子量が、例示化合物（１ａ）の分子量と一致することがわかった。
これらの結果より、この黄色の液体が、例示化合物（１ａ）で示される構造（前記スキーム１に示す化合物（１）においてＲが水素原子である構造）を有することが確認された。
From the 1 H-NMR data shown in FIG. 1, the integration ratio of the single hydrogen peak derived from acrylic at around 5.6 ppm is 6 to the integral ratio of singlet peak at 3.75 ppm (peak derived from the mother skeleton). Since it was 4, it turned out that the said compound has four acrylamide groups. From the 13 C-NMR data shown in FIG. 2, carbonyl groups and olefin peaks are observed at characteristic positions, and the coincidence of the total number of carbon atoms and the total number of peaks can be confirmed. Therefore, the structure represented by the exemplary compound (1a) I found out that Moreover, it was found from the IR data shown in FIG. 3 that acrylamide absorption exists. Furthermore, it was found that the molecular weight obtained from the MS data shown in FIG. 4 was consistent with the molecular weight of the exemplary compound (1a).
From these results, it was confirmed that this yellow liquid has a structure represented by the exemplary compound (1a) (a structure in which R is a hydrogen atom in the compound (1) shown in the above-mentioned scheme 1).
（４）例示化合物（１ｂ）の合成
攪拌機を備えた２Ｌ容の三口フラスコに先に得られた中間体（Ｃ）２０ｇ、ＮａＨＣＯ３ ８０．５ｇ（１４当量）、ジクロロメタン６８４ｍｌ、水３２ｍｌを加えて、氷浴下、ジメタクリル酸無水物１０５．５ｇ（１０当量）を３時間かけて滴下し、その後、室温で１２時間攪拌した。原料の消失を１Ｈ−ＮＭＲにて確認した後、反応混合物を減圧下溶媒留去し、硫酸マグネシウムで反応混合物を乾燥させ、セライトろ過を行い、減圧下溶媒留去した。最後に、カラムクロマトグラフィー（酢酸エチル／メタノール＝４：１）にて精製することで、常温で緑黄色の液体（収率４３％）を得た。
(4) Synthesis of Exemplified Compound (1b) To a 2 L three-necked flask equipped with a stirrer was added 20 g of the intermediate (C) obtained earlier, 80.5 g (14 equivalents) of NaHCO 3, 684 ml of dichloromethane and 32 ml of water. In an ice bath, 105.5 g (10 equivalents) of dimethacrylic anhydride was added dropwise over 3 hours, and then stirred at room temperature for 12 hours. After confirming disappearance of the raw material by 1 H-NMR, the solvent was distilled off from the reaction mixture under reduced pressure, the reaction mixture was dried over magnesium sulfate, filtered through celite, and the solvent was distilled off under reduced pressure. Finally, it was purified by column chromatography (ethyl acetate / methanol = 4: 1) to obtain a greenish yellow liquid (43% yield) at room temperature.
得られた緑黄色の液体を、下記の測定条件にて、１Ｈ−ＮＭＲ、１３Ｃ−ＮＭＲ、ＩＲ、ＭＳにより同定した。同定データを図５〜８示す。
１Ｈ−ＮＭＲ 溶媒：重クロロホルム、内部標準：ＴＭＳ
１３Ｃ−ＮＭＲ 溶媒：重クロロホルム、内部標準：ＴＭＳ
ＩＲ 銅箔上に塗布して反射スペクトルを測定し、吸光度に変換した。
ＭＳ 溶媒：ＭｅＯＨ／Ｈ２Ｏ＝９／１、１０ｍＭ ＣＨ３ＣＯＯＮＨ４
The obtained greenish yellow liquid was identified by 1 H-NMR, 13 C-NMR, IR, and MS under the following measurement conditions. Identification data are shown in FIGS.
1 H-NMR Solvent: deuterated chloroform, internal standard: TMS
13 C-NMR Solvent: deuterated chloroform, internal standard: TMS
It was coated on an IR copper foil, the reflection spectrum was measured, and converted to absorbance.
MS solvent: MeOH / H 2 O = 9/1, 10 mM CH 3 COONH 4
図５に示す１Ｈ−ＮＭＲのデータから、３．７２ｐｐｍ付近のシングレットピーク（母骨格由来のピーク）の積分比６に対して、５．３ｐｐｍ付近のメタクリル由来の１水素のピークの積分比が４であることから、当該化合物が４つのメタクリルアミド基を有することがわかった。図６に示す１３Ｃ−ＮＭＲのデータより、カルボニル基、オレフィンのピークが特徴的な位置に観測され、全炭素数と全ピーク数の一致が確認できることから、例示化合物（１ｂ）で示される構造であることがわかった。また、図７に示すＩＲのデータから、メタクリルアミドの吸収が存在することがわかった。さらに、図８に示すＭＳのデータから得られる分子量が、例示化合物（１ｂ）の分子量と一致することがわかった。
これらの結果より、この黄色の液体が前記スキームの例示化合物（１ｂ）で示される構造（前記スキーム１に示す化合物（１）においてＲがメチル基である構造）を有することが確認された。
From the 1 H-NMR data shown in FIG. 5, the integration ratio of the single hydrogen peak derived from methacryl near 5.3 ppm is 6 for the
From these results, it was confirmed that the yellow liquid had a structure represented by the exemplary compound (1b) in the scheme (a structure in which R is a methyl group in the compound (1) illustrated in the scheme 1).
実施例２ 硬化性の評価
実施例１で合成した例示化合物（１ａ）及び（１ｂ）の熱硬化性を、下記の手順で評価した。
硬化性の評価は、例示化合物（１ａ）又は（１ｂ）、ラジカル重合開始剤及び有機溶剤からなるサンプル溶液を銅版上に塗布し、これを加熱して、ラジカル重合の進行及び加熱前後の触感を評価することにより行った。なお、ラジカル重合の進行は、ＦＴ−ＩＲ（ＶＡＲＩＡＮ ３１００（商品名）、ＶＡＲＩＡＮ社製）を用いて、加熱によるアクリル基由来の８０６ｃｍ−１ピークの減少により確認した。詳細を以下に示す。
Example 2 Evaluation of Curability The thermosetting properties of the exemplary compounds (1a) and (1b) synthesized in Example 1 were evaluated by the following procedure.
The evaluation of curability is carried out by applying a sample solution consisting of the exemplified compound (1a) or (1b), a radical polymerization initiator and an organic solvent on a copper plate, and heating it to determine the progress of radical polymerization and the tactile sensation before and after heating. This was done by evaluating. The progress of radical polymerization was confirmed by the decrease in the 806 cm −1 peak derived from the acrylic group by heating using FT-IR (Varian 3100 (trade name), manufactured by Varian). Details are shown below.
例示化合物（１ａ）２５０ｍｇ、ラジカル重合開始剤としてＡＩＢＮ（アゾビスイソブチロニトリル）２５ｍｇを、メタノール １ｍｌに溶かし、評価用サンプル液１Ａを調製した。この評価用サンプル液１Ａを１０μｌ量りとり、銅板上に塗布した。
サンプル液を塗布した銅板をＦＴ−ＩＲで測定し、アクリル基由来の８０６ｃｍ−１ピークを確認した。その後、当該銅板を窒素雰囲気下、オーブンで１００度、１時間加熱した。加熱後の銅板を再びＦＴ−ＩＲで測定したところ、アクリル基由来の８０６ｃｍ−１ピークが減少していた。この結果から、例示化合物（１ａ）のラジカル重合が進行していることが確認された。
さらに、加熱前後の触感を評価したところ、加熱後のサンプル板では触れても粘性が無く、指の腹で擦っても擦る前と比べ変化しなかった。このことから、加熱により銅版上に塗布されたサンプル液が硬化したことが確認された。
250 mg of exemplary compound (1a) and 25 mg of AIBN (azobisisobutyronitrile) as a radical polymerization initiator were dissolved in 1 ml of methanol to prepare a sample solution 1A for evaluation. 10 μl of this sample solution for evaluation 1A was weighed and applied on a copper plate.
The copper plate coated with the sample solution was measured with FT-IR, and an 806 cm −1 peak derived from an acrylic group was confirmed. Thereafter, the copper plate was heated in an oven at 100 degrees for 1 hour in a nitrogen atmosphere. When the copper plate after heating was measured again by FT-IR, the 806 cm −1 peak derived from the acrylic group was decreased. From this result, it was confirmed that the radical polymerization of the exemplary compound (1a) is proceeding.
Furthermore, when the tactile sensation before and after heating was evaluated, the sample plate after heating had no viscosity even when touched, and it did not change even before rubbing with the belly of the finger. From this, it was confirmed that the sample liquid applied on the copper plate was cured by heating.
続いて、例示化合物（１ｂ）について、上記例示化合物（１ａ）と同様に硬化性の評価を行った。その結果、例示化合物（１ｂ）も、例示化合物（１ａ）と同程度の硬化性を有することが確認された。 Then, sclerosis | hardenability evaluation was performed similarly to the said exemplary compound (1a) about the exemplary compound (1b). As a result, it was confirmed that the exemplified compound (1b) also has the same degree of curability as the exemplified compound (1a).
Claims (2)
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| RU2013148099/04A RU2538209C1 (en) | 2011-03-30 | 2012-03-23 | Polyether compound, curing agent using polyether compound, and method of producing polyether compound |
| KR1020137025199A KR101386312B1 (en) | 2011-03-30 | 2012-03-23 | Polyether compound, curing agent using polyether compound, and method for producing polyether compound |
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| EP12765724.5A EP2698364B1 (en) | 2011-03-30 | 2012-03-23 | Polyether compound, curing agent using the polyether compound, and producing method of the polyether compound |
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