JP2007314665A - Vinyl ether derivative polymer, method for producing the same, and use thereof - Google Patents
Vinyl ether derivative polymer, method for producing the same, and use thereof Download PDFInfo
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- vinyl ether
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- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 5
- 229920000642 polymer Polymers 0.000 title claims description 33
- 229920001519 homopolymer Polymers 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000009826 distribution Methods 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 7
- 239000002841 Lewis acid Substances 0.000 claims description 3
- 150000007517 lewis acids Chemical class 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 239000007848 Bronsted acid Substances 0.000 claims description 2
- 150000000093 1,3-dioxanes Chemical class 0.000 claims 4
- 239000011342 resin composition Substances 0.000 claims 3
- 239000012776 electronic material Substances 0.000 claims 1
- CBWIXQUJOYPIAB-UHFFFAOYSA-N 5-(ethenoxymethyl)-5-ethyl-2-methyl-1,3-dioxane Chemical compound C=COCC1(CC)COC(C)OC1 CBWIXQUJOYPIAB-UHFFFAOYSA-N 0.000 abstract description 13
- CYIPZJOFQPGQLJ-UHFFFAOYSA-N 2-(ethenoxymethyl)-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COC=C CYIPZJOFQPGQLJ-UHFFFAOYSA-N 0.000 abstract description 11
- 238000006116 polymerization reaction Methods 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000002904 solvent Substances 0.000 description 8
- 238000005481 NMR spectroscopy Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 239000003999 initiator Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229930182556 Polyacetal Natural products 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 125000000532 dioxanyl group Chemical group 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920006324 polyoxymethylene Polymers 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 206010040880 Skin irritation Diseases 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 231100000053 low toxicity Toxicity 0.000 description 3
- 238000007142 ring opening reaction Methods 0.000 description 3
- 230000036556 skin irritation Effects 0.000 description 3
- 231100000475 skin irritation Toxicity 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- 239000012969 di-tertiary-butyl peroxide Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- UWKQJZCTQGMHKD-UHFFFAOYSA-N 2,6-di-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=N1 UWKQJZCTQGMHKD-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 125000004036 acetal group Chemical group 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 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
- 239000000010 aprotic solvent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- -1 cyclic acetals Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000010550 living polymerization reaction Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001289 polyvinyl ether Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
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Abstract
Description
本発明は、新規なビニルエーテル誘導体ホモポリマー並びにその製造方法及び用途に関し、更に詳しくは例えばインク、塗料、レジスト、カラーフィルタ等の用途並びに接着剤、製版材、封止剤、画像形成剤、界面活性剤の原料等に用いられる低臭気、低揮発性且つ低皮膚刺激性であって、毒性が低く、また、高機能性であって、硬化性、密着性、透明性、剛直性に優れたカチオン重合性組成物として有用な２−メチル−５−エチル−５−ビニロキシメチル−１，３−ジオキサンホモポリマー及び１，１−ジメチロール−１−ビニロキシメチルプロパンホモポリマーに関する。 The present invention relates to a novel vinyl ether derivative homopolymer and a production method and use thereof, and more specifically, for example, use of ink, paint, resist, color filter, etc. Low odor, low volatility, low skin irritation, low toxicity, high functionality, cation, excellent curability, adhesion, transparency and rigidity The invention relates to 2-methyl-5-ethyl-5-vinyloxymethyl-1,3-dioxane homopolymers and 1,1-dimethylol-1-vinyloxymethylpropane homopolymers useful as polymerizable compositions.
本発明に係る２−メチル−５−エチル−５−ビニロキシメチル−１，３−ジオキサンホモポリマー及び１，１−ジメチロール−１−ビニロキシメチルプロパンホモポリマーに関しては、ケミカルアブストラクト（Ｃｈｅｍｉｃａｌ Ａｂｓｔｒａｃｔ）には記載がなく、また、本発明者等の知るかぎりでは、その他の文献にも記載が見当たらない新規化合物（ポリマー）であると考えられる。 Regarding the 2-methyl-5-ethyl-5-vinyloxymethyl-1,3-dioxane homopolymer and 1,1-dimethylol-1-vinyloxymethylpropane homopolymer according to the present invention, Chemical Abstract Is not described, and as far as the present inventors know, it is considered to be a novel compound (polymer) that is not found in other literature.
通常、この骨格を持った化合物を合成しようとする場合、相当するモノビニル体を原料とし、直接重合する方法が考えられる。しかしながら、まず、下記反応式で示されるように、この化合物（Ｅ）を定法（レッペ法）に従って、トリメチロールプロパン（Ｄ）を出発物質として調製しようとしても、そのままではアセチレンが次々と反応し、ジビニル体（Ｆ）を経て、トリビニルエーテル（Ｇ）が生成してしまう。 Usually, when synthesizing a compound having this skeleton, a method of directly polymerizing a corresponding monovinyl body as a raw material can be considered. However, first, as shown in the following reaction formula, even if this compound (E) is prepared according to a conventional method (Leppe method) using trimethylolpropane (D) as a starting material, acetylene reacts one after another as it is, Trivinyl ether (G) is produced via the divinyl body (F).
更に、仮に化合物（Ｅ）が得られたとしても、下記反応式に示すようにしてポリマー（Ｉ）（式中、ｎは平均５〜６００の数である）を製造しようとしても重合時に水酸基の存在が影響し、直接目的とするホモポリマーは得られない。 Furthermore, even if the compound (E) is obtained, even if an attempt is made to produce the polymer (I) (wherein n is an average of 5 to 600) as shown in the following reaction formula, The target homopolymer cannot be obtained because of its presence.
ただし、この段階で条件を調節さえすれば、２−メチル−５−エチル−５−ビニロキシメチル−１，３−ジオキサン（Ａ）を選択的に製造することが可能である（特許文献１参照）。 However, 2-methyl-5-ethyl-5-vinyloxymethyl-1,3-dioxane (A) can be selectively produced by adjusting the conditions at this stage (see Patent Document 1). ).
しかしながら、この化合物を重合させようとすると、一般的にビニルエーテルモノマーのホモ重合はカチオン触媒でしか進まないことが知られているが、酸触媒によりジオキサン環が開環して水酸基が生成し、上記と同様目的とするポリマーが得られないおそれがある。 However, when this compound is polymerized, it is known that homopolymerization of vinyl ether monomers generally proceeds only with a cation catalyst, but a dioxane ring is opened by an acid catalyst to generate a hydroxyl group, The target polymer may not be obtained in the same manner as in the above.
従って、本発明の目的は前記２−メチル−５−エチル−５−ビニロキシメチル−１，３−ジオキサンホモポリマー及び１，１−ジメチロール−１−ビニロキシメチルプロパンホモポリマー並びにそれらの製造方法及び用途を提供することにある。 Accordingly, an object of the present invention is to provide the 2-methyl-5-ethyl-5-vinyloxymethyl-1,3-dioxane homopolymer and the 1,1-dimethylol-1-vinyloxymethylpropane homopolymer, a process for producing them, and To provide a use.
本発明に従えば、式（Ｉ）：
で表わされるビニルエーテル誘導体ホモポリマーが提供される。
According to the invention, the formula (I):
The vinyl ether derivative homopolymer represented by these is provided.
本発明に従えば、更に式（II）：
で表わされるビニルエーテル誘導体ホモポリマーが提供される。
According to the present invention, further formula (II):
The vinyl ether derivative homopolymer represented by these is provided.
本発明に係る２−メチル−５−エチル−５−ビニロキシメチル−１，３−ジオキサンホモポリマー及び１，１−ジメチロール−１−ビニロキシメチルプロパンホモポリマーは、低臭気、低揮発性、且つ、低皮膚刺激性であって、毒性が低く、また、硬化性、密着性に優れたカチオン重合性組成物として極めて有用であると共に、これらのポリマーは加水分解によりジオキサン環を開環させて２つの水酸基を生じさせることができ、次いでこの水酸基をアセチル化、エステル化、ハロゲン化などすることができるなど、各種の樹脂の改質剤や架橋剤としても優れた特性を発揮しうる化合物である。 2-methyl-5-ethyl-5-vinyloxymethyl-1,3-dioxane homopolymer and 1,1-dimethylol-1-vinyloxymethylpropane homopolymer according to the present invention have low odor, low volatility, and The polymer is extremely useful as a cationic polymerizable composition having low skin irritation, low toxicity, and excellent curability and adhesion, and these polymers have a dioxane ring opening by hydrolysis. It is a compound that can produce two hydroxyl groups, and then can be acetylated, esterified, halogenated, etc., and can exhibit excellent properties as a modifier and crosslinking agent for various resins. .
本発明に係る２−メチル−５−エチル−５−ビニロキシメチル−１，３−ジオキサンホモポリマーは、ポリアセタールと同様、機械的特性、熱的特性、電気的特性、摺動性、耐疲労性、耐摩擦性、耐摩耗性、耐薬品性及び成形性等において優れた特性を有することが期待できる。一方、本発明に係る１，１−ジメチロール−１−ビニロキシメチルプロパンホモポリマーは、ポリエステルやポリビニルアルコール等と同様、親水性、密着性等が期待でき、更に、ノニオン性界面活性剤として、インクを被記録材としての紙面に浸透させる効果もあるので、印字物の耐擦過性、耐水性などが良好となることが期待できる。 The 2-methyl-5-ethyl-5-vinyloxymethyl-1,3-dioxane homopolymer according to the present invention is similar to polyacetal in mechanical properties, thermal properties, electrical properties, slidability and fatigue resistance. It can be expected to have excellent characteristics in friction resistance, wear resistance, chemical resistance, moldability, and the like. On the other hand, the 1,1-dimethylol-1-vinyloxymethylpropane homopolymer according to the present invention can be expected to have hydrophilicity, adhesiveness, etc., as well as polyester and polyvinyl alcohol. Further, as a nonionic surfactant, Has the effect of permeating the paper as a recording material, it can be expected that the printed material will have good scratch resistance, water resistance, and the like.
本発明者らは前記課題を解決すべく研究を進めた結果、例えば紫外線硬化型樹脂や電子線硬化型樹脂などの活性放射線硬化型樹脂の反応性希釈剤として有用な架橋性単量体である２−メチル−５−エチル−５−ビニロキシメチル−１，３−ジオキサンをルイス酸で重合させたところ、反応途中でジオキサン環は開かず、目的の２−メチル−５−エチル−５−ビニロキシメチル−１，３−ジオキサンホモポリマー（Ｉ）が生成することを見出した。 As a result of advancing research to solve the above problems, the present inventors are a crosslinkable monomer useful as a reactive diluent for active radiation curable resins such as ultraviolet curable resins and electron beam curable resins. When 2-methyl-5-ethyl-5-vinyloxymethyl-1,3-dioxane was polymerized with Lewis acid, the dioxane ring was not opened during the reaction, and the desired 2-methyl-5-ethyl-5-vinyl It was found that loxymethyl-1,3-dioxane homopolymer (I) was produced.
そこで、前記ポリマー（Ｉ）について、その利用法につき検討を行ったところ、これらのポリマーは低臭気、低揮発性、且つ、低皮膚刺激性であって毒性が低い等の優れた性質を有しており、硬化性、密着性に優れた特性を発揮しうる化合物であることを見出した。 Therefore, the use of the polymer (I) has been examined. These polymers have excellent properties such as low odor, low volatility, low skin irritation and low toxicity. It has been found that the compound can exhibit excellent properties in curability and adhesion.
また、前記ホモポリマー（Ｉ）を加水分解することにより、ジオキサン環を開環させて２つの水酸基を生じさせることができる。加水分解の程度により、疎水性及び親水性を制御することができ、更にこの性質を利用し、一旦材料として用いた後に、加水分解して回収することもできる。 Also, by hydrolyzing the homopolymer (I), the dioxane ring can be opened to produce two hydroxyl groups. Hydrophobicity and hydrophilicity can be controlled depending on the degree of hydrolysis. Further, by utilizing this property, it can be recovered as a material after being used once as a material.
更に、本発明の２−メチル−５−エチル−５−ビニロキシメチル−１，３−ジオキサンホモポリマー（Ｉ）及び１，１−ジメチロール−１−ビニロキシメチルプロパンホモポリマー（II）とのコポリマー（又はブレンド）は、それらポリマー各分子中の水酸基の存在比により、例えば硬化性、基材密着性、速硬化性、耐熱性、耐水性に優れた組成物が得られる。 Further, the copolymer of the present invention with 2-methyl-5-ethyl-5-vinyloxymethyl-1,3-dioxane homopolymer (I) and 1,1-dimethylol-1-vinyloxymethylpropane homopolymer (II) For (or blend), a composition excellent in, for example, curability, substrate adhesion, fast curability, heat resistance, and water resistance is obtained depending on the abundance ratio of hydroxyl groups in each molecule of the polymer.
次いで前記ホモポリマー（II）は、その水酸基を、アセチル化、エステル化、ハロゲン化などすることができ、各種の樹脂の改質剤としても、あるいは、イソシアネート等と反応させることで架橋剤としても優れた特性を発揮しうる化合物であることを見出した。 Subsequently, the homopolymer (II) can be acetylated, esterified, halogenated, etc. of the hydroxyl group, and can be used as a modifier for various resins or as a crosslinking agent by reacting with isocyanate or the like. It was found that the compound can exhibit excellent properties.
本発明の新規化合物２−メチル−５−エチル−５−ビニロキシメチル−１，３−ジオキサンホモポリマー及び１，１−ジメチロール−１−ビニロキシメチルプロパンホモポリマーは、それぞれ、前記式（Ｉ）及び（II）で表されるものである。 The novel compounds 2-methyl-5-ethyl-5-vinyloxymethyl-1,3-dioxane homopolymer and 1,1-dimethylol-1-vinyloxymethylpropane homopolymer of the present invention each have the above formula (I) And (II).
本発明に係るポリマー（Ｉ）は、次のような反応式に従って重合することができる。 The polymer (I) according to the present invention can be polymerized according to the following reaction formula.
即ち、本発明に係る式（Ｉ）のポリマーは前記式（Ａ）の化合物２−メチル−５−エチル−５−ビニロキシメチル−１，３−ジオキサンを、例えば次のような方法で重合させることができる。 That is, the polymer of the formula (I) according to the present invention polymerizes the compound 2-methyl-5-ethyl-5-vinyloxymethyl-1,3-dioxane of the formula (A) by the following method, for example. be able to.
即ち、化合物（Ａ）の重合反応は、トルエン等の非極性溶媒中でポリマーの濃度として０．０１〜１．０モル容量％で行うのが好ましく、０．１〜０．５モル容量％がより好ましい。重合条件としては、−１０℃〜１０℃の温度で０．１〜２５０時間であるのが好ましい。より好ましくは−５℃〜５℃で１〜５０時間、最も好ましくは−１℃〜１℃で２０〜３０時間である。 That is, the polymerization reaction of the compound (A) is preferably carried out in a nonpolar solvent such as toluene at a polymer concentration of 0.01 to 1.0 mol% by volume, and 0.1 to 0.5 mol% by volume. More preferred. As polymerization conditions, it is preferable that it is 0.1 to 250 hours at the temperature of -10 degreeC-10 degreeC. More preferably, it is 1-50 hours at -5 degreeC-5 degreeC, Most preferably, it is 20-30 hours at -1 degreeC-1 degreeC.
前記重合に用いる重合触媒としては、ルイス酸（例えばＢＦ3，ＢＣｌ3，ＢＢｒ3，ＡｌＣｌ3，ＳｎＢｒ4など）及びその錯体（例えばＢＦ3ＯＥｔ2，（ＣＨ3ＣＨ（Ｏi-Ｂｕ）ＯＣＯＣＨ3／ＳｎＢｒ4，ＣＨ3ＣＨ（Ｏi-Ｂｕ）ＯＣＯＣＨ3／Ｅｔ1.5ＡｌＣｌ1.5／酢酸エチル）等を挙げることができ、分子量分布を制御する上では、これらの錯体を用いることが特に好ましい。触媒の使用量には特に制限はないが、０．１〜１０ミリモル容量％であるのが好ましい。 Examples of the polymerization catalyst used in the polymerization include Lewis acids (for example, BF 3 , BCl 3 , BBr 3 , AlCl 3 , SnBr 4 ) and complexes thereof (for example, BF 3 OEt 2 , (CH 3 CH (Oi-Bu) OCOCH 3 ). / SnBr 4 , CH 3 CH (Oi-Bu) OCOCH 3 / Et 1.5 AlCl 1.5 / ethyl acetate), etc., and these complexes are particularly preferred for controlling the molecular weight distribution. Although there is no restriction | limiting in particular in the usage-amount, it is preferable that it is 0.1-10 mmol volume%.
得られるポリマーの数平均分子量Ｍnは、５００〜２００，０００が好ましく、２，０００〜５０，０００であるのが更に好ましく、５，０００〜１５，０００であるのが特に好ましい。またポリマーの分子量分布（重量平均分子量Ｍw／数平均分子量Ｍn）は１〜５であるのが好ましく、１．１〜４．０であるのが更に好ましく、１．１〜１．４が特に好ましい。 The number average molecular weight Mn of the obtained polymer is preferably 500 to 200,000, more preferably 2,000 to 50,000, and particularly preferably 5,000 to 15,000. The molecular weight distribution (weight average molecular weight Mw / number average molecular weight Mn ) of the polymer is preferably 1 to 5, more preferably 1.1 to 4.0, and 1.1 to 1.4. Particularly preferred.
次に得られたポリマー（Ｉ）は加水分解することにより、下記反応式で１，１−ジメチロール−１−ビニロキシメチルプロパンホモポリマー（II）を製造することができる。
この加水分解反応は、ポリマーの濃度として０．０１〜１．０モル容量％で行うのが好ましく、０．１〜０．５モル容量％が更に好ましい。反応温度としては、０〜１００℃が好ましく、より好ましくは１０〜５０℃で、反応時間は最大１００時間程度が好ましい。 This hydrolysis reaction is preferably carried out at a polymer concentration of 0.01 to 1.0 mol%, more preferably 0.1 to 0.5 mol%. The reaction temperature is preferably 0 to 100 ° C, more preferably 10 to 50 ° C, and the reaction time is preferably about 100 hours at the maximum.
本発明における加水分解ポリマー（II）の数平均分子量Ｍnは、塗布用組成物の保存安定性及び薄膜の均一性の観点から、５００〜２００，０００であるのが好ましく、更に好ましくは２，０００〜５０，０００、特に好ましくは５，０００〜１５，０００である。本発明のポリマー（II）の分子量分布（重量平均分子量Ｍw／数平均分子量Ｍn）は１〜５が好ましく、１．１〜４．０であるのが更に好ましく、１．１〜１．４であるのが特に好ましい。 The number average molecular weight M n of the hydrolyzed polymer (II) in the present invention is preferably 500 to 200,000, more preferably 2, from the viewpoint of the storage stability of the coating composition and the uniformity of the thin film. 000 to 50,000, particularly preferably 5,000 to 15,000. The molecular weight distribution (weight average molecular weight M w / number average molecular weight M n ) of the polymer (II) of the present invention is preferably 1 to 5, more preferably 1.1 to 4.0, and even more preferably 1.1 to 1. 4 is particularly preferred.
本発明で用いる加水分解触媒としては、無機酸、有機酸、無機の酸性化合物等のブレンステッド酸を使用することができる。無機酸としては、例えば塩酸、硫酸、硝酸等をあげることができ、有機酸としては、例えば酢酸を挙げることができ、そして触媒の使用量には特に制限はないが、０．１〜１０ミリモル容量％であるのが好ましい。 As the hydrolysis catalyst used in the present invention, a Bronsted acid such as an inorganic acid, an organic acid, or an inorganic acidic compound can be used. Examples of the inorganic acid include hydrochloric acid, sulfuric acid, nitric acid, and the like. Examples of the organic acid include acetic acid. The amount of the catalyst used is not particularly limited, but is 0.1 to 10 mmol. It is preferable that it is volume%.
前記加水分解反応は、無溶剤で行っても良いが、溶剤希釈下で行うことが好ましい。使用する溶剤としては、本発明のホモポリマー（Ｉ）、水、触媒などの反応に使用する化合物が溶解又は分散すれば制限は無く、芳香族炭化水素類、双極子非プロトン系溶剤類、ケトン類、エステル類、エーテル類、ハロゲン化炭化水素類などが挙げられる。 The hydrolysis reaction may be performed without a solvent, but is preferably performed under solvent dilution. The solvent to be used is not limited as long as the compound used in the reaction such as the homopolymer (I) of the present invention, water, catalyst, etc. is dissolved or dispersed. Aromatic hydrocarbons, dipolar aprotic solvents, ketones , Esters, ethers, halogenated hydrocarbons and the like.
加水分解反応はアルカリの水溶液又はアミン類のアルコール溶液などで停止させ、その後は、添加した水、アルコール及び生成するアルデヒド類や塩類等を除去するため水洗、逆抽出することが好ましい。更に精製が必要な場合は、溶媒を留去、乾燥後、テトラヒドロフラン（ＴＨＦ）等のエーテルで希釈し、アルコールで沈殿させることができる。 The hydrolysis reaction is preferably stopped with an aqueous alkali solution or an alcohol solution of amines, and then washed with water and back-extracted to remove added water, alcohol, aldehydes and salts generated, and the like. If further purification is required, the solvent can be distilled off, dried, diluted with ether such as tetrahydrofuran (THF), and precipitated with alcohol.
以下、実施例によって本発明を更に説明するが、本発明の範囲をこれらの実施例に限定するものでないことはいうまでもない。 EXAMPLES Hereinafter, although an Example demonstrates this invention further, it cannot be overemphasized that the scope of the present invention is not limited to these Examples.
実施例１
まず、開始剤にＢＦ3ＯＥｔ2を用いて重合を行った。モノマー濃度０．３mol／Ｌ開始剤濃度５．０mmol／Ｌで、シュレンク管にモノマー溶液４．５mLと開始剤溶液０．５mLを順に注射器で注入して重合を開始した。トルエン中、０℃で重合を行ったところ、２０分で重合率１００％に達し、数平均分子量Ｍn＝８３，５００、分子量分布（多分散度）Ｍw／Ｍn＝４．３８の比較的高分子量のポリマーを得た。
Example 1
First, polymerization was performed using BF 3 OEt 2 as an initiator. At a monomer concentration of 0.3 mol / L and an initiator concentration of 5.0 mmol / L, 4.5 mL of the monomer solution and 0.5 mL of the initiator solution were sequentially injected into the Schlenk tube with a syringe to initiate polymerization. When polymerization was carried out in toluene at 0 ° C., the polymerization rate reached 100% in 20 minutes, and the number average molecular weight M n = 83,500 and the molecular weight distribution (polydispersity) M w / M n = 4.38 were compared. A high molecular weight polymer was obtained.
実施例２
次に、リビング重合開始剤である二成分系開始剤（ＣＨ3ＣＨ（Ｏｉ−Ｂｕ）ＯＣＯＣＨ3／ＳｎＢｒ4）を用いた重合では、シュレンク管にモノマー溶液４．０mL、開始剤溶液０．５mL、活性化溶液０．５mLをこの順で注射器を用いて注入し重合を開始した。トルエン中、２，６−ｄｉ−ｔｅｒｔ−ブチルピリジン（ＤＴＢＰ）存在下、０℃、モノマー濃度０．３mol／Ｌ，ＣＨ3ＣＨ（Ｏｉ−Ｂｕ）ＯＣＯＣＨ3５．０mmol／Ｌ，ＳｎＢｒ4２．０mmol／Ｌ，ＤＴＢＰ０．２mmol／Ｌで行った。重合は、４８時間で重合率９９％に達し、重合系にアンモニア水を少量加えたメタノールを２．０ml加えて停止した。
Example 2
Next, in polymerization using a two-component initiator (CH 3 CH (Oi-Bu) OCOCH 3 / SnBr 4 ) that is a living polymerization initiator, a monomer solution of 4.0 mL and an initiator solution of 0.5 mL are added to a Schlenk tube. Then, 0.5 mL of the activation solution was injected in this order using a syringe to initiate polymerization. 1. In toluene, in the presence of 2,6-di-tert-butylpyridine (DTBP), 0 ° C., monomer concentration 0.3 mol / L, CH 3 CH (Oi-Bu) OCOCH 3 5.0 mmol / L, SnBr 4 The measurement was performed at 0 mmol / L and DTBP 0.2 mmol / L. The polymerization reached a polymerization rate of 99% in 48 hours, and was stopped by adding 2.0 ml of methanol with a small amount of aqueous ammonia to the polymerization system.
生成ポリマーは、重合を停止した溶液を分液ロートに移し、イオン交換水で三回洗浄し、次いで有機層からエバポレーターにより溶媒を除去し、減圧乾燥して回収した。更に精製が必要な時は、得られたポリマーのテトラヒドロフラン溶液をメタノール中に沈殿させ精製した。Ｍnは重合率に比例して増加し、分子量分布の比較的狭いポリマーが合成できた（数平均分子量Ｍn＝１２，６００、分子量分布Ｍw／Ｍn＝１．３２）。 The polymer produced was transferred to a separatory funnel after the polymerization was stopped, washed three times with ion-exchanged water, and then the solvent was removed from the organic layer by an evaporator, followed by drying under reduced pressure. When further purification was required, the resulting polymer solution in tetrahydrofuran was purified by precipitation in methanol. M n increased in proportion to the polymerization rate, and a polymer having a relatively narrow molecular weight distribution could be synthesized (number average molecular weight M n = 1,600, molecular weight distribution M w / M n = 1.32).
実施例３
実施例１と同様な条件で重合したポリマー（数平均分子量Ｍn１１０，０００、分子量分布Ｍw／Ｍn３．４１）のガラス転移温度Ｔｇ（ＤＳＣにより測定）は室温より高く３５℃であった。生成ポリマーの構造をスペクトルにより検討した。ビニル基のピークは完全に消失し、環状アセタール基の存在を示すピークはそのまま観測された。各ピークの、積分強度比の検討により、ポリビニルエーテルの全ての繰り返し単位に環状アセタールが存在することがわかった。また、このポリマーの熱分解温度は３０５℃であった。得られたポリマー（Ｉ）のＨ1−ＮＭＲチャート（測定条件：溶媒にＣＤＣｌ3を用い室温で測定）を図１にしめす。
Example 3
The glass transition temperature Tg (measured by DSC) of a polymer (number average molecular weight M n 110,000, molecular weight distribution M w / M n 3.41) polymerized under the same conditions as in Example 1 was higher than room temperature and 35 ° C. It was. The structure of the produced polymer was examined by spectrum. The vinyl group peak disappeared completely, and the peak indicating the presence of the cyclic acetal group was observed as it was. Examination of the integrated intensity ratio of each peak revealed that cyclic acetals were present in all repeating units of polyvinyl ether. The thermal decomposition temperature of this polymer was 305 ° C. FIG. 1 shows an H 1 -NMR chart (measurement conditions: measured at room temperature using CDCl 3 as a solvent) of the obtained polymer (I).
ポリマー（Ｉ）０．２５０８ｇを１mol／Ｌに調整した塩化水素溶液２０mL（ＴＨＦ／１，４−ジオキサン＝１５mL／５mL）に溶解し、そのまま室温で２４時間反応させた。なお、その間、水を数滴加える作業を行った。その後、エバポレーターにより溶媒を除去しポリマー（II）を得、ＮＭＲを測定したところ、開環率は１２％であった。 0.2508 g of polymer (I) was dissolved in 20 mL of a hydrogen chloride solution adjusted to 1 mol / L (THF / 1,4-dioxane = 15 mL / 5 mL) and reacted at room temperature for 24 hours. Meanwhile, an operation of adding a few drops of water was performed. Thereafter, the solvent was removed by an evaporator to obtain polymer (II), and NMR was measured. The ring opening rate was 12%.
得られたポリマー（II）のＨ1−ＮＭＲ分析を上と同様にして行なって得られたＨ1−ＮＭＲチャートを図２に示す。 FIG. 2 shows an H 1 -NMR chart obtained by conducting H 1 -NMR analysis of the obtained polymer (II) in the same manner as above.
実施例４
実施例１と同様にして得られたポリアセタールビニルエーテルを以下のようにして脱保護した。即ち、ポリアセタールビニルエーテル０．２５３８ｇを、１mol／Ｌに調整した塩化水素溶液２０mL（ＴＨＦ／１，４−ジオキサン＝１５mL／５mL）に溶解し、そのまま室温で７日間反応させた。なお７日間に水を４〜５滴加える作業を４回行なった。その後、エバポレーターにより溶媒を除去しＮＭＲを測定したところ、開環率は３７％であった。
Example 4
The polyacetal vinyl ether obtained in the same manner as in Example 1 was deprotected as follows. That is, 0.2538 g of polyacetal vinyl ether was dissolved in 20 mL of a hydrogen chloride solution adjusted to 1 mol / L (THF / 1,4-dioxane = 15 mL / 5 mL) and allowed to react at room temperature for 7 days. The work of adding 4 to 5 drops of water in 7 days was performed 4 times. Then, when the solvent was removed with an evaporator and NMR was measured, the ring opening rate was 37%.
本発明に係る２−メチル−５−エチル−５−ビニロキシメチル−１，３−ジオキサンホモポリマー（Ｉ）は、ポリアセタールと同様、機械的特性、熱的特性、電気的特性、摺動性、耐疲労性、耐摩擦性、耐摩耗性、耐薬品性及び成形性等において優れた特性を有することが期待できる。また本発明に係る１，１−ジメチロール−１−ビニロキシメチルプロパンホモポリマー（II）は、ポリエステルやポリビニルアルコール等と同様、親水性、密着性等が期待でき、更に、ノニオン性界面活性剤として、インクを被記録材としての紙面に浸透させる効果もあるので、印字物の耐擦過性、耐水性などが良好となることが期待できる。 The 2-methyl-5-ethyl-5-vinyloxymethyl-1,3-dioxane homopolymer (I) according to the present invention, like polyacetal, has mechanical properties, thermal properties, electrical properties, slidability, It can be expected to have excellent characteristics in fatigue resistance, friction resistance, wear resistance, chemical resistance, moldability, and the like. Further, 1,1-dimethylol-1-vinyloxymethylpropane homopolymer (II) according to the present invention can be expected to have hydrophilicity, adhesion, etc., as well as polyester and polyvinyl alcohol, and further, as a nonionic surfactant. Also, since the ink has an effect of penetrating the paper surface as a recording material, it can be expected that the printed matter has excellent scratch resistance, water resistance, and the like.
Claims (11)
で表わされるビニルエーテル誘導体ホモポリマー。 Formula (I):
A vinyl ether derivative homopolymer represented by:
で表わされるビニルエーテル誘導体ホモポリマー。 Formula (II):
A vinyl ether derivative homopolymer represented by:
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