JP5066938B2 - Process for producing tricyclo [5.2.1.02,6] dec-3-en-8 (or 9) ol - Google Patents
Process for producing tricyclo [5.2.1.02,6] dec-3-en-8 (or 9) ol Download PDFInfo
- Publication number
- JP5066938B2 JP5066938B2 JP2007045780A JP2007045780A JP5066938B2 JP 5066938 B2 JP5066938 B2 JP 5066938B2 JP 2007045780 A JP2007045780 A JP 2007045780A JP 2007045780 A JP2007045780 A JP 2007045780A JP 5066938 B2 JP5066938 B2 JP 5066938B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- dec
- acid catalyst
- tricyclo
- solid acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000000034 method Methods 0.000 title claims description 11
- 239000003054 catalyst Substances 0.000 claims description 28
- 239000011973 solid acid Substances 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 11
- 238000006703 hydration reaction Methods 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 230000036571 hydration Effects 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 30
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 description 17
- 238000004817 gas chromatography Methods 0.000 description 10
- 239000012295 chemical reaction liquid Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 5
- 239000003456 ion exchange resin Substances 0.000 description 5
- 229920003303 ion-exchange polymer Polymers 0.000 description 5
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 229920000307 polymer substrate Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- -1 alicyclic alcohols Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- ALRSUOBUWMQKPO-UHFFFAOYSA-N dec-7-en-2-ol Chemical compound CCC=CCCCCC(C)O ALRSUOBUWMQKPO-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
本発明は、トリシクロ〔５．２．１．０２，６〕デカ−３−エン−８（又は９）オールの製造方法に関する。 The present invention relates to a method for producing tricyclo [5.2.1.0 2,6 ] dec-3-en-8 (or 9) ol.
紫外線硬化型、あるいは電子線硬化型樹脂には、硬化性成分として種々の（メタ）アクリル酸エステルが使用されている。例えば、ポリエチレングリコ−ルジ（メタ）アクリレ−ト、ポリプロピレングリコ−ルジ（メタ）アクリレ−ト、ポリオキシエチルトリメチロ−ルプロパントリ（メタ）アクリレ−ト、ポリオキシエチレン化ビスフェノ−ルＡジ（メタ）アクリレ−ト、シクロヘキシルアルコ−ルの（メタ）アクリル酸エステル、トリシクロ〔５．２．１．０２，６〕デカ−３−エン−８（又は９）オール等の（メタ）アクリル酸エステルなどの様々な（メタ）アクリル酸エステルが使用されている。これら（メタ）アクリル酸エステルのなかでも、脂環式アルコ−ル特にトリシクロ〔５．２．１．０２，６〕デカ−３−エン−８（又は９）オールの（メタ）アクリル酸エステルは、その構造より耐熱性や密着性等の向上が特に期待出来る化合物である。 Various (meth) acrylic acid esters are used as a curable component in ultraviolet curable or electron beam curable resins. For example, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polyoxyethyltrimethylolpropane tri (meth) acrylate, polyoxyethylenated bisphenol A di (meth) (Meth) acrylic acid ester of acrylate, cyclohexyl alcohol, (meth) acrylic acid ester such as tricyclo [5.2.1.0 2,6 ] dec-3-en-8 (or 9) ol, etc. Various (meth) acrylic acid esters are used. Among these (meth) acrylic acid esters, alicyclic alcohols, especially tricyclo [5.2.1.0 2,6 ] dec-3-en-8 (or 9) ol (meth) acrylic acid esters. Is a compound that can be particularly expected to improve heat resistance, adhesion and the like due to its structure.
トリシクロ〔５．２．１．０２，６〕デカ−３−エン−８（又は９）オールを製造する方法としては、従来より知られている液相でオレフィンを水和してアルコ−ルを製造する方法、即ち鉱酸、芳香族スルホン酸、ヘテロポリ酸等の均一系の酸触媒を使用する方法、あるいは強酸性イオン交換樹脂、結晶性アミノシリケ−ト等のゼオライト類等の固体酸触媒を使用する方法が適用出来る（例えば、特公昭４７−４５３２３号公報、特公昭５３−１５４８５号公報、特開昭５７−７０８２８号公報、特開昭５８−１２４７２８号公報、特開昭５８−１９４８２８号公報、特開昭６０−１０４０２８号公報、特開昭６１−１８０７３５号公報、特公昭６３−４７６９５号公報、特開平７−１６５６４６号公報、特開平１０−２７３４５７号公報、特開２００６−２３２７４９号公報等）。これら方法の内、液相反応系は粗生成物から酸触媒を除くために中和水洗工程が必要であること、廃水が発生すること、シクロペンタジエンのポリマ−等の副生成物が多量生成し目的物の収率が低下すること等の問題点があった。これら問題点を解決する方法として、固体酸触媒を使用する方法が提案されているが、固体酸触媒重量／水重量の比率が３未満と少なく、この条件でジシクロペンタジエンを水和反応させると反応の進行が遅く工業的にトリシクロ〔５．２．１．０２，６〕デカ−３−エン−８（又は９）オールを製造するには不適当であった。
本発明の目的は、固体酸触媒を使用してトリシクロ〔５．２．１．０２，６〕デカ−３−エン−８（又は９）オールを効率よく合成できる方法を提供することである。 An object of the present invention is to provide a method capable of efficiently synthesizing tricyclo [5.2.1.0 2,6 ] dec-3-en-8 (or 9) ol using a solid acid catalyst. .
本発明は、（１）ジシクロペンタジエンを固体酸触媒の存在下に水和反応させてトリシクロ〔５．２．１．０２，６〕デカ−３−エン−８（又は９）オールを製造する方法において、固体酸触媒を水に対して３．０〜１０重量用い、５０〜１５０℃で水和反応させることを特徴とする、トリシクロ〔５．２．１．０２，６〕デカ−３−エン−８（又は９）オールの製造方法に関する。 In the present invention, (1) dicyclopentadiene is hydrated in the presence of a solid acid catalyst to produce tricyclo [5.2.1.0 2,6 ] dec-3-ene-8 (or 9) ol. In this method, a tricyclo [5.2.1.0 2,6 ] deca-character is characterized in that the solid acid catalyst is used in an amount of 3.0 to 10 wt. The present invention relates to a method for producing 3-ene-8 (or 9) ol.
また、本発明は、（２）８０〜１１０℃で水和反応させることを特徴とするトリシクロ〔５．２．１．０２，６〕デカ−３−エン−８（又は９）オールの前記（１）記載の方法に関する。 The present invention also relates to (2) the above-mentioned tricyclo [5.2.1.0 2,6 ] dec-3-en-8 (or 9) ol, characterized in that the hydration reaction is carried out at 80 to 110 ° C. (1) The method described above.
本発明の製造によれば、固体酸触媒を使用してトリシクロ〔５．２．１．０２，６〕デカ−３−エン−８（又は９）オールを効率よく製造することができる。 According to the production of the present invention, tricyclo [5.2.1.0 2,6 ] dec-3-en-8 (or 9) ol can be efficiently produced using a solid acid catalyst.
本発明の製造方法は、ジシクロペンタジエンを固体酸触媒の存在下に水和反応させてトリシクロ〔５．２．１．０２，６〕デカ−３−エン−８（又は９）オールを製造する方法において、固体酸触媒を水に対して３．０〜１０倍重量用い、５０〜１５０℃で水和反応させることを特徴とする。 In the production method of the present invention, dicyclopentadiene is hydrated in the presence of a solid acid catalyst to produce tricyclo [5.2.1.0 2,6 ] dec-3-ene-8 (or 9) ol. In this method, the solid acid catalyst is used in a weight of 3.0 to 10 times with respect to water and hydrated at 50 to 150 ° C.
本発明において、トリシクロ〔５．２．１．０２，６〕デカ−３−エン−８（又は９）オールは、トリシクロ〔５．２．１．０２，６〕デカ−３−エン−８−オールとトリシクロ〔５．２．１．０２，６〕デカ−３−エン−９−オールの混合物を示す。
本発明では水和反応を行う際の水に対する固体酸触媒の使用量が重要であり、固体酸触媒を水に対して３．０〜１０倍重量、好ましくは４．０〜１０．０倍重量用いる。水に対する固体酸触媒の使用量が３．０倍重量未満である場合は、水分で固体酸触媒の表面が覆われてしまいジシクロペンタジエンの水和反応が著しく遅くなってしまう。一方、水に対する固体酸触媒の使用量が１０倍重量を超える場合は、副生成物であるトリシクロペンタジエン（以下、ＴＣＰＤと記す。）やビスジシクロペンタジエニルエ−テル（以下、ＤＯＤと記す。）が生成し、目的物である２−（トリシクロ〔５．２．１．０２，６〕デカ−３−エン−８（又は９）オールの収率が低下してしまう。
In the present invention, tricyclo [5.2.1.0 2,6 ] dec-3-ene-8 (or 9) ol is tricyclo [5.2.1.0 2,6 ] dec-3-ene- A mixture of 8-ol and tricyclo [5.2.1.0 2,6 ] dec-3-en-9-ol is shown.
In the present invention, the amount of the solid acid catalyst used for water during the hydration reaction is important, and the solid acid catalyst is 3.0 to 10 times by weight, preferably 4.0 to 10.0 times by weight with respect to water. Use. When the amount of the solid acid catalyst used relative to water is less than 3.0 times the weight, the surface of the solid acid catalyst is covered with moisture, and the hydration reaction of dicyclopentadiene is remarkably slowed. On the other hand, when the amount of the solid acid catalyst used with respect to water exceeds 10 times the weight, by-products such as tricyclopentadiene (hereinafter referred to as TCPD) and bisdicyclopentadienyl ether (hereinafter referred to as DOD). The yield of 2- (tricyclo [5.2.1.0 2,6 ] dec-3-en-8 (or 9) ol, which is the target product, is reduced.
水和に使用される固体酸触媒は酸性の固体物質であり、酸性イオン交換樹脂、ゼオライト、二酸化チタン、酸化アルミニウム、二酸化ケイ素等の無機酸化物あるいはこれらの複合酸化物、さらにスクメタイト、カオリタイト等の層状化合物をアルミニウム、ケイ素、チタン、ジルコニウムの中から選ばれる１種以上の金属酸化物で処理したイオン交換型層状化合物などが例示されるが、本発明における固体酸触媒としては酸性イオン交換樹脂が好ましい。酸性イオン交換樹脂の例として、イオン交換体としてスルホン基またはカルボン酸基を有し、高分子基体としてフェノ−ルとホルムアルデヒドを重縮合して得られる高分子基体や、スチレンまたはハロゲン化スチレンとジビニルベンゼンとの共重合体を高分子基体として有するものがあげられる。これらの中でも、スルホン基を有する強酸性イオン交換樹脂が入手性、取り扱い性等の面で特に好ましい。 The solid acid catalyst used for hydration is an acidic solid substance, such as an acidic ion exchange resin, an inorganic oxide such as zeolite, titanium dioxide, aluminum oxide, and silicon dioxide, or a composite oxide thereof, and also scumite, kaolitite, etc. Examples of the solid acid catalyst in the present invention include an ion exchange layered compound obtained by treating the layered compound of 1 with one or more metal oxides selected from aluminum, silicon, titanium, and zirconium. Is preferred. Examples of acidic ion exchange resins include polymer substrates obtained by polycondensation of phenol and formaldehyde, styrene or halogenated styrene and divinyl. Examples include those having a copolymer with benzene as a polymer substrate. Among these, a strongly acidic ion exchange resin having a sulfone group is particularly preferable in terms of availability, handleability, and the like.
酸性イオン交換樹脂の好ましい具体例としては、オルガノ(株)製のアンバ−リスト１５ＤＲＹ、アンバ−リスト１６ＤＲＹ、アンバ−リスト３１ＤＲＹ（商品名）、三菱化学（株）製のダイヤイオンＰＫ２０８ＬＨ，ＰＫ２１６ＬＨ，ＰＫ２２８ＬＨ（商品名）等が挙げられる。 Preferable specific examples of the acidic ion exchange resin include Amber List 15DRY, Amber List 16DRY, Amber List 31DRY (trade name) manufactured by Organo Corporation, Diaion PK208LH, PK216LH, PK228LH manufactured by Mitsubishi Chemical Corporation. (Brand name) etc. are mentioned.
固定酸触媒としては水を殆ど含有しないもの（ドライタイプ）であっても、水を含有するもの（ウエットタイプ）であってもよいが、本明細書において固体酸触媒の重量とは、固体酸触媒の水以外の固形分の重量を意味する。
固体酸触媒の形状は特に限定されず、粉末状でも、粒状物でもよい。粒状物の外観形状としては、球状、円盤状、円柱状、円筒状などが例示される。
本発明における反応温度は５０〜１５０℃であり、好ましくは８０〜１１０℃である。反応温度が５０℃未満では反応速度が遅く、効率よくトリシクロ〔５．２．１．０２，６〕デカ−３−エン−８（又は９）オールを製造することができない。一方、反応温度が１５０℃を超える場合は、副生成物であるトリシクロペンタジエン（ＴＣＰＤ）やビスジシクロペンタジエニルエ−テル（ＤＯＤ）が生成し、２−（トリシクロ〔５．２．１．０２，６〕デカ−３−エン−８（又は９）オールの収率が低下してしまう。
The fixed acid catalyst may be one that contains almost no water (dry type) or one that contains water (wet type). In this specification, the weight of the solid acid catalyst refers to the solid acid catalyst. It means the weight of solids other than water in the catalyst.
The shape of the solid acid catalyst is not particularly limited, and may be powdery or granular. Examples of the external shape of the granular material include a spherical shape, a disk shape, a columnar shape, and a cylindrical shape.
The reaction temperature in this invention is 50-150 degreeC, Preferably it is 80-110 degreeC. If the reaction temperature is less than 50 ° C., the reaction rate is low, and tricyclo [5.2.1.0 2,6 ] dec-3-en-8 (or 9) ol cannot be produced efficiently. On the other hand, when the reaction temperature exceeds 150 ° C., by-products such as tricyclopentadiene (TCPD) and bisdicyclopentadienyl ether (DOD) are produced and 2- (tricyclo [5.2.1]. 0.0 2,6 ] dec-3-en-8 (or 9) ol yield is reduced.
ジシクロペンタジエンの水和反応は、連続式、非連続式(バッチ式)どちらの形態も適用することが出来る。連続式の場合は、ジシクロペンタジエンと水の混合物、例えばジシクロペンタジエン中に水を連続的に混合した液を、固体酸触媒に連続的に供給して水和反応を行う。連続式の場合、本発明における水に対する固体酸触媒の使用量は、水に接する時の固体酸触媒の量を指す。
本発明における反応圧力は特に限定されるものではないが、原料のジシクロペンタジエンが常温で固体となるため、反応条件下で液状を維持することが出来る圧力であることが好ましい。
For the hydration reaction of dicyclopentadiene, both continuous and discontinuous (batch) forms can be applied. In the case of a continuous type, a mixture of dicyclopentadiene and water, for example, a liquid obtained by continuously mixing water in dicyclopentadiene is continuously supplied to a solid acid catalyst to carry out a hydration reaction. In the case of the continuous type, the amount of the solid acid catalyst used in the water in the present invention refers to the amount of the solid acid catalyst when in contact with water.
Although the reaction pressure in this invention is not specifically limited, Since the raw material dicyclopentadiene becomes solid at normal temperature, it is preferable that it is a pressure which can maintain a liquid state on reaction conditions.
反応後、反応生成物をろ過、抽出、蒸留などの通常の操作を行うことにより、２−（トリシクロ〔５．２．１．０２，６〕デカ−３−エン−８（又は９）オールを得ることができる。 After the reaction, the reaction product is subjected to usual operations such as filtration, extraction, and distillation to give 2- (tricyclo [5.2.1.0 2,6 ] dec-3-en-8 (or 9) ol. Can be obtained.
以下、実施例を挙げて説明するが、本発明はこれらに限定されるものではない。 Hereinafter, although an example is given and explained, the present invention is not limited to these.
実施例１
攪拌機、温度計及び水滴下用ロ−トを備えているフラスコに、ジシクロペンタジエン １１３．５ｇ（０．８６ｍｏｌ）、アンバ−リスト１５ＤＲＹ ３４．１ｇ（オルガノ製）を仕込み、オイルバスにより加温を開始した。また、水滴下用ロ−トにを準備した。フラスコ内の液温が１００℃となったところで、オイルバスの高さ調整により液温を１００±５℃に保つようにした。そこに固体酸触媒重量／水重量の比が４．０〜５．０となるように反応系の組成を常に分析しながら、水滴下用ロ−トより水を滴下した。滴下完了後も液温を１００±５℃に保つようにし反応を行った。圧力は常圧で行った。反応開始から５時間経過時に、フラスコ内の反応液をガスクロマトグラフィ−により分析した結果、ジシクロペンタジエン（以下、ＤＣＰＤと記す。）／２−（トリシクロ〔５．２．１．０２，６〕デカ−３−エン−８（又は９）オール（以下、ＣＤＣと記す。）／トリシクロペンタジエン（以下、ＴＣＰＤと記す。）／ビスジシクロペンタジエニルエ−テル（以下、ＤＯＤと記す。）のそれぞれの面積百分率での比率は１．１／９１．６／０．２／７．１であった。原料のＤＣＰＤがほぼ消失し、目的物のＣＤＣが高選択的に生成していた。
Example 1
A flask equipped with a stirrer, a thermometer and a water dropping funnel is charged with 113.5 g (0.86 mol) of dicyclopentadiene and 34.1 g of Amberlist 15DRY (manufactured by Organo), and heated with an oil bath. Started. In addition, a water dropping funnel was prepared. When the liquid temperature in the flask reached 100 ° C., the liquid temperature was kept at 100 ± 5 ° C. by adjusting the height of the oil bath. While constantly analyzing the composition of the reaction system so that the ratio of solid acid catalyst weight / water weight was 4.0 to 5.0, water was dropped from a water dropping funnel. After completion of the dropwise addition, the reaction was carried out while maintaining the liquid temperature at 100 ± 5 ° C. The pressure was normal pressure. As a result of analyzing the reaction solution in the flask by gas chromatography after 5 hours from the start of the reaction, dicyclopentadiene (hereinafter referred to as DCPD) / 2- (tricyclo [5.2.1.0 2,6 ]. Dec-3-ene-8 (or 9) ol (hereinafter referred to as CDC) / tricyclopentadiene (hereinafter referred to as TCPD) / bisdicyclopentadienyl ether (hereinafter referred to as DOD) The ratio of each area percentage was 1.1 / 91.6 / 0.2 / 7.1, and the raw material DCPD almost disappeared and the target CDC was produced with high selectivity.
実施例２
フラスコ内の液温を７０±５℃に保つようにすること以外は、実施例１と同様に操作を行った。反応開始から５時間経過時、フラスコ内の反応液をガスクロマトグラフィ−により分析した結果、ＤＣＰＤ／ＣＤＣ／ＴＣＰＤ／ＤＯＤのそれぞれの面積百分率での比率は３０．２／６５．６／０．１／４．２であった。引き続き反応を行い、反応１０時間経過時に、再度フラスコ内の反応液をガスクロマトグラフィ−により分析した結果、ＤＣＰＤ／ＣＤＣ／ＴＣＰＤ／ＤＯＤのそれぞれの面積百分率での比率は１．２／９３．６／０．２／５．０であった。原料のＤＣＰＤがほぼ消失し、目的物のＣＤＣが高選択的に生成していた。
Example 2
The same operation as in Example 1 was performed except that the liquid temperature in the flask was maintained at 70 ± 5 ° C. When the reaction liquid in the flask was analyzed by gas chromatography after 5 hours from the start of the reaction, the ratio of each area percentage of DCPD / CDC / TCPD / DOD was 30.2 / 65.6 / 0.1 / 4.2. The reaction was continued, and the reaction liquid in the flask was analyzed again by gas chromatography after 10 hours of reaction. As a result, the ratio of each area percentage of DCPD / CDC / TCPD / DOD was 1.2 / 93.6 / It was 0.2 / 5.0. The raw material DCPD almost disappeared, and the target CDC was generated with high selectivity.
実施例３
固体酸触媒重量／水重量の比を９．０〜１０．０とすること以外は実施例１と同様に操作を行った。反応開始から５時間経過時に、フラスコ内の反応液をガスクロマトグラフィ−により分析した結果、ＤＣＰＤ／ＣＤＣ／ＴＣＰＤ／ＤＯＤのそれぞれの面積百分率での比率は１．２／８９．６／０．３／８．９であった。原料のＤＣＰＤがほぼ消失、目的物のＣＤＣが高選択的に生成していた。
Example 3
The operation was performed in the same manner as in Example 1 except that the ratio of the weight of the solid acid catalyst / water was 9.0 to 10.0. As a result of analyzing the reaction liquid in the flask by gas chromatography after 5 hours from the start of the reaction, the ratio of each area percentage of DCPD / CDC / TCPD / DOD was 1.2 / 89.6 / 0.3 / It was 8.9. The raw material DCPD almost disappeared and the target CDC was generated with high selectivity.
比較例１
フラスコ内の液温を４０±５℃に保つようにすること以外は、実施例１と同様に操作を行った。反応開始から５時間経過時に、フラスコ内の反応液をガスクロマトグラフィ−により分析した結果、ＤＣＰＤ／ＣＤＣ／ＴＣＰＤ／ＤＯＤのそれぞれの面積百分率での比率は９５．５／３．１／０．１／１．３であった。引き続き反応を行い、反応開始から１０時間経過時に、再度フラスコ内の反応液をガスクロマトグラフィ−により分析した結果、ＤＣＰＤ／ＣＤＣ／ＴＣＰＤ／ＤＯＤのそれぞれの面積百分率での比率は９３．１／５．０／０．１／１．８であり、原料のＤＣＰＤは大量に残存しており反応が進行していなかった。
比較例２
フラスコ内の液温を１６０±５℃に保つようにすること以外は、実施例１と同様に操作を行った。反応開始から５時間経過時に、フラスコ内の反応液をガスクロマトグラフィ−により分析した結果、ＤＣＰＤ／ＣＤＣ／ＴＣＰＤ／ＤＯＤのそれぞれの面積百分率での比率は１．１／５５．２／４．５／３９．２であった。原料のＤＣＰＤはほぼ消失しており反応は完了していたが、副生成物のＴＣＰＤ及びＤＯＤが多量に生成していた。
Comparative Example 1
The same operation as in Example 1 was carried out except that the liquid temperature in the flask was kept at 40 ± 5 ° C. As a result of analyzing the reaction liquid in the flask by gas chromatography after 5 hours from the start of the reaction, the ratio of each area percentage of DCPD / CDC / TCPD / DOD was 95.5 / 3.1 / 0.1 / 1.3. The reaction was continued, and the reaction liquid in the flask was analyzed again by gas chromatography after 10 hours from the start of the reaction. As a result, the ratio of each area percentage of DCPD / CDC / TCPD / DOD was 93.1 / 5. The raw material DCPD remained in a large amount and the reaction did not proceed.
Comparative Example 2
The same operation as in Example 1 was carried out except that the liquid temperature in the flask was kept at 160 ± 5 ° C. As a result of analyzing the reaction liquid in the flask by gas chromatography after 5 hours from the start of the reaction, the ratio of each area percentage of DCPD / CDC / TCPD / DOD was 1.1 / 55.2 / 4.5 / 39.2. The raw material DCPD almost disappeared and the reaction was completed, but a large amount of by-products TCPD and DOD were produced.
比較例３
固体酸触媒重量／水重量の比を１．０〜２．０とすること以外は実施例１と同様に操作を行った。反応開始から５時間経過時に、フラスコ内の反応液をガスクロマトグラフィ−により分析した結果、ＤＣＰＤ／ＣＤＣ／ＴＣＰＤ／ＤＯＤのそれぞれの面積百分率での比率は９０．２／８．１／０．２／１．５であった。引き続き反応を行い、反応１０時間経過時に、再度フラスコ内の反応液をガスクロマトグラフィ−により分析した結果、ＤＣＰＤ／ＣＤＣ／ＴＣＰＤ／ＤＯＤのそれぞれの面積百分率での比率は８２．４／１５．９／０．２／１．５であり、原料のＤＣＰＤは大量に残存しており反応が進行していなかった。
比較例４
固体酸触媒重量／水重量の比を１１．０〜１２．０とすること以外は実施例１と同様に操作を行った。反応開始から５時間経過時に、フラスコ内の反応液をガスクロマトグラフィ−により分析した結果、ＤＣＰＤ／ＣＤＣ／ＴＣＰＤ／ＤＯＤのそれぞれの面積百分率での比率は０．８／８０．９／３．２／１５．１であった。原料のＤＣＰＤはほぼ消失しており反応は完了していたが、副生成物のＴＣＰＤ及びＤＯＤが多量に生成していた。
Comparative Example 3
The same operation as in Example 1 was performed except that the ratio of the weight of the solid acid catalyst / water was 1.0 to 2.0. As a result of analyzing the reaction liquid in the flask by gas chromatography after 5 hours from the start of the reaction, the ratio of each area percentage of DCPD / CDC / TCPD / DOD was 90.2 / 8.1 / 0.2 / 1.5. The reaction was continued, and when the reaction was continued for 10 hours, the reaction liquid in the flask was analyzed again by gas chromatography. As a result, the ratio of each area percentage of DCPD / CDC / TCPD / DOD was 82.4 / 15.9 /. The raw material DCPD remained in a large amount and the reaction did not proceed.
Comparative Example 4
The operation was performed in the same manner as in Example 1 except that the ratio of the weight of the solid acid catalyst / water was 11.0 to 12.0. As a result of analyzing the reaction solution in the flask by gas chromatography after 5 hours from the start of the reaction, the ratio of each area percentage of DCPD / CDC / TCPD / DOD was 0.8 / 80.9 / 3.2 / 15.1. The raw material DCPD almost disappeared and the reaction was completed, but a large amount of by-products TCPD and DOD were produced.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007045780A JP5066938B2 (en) | 2007-02-26 | 2007-02-26 | Process for producing tricyclo [5.2.1.02,6] dec-3-en-8 (or 9) ol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007045780A JP5066938B2 (en) | 2007-02-26 | 2007-02-26 | Process for producing tricyclo [5.2.1.02,6] dec-3-en-8 (or 9) ol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2008208062A JP2008208062A (en) | 2008-09-11 |
| JP5066938B2 true JP5066938B2 (en) | 2012-11-07 |
Family
ID=39784691
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2007045780A Active JP5066938B2 (en) | 2007-02-26 | 2007-02-26 | Process for producing tricyclo [5.2.1.02,6] dec-3-en-8 (or 9) ol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5066938B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8742879B2 (en) | 2011-06-30 | 2014-06-03 | Samsung Electro-Mechanics Co., Ltd. | Transformer and display device using the same |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5220664B2 (en) * | 2009-03-17 | 2013-06-26 | 富士フイルム株式会社 | Ink composition and inkjet recording method |
| CN102351652B (en) * | 2011-08-05 | 2013-07-03 | 聊城大学 | Method for preparing dihydrodicyclopentadiene through continuous reaction |
| CN109912410B (en) * | 2019-03-28 | 2022-02-15 | 浙江师范大学 | Method for preparing tricyclodecenyl alcohol, reaction intermediate and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3345419A (en) * | 1963-09-25 | 1967-10-03 | Union Carbide Corp | Hydration of bicyclo-(2.2.1) heptenes and related nortricyclenes |
| JPS5659723A (en) * | 1979-10-18 | 1981-05-23 | Hitachi Chem Co Ltd | Preparation of tricyclo 5.2.1.02,6 -3-decen-8- or 9 -ol |
-
2007
- 2007-02-26 JP JP2007045780A patent/JP5066938B2/en active Active
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8742879B2 (en) | 2011-06-30 | 2014-06-03 | Samsung Electro-Mechanics Co., Ltd. | Transformer and display device using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2008208062A (en) | 2008-09-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101157813B1 (en) | Process for preparing tert-butanol from isobutene-containing hydrocarbon mixtures | |
| Hara et al. | Highly efficient C− C bond-forming reactions in aqueous media catalyzed by monomeric vanadate species in an apatite framework | |
| Zielinska-Nadolska et al. | Zeolite and other heterogeneous catalysts for the transesterification reaction of dimethyl carbonate with ethanol | |
| CA2083346A1 (en) | A catalyzed esterification process | |
| JP5066938B2 (en) | Process for producing tricyclo [5.2.1.02,6] dec-3-en-8 (or 9) ol | |
| JP4902988B2 (en) | Method for producing vicinal alkanediol and alkanetriol and use thereof | |
| CN109715596A (en) | The method for producing hydroxyacetic acid | |
| JP5049073B2 (en) | Method for producing alcohol having fluorene skeleton | |
| JP5890849B2 (en) | Method for producing high-purity isobutene using glycol ether | |
| WO2011087600A2 (en) | Process for the conversion of alcohols to olefins | |
| WO2010071011A1 (en) | Method for producing acetic acid ester | |
| JP5608403B2 (en) | Method for producing n-propyl acetate | |
| WO2012114875A1 (en) | Method for producing bicyclomonoterpene (meth)acrylate | |
| JP5662835B2 (en) | Method for producing glycerin mono (meth) acrylate | |
| RU2339609C2 (en) | Combined method of obtaining diphenol a from cumene hydroperoxide | |
| CN112441866A (en) | Method for producing n-butene from isobutene | |
| JP4609642B2 (en) | Method for producing cycloalkyl alkyl ether | |
| RU2339608C2 (en) | Combined method of obtaining diphenol a from cumane hydroperoxide | |
| JP2005082510A (en) | Method for producing cycloalkyl alkyl ether | |
| JPS58194840A (en) | Liquid phase manufacture of delta-ketocarboxylic acid ester with liquid phase-insoluble catalyst | |
| JP2002226433A (en) | Method for producing cyclohexyl (meth)acrylate | |
| JP4586504B2 (en) | Method for producing aromatic ester compound | |
| JP3360759B2 (en) | Olefin catalytic hydration method | |
| JP5056313B2 (en) | Continuous production method of 2-alkyl-2-cycloalkenone | |
| JP2005097274A (en) | Method for producing high purity olefinic compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20100129 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20101217 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20120418 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20120424 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20120717 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20120730 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20150824 Year of fee payment: 3 |
|
| R151 | Written notification of patent or utility model registration |
Ref document number: 5066938 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R151 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20150824 Year of fee payment: 3 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20150824 Year of fee payment: 3 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |