WO2012046880A1 - 新規なジビニルエーテル化合物及びその製造方法 - Google Patents
新規なジビニルエーテル化合物及びその製造方法 Download PDFInfo
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- WO2012046880A1 WO2012046880A1 PCT/JP2011/073597 JP2011073597W WO2012046880A1 WO 2012046880 A1 WO2012046880 A1 WO 2012046880A1 JP 2011073597 W JP2011073597 W JP 2011073597W WO 2012046880 A1 WO2012046880 A1 WO 2012046880A1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
- C07C43/14—Unsaturated ethers
- C07C43/162—Unsaturated ethers containing rings other than six-membered aromatic rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/05—Preparation of ethers by addition of compounds to unsaturated compounds
- C07C41/06—Preparation of ethers by addition of compounds to unsaturated compounds by addition of organic compounds only
- C07C41/08—Preparation of ethers by addition of compounds to unsaturated compounds by addition of organic compounds only to carbon-to-carbon triple bonds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/36—Systems containing two condensed rings the rings having more than two atoms in common
- C07C2602/42—Systems containing two condensed rings the rings having more than two atoms in common the bicyclo ring system containing seven carbon atoms
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- the present invention relates to novel divinyl ether compounds, more particularly 2,2-bis [(ethenyloxy) methyl] bicyclo [2.2.1] heptane and 5,5-bis [(ethenyloxy) methyl] bicyclo [2.2. .1] It relates to hept-2-ene and a method for producing the same.
- Divinyl ether compounds according to the present invention specifically 2,2-bis [(ethenyloxy) methyl] bicyclo [2.2.1] heptane (also known as 2,2-norbornane dimethanol divinyl ether) and 5,5- Bis [(ethenyloxy) methyl] bicyclo [2.2.1] hept-2-ene (also known as 5-norbornene-2,2-dimethanol divinyl ether) has not been reported so far and is a novel compound. Conceivable.
- Patent Document 1 describes pentaerythritol acetal divinyl ether. Since this compound has an acetal structure, it is easily hydrolyzed and is different from the divinyl ether compound according to the present invention in terms of stability to water.
- Patent Document 2 describes 1,3-adamantane dimethanol divinyl ether, but this compound is different from the divinyl ether compound according to the present invention in terms of ease of cyclopolymerization.
- the object of the present invention is to provide novel divinyl ether compounds, specifically 2,2-bis [(ethenyloxy) methyl] bicyclo [2.2.1] heptane and 5,5-bis [(ethenyloxy) methyl] bicyclo [ 2.2.1] To provide hept-2-ene and a method for producing the same.
- novel divinyl ether compounds according to the invention in particular 2,2-bis [(ethenyloxy) methyl] bicyclo [2.2.1] heptane and 5,5-bis [(ethenyloxy) methyl] bicyclo [2. 2.1] Hept-2-ene is useful as a polymer composition raw material, a crosslinking agent, and various synthetic reagents because it is excellent in curability, adhesion, ultraviolet light permeability, and rigidity. Therefore, the novel divinyl ether compound of the present invention can be used for applications such as inks, paints, resists, color filters, adhesives, plate making materials, sealants, and image forming agents.
- the formula (I) (In the formula, A represents a single bond or a double bond.)
- the novel divinyl ether compound represented by these is provided.
- the formula (II) (In the formula, A represents a single bond or a double bond.) Is reacted with 2,2-norbornanedimethanol or 5-norbornene-2,2-dimethanol represented by the formula (I) in an aprotic polar solvent in the presence of an alkaline compound catalyst.
- the novel divinyl ether compound of the present invention has a low odor, low volatility and low skin irritation, has low toxicity, and is a raw material for a polymerization composition having excellent curability, adhesion, and ultraviolet light permeability. It can be expected to have useful properties. Further, the novel divinyl ether compound represented by the formula (I) of the present invention is characterized by having two vinyl ether groups having special reactivity at a specific position either alone or with other compounds. Have.
- 1 is a 1 H-NMR chart of 2,2-bis [(ethenyloxy) methyl] bicyclo [2.2.1] heptane.
- 1 is a 13 C-NMR chart of 2,2-bis [(ethenyloxy) methyl] bicyclo [2.2.1] heptane.
- 1 is a 1 H-NMR chart of 5,5-bis [(ethenyloxy) methyl] bicyclo [2.2.1] hept-2-ene. It is a 13 C-NMR chart of 5,5-bis [(ethenyloxy) methyl] bicyclo [2.2.1] hept-2-ene.
- the divinyl ether compound (I) according to the present invention can be synthesized according to the following reaction formula. (In the formula, A represents a single bond or a double bond.)
- 2,2-bis [(ethenyloxy) methyl] bicyclo [2.2.1] heptane (I ′) is present in an aprotic solvent in the presence of an alkaline compound catalyst. And can be synthesized according to the following reaction formula.
- 5,5-bis [(ethenyloxy) methyl] bicyclo [2.2.1] hept-2-ene (I ′′) is non-dehydrated in the presence of an alkaline compound catalyst. It can be synthesized according to the following reaction formula in a protic solvent.
- a reaction vessel such as a pressure resistant reaction vessel made of stainless steel (SUS)
- an aprotic polar solvent such as dimethyl sulfoxide, N-methylpyrrolidone, N, N′-dimethylethyleneurea, N, N′-dimethyl is used as a solvent.
- the amount of the aprotic polar solvent used is not particularly limited, but the amount of the aprotic polar solvent used is 100 parts by mass of 2,2-norbornanedimethanol or 5-norbornene-2,2-dimethanol. The amount is preferably 100 to 1,000 parts by mass, more preferably 200 to 700 parts by mass.
- the amount of the aprotic polar solvent used is less than 100 parts by mass with respect to 100 parts by mass of 2,2-norbornanedimethanol or 5-norbornene-2,2-dimethanol, the selectivity of the reaction may decrease. This is not preferable.
- the amount of the aprotic polar solvent used exceeds 1000 parts by mass with respect to 100 parts by mass of 2,2-norbornanedimethanol or 5-norbornene-2,2-dimethanol, the solvent after completion of the reaction Since removal may be complicated, it is not preferable.
- the usage-amount of the alkaline compound which is a reaction catalyst is with respect to 100 mass parts of 2, 2- norbornane dimethanol or 5-norbornene-2,2-dimethanol.
- the amount is preferably at least 2 parts by mass, and more preferably 4 to 50 parts by mass.
- the pressure of acetylene is preferably 0.01 MPa or more in terms of gauge pressure, and productivity, side reaction suppression, and safety are improved. From the viewpoint, the acetylene pressure is more preferably from 0.15 MPa to 1.0 MPa in terms of gauge pressure.
- the reaction temperature is preferably 80 to 140 ° C., preferably 100 ° C. or higher from the viewpoint of reaction rate, and preferably 130 ° C. or lower from the viewpoint of economy and side reaction suppression.
- 2,2-norbornanedimethanol or 5-norbornene-2,2-dimethanol (II) of the formula (II), which is a raw material used in the present invention is a known compound and is produced by a conventionally known method.
- 2,2-norbornanedimethanol can be obtained, for example, by the method described in Synthesis Example 4 of JP-A-2005-29608. Specifically, it can be produced from 5-norbornene-2,2-dimethanol commercially available from Tokyo Chemical Industry Co., Ltd. under the product name 5-norbornene-2,2-dimethanol.
- the divinyl ether compound represented by the formula (I) according to the present invention can be homopolymerized or copolymerized with another monomer (for example, n-butyl vinyl ether), and a polymer having a high glass transition temperature can be obtained. .
- another monomer for example, n-butyl vinyl ether
- a polymer having a high glass transition temperature can be obtained.
- No particular limitation is imposed on the polymerization process it can be polymerized by reaction of for example in toluene in which the HCl / ZnCl 2 is a general polymerization method and a polymerization initiator.
- Example 1 In a pressure resistant reaction vessel made of SUS having a capacity of 300 ml equipped with a stirrer, pressure gauge, thermometer, gas introduction pipe and gas purge line, 70.07 g of dimethyl sulfoxide and 8.00 g of 2,2-norbornane dimethanol prepared in Preparation Example 1 were prepared. (0.044 mol) and 1.52 g (0.031 mol) of potassium hydroxide having a purity of 95.0% were charged, nitrogen gas was allowed to flow for about 60 minutes with stirring, and the inside of the container was replaced with nitrogen. Next, the reaction vessel was sealed, and acetylene gas was injected into the vessel at a pressure of 0.18 MPa.
- FIG. 1 shows a 1 H-NMR chart of the obtained 2,2-bis [(ethenyloxy) methyl] bicyclo [2.2.1] heptane
- FIG. 2 shows a 13 C-NMR chart.
- Example 1 HCl / ZnCl 2 was used as the polymerization initiator and Lewis acid.
- a Schlenk tube 4.0 mL of a 9% by weight toluene solution of 2,2-bis [(ethenyloxy) methyl] bicyclo [2.2.1] heptane obtained in Example 1, 0.5 mL of a 0.18% HCl solution, Polymerization was initiated by injecting 0.5 mL of ZnCl 2 solution in this order with a syringe.
- the produced polymer was recovered by transferring the solution in which polymerization was stopped to a separatory funnel, diluting with methylene chloride, washing with ion-exchanged water three times, removing the solvent from the organic layer with an evaporator, and drying under reduced pressure.
- the polymer was further purified by decantation with methanol.
- the number average molecular weight (Mn) of the obtained polymer was 13,200
- the molecular weight distribution (Mw / Mn) was 1.45
- the glass transition temperature (Tg) was 165 ° C.
- the thermal decomposition temperature (Td) was 337 ° C. It was.
- the measurement was performed using a differential scanning calorimeter (RIGAKU Thermo Plus DSC8230L) (the same applies hereinafter).
- the divinyl ether homopolymer obtained in Use Example 1 When the divinyl ether homopolymer obtained in Use Example 1 is used as a raw material for coating, it has low odor, low volatility, low skin irritation and low toxicity, and also has a high glass transition temperature, so it has high hardness and drying properties. And the coating film excellent in stain resistance was obtained. Further, when this was used as a raw material for photoresist, a resist having good strength was obtained because of low odor, low volatility, low skin irritation and low toxicity and high glass transition temperature.
- Example 2 To a 300 ml SUS pressure-resistant reaction vessel equipped with a stirrer, pressure gauge, thermometer, gas introduction pipe and gas purge line, 70.07 g of dimethyl sulfoxide, 5-norbornene-2,2-dimethanol (Tokyo Chemical Industry Co., Ltd.) )) 7.00 g (0.038 mol) and 1.30 g (0.027 mol) of potassium hydroxide having a purity of 95.0% were charged, and nitrogen gas was allowed to flow for about 60 minutes with stirring. Replaced. Next, the reaction vessel was sealed, and acetylene gas was injected into the vessel at a pressure of 0.18 MPa.
- FIG. 3 shows a 1 H-NMR chart of the obtained 5,5-bis [(ethenyloxy) methyl] bicyclo [2.2.1] hept-2-ene
- FIG. 4 shows a 13 C-NMR chart. It was.
- Example 2 As the polymerization initiator and Lewis acid, HCl / ZnCl 2 was used. To a Schlenk tube, 4.0 mL of a 9% by mass toluene solution of 5,5-bis [(ethenyloxy) methyl] bicyclo [2.2.1] hept-2-ene obtained in Example 2, 0.18% HCl solution Polymerization was initiated by injecting 0.5 mL of ZnCl 2 solution in this order with a syringe.
- the produced polymer was recovered by transferring the solution in which polymerization was stopped to a separatory funnel, diluting with methylene chloride, washing with ion-exchanged water three times, removing the solvent from the organic layer with an evaporator, and drying under reduced pressure.
- the polymer was further purified by decantation with methanol.
- the number average molecular weight (Mn) of the obtained polymer was 12,900, the molecular weight distribution (Mw / Mn) was 1.92, the glass transition temperature (Tg) was 162 ° C., and the thermal decomposition temperature (Td) was 271 ° C. It was.
- the divinyl ether homopolymer obtained in Use Example 2 When the divinyl ether homopolymer obtained in Use Example 2 is used as a raw material for coating, it has low odor, low volatility, low skin irritation and low toxicity, and also has a high glass transition temperature, so it has high hardness and drying properties. And the coating film excellent in stain resistance was obtained. Further, when this was used as a raw material for photoresist, a resist having good strength was obtained because of its low odor, low volatility, low skin irritation and low toxicity and high glass transition temperature.
- the novel divinyl ether of formula (I) according to the present invention can be polymerized into a divinyl ether homopolymer to give a polymer having excellent performance such as a high glass transition temperature.
- a polymer having excellent performance such as a high glass transition temperature.
- ink raw materials represented by inks and paints, as well as resists, color filters, adhesives, platemaking materials, sealants, and image formation It is useful as a raw material for electronic materials represented by
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Abstract
Description
特許文献2には1,3−アダマンタンジメタノールジビニルエーテルが記載されているが、この化合物は本発明に係るジビニルエーテル化合物とは環化重合のしやすさの点で相違するものである。
ステンレス鋼(SUS)製の耐圧反応容器等の反応容器中に、溶媒として、非プロトン性極性溶媒、例えばジメチルスルホキシド、N−メチルピロリドン、N,N’−ジメチルエチレン尿素、N,N’−ジメチルプロピレン尿素、N,N’−ジエチルエチレン尿素、N,N’−ジイソプロピルエチレン尿素、N,N,N’,N’,N’’,N’’−ヘキサメチルリン酸トリアミド、1,3,4−トリメチル−2−イミダゾリジノン、ジエチレングリコールジメチルエーテル、トリエチレングリコールジメチルエーテル、テトラエチレングリコールジメチルエーテル、ポリエチレングリコールジメチルエーテル等から選択される少なくとも1種の非プロトン性溶媒を入れ、次に原料化合物である2,2−ノルボルナンジメタノール又は5−ノルボルネン−2,2−ジメタノールを供給し、反応触媒として、例えば水酸化カリウム、水酸化ナトリウム等のアルカリ金属水酸化物等のアルカリ性化合物を添加する。この際、非プロトン性極性溶媒の使用量には特に制限はないが、非プロトン性極性溶媒の使用量は、2,2−ノルボルナンジメタノール又は5−ノルボルネン−2,2−ジメタノール100質量部に対して、好ましくは100~1,000質量部、更に好ましくは200~700質量部である。非プロトン性極性溶媒の使用量が、2,2−ノルボルナンジメタノール又は5−ノルボルネン−2,2−ジメタノール100質量部に対して、100質量部未満の場合、反応の選択性が低下するおそれがあるので好ましくない。一方、非プロトン性極性溶媒の使用量が、2,2−ノルボルナンジメタノール又は5−ノルボルネン−2,2−ジメタノール100質量部に対して、1000質量部を超えた場合、反応終了後の溶媒除去が煩雑になるおそれがあるので好ましくない。また、反応触媒であるアルカリ性化合物の使用量にも、特に制限はないが、アルカリ性化合物の使用量は、2,2−ノルボルナンジメタノール又は5−ノルボルネン−2,2−ジメタノール100質量部に対して、好ましくは少なくとも2質量部であり、更に好ましくは4~50質量部である。
2,2−ノルボルナンジメタノールの調製
5−ノルボルネン−2,2−ジメタノール(東京化成工業(株)より市販)138.18gをエタノール481.63gに溶解し、5%Pd−C 6.92gを加え、水素風船を付け6時間撹拌した。Pd−Cを濾別後、反応溶液を濃縮し、乾燥することにより2,2−ノルボルナンジメタノール129.83gを得た(ガスグロマトグラフィーによる純度99.1%、収率92.9%)。
攪拌器、圧力ゲージ、温度計、ガス導入管及びガスパージラインを備えた容量300mlのSUS製耐圧反応容器に、ジメチルスルホキシド70.07g、調製例1で調製した2,2−ノルボルナンジメタノール8.00g(0.044mol)及び純度95.0%の水酸化カリウム1.52g(0.031mol)を仕込み、攪拌下に約60分間窒素ガスを流し、容器内を窒素にて置換した。次いで、反応容器を密封し、容器内にアセチレンガスを0.18MPaの圧力で圧入した。次いで、ゲージ圧力を0.18MPaに保ちながら徐々に昇温し、反応容器内温が90℃を越えないように制御し、約2時間反応させた。この間、逐次アセチレンガスを補充して反応容器内の圧力を常に0.18MPaに保った。反応終了後、残留するアセチレンガスをパージして、反応液95.90gを得た。この反応液のガスクロ分析の結果、2,2−ノルボルナンジメタノールの転化は定量的に進行し、所望の2,2−ビス[(エテニロキシ)メチル]ビシクロ[2.2.1]ヘプタンの選択率は99.2%であった。
重合開始剤及びルイス酸としては、HCl/ZnCl2を用いた。シュレンク管に、実施例1で得た2,2−ビス[(エテニロキシ)メチル]ビシクロ[2.2.1]ヘプタンの9質量%トルエン溶液4.0mL、0.18%HCl溶液0.5mL、ZnCl2溶液0.5mLを、この順に注射器で注入して、重合を開始した。トルエン中、−30℃、モノマー濃度0.30mol/L(ガスクロマトグラフィーの内部標準としてテトラリンを含有)、HCl濃度5.0mmol/L、ZnCl2濃度2.0mmol/Lで行った。重合は、180分で重合率100%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加えて、重合を停止させた。
また、これをフォトレジスト用原料に用いたところ、低臭気、低揮発性、低皮膚刺激性及び低毒性であり、さらにガラス転移温度が高いため、良好な強度を有するレジストが得られた。
攪拌器、圧力ゲージ、温度計、ガス導入管及びガスパージラインを備えた容量300mlのSUS製耐圧反応容器に、ジメチルスルホキシド70.07g、5−ノルボルネン−2,2−ジメタノール(東京化成工業(株)より市販)7.00g(0.038mol)及び純度95.0%の水酸化カリウム1.30g(0.027mol)を仕込み、攪拌下に約60分間窒素ガスを流し、容器内を窒素にて置換した。次いで、反応容器を密封し、容器内にアセチレンガスを0.18MPaの圧力で圧入した。次いで、ゲージ圧力を0.18MPaに保ちながら徐々に昇温し、反応容器内温が90℃を越えないように制御し、約2時間30分反応させた。この間、逐次アセチレンガスを補充して反応容器内の圧力を常に0.18MPaに保った。反応終了後、残留するアセチレンガスをパージして、反応液81.99gを得た。この反応液のガスクロ分析の結果、5−ノルボルネン−2,2−ジメタノールの転化は定量的に進行し、所望の5,5−ビス[(エテニロキシ)メチル]ビシクロ[2.2.1]ヘプト−2−エンの選択率は99.9%であった。
重合開始剤及びルイス酸は、HCl/ZnCl2を用いた。シュレンク管に、実施例2で得た5,5−ビス[(エテニロキシ)メチル]ビシクロ[2.2.1]ヘプト−2−エンの9質量%トルエン溶液4.0mL、0.18%HCl溶液0.5mL、ZnCl2溶液0.5mLを、この順に注射器で注入して、重合を開始した。トルエン中、−30℃、モノマー濃度0.30mol/L(ガスクロマトグラフィーの内部標準としてテトラリンを含有)、HCl濃度5.0mmol/L、ZnCl2濃度2.0mmol/Lで行った。重合は、60分で重合率91%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加えて、重合を停止した。
また、これをフォトレジスト用原料)に用いたところ、低臭気、低揮発性、低皮膚刺激性及び低毒性であり、さらにガラス転移温度が高いため、良好な強度を有するレジストが得られた。
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WO2012147511A1 (ja) * | 2011-04-28 | 2012-11-01 | 日本カーバイド工業株式会社 | 4,4-ビス[(エテニロキシ)メチル]シクロヘキセンおよびその製造方法 |
JP2012233062A (ja) * | 2011-04-28 | 2012-11-29 | Univ Of Fukui | ジビニルエーテルホモポリマー、その製造方法およびその用途 |
JPWO2013157388A1 (ja) * | 2012-04-18 | 2015-12-21 | 日本カーバイド工業株式会社 | 2−エテニルオキシメチル−2−ヒドロキシメチルアダマンタン及び2,2−ビス(エテニルオキシメチル)アダマンタン並びにその製造方法 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001278829A (ja) * | 2000-03-31 | 2001-10-10 | Showa Denko Kk | 新規な不飽和エーテル化合物、該化合物の製造方法、該化合物を含む組成物及びその硬化物 |
JP2005029608A (ja) | 2003-07-08 | 2005-02-03 | Idemitsu Kosan Co Ltd | ポリチオカーボネート樹脂、その製造方法、それを用いた光学材料及び眼鏡用レンズ |
JP2009242484A (ja) | 2008-03-28 | 2009-10-22 | Nippon Carbide Ind Co Inc | ジビニルエーテル誘導体ポリマー並びにその製造方法及び用途 |
JP2010053087A (ja) | 2008-08-29 | 2010-03-11 | Nippon Carbide Ind Co Inc | 1,3−アダマンタンジメタノールモノビニルエーテル及び1,3−アダマンタンジメタノールジビニルエーテル並びにその製法 |
WO2010035903A1 (ja) * | 2008-09-29 | 2010-04-01 | 日本カーバイド工業株式会社 | ビニルオキシ基含有ビニル重合体 |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE69803117T2 (de) * | 1997-05-12 | 2002-10-02 | Fuji Photo Film Co Ltd | Positiv arbeitende Resistzusammensetzung |
JP3731777B2 (ja) * | 1997-05-12 | 2006-01-05 | 富士写真フイルム株式会社 | ポジ型レジスト組成物 |
JP3856270B2 (ja) * | 1998-09-24 | 2006-12-13 | 富士フイルムホールディングス株式会社 | ポジ型レジスト組成物 |
JP5835723B2 (ja) * | 2011-04-28 | 2015-12-24 | 国立大学法人福井大学 | ジビニルエーテルホモポリマー、その製造方法およびその用途 |
-
2011
- 2011-10-06 JP JP2012537787A patent/JP5868326B2/ja active Active
- 2011-10-06 US US13/824,072 patent/US9133090B2/en active Active
- 2011-10-06 WO PCT/JP2011/073597 patent/WO2012046880A1/ja active Application Filing
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Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001278829A (ja) * | 2000-03-31 | 2001-10-10 | Showa Denko Kk | 新規な不飽和エーテル化合物、該化合物の製造方法、該化合物を含む組成物及びその硬化物 |
JP2005029608A (ja) | 2003-07-08 | 2005-02-03 | Idemitsu Kosan Co Ltd | ポリチオカーボネート樹脂、その製造方法、それを用いた光学材料及び眼鏡用レンズ |
JP2009242484A (ja) | 2008-03-28 | 2009-10-22 | Nippon Carbide Ind Co Inc | ジビニルエーテル誘導体ポリマー並びにその製造方法及び用途 |
JP2010053087A (ja) | 2008-08-29 | 2010-03-11 | Nippon Carbide Ind Co Inc | 1,3−アダマンタンジメタノールモノビニルエーテル及び1,3−アダマンタンジメタノールジビニルエーテル並びにその製法 |
WO2010035903A1 (ja) * | 2008-09-29 | 2010-04-01 | 日本カーバイド工業株式会社 | ビニルオキシ基含有ビニル重合体 |
Non-Patent Citations (1)
Title |
---|
See also references of EP2626342A4 |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2012147511A1 (ja) * | 2011-04-28 | 2012-11-01 | 日本カーバイド工業株式会社 | 4,4-ビス[(エテニロキシ)メチル]シクロヘキセンおよびその製造方法 |
JP2012233062A (ja) * | 2011-04-28 | 2012-11-29 | Univ Of Fukui | ジビニルエーテルホモポリマー、その製造方法およびその用途 |
US9156762B2 (en) | 2011-04-28 | 2015-10-13 | Nippon Carbide Industries Co., Inc. | 4,4-bis[(ethenyloxy)methyl]cyclohexene and method for producing same |
JP5893008B2 (ja) * | 2011-04-28 | 2016-03-23 | 日本カーバイド工業株式会社 | 4,4−ビス[(エテニロキシ)メチル]シクロヘキセンおよびその製造方法 |
JPWO2013157388A1 (ja) * | 2012-04-18 | 2015-12-21 | 日本カーバイド工業株式会社 | 2−エテニルオキシメチル−2−ヒドロキシメチルアダマンタン及び2,2−ビス(エテニルオキシメチル)アダマンタン並びにその製造方法 |
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US9133090B2 (en) | 2015-09-15 |
EP2626342A4 (en) | 2015-08-26 |
US20130178658A1 (en) | 2013-07-11 |
EP2626342B1 (en) | 2016-08-03 |
EP2626342A1 (en) | 2013-08-14 |
JP5868326B2 (ja) | 2016-02-24 |
JPWO2012046880A1 (ja) | 2014-02-24 |
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