JP2010077331A - Curable resin composition - Google Patents
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Abstract
Description
本発明は、開環メタセシス重合によって得られる新規なビニルエーテル重合体に関するものである。 The present invention relates to a novel vinyl ether polymer obtained by ring-opening metathesis polymerization.
従来、開環メタセシス重合性組成物としては、メタセシス重合性環状オレフィンモノマーとしてジシクロペンタジエンが用いられている例が多く、反応射出成型法と呼ばれる技術により、架橋重合体成型物が得られることが知られている（例えば特許文献１）。 Conventionally, as a ring-opening metathesis polymerizable composition, dicyclopentadiene is often used as a metathesis polymerizable cyclic olefin monomer, and a crosslinked polymer molded product can be obtained by a technique called a reaction injection molding method. Known (for example, Patent Document 1).
一方、メタセシス重合性環状オレフィンポリマーを、開環メタセシス重合に用いる例は少なく、ノルボルネニル基を側鎖又は末端に導入したポリジメチルシロキサンやカルボキシレートウレタンポリエーテルが報告されているにすぎない（例えば特許文献２、３）。
本発明は、耐熱性に優れた硬化性樹脂組成物として有用な開環メタセシス重合によって得られる新規なビニルエーテル重合体を提供することにある。 An object of the present invention is to provide a novel vinyl ether polymer obtained by ring-opening metathesis polymerization useful as a curable resin composition having excellent heat resistance.
以前、本発明者らは、新規な脂環式ビニルエーテル重合体であるノルボルネニルビニルエーテル重合体に関する報告を行った（特願２００７−７２１６６）。 Previously, the present inventors reported on a norbornenyl vinyl ether polymer which is a novel alicyclic vinyl ether polymer (Japanese Patent Application No. 2007-72166).
本発明者らは、上記特許出願を基に鋭意研究を行った結果、ビニルエーテル系モノマーを主体とする重合体であって、少なくとも下記〔Ｉ〕式で表される構成単位を含む重合体を開環メタセシス重合させることによって得られるビニルエーテル重合体が、耐熱性等に優れることを見出した。 As a result of intensive research based on the above patent application, the present inventors have found that a polymer mainly composed of a vinyl ether monomer and containing at least a structural unit represented by the following formula [I]: It has been found that a vinyl ether polymer obtained by ring metathesis polymerization is excellent in heat resistance and the like.
また、下記〔ＩＩ〕式で表されることを特徴とするビニルエーテル重合体が、耐熱性等に優れることを見出した。 Moreover, it discovered that the vinyl ether polymer characterized by being represented by following [II] Formula was excellent in heat resistance.
また、ビニルエーテル系モノマーを主体とする重合体であって、少なくとも下記〔Ｉ〕式で表される構成単位を含む共重合体を開環メタセシス重合させることによって得られるビニルエーテル重合体が、耐熱性等に優れることを見出した。 In addition, a vinyl ether polymer obtained mainly by ring-opening metathesis polymerization of a copolymer containing at least a structural unit represented by the following formula [I] is a polymer mainly composed of a vinyl ether monomer. It was found to be excellent.
さらに、下記〔ＩＩＩ〕式で表されることを特徴とするビニルエーテル重合体が、耐熱性等に優れることを見出した。 Furthermore, it discovered that the vinyl ether polymer characterized by being represented by following [III] Formula was excellent in heat resistance.
上記式〔ＩＩＩ〕において、ｌおよびｎは互いに独立して２〜３，００００の範囲であり、ｍは０または１であり、Ｒは一価の有機基である。 In the above formula [III], l and n are independently in the range of 2 to 30,000, m is 0 or 1, and R is a monovalent organic group.
本発明におけるビニルエーテル重合体は、耐熱性だけでなく透明性に優れているため、インクジェット用インク等のインク用材料、レンズ、液晶用フィルム等の光学用材料、各種コーティング用材料、接着剤用材料として有用である。さらに、本発明におけるビニルエーテル重合体は、有害性が極めて低く安全性に優れたものである。従って、医療用フィルムや医療用粘着剤等の高い安全性が要求される分野において有用である。 Since the vinyl ether polymer in the present invention is excellent not only in heat resistance but also in transparency, ink materials such as inkjet inks, optical materials such as lenses and liquid crystal films, various coating materials, and adhesive materials Useful as. Furthermore, the vinyl ether polymer in the present invention has extremely low harmfulness and excellent safety. Therefore, it is useful in fields requiring high safety such as medical films and medical adhesives.
本発明におけるビニルエーテル重合体の第１の様態は、ビニルエーテル系モノマーを主体とする重合体であって、少なくとも下記〔Ｉ〕式で表される構成単位を含む重合体を開環メタセシス重合させることによって得られるビニルエーテル重合体である。 A first aspect of the vinyl ether polymer in the present invention is a polymer mainly composed of a vinyl ether monomer, and is obtained by ring-opening metathesis polymerization of a polymer containing at least a structural unit represented by the following formula [I]: The resulting vinyl ether polymer.
また、本発明におけるビニルエーテル重合体の第２の様態は、下記〔ＩＩ〕式で表されることを特徴とするビニルエーテル重合体である。 Moreover, the 2nd aspect of the vinyl ether polymer in this invention is represented by the following [II] formula, It is a vinyl ether polymer characterized by the above-mentioned.
本発明におけるビニルエーテル重合体の第３の様態は、ビニルエーテル系モノマーを主体とする重合体であって、少なくとも下記〔Ｉ〕式で表される構成単位を含む共重合体を開環メタセシス重合させることによって得られるビニルエーテル重合体。 A third embodiment of the vinyl ether polymer in the present invention is a polymer mainly composed of a vinyl ether monomer, and comprises ring-opening metathesis polymerization of a copolymer containing at least a constituent unit represented by the following formula [I]: Vinyl ether polymer obtained by
本発明におけるビニルエーテル重合体の第４の様態は、下記〔ＩＩＩ〕式で表されることを特徴とするビニルエーテル重合体である。 The 4th aspect of the vinyl ether polymer in this invention is represented by the following [III] formula, It is a vinyl ether polymer characterized by the above-mentioned.
上記式〔ＩＩＩ〕において、ｌおよびｎは互いに独立して２〜３，００００の範囲であり、ｍは０または１であり、Ｒはビニルエーテル系モノマー由来の一価の有機基である。 In the above formula [III], l and n are each independently in the range of 2 to 30,000, m is 0 or 1, and R is a monovalent organic group derived from a vinyl ether monomer.
前記ビニルエーテル系モノマーの具体例としては、メチルビニルエーテル、エチルビニルエーテル、ｎ−プロピルビニルエーテル、イソプロピルビニルエーテル、ｎ―ブチルビニルエーテル、ｓｅｃ−ブチルビニルエーテル、ｔｅｒｔ−ブチルビニルエーテル、イソブチルビニルエーテル、（１―エチルプロピル）ビニルエーテル、ネオペンチルビニルエーテル、ｎ―ヘキシルビニルエーテル、シクロヘキシルビニルエーテル、シクロヘキサンメタノールビニルエーテル、２―エチルヘキシルビニルエーテル、ドデシルビニルエーテル、オクタデシルビニルエーテル、アリルビニルエーテル、ノルボルニルビニルエーテル、ノルボルニルメチルビニルエーテル、ノルボルネニルメチルビニルエーテル、２―アセトキシエチルビニルエーテル、４―アセトキシブチルビニルエーテル、アセトキシシクロヘキサンメタノールビニルエーテル、アセトキシジエチレングリコールビニルエーテル、アセトキシトリエチレングリコールビニルエーテル等が挙げられるが、これらに限定されるものではない。上記ビニルエーテル系モノマーは、所望により１種または２種以上を組み合わせて用いても良い。 Specific examples of the vinyl ether monomer include methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, sec-butyl vinyl ether, tert-butyl vinyl ether, isobutyl vinyl ether, (1-ethylpropyl) vinyl ether, Neopentyl vinyl ether, n-hexyl vinyl ether, cyclohexyl vinyl ether, cyclohexane methanol vinyl ether, 2-ethylhexyl vinyl ether, dodecyl vinyl ether, octadecyl vinyl ether, allyl vinyl ether, norbornyl vinyl ether, norbornyl methyl vinyl ether, norbornenyl methyl vinyl ether, 2-acetoxy Ethyl vinyl ether, - acetoxy butyl ether, acetoxy cyclohexanemethanol vinyl ether, acetoxy diethylene vinyl ether, but acetoxy triethylene glycol vinyl ether, but is not limited thereto. The vinyl ether monomers may be used alone or in combination of two or more as desired.
前記式〔ＩＩ〕で表されるビニルエーテル重合体は、前記式〔Ｉ〕で表される構成単位を含むビニルエーテル重合体を開環メタセシス重合させることによって得ることができる。また、上記式〔ＩＩＩ〕で表されるビニルエーテル重合体は、前記式〔Ｉ〕で表される構成単位を含むビニルエーテル共重合体を開環メタセシス重合させることによって得ることができる。 The vinyl ether polymer represented by the formula [II] can be obtained by subjecting the vinyl ether polymer containing the structural unit represented by the formula [I] to ring-opening metathesis polymerization. The vinyl ether polymer represented by the formula [III] can be obtained by ring-opening metathesis polymerization of a vinyl ether copolymer containing the structural unit represented by the formula [I].
本願における開環メタセシス重合に利用できる触媒としては、下記式〔ＩＶ〕で示される第二世代Ｇｒｕｂｂｓ触媒が挙げられる（式中、Ｃｙはシクロヘキシルを示す）。 Examples of the catalyst that can be used for the ring-opening metathesis polymerization in the present application include a second generation Grubbs catalyst represented by the following formula [IV] (wherein Cy represents cyclohexyl).
以下に実施例を挙げて本発明を具体的に説明するが、本発明はこれらの実施例に何ら限定されるものではない。 EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
本明細書中において、「数平均分子量（以下Ｍｎと略す）」とは、ゲルパーミエーションクロマトグラフィー（以下ＧＰＣと略す）を用いた標準ポリスチレン換算法により算出するものである。 In this specification, “number average molecular weight (hereinafter abbreviated as Mn)” is calculated by a standard polystyrene conversion method using gel permeation chromatography (hereinafter abbreviated as GPC).
本明細書中において、「５％重量減少温度」とは、示差熱熱重量同時測定装置（以下ＴＧ−ＤＴＡ）にて窒素流量２００ｍＬ／分、５０℃から５００℃までの昇温速度１０℃／分の条件で、初期重量の５％が減少した時点の温度のことである。 In this specification, “5% weight loss temperature” means a nitrogen flow rate of 200 mL / min and a temperature increase rate of 10 ° C./min from 50 ° C. to 500 ° C. using a differential thermothermal gravimetric simultaneous measurement apparatus (hereinafter referred to as TG-DTA). This is the temperature at which 5% of the initial weight is reduced under the condition of minutes.
（合成例１）
〔ノルボルネニルビニルエーテル単独重合体の合成〕
十分乾燥し窒素置換を行った重合管に、ノルボルネニルビニルエーテル１．５ｇ（１１ｍｍｏｌ）、トルエン９．９ｍＬ、ジエチルエーテル０．６６ｍＬを仕込み、０℃に冷却した。２０分後、トリフルオロ酢酸１２５ｍｇ（１．１ｍｍｏｌ）を添加した。３０分後、塩化亜鉛のジエチルエーテル溶液（１ｍｏｌ／Ｌ）０．４４ｍＬ（０．４４ｍｍｏｌ）を添加して重合を開始した。１分後、アリルトリメチルシラン３７７ｍｇ（３．３ｍｍｏｌ）を添加し、２５℃で１時間、アリルトリメチルシランとの重合停止反応を行った。反応終了後、反応液をジエチルエーテルで希釈して、脱イオン水で３回洗浄し、溶媒の減圧除去を行って、目的物であるノルボルネニルビニルエーテル単独重合体１．４ｇを得た。
(Synthesis Example 1)
[Synthesis of norbornenyl vinyl ether homopolymer]
A polymerization tube that had been sufficiently dried and purged with nitrogen was charged with 1.5 g (11 mmol) of norbornenyl vinyl ether, 9.9 mL of toluene, and 0.66 mL of diethyl ether, and cooled to 0 ° C. After 20 minutes, 125 mg (1.1 mmol) of trifluoroacetic acid was added. After 30 minutes, 0.44 mL (0.44 mmol) of zinc chloride in diethyl ether (1 mol / L) was added to initiate polymerization. After 1 minute, 377 mg (3.3 mmol) of allyltrimethylsilane was added, and a polymerization termination reaction with allyltrimethylsilane was performed at 25 ° C. for 1 hour. After completion of the reaction, the reaction solution was diluted with diethyl ether, washed three times with deionized water, and the solvent was removed under reduced pressure to obtain 1.4 g of norbornenyl vinyl ether homopolymer as the target product.
得られた重合体はＧＰＣ測定により、Ｍｎ：１０８０であった。さらに、得られた重合体の１ＨＮＭＲ測定を行ったところ、ビニルエーテル基に由来するビニル基のピークは消失し、５．９−６．４ｐｐｍにノルボルネニル基のビニル基に由来するピークが認められた。 The obtained polymer was Mn: 1080 by GPC measurement. Furthermore, when 1 HNMR measurement of the obtained polymer was performed, the peak of the vinyl group derived from the vinyl ether group disappeared, and the peak derived from the vinyl group of the norbornenyl group was observed at 5.9 to 6.4 ppm. .
（合成例２）
〔シクロヘキシルビニルエーテルとノルボルネニルビニルエーテルの共重合体の合成〕
モノマーを、シクロヘキシルビニルエーテルとノルボルネニルビニルエーテルのモル組成比が９０／１０である混合モノマーに変更した以外は、合成例１と全く同じ触媒、溶媒を用いて、同一モル比、モル濃度とし、重合反応温度、重合反応時間、重合後の処理方法も同じ条件にて目的物を得た。
(Synthesis Example 2)
[Synthesis of Copolymer of Cyclohexyl Vinyl Ether and Norbornenyl Vinyl Ether]
Except that the monomer was changed to a mixed monomer having a molar composition ratio of cyclohexyl vinyl ether and norbornenyl vinyl ether of 90/10, the same molar ratio and molar concentration were used with the same catalyst and solvent as in Synthesis Example 1, and polymerization was performed. The desired product was obtained under the same conditions for the reaction temperature, polymerization reaction time, and post-polymerization treatment.
得られた重合体はＧＰＣ測定により、Ｍｎ：１１３０であった。さらに、得られた重合体の１ＨＮＭＲ測定を行ったところ、ビニルエーテル基に由来するビニル基のピークは消失し、５．９−６．４ｐｐｍにノルボルネニル基のビニル基に由来するピークが認められた。 The obtained polymer was Mn: 1130 by GPC measurement. Furthermore, when 1 HNMR measurement of the obtained polymer was performed, the peak of the vinyl group derived from the vinyl ether group disappeared, and the peak derived from the vinyl group of the norbornenyl group was observed at 5.9 to 6.4 ppm. .
（実施例１）
〔合成例１の単独重合体による架橋重合体の合成〕
合成例１で得られた樹脂２２０ｍｇをトルエン１．５ｍＬに溶解し、式〔ＩＶ〕の第二世代Ｇｒｕｂｂｓ触媒２．１ｍｇを添加して、窒素雰囲気下、室温で反応を開始させた。６０分後、不溶化物が生じ、１１０ｍｇのエチルビニルエーテルを添加して反応を停止した。反応後、反応液のろ過を行って不溶化物を採取し、減圧乾燥を行い架橋重合体２１２ｍｇ得た。架橋重合体の５％重量減少温度は、１９３℃であった。
Example 1
[Synthesis of Crosslinked Polymer by Homopolymer of Synthesis Example 1]
220 mg of the resin obtained in Synthesis Example 1 was dissolved in 1.5 mL of toluene, 2.1 mg of the second generation Grubbs catalyst of the formula [IV] was added, and the reaction was started at room temperature in a nitrogen atmosphere. After 60 minutes, an insolubilized product was formed, and the reaction was stopped by adding 110 mg of ethyl vinyl ether. After the reaction, the reaction solution was filtered to collect an insolubilized product, followed by drying under reduced pressure to obtain 212 mg of a crosslinked polymer. The 5% weight loss temperature of the crosslinked polymer was 193 ° C.
（実施例２）
〔合成例２の共重合体による架橋共重合体の合成〕
合成例２で得られた共重合物に変更した以外は、実施例１と全く同じ条件にて組成物を調整した。架橋共重合体の５％重量減少温度は２３２℃であった。
(Example 2)
[Synthesis of Crosslinked Copolymer by Copolymer of Synthesis Example 2]
The composition was adjusted under exactly the same conditions as in Example 1 except that the copolymer obtained in Synthesis Example 2 was used. The 5% weight loss temperature of the crosslinked copolymer was 232 ° C.
（比較例１）
〔ノルボルネン重合体の合成〕
ノルボルネン１９０ｍｇをトルエン１．５ｍＬに溶解し、式〔ＩＶ〕の第二世代Ｇｒｕｂｂｓ触媒２．１ｍｇを添加して、窒素雰囲気下、室温で反応を開始させた。３分後、不溶化物が生じ、１１０ｍｇのエチルビニルエーテルを添加して反応を停止した。反応後、反応液のろ過を行って不溶化物を採取し、減圧乾燥を行い架橋重合体１５０ｍｇ得た。架橋重合体の５％重量減少温度は、８７℃であった。
(Comparative Example 1)
[Synthesis of norbornene polymer]
190 mg of norbornene was dissolved in 1.5 mL of toluene, 2.1 mg of the second generation Grubbs catalyst of the formula [IV] was added, and the reaction was started at room temperature under a nitrogen atmosphere. After 3 minutes, an insolubilized product was formed, and the reaction was stopped by adding 110 mg of ethyl vinyl ether. After the reaction, the reaction solution was filtered to collect an insolubilized product and dried under reduced pressure to obtain 150 mg of a crosslinked polymer. The 5% weight loss temperature of the crosslinked polymer was 87 ° C.
本発明におけるビニルエーテル重合体は、耐熱性に優れるばかりでなく、透明性に優れるものである。従って、インクジェット用インク等のインク用材料、レンズ、液晶用フィルム等の光学用材料、各種コーティング用材料、接着剤用材料として有用である。さらに、本発明におけるビニルエーテル重合体は、有害性が極めて低く安全性に優れるものである。従って、医療用フィルムや医療用粘着剤等の高い安全性が要求される分野において有用である。 The vinyl ether polymer in the present invention is not only excellent in heat resistance but also excellent in transparency. Therefore, it is useful as an ink material such as an ink jet ink, an optical material such as a lens and a liquid crystal film, various coating materials, and an adhesive material. Furthermore, the vinyl ether polymer in the present invention is extremely harmful and excellent in safety. Therefore, it is useful in fields requiring high safety such as medical films and medical adhesives.
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Cited By (2)
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| JP2010077330A (en) * | 2008-09-29 | 2010-04-08 | Nippon Carbide Ind Co Inc | Vinyl ether polymer excellent in storage stability |
| WO2016152310A1 (en) * | 2015-03-25 | 2016-09-29 | 日本ゼオン株式会社 | Polymer, molding material and resin molded body |
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