JPS6136740B2 - - Google Patents
Info
- Publication number
- JPS6136740B2 JPS6136740B2 JP15835979A JP15835979A JPS6136740B2 JP S6136740 B2 JPS6136740 B2 JP S6136740B2 JP 15835979 A JP15835979 A JP 15835979A JP 15835979 A JP15835979 A JP 15835979A JP S6136740 B2 JPS6136740 B2 JP S6136740B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- malonic acid
- acid diester
- methylene malonic
- cyclopentadiene
- 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.)
- Expired
Links
- -1 methylene malonic acid diester Chemical class 0.000 claims description 57
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 56
- 238000000034 method Methods 0.000 claims description 35
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 description 44
- 239000002904 solvent Substances 0.000 description 18
- 238000001816 cooling Methods 0.000 description 17
- 239000007795 chemical reaction product Substances 0.000 description 13
- 239000007789 gas Substances 0.000 description 12
- 238000004821 distillation Methods 0.000 description 10
- 239000012535 impurity Substances 0.000 description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 8
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 238000000926 separation method Methods 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000000746 purification Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 238000000197 pyrolysis Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 5
- BQHDXNZNSPVVKB-UHFFFAOYSA-N diethyl 2-methylidenepropanedioate Chemical compound CCOC(=O)C(=C)C(=O)OCC BQHDXNZNSPVVKB-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000010453 quartz Substances 0.000 description 5
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 4
- KTLZQSZGORXBED-UHFFFAOYSA-N dimethyl 2-methylidenepropanedioate Chemical compound COC(=O)C(=C)C(=O)OC KTLZQSZGORXBED-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000005292 vacuum distillation Methods 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- 229930040373 Paraformaldehyde Natural products 0.000 description 2
- 239000007868 Raney catalyst Substances 0.000 description 2
- 229910000564 Raney nickel Inorganic materials 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- FZFAMSAMCHXGEF-UHFFFAOYSA-N chloro formate Chemical compound ClOC=O FZFAMSAMCHXGEF-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229940076286 cupric acetate Drugs 0.000 description 2
- 125000000392 cycloalkenyl group Chemical group 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 150000002148 esters Chemical group 0.000 description 2
- 125000002425 furfuryl group Chemical group C(C1=CC=CO1)* 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920002866 paraformaldehyde Polymers 0.000 description 2
- 238000011403 purification operation Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical compound COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 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 1
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000003678 cyclohexadienyl group Chemical group C1(=CC=CCC1)* 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- HXUSPLIAARMGEV-UHFFFAOYSA-N diethyl bicyclo[2.2.1]hept-2-ene-2,3-dicarboxylate Chemical compound C1CC2C(C(=O)OCC)=C(C(=O)OCC)C1C2 HXUSPLIAARMGEV-UHFFFAOYSA-N 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- ZJAJYXYKRRRCMK-UHFFFAOYSA-N dimethyl 2-(methoxymethyl)propanedioate Chemical compound COCC(C(=O)OC)C(=O)OC ZJAJYXYKRRRCMK-UHFFFAOYSA-N 0.000 description 1
- BEPAFCGSDWSTEL-UHFFFAOYSA-N dimethyl malonate Chemical compound COC(=O)CC(=O)OC BEPAFCGSDWSTEL-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 229940093915 gynecological organic acid Drugs 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 125000004344 phenylpropyl group Chemical group 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000006561 solvent free reaction Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
Description
【発明の詳細な説明】
本発明は主として瞬間接着剤用のメチレンマロ
ン酸ジエステルの精製法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention primarily relates to a method for purifying methylene malonic acid diester for use in instant adhesives.
従来からメチレンマロン酸ジエステルの製法
は、例えば工業化学雑誌第56巻901頁に記載され
たマロン酸ジエステルとホルムアルデヒドから酢
酸溶媒中、銅又は亜鉛で代表される触媒の存在下
に縮合させて得られた反応物から粗製のメチレン
マロン酸ジエステルを減圧蒸留で得る方法、又米
国特許第3221745号明細書に記載されたアルコキ
シメチルマロン酸ジエステルの減圧加熱分解によ
る方法がある。 Conventionally, methylene malonic acid diester is produced by condensing malonic acid diester and formaldehyde in an acetic acid solvent in the presence of a catalyst represented by copper or zinc, as described in, for example, Kogyo Kagaku Zasshi Vol. 56, page 901. There is a method of obtaining crude methylene malonic acid diester from a reactant obtained by vacuum distillation, and a method of vacuum thermal decomposition of alkoxymethyl malonic acid diester described in US Pat. No. 3,221,745.
しかし、これらの方法によつて得られるメチレ
ンマロン酸ジエステルは２枚の基材の瞬間接着剤
として用いると、２枚の基材の間でもろい微粉末
状硬化物となつたり、軟らかい膜面が形成された
りし、十分な接着効果を発揮しない。またメチレ
ンマロン酸ジエステルを長期間密閉保存しておく
と固化するので、重合防止剤が添加しても、あま
り効果はない。これらの原因は不純物の影響と考
えられるが、単に粗メチレンマロン酸ジエステル
を精留しても、精留中に固化するか、近似沸点の
不純物が混入するので望ましくない。 However, when the methylene malonic acid diester obtained by these methods is used as an instant adhesive between two base materials, it becomes a brittle fine powder-like cured product between the two base materials, and the soft film surface becomes The adhesion effect is not sufficient. Furthermore, if methylene malonic acid diester is stored in a sealed container for a long period of time, it will solidify, so even if a polymerization inhibitor is added, it will not be very effective. Although these causes are thought to be the effects of impurities, simply rectifying crude methylene malonic acid diester is not desirable because it solidifies during rectification or impurities having a similar boiling point are mixed in.
米国特許第4056543号明細書にはアクリル酸エ
ステルとシクロペンタジエンから５−アルコキシ
カルボニル−２−ノルボルネンとし、これにさら
にリチウムジアルキルアミドを反応させた後、ク
ロロギ酸エステルを加えてエンド及びエキソ−
５，５−ジアルコキシカルボニル−２−ノルボル
ネンとし、英国特許第1364352号に記載の方法の
応用によつて熱分解して、比較的純度のよいメチ
レンマロン酸ジエステルを得る方法がある。しか
し、この方法は高価なアルキルリチウムを用いる
こと及びホスゲンを原料とするクロロギ酸エステ
ルを用いること、更に工程が長くなること等の理
由で工業的ではない。 US Pat. No. 4,056,543 discloses that 5-alkoxycarbonyl-2-norbornene is produced from acrylic ester and cyclopentadiene, and this is further reacted with lithium dialkylamide, and then chloroformate is added to give endo- and exo-
There is a method in which 5,5-dialkoxycarbonyl-2-norbornene is thermally decomposed by applying the method described in British Patent No. 1,364,352 to obtain relatively pure methylene malonic acid diester. However, this method is not industrially viable because it uses expensive alkyl lithium, uses chloroformate made from phosgene, and requires a long process.
本発明は、これらの欠点を解決したもので、粗
製メチレンマロン酸ジエステルとシクロペンタジ
エンとの反応生成物を蒸溜し、次いでその主留分
を熱分解し、蒸溜して精製することにより得られ
るメチレンマロン酸ジエステルは優れた瞬間接着
性を示し、接着塗膜も強固であり、且つ亜硫酸ガ
ス雰囲気下での安定性も良く、長期間の保存にも
耐える性質を有するメチレンマロン酸ジエステル
の精製法を提供しようとするものである。 The present invention has solved these drawbacks, and is a method of distilling the reaction product of crude methylene malonic acid diester and cyclopentadiene, followed by thermal decomposition of the main fraction, and purification by distillation. We developed a method for purifying methylene malonic acid diester, which exhibits excellent instantaneous adhesion, has a strong adhesive coating, has good stability in sulfur dioxide gas atmosphere, and has properties that can withstand long-term storage. This is what we are trying to provide.
すなわち本発明は、粗製メチレンマロン酸ジエ
ステルとシクロペンタジエンを反応させて、エン
ド及びエキソ−５，５−ジアルコキシカルボニル
−２−ノルボルネンを主とする生成物を得、次い
で該生成物からエンド及びエキソ−５，５−ジア
ルコキシカルボニル−２−ノルボルネン組成物を
分取した後、これを熱分解し、その熱分解生成物
からメチレンマロン酸ジエステルを分取すること
を特徴とするメチレンマロン酸ジエステルの精製
法である。 That is, the present invention reacts crude methylene malonic acid diester with cyclopentadiene to obtain a product mainly consisting of endo- and exo-5,5-dialkoxycarbonyl-2-norbornene, and then converts the product into endo- and exo-5,5-dialkoxycarbonyl-2-norbornene. - A method for producing methylene malonic acid diester, which comprises separating a 5,5-dialkoxycarbonyl-2-norbornene composition, then thermally decomposing it, and separating methylene malonic acid diester from the thermal decomposition product. It is a purification method.
メチレンマロン酸ジエステルのエステル部分は
エンド及びエキソ−５，５−ジアルコキシカルボ
ニル−２−ノルボルネンのアルコキシ部分に対応
し、同一又は異種のアルキル基、シクロアルキル
基、アルケニル基、シクロアルケニル基、アラル
キル基およびこれらの基のアルコキシ置換体、グ
リシジル基、ビニル基、プロパギル基又はフルフ
リル基から選ばれる。 The ester moiety of methylene malonic acid diester corresponds to the alkoxy moiety of endo- and exo-5,5-dialkoxycarbonyl-2-norbornene, and is the same or different alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, aralkyl group. and an alkoxy substituted product of these groups, a glycidyl group, a vinyl group, a propargyl group, or a furfuryl group.
上記アルキル基の炭素数は１〜18から選ばれ、
メチル、エチル、プロピル、イソプロピル、ｎ−
ブチル、オクチルおよびステアリルの基が好し
い。 The number of carbon atoms in the alkyl group is selected from 1 to 18,
Methyl, ethyl, propyl, isopropyl, n-
Butyl, octyl and stearyl groups are preferred.
シクロアルキル基の炭素数は３以上で、シクロ
プロピル、シクロペンチル、シクロヘキシルの基
が好ましく、これらのアルキル置換基を有するも
のも使用できる。 The cycloalkyl group has 3 or more carbon atoms and is preferably a cyclopropyl, cyclopentyl, or cyclohexyl group, and those having these alkyl substituents can also be used.
アルケニル基の炭素数は３〜18から選ばれ、プ
ロペニル、ブテニル、オクテニルおよびリノール
の基が好ましい。 The number of carbon atoms in the alkenyl group is selected from 3 to 18, and propenyl, butenyl, octenyl and linole groups are preferred.
シクロアルケニル基はシクロペンテニル、シク
ロヘキセニル、シクロヘキサジエニルの基が好し
く、これらのアルキル置換基を有するものも使用
できる。 The cycloalkenyl group is preferably a cyclopentenyl, cyclohexenyl, or cyclohexadienyl group, and those having these alkyl substituents can also be used.
アラルキル基は炭素数７以上のベンジル、フエ
ニルプロピル、フエニルオクチル等の基が好し
い。 The aralkyl group is preferably a group having 7 or more carbon atoms such as benzyl, phenylpropyl, and phenyloctyl.
さらに、これらの基がアルコキシ化、ハロゲン
化およびアルコキシカルボニル化されたものも含
まれる。 Furthermore, those in which these groups are alkoxylated, halogenated, and alkoxycarbonylated are also included.
以上の他にグリシジル基、プロパギル基、ビニ
ル基、フルフリル基等も使用される。 In addition to the above, glycidyl groups, propargyl groups, vinyl groups, furfuryl groups, etc. can also be used.
本発明で云う、粗メチレンマロン酸ジエステル
とは、メチレンマロン酸ジエステルを主成分とす
るが、その製造工程で使用される原料、溶媒、触
媒、その他副原料、および反応副生物等を含む混
合物を意味する。 In the present invention, crude methylene malonic acid diester is a mixture containing methylene malonic acid diester as the main component, but also includes raw materials, solvents, catalysts, other auxiliary raw materials, and reaction by-products used in the manufacturing process. means.
例えば、マロン酸ジエステル類とホルマリン水
溶液、パラホルムアルデヒド、又はトリオキサン
等を有機酸溶媒中で触媒の存在下で縮合させ、こ
の反応生成物から減圧蒸留によりメチレンマロン
酸ジエステルを単離する場合、単離されたメチレ
ンマロン酸ジエステル中には、未反応原料のマロ
ン酸ジエステル、およびホルムアルデヒドの他
に、溶媒の有機酸、水分、副反応生成物等が含ま
れている。 For example, when malonic acid diesters are condensed with formalin aqueous solution, paraformaldehyde, trioxane, etc. in an organic acid solvent in the presence of a catalyst, and methylene malonic acid diester is isolated from this reaction product by vacuum distillation, the isolation The resulting methylene malonic acid diester contains, in addition to the unreacted raw materials malonic acid diester and formaldehyde, an organic acid as a solvent, water, side reaction products, and the like.
さらには、エンド及びエキソ−５，５−ジアル
コキシカルボニル−２−ノルボルネンの熱分解反
応において、適正な反応条件が維持されない場
合、副生物の増大にともなう品質の低下した製品
が得られることも有り、この製品を再度シクロペ
ンタジエンと反応させ、本発明の方法に従つて精
製することも本発明に含まれる。 Furthermore, in the thermal decomposition reaction of endo- and exo-5,5-dialkoxycarbonyl-2-norbornene, if appropriate reaction conditions are not maintained, products of reduced quality may be obtained due to an increase in by-products. It is also within the invention that this product is reacted again with cyclopentadiene and purified according to the method of the invention.
本発明で、出発物質が粗メチレンマロン酸ジエ
ステルであれば、如何なる方法によつて製造され
てもすべて含まれ、前記の例に限られるものでは
ない。 In the present invention, as long as the starting material is crude methylene malonic acid diester, any method produced by it is included, and the starting material is not limited to the above-mentioned examples.
粗メチレンマロン酸ジエステルを次のシクロペ
ンタジエンと反応させる工程に供給するに際して
は、粗メチレンマロン酸ジエステル単独又は適当
な有機溶媒に溶解した溶液でもよい。又、粗メチ
レンマロン酸ジエステルの保存、次工程への供給
およびシクロペンタジエンとの反応に際して、ハ
イドロキノン等の重合防止剤の添加炭酸ガス又は
亜硫酸ガス等の重合防止効果を有するガスの封入
等の処置もとれる。 When the crude methylene malonic acid diester is supplied to the next step of reacting with cyclopentadiene, the crude methylene malonic acid diester may be used alone or as a solution dissolved in a suitable organic solvent. In addition, when storing crude methylene malonic acid diester, supplying it to the next process, and reacting with cyclopentadiene, measures such as adding a polymerization inhibitor such as hydroquinone and enclosing a gas that has a polymerization inhibiting effect such as carbon dioxide gas or sulfur dioxide gas may be taken. It can be taken.
粗メチレンマロン酸ジエステルを溶液にして次
のシクロペンタジエンとの反応工程に供給する方
法は、メチレンマロン酸ジエステルの重合防止、
およびシクロペンタジエンとの反応において反応
熱の温度制御等にしばしば有効である。 The method of supplying crude methylene malonic acid diester as a solution to the next reaction step with cyclopentadiene is to prevent polymerization of methylene malonic acid diester,
It is often effective for temperature control of reaction heat in reactions with cyclopentadiene and cyclopentadiene.
このような目的に使用される溶媒は、メチレン
マロン酸ジエステル、およびシクロペンタジエン
に不活性であるとともに、生成したエンド及びエ
キソ−５，５−ジアルコキシカルボニル−２−ノ
ルボルネンに対しても不活性であり、且つ、該ノ
ルボルネン化合物と分離し易いものが好ましい。 Solvents used for this purpose should be inert to the methylene malonic acid diester and cyclopentadiene, as well as to the endo- and exo-5,5-dialkoxycarbonyl-2-norbornenes formed. It is preferable to use a compound that can be easily separated from the norbornene compound.
具体的な溶剤としては、アルコール類、エーテ
ル類、アルコキシエーテル類、有機酸又はそのエ
ステル類、ケトン類、脂肪族および芳香族炭化水
素類又はこれらのハロゲン化物等を挙げることが
できる。 Specific examples of the solvent include alcohols, ethers, alkoxy ethers, organic acids or esters thereof, ketones, aliphatic and aromatic hydrocarbons, and halides thereof.
この粗メチレンマロン酸ジエステル又はその溶
液とシクロペンタジエン又はその溶液との反応工
程につき説明する。 The reaction process of this crude methylene malonic acid diester or its solution with cyclopentadiene or its solution will be explained.
シクロペンタジエンを溶液として反応系に供給
する場合は、使用する溶媒は、具体的には前述し
た粗メチレンマロン酸ジエステル類の溶媒から選
択されることが好ましく、粗メチレンマロン酸ジ
エステルの溶媒と同一又は異なるものであつても
よいが、同一のものである方が便利である。 When cyclopentadiene is supplied to the reaction system as a solution, the solvent used is preferably selected from the above-mentioned solvents for crude methylene malonic acid diesters, and is either the same as the solvent for crude methylene malonic acid diesters or They may be different, but it is more convenient if they are the same.
シクロペンタジエンの添加量は、メチレンマロ
ン酸ジエステルに対し等モル以上であるが、通常
は1.0〜2.0倍モルがよい。 The amount of cyclopentadiene added is equal to or more than the molar amount of methylene malonic acid diester, but it is usually 1.0 to 2.0 times the molar amount.
反応を促進させるために、ルイス酸等の触媒を
添加することは構わないが、シクロペンタジエン
とメチレンマロン酸ジエステル類との反応性は一
般に高く、通常は無触媒でも、反応条件を適当に
選べば、反応は充分に進行する。 Although it is okay to add a catalyst such as a Lewis acid to accelerate the reaction, the reactivity between cyclopentadiene and methylene malonic acid diesters is generally high, and it is usually possible to add a catalyst such as a Lewis acid to accelerate the reaction, so if the reaction conditions are selected appropriately, the reaction can be achieved even without a catalyst. , the reaction proceeds satisfactorily.
反応熱の制御等の目的で、いづれか一方の原料
を反応系に分添する方法も採用されるが、一括仕
込み方式、連続反応方式等反応方式は特に限定さ
れるものでない。 For the purpose of controlling the reaction heat, etc., a method of adding one of the raw materials to the reaction system in portions is also adopted, but the reaction method is not particularly limited, such as a batch charging method or a continuous reaction method.
反応温度は０〜180℃好ましくは20〜120℃であ
る。 The reaction temperature is 0 to 180°C, preferably 20 to 120°C.
反応圧力は、反応温度、溶媒、シクロペンタジ
エンの濃度等により決定され、通常は常圧ないし
５気圧の範囲で実施される。 The reaction pressure is determined by the reaction temperature, solvent, concentration of cyclopentadiene, etc., and is usually carried out in the range of normal pressure to 5 atm.
反応時間は、反応条件、および反応方式によつ
て左右されるが、通常は数十分ないし十数時間を
要する。 The reaction time depends on the reaction conditions and reaction method, but usually takes several tens of minutes to more than ten hours.
粗メチレンマロン酸ジエステル中に含有される
不純物の影響により、上記の如き条件下でも反応
が阻害される場合は、不純物の活性を低下もしく
は無くする目的に有効な添加剤の添加等の手段を
講じることができる。 If the reaction is inhibited even under the above conditions due to the influence of impurities contained in the crude methylene malonic acid diester, take measures such as adding effective additives to reduce or eliminate the activity of the impurities. be able to.
このようにして得られる反応生成物は、エンド
及びエキソ−５，５−ジアルコキシカルボニル−
２−ノルボルネンの混合体であるが、本発明の目
的から、両者の混合比の如何を問わず、任意の混
合比で次の分離及び熱分解工程に供給される。 The reaction products thus obtained are endo- and exo-5,5-dialkoxycarbonyl-
Although it is a mixture of 2-norbornene, for the purposes of the present invention, it is supplied to the next separation and thermal decomposition step at any mixing ratio, regardless of the mixing ratio of the two.
粗メチレンマロン酸ジエステルとシクロペンタ
ジエンの反応により生成したエンド及びエキソ−
５，５−ジアルコキシカルボニル−２−ノルボル
ネンの反応生成物系からの分離について説明す
る。 Endo and exo- produced by the reaction of crude methylene malonic acid diester and cyclopentadiene
The separation of 5,5-dialkoxycarbonyl-2-norbornene from the reaction product system will be explained.
この反応生成物において、粗メチレンマロン酸
ジエステル中に含まれていた不純物類と、生成し
たエンド及びエキソ−５，５−ジアルコキシカル
ボニル−２−ノルボルネンとの間に沸点差が広が
ると共に、該ノルボルネンは、通常採用される蒸
留条件下では熱的に安定である。従つて、一般に
は、直接減圧蒸溜等により、粗メチレンマロン酸
ジエステル類に含まれていた不純物や反応に使用
した溶媒類との分離が容易になり、精製された、
エンド及びエキソ−５，５−ジアルコキシカルボ
ニル−２−ノルボルネンが得られる。 In this reaction product, the boiling point difference widens between the impurities contained in the crude methylene malonic acid diester and the endo- and exo-5,5-dialkoxycarbonyl-2-norbornene produced, and the norbornene is thermally stable under commonly employed distillation conditions. Therefore, in general, it is easy to separate the impurities contained in the crude methylene malonic acid diesters and the solvents used in the reaction by direct vacuum distillation, etc., and the purified methylene malonic acid diesters are purified.
Endo and exo-5,5-dialkoxycarbonyl-2-norbornene are obtained.
本発明では、上記の蒸留操作以外の通常用いら
れる分離、精製の手段も採用される。又、蒸留操
作、その他の分離、および精製操作の組合せ方式
も用いられる。 In the present invention, commonly used separation and purification means other than the above-mentioned distillation operation are also employed. Combinations of distillation operations, other separations, and purification operations may also be used.
具体的な例としては、水溶性不純物を含む場合
は水洗、又酸性及びアルカリ性の不純物に対して
は、各々、アルカリ性及び酸性の水溶液による不
純物の除去が挙げられ、その他、中和およびその
他の方法による不純物の結晶化分離、活性炭処理
及びイオン交換樹脂処理等の方法が挙げられる
が、これらの例に限定されるものでなく、一般に
採用される各種の分離、精製方法も含まれる。溶
媒を含む反応生成物をこれらの分離、精製手段に
より処理する場合、溶媒を含んだままの状態又は
溶媒の一部又は大部分を除去した後のいづれであ
つてもよい。 Specific examples include washing with water if it contains water-soluble impurities, and removing impurities with alkaline and acidic aqueous solutions, respectively, for acidic and alkaline impurities, as well as neutralization and other methods. Examples include methods such as crystallization separation of impurities, activated carbon treatment, and ion exchange resin treatment, but are not limited to these examples, and also include various commonly employed separation and purification methods. When a reaction product containing a solvent is treated by these separation and purification means, it may be treated either while still containing the solvent or after some or most of the solvent has been removed.
溶媒を含まない反応生成物の場合、このような
精製操作の後、直接、精製されたエンド及びエキ
ソ−５，５−ジアルコキシカルボニル−２−ノル
ボネンとして次の熱分解工程に供給されてもよい
し、又は、さらに蒸溜操作により精製して熱分解
工程に供給される。溶媒を含む反応生成物の場合
も同様のことが云えるが、次の熱分解工程で溶媒
自体の熱分解による副生物の生成等が懸念される
ときは、溶媒除去さらには蒸留により、精製され
た、エンド及びエキソ−５，５−ジアルコキシカ
ルボニル−２−ノルボルネンとして次の熱分解工
程に供給される。 In the case of solvent-free reaction products, after such purification operations they may be fed directly to the next pyrolysis step as purified endo- and exo-5,5-dialkoxycarbonyl-2-norbornene. Alternatively, it is further purified by distillation and supplied to the thermal decomposition process. The same can be said for reaction products containing solvents, but if there is a concern that by-products may be generated due to thermal decomposition of the solvent itself in the next thermal decomposition step, the reaction products may be purified by solvent removal and distillation. It is also supplied to the next thermal cracking step as endo- and exo-5,5-dialkoxycarbonyl-2-norbornene.
以上の方法により、精製された、エンド及びエ
キソ−５，５−ジアルコキシカルボニル−２−ノ
ルボルネンの熱分解は次のように実施される。 Thermal decomposition of endo- and exo-5,5-dialkoxycarbonyl-2-norbornene purified by the above method is carried out as follows.
熱分解反応は、通常は100〜800℃、好ましく
は、200〜700℃の温度範囲において、常圧もしく
は減圧下で実施され、好ましい圧力範囲は700〜
0.1mmHgの範囲にある。又、窒素ガス、炭酸ガ
ス、亜硫酸ガス等の不活性ガスの希釈下で熱分解
反応を行つても良い。熱分解反応方式としては、
バツチ反応方式、気相流通反応方式、その他通常
の熱分解反応に採用される方式が採用され、それ
ぞれの反応方式に適した熱分解反応装置が使用さ
れる。 The thermal decomposition reaction is usually carried out at a temperature range of 100 to 800°C, preferably 200 to 700°C, under normal pressure or reduced pressure, with a preferred pressure range of 700 to 700°C.
It is in the range of 0.1mmHg. Alternatively, the thermal decomposition reaction may be carried out under dilution with an inert gas such as nitrogen gas, carbon dioxide gas, or sulfur dioxide gas. As for the thermal decomposition reaction method,
A batch reaction method, a gas phase flow reaction method, and other methods used for ordinary thermal decomposition reactions are employed, and a thermal decomposition reaction apparatus suitable for each reaction method is used.
熱分解反応装置の材質は、熱分解反応条件を考
慮して、その反応条件に耐えるものが選ばれ、そ
の具体例としてはパイレツクスガラスに代表され
る耐熱ガラス、耐熱ガラスライニングの鋼製反応
器、石英製、耐熱ステンレス鋼、高ニツケル含有
合金等が挙げられる。 The material of the pyrolysis reactor is selected in consideration of the pyrolysis reaction conditions, and is selected to withstand the reaction conditions.Specific examples include heat-resistant glass such as Pyrex glass, and steel reactors with heat-resistant glass lining. , quartz, heat-resistant stainless steel, high nickel-containing alloy, etc.
反応器内の温度分布をできるだけ均一にすると
共に、熱伝導の効率を向上させるために、反応器
内に適当な充填物を充填することも有効であり、
この目的に、上記の材質類等から選ばれた各種の
形状の充填剤が使用される。 In order to make the temperature distribution in the reactor as uniform as possible and to improve the efficiency of heat conduction, it is also effective to fill the reactor with an appropriate packing material.
For this purpose, fillers of various shapes selected from the above-mentioned classes of materials are used.
熱分解されたガスは、未反応のエンド及びエキ
ソ−５，５ジアルコキシカルボニル−２−ノルボ
ルネンと共に、分解反応により再生されたメチレ
ンマロン酸ジエステル、およびシクロペンタジエ
ンからなる組成物である。 The thermally decomposed gas is a composition consisting of unreacted endo- and exo-5,5-dialkoxycarbonyl-2-norbornene, methylene malonic acid diester regenerated by the decomposition reaction, and cyclopentadiene.
この熱分解ガスは、冷却、液化されるが、この
冷却操作は、二段階で実施される。 This pyrolysis gas is cooled and liquefied, and this cooling operation is carried out in two stages.
第一段目の冷却ゾーンは、再生されたメチレン
マロン酸ジエステル、および未反応のエンド及び
エキソ−５，５−ジアルコキシカルボニル−２−
ノルボルネンが液化し、シクロペンタジエンは液
化しない温度および圧力条件が設定される。 The first cooling zone contains regenerated methylene malonic acid diester and unreacted endo- and exo-5,5-dialkoxycarbonyl-2-
Temperature and pressure conditions are set so that norbornene is liquefied but cyclopentadiene is not liquefied.
即ち、この冷却ゾーンでシクロペンタジエンが
液化してメチレンマロン酸ジエステル中に凝縮、
液化すると、再び原料であるエンド及びエキソ−
５，５−ジアルコキシカルボニル−２−ノルボル
ネンになるため、この冷却ゾーンではシクロペン
タジエンが、できるだけ凝縮、液化しない条件を
選択しなければならない。 That is, in this cooling zone, cyclopentadiene liquefies and condenses into methylene malonic acid diester.
When liquefied, the raw materials endo and exo
Since cyclopentadiene becomes 5,5-dialkoxycarbonyl-2-norbornene, conditions must be selected in this cooling zone to prevent condensation and liquefaction of cyclopentadiene as much as possible.
次いで、未凝縮のシクロペンタジエンは、任意
の方法により第二段階目の冷却ゾーンで液化回収
される。 The uncondensed cyclopentadiene is then liquefied and recovered in the second stage cooling zone by any method.
上記の熱分解の方法により、メチレンマロン酸
ジエステルは高い反応率と、高い選択率で再生さ
れ、極めて副反応の少ない反応生成物が第一段階
の冷却ゾーンから得られる。 By the above thermal decomposition method, methylene malonic acid diester is regenerated with high reaction rate and high selectivity, and a reaction product with extremely few side reactions can be obtained from the cooling zone of the first stage.
第一段階の冷却ゾーンで、再生されたメチレン
マロン酸ジエステルの大部分が液化して捕集され
るが、その中には、未反応、もしくは、この冷却
ゾーンで液化したメチレンマロン酸ジエステルに
一部溶解したシクロペンタジエンとの再結合反応
により生成した、エンド及びエキソ−５，５−ジ
アルコキシカルボニル−２−ノルボルネン及び少
量のシクロペンタジエン等が含まれているので、
次の、分離、精製工程に移され、精製されたメチ
レンマロン酸ジエステルが得られる。 Most of the regenerated methylene malonic acid diester is liquefied and collected in the cooling zone of the first stage, but some of it is unreacted or is combined with the methylene malonic acid diester liquefied in this cooling zone. Since it contains endo- and exo-5,5-dialkoxycarbonyl-2-norbornene and a small amount of cyclopentadiene, etc. produced by the recombination reaction with partially dissolved cyclopentadiene,
The mixture is transferred to the next separation and purification step to obtain purified methylene malonic acid diester.
エンド及びエキソ−５，５−ジアルコキシカル
ボニル−２−ノルボルネンの熱分解反応によつ
て、再生されたメチレンマロン酸ジエステルを主
成分とする上記の反応生成物は、減圧蒸留等の通
常の蒸留方式により、他の成分と分離とされ、高
純度のメチレンマロン酸ジエステルが得られる。 The above-mentioned reaction product, which is mainly composed of methylene malonic acid diester regenerated by the thermal decomposition reaction of endo- and exo-5,5-dialkoxycarbonyl-2-norbornene, can be produced by ordinary distillation methods such as vacuum distillation. By this, it is separated from other components and a highly pure methylene malonic acid diester is obtained.
本発明の方法において得られるメチレンマロン
酸ジエステルは、ハイドロキノン類等の重合防止
剤、亜硫酸ガス又は炭酸ガス等の酸性物質の濃度
が任意に調節された組成物の状態において、優れ
た瞬間接着性を示し、接着強度も極めて強靭であ
る。 The methylene malonic acid diester obtained by the method of the present invention exhibits excellent instant adhesive properties in the form of a composition in which the concentration of a polymerization inhibitor such as hydroquinone and an acidic substance such as sulfur dioxide gas or carbon dioxide gas is arbitrarily adjusted. The adhesive strength is also extremely strong.
又、長期の保存に対しても変質せず、各種の有
機化学反応の出発物質又は中間体にも利用し得る
ようになつた。 Moreover, it does not deteriorate even after long-term storage, and can now be used as a starting material or intermediate for various organic chemical reactions.
以下、本発明の実施例について説明するが、本
発明はこれに限定されるものでない。尚、実施例
中％は重量％を表わす。 Examples of the present invention will be described below, but the present invention is not limited thereto. In the examples, % represents weight %.
実施例 １
パラホルムアルデヒド15ｇ（0.5モル）、酢酸第
二銅５ｇ、氷酢酸100ｇを300ml反応器に仕込み、
内温を60℃に加熱して均一溶液になつたところ
で、マロン液ジエチル40ｇ（0.25モル）をこの溶
液に加え、100℃で４時間反応させた。反応後、
この反応液を室温で一昼夜放冷し、反応液から酢
酸第二銅を晶析させ、この結晶を別した液を
バツチ式の蒸溜器に移し、20mmHgの減圧下で、
塔頂温度70℃で、90％以上の酢酸を留去した。次
いで、３mmHgの減圧下で蒸留器の缶温を105℃〜
135℃の範囲で加熱し、この間の塔頂温度37℃か
ら65℃の留分、30.7ｇを分取した。この留分中の
メチレンマロン酸ジエチルの含有量はガスクロマ
トグラフイーによる分析で28.2ｇ（純度91.9％）
であつた。この粗メチレンマロン酸ジエチルにシ
クロペンタジエン12ｇ（0.18モル）を加え、60℃
で１時間加熱し、反応を行なつた。反応後、この
反応液を精溜し、３mmHgで81℃の主留分31ｇを
得た。この留分中のエンド及びエキソ−５，５−
ジエトキシカルボニル−２−ノルボルネンの純度
はガスクロマトグラフイー分析により、99％以上
であつた。Example 1 15 g (0.5 mol) of paraformaldehyde, 5 g of cupric acetate, and 100 g of glacial acetic acid were charged into a 300 ml reactor.
When the internal temperature was heated to 60°C to become a homogeneous solution, 40 g (0.25 mol) of diethyl marron liquid was added to this solution, and the mixture was reacted at 100°C for 4 hours. After the reaction,
This reaction solution was left to cool at room temperature for a day and night, and cupric acetate was crystallized from the reaction solution.The liquid from which the crystals were separated was transferred to a batch distiller, and under a reduced pressure of 20 mmHg,
More than 90% of acetic acid was distilled off at a tower top temperature of 70°C. Next, the temperature of the distiller was increased to 105℃ under reduced pressure of 3mmHg.
The mixture was heated in a range of 135°C, and 30.7 g of the fraction whose tower top temperature ranged from 37°C to 65°C during this period was collected. The content of diethyl methylenemalonate in this fraction was determined to be 28.2g (purity 91.9%) by gas chromatography analysis.
It was hot. 12 g (0.18 mol) of cyclopentadiene was added to this crude diethyl methylenemalonate, and the mixture was heated to 60°C.
The mixture was heated for 1 hour to carry out the reaction. After the reaction, the reaction solution was rectified to obtain 31 g of a main fraction at 81° C. and 3 mmHg. Endo and exo-5,5- in this fraction
The purity of diethoxycarbonyl-2-norbornene was 99% or more as determined by gas chromatography analysis.
次いで、この主留分を熱分解工程に移した。熱
分解反応装置は、次の通りである。内径25mmφ、
長さ600mmの石英ガラス管を垂直に設置し、その
300mmの長さの部分を電気炉で加熱し、この加熱
部分にあたる石英管内には５mmφ×５mmの磁製ラ
シヒリングを充填した。第一番目の冷却トラツプ
はこの石英管の底部に接続され、第二番目の冷却
トラツプは、石英管と第一番目の冷却トラツプの
間に接続された真空ラインに接続された。原料供
給タンクは石英管の頂項と接続し、この間に流量
調節バルブを取付け、且つ、タンク内は反応系の
真空ラインと接続し、反応中は均圧がとれるよう
にした。 This main fraction was then transferred to a pyrolysis step. The pyrolysis reactor is as follows. Inner diameter 25mmφ,
A quartz glass tube with a length of 600 mm is installed vertically.
A 300 mm long section was heated in an electric furnace, and a 5 mmφ x 5 mm porcelain Raschig ring was filled in the quartz tube corresponding to this heated section. A first cooling trap was connected to the bottom of the quartz tube, and a second cooling trap was connected to a vacuum line connected between the quartz tube and the first cooling trap. The raw material supply tank was connected to the top of the quartz tube, and a flow control valve was installed between the tanks, and the inside of the tank was connected to the vacuum line of the reaction system, so that the pressure could be equalized during the reaction.
反応開始前に装置内を炭酸ガスで充分に置換し
た後、反応器部分の外温を600℃に加熱し、第一
番目の冷却トラツプの冷却層は−15〜−20℃、第
二番目の冷却トラツプは−78℃（ドライアイス−
メタール）で冷却した。系内の圧力は２〜３mm
Hgにまで減圧した。このような条件下で、エン
ド及びエキソ−５，５−ジエトキシカルボニル−
２−ノルボルネンを平均0.8ｇ／分の速度で反応
器頂部のタンクより調節バルブを調節しながら、
反応器内に滴下した。 After sufficiently replacing the inside of the apparatus with carbon dioxide gas before starting the reaction, the outside temperature of the reactor section is heated to 600℃, the cooling layer of the first cooling trap is -15 to -20℃, and the cooling layer of the second trap is heated to -15 to -20℃. Cooling trap: -78℃ (dry ice)
cooled with metal). The pressure inside the system is 2 to 3 mm.
The pressure was reduced to Hg. Under these conditions, endo- and exo-5,5-diethoxycarbonyl-
2-Norbornene was fed into the tank at the top of the reactor at an average rate of 0.8 g/min while adjusting the control valve.
It was added dropwise into the reactor.
反応終了後、第１冷却トラツプには、26ｇの反
応生成物が得られた。これを減圧精溜し12mmHg
の減圧下、97〜98℃の溜分22ｇを得た。又缶残は
大部分が未反応原料として回収され、一部メチレ
ンマロン酸ジエチルを含むのでこれは、シクロペ
ンタジエンと粗メチレンマロン酸ジエチルの反応
系にもどした。 After the reaction was completed, 26 g of reaction product was obtained in the first cooling trap. This is distilled under reduced pressure to 12mmHg.
22 g of a fraction having a temperature of 97 to 98°C was obtained under reduced pressure. Also, most of the residue from the can was recovered as an unreacted raw material, and since it partially contained diethyl methylenemalonate, this was returned to the reaction system of cyclopentadiene and crude diethyl methylenemalonate.
このようにして得たメチレンマロン酸ジエチル
をガラス面に塗布し、他のガラス板を接着させた
ところ、数十秒後に強固な接着性が得られた。又
SO2封入後、１ケ月放置しても何ら固化は起らな
かつた。 When diethyl methylenemalonate thus obtained was applied to a glass surface and another glass plate was adhered to it, strong adhesion was obtained after several tens of seconds. or
After filling with SO 2 , no solidification occurred even if it was left for one month.
参考例
オルトギ酸メチル119ｇ（1.12mol）、マロン酸
ジメチル132ｇ（1.0mol）、無水酢酸210ｇ
（2.05mol）、無水塩化亜鉛0.5ｇを１の反応器に
仕込み、150℃で14時間反応させた。反応後を放
冷後過し、減圧蒸留したところメトキシメチレ
ンマロン酸ジメチル104ｇ（0.6mol）を110℃／
0.5mmの留分として得た。Reference example: Methyl orthoformate 119g (1.12mol), dimethyl malonate 132g (1.0mol), acetic anhydride 210g
(2.05 mol) and 0.5 g of anhydrous zinc chloride were charged into the reactor No. 1, and reacted at 150°C for 14 hours. After the reaction was left to cool, it was filtered and distilled under reduced pressure.
Obtained as a 0.5 mm fraction.
メトキシメチレンマロン酸ジメチル87ｇ
（0.5mol）を無水メタノール100mlに溶解し、ラネ
ーニツケル10ｇとともに、オートクレーブに仕込
み、水素圧70Kg／cm2、温度45℃で20時間反応し
た。放冷後ラネーニツケルを過し、常温、減圧
下で溶媒を留去すると、メトキシメチルマロン酸
ジメチルが無色透明のオイルとして得られた。さ
らに加熱しながら蒸留を行ない、常圧下でゆつく
り加熱することにより、100℃までの加熱でメタ
ノールが留出し、その後減圧下で加熱蒸留するこ
とにより、40〜50℃／２mmHgの留分72.1ｇを得
た。この留分をガスクロマトグラフイーにより分
析した結果メチレンマロン酸ジメチルが65.0ｇ
（純度90.2％）が含まれていた。この粗メチレン
マロン酸ジメチルは、ガラス面上に塗布し、他の
ガラス板を接着させたところ、瞬間的な接着性は
見られず、また数十分経過後もあまり接着強度が
上がらず、ガラス板を剥離させて観察したとこ
ろ、接着面は強固な樹脂膜を形成しておらず、も
ろい微粉末状を呈していた。 Methoxymethylene dimethyl malonate 87g
(0.5 mol) was dissolved in 100 ml of anhydrous methanol, charged into an autoclave together with 10 g of Raney nickel, and reacted for 20 hours at a hydrogen pressure of 70 Kg/cm 2 and a temperature of 45°C. After cooling, the mixture was filtered through a Raney nickel filter and the solvent was distilled off at room temperature under reduced pressure to obtain dimethyl methoxymethylmalonate as a colorless and transparent oil. Distillation is further carried out while heating, and by heating slowly under normal pressure, methanol is distilled out by heating up to 100℃, and then by heating and distilling under reduced pressure, 72.1g of distillate at 40-50℃/2 mmHg is obtained. I got it. Analysis of this fraction by gas chromatography revealed 65.0g of dimethyl methylenemalonate.
(purity 90.2%). When this crude dimethyl methylene malonate was applied to a glass surface and other glass plates were bonded, no instantaneous adhesion was observed, and the adhesive strength did not increase much even after several tens of minutes had passed. When the plate was peeled off and observed, it was found that the adhesive surface did not form a strong resin film and was in the form of a brittle fine powder.
実施例 ２
参考例の粗メチレンマロン酸ジメチルを実施例
１と同様の方法でシクロペンタジエンと反応させ
て、エンド及びエキソ−５，５−ジメトキシカル
ボニル−２−ノルボルネンとした後、蒸留精製
し、これを熱分解した後、蒸留精製することによ
り高純度のメチレンマロン酸ジメチルが得られ
た。これはガラス塗布によるテストの結果、数十
秒で強固な接着性能を示し、SO2雰囲気下で保存
したところ１ケ月経過後も固化は見られなかつ
た。Example 2 The crude dimethyl methylene malonate of the reference example was reacted with cyclopentadiene in the same manner as in Example 1 to obtain endo- and exo-5,5-dimethoxycarbonyl-2-norbornene, which was then purified by distillation. After thermal decomposition, highly pure dimethyl methylenemalonate was obtained by distillation purification. As a result of a test using glass coating, it showed strong adhesion within several tens of seconds, and when stored in an SO 2 atmosphere, no solidification was observed even after one month had passed.
Claims (1)
ンタジエンを反応させて、エンド及びエキソ−
５，５−ジアルコキシカルボニル−２−ノルボル
ネンを主とする生成物を得、次いで該生成物から
エンド及びエキソ−５，５−ジアルコキシカルボ
ニル−２−ノルボルネン組成物を分取した後、こ
れを熱分解し、その熱分解生成物からメチレンマ
ロン酸ジエステルを分取することを特徴とするメ
チレンマロン酸ジエステルの精製法。1. React crude methylene malonic acid diester with cyclopentadiene to form endo- and exo-
A product mainly composed of 5,5-dialkoxycarbonyl-2-norbornene is obtained, and then endo- and exo-5,5-dialkoxycarbonyl-2-norbornene compositions are separated from the product. A method for purifying methylene malonic acid diester, which comprises thermally decomposing it and separating methylene malonic acid diester from the thermal decomposition product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15835979A JPS5681537A (en) | 1979-12-06 | 1979-12-06 | Purification of methylenemalonic diester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15835979A JPS5681537A (en) | 1979-12-06 | 1979-12-06 | Purification of methylenemalonic diester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5681537A JPS5681537A (en) | 1981-07-03 |
| JPS6136740B2 true JPS6136740B2 (en) | 1986-08-20 |
Family
ID=15669939
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15835979A Granted JPS5681537A (en) | 1979-12-06 | 1979-12-06 | Purification of methylenemalonic diester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5681537A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63254247A (en) * | 1987-04-09 | 1988-10-20 | Kajima Corp | Pendulum type dynamic vibration absorber |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AT379602B (en) * | 1983-07-11 | 1986-02-10 | Vianova Kunstharz Ag | METHOD FOR PRODUCING CROSSLINKING COMPONENTS FOR LACQUER BINDING AGENTS |
| CA2815198A1 (en) * | 2010-10-20 | 2012-04-26 | Bioformix Inc. | Synthesis of methylene malonates using rapid recovery in the presence of a heat transfer agent |
| US10414839B2 (en) | 2010-10-20 | 2019-09-17 | Sirrus, Inc. | Polymers including a methylene beta-ketoester and products formed therefrom |
| US9279022B1 (en) | 2014-09-08 | 2016-03-08 | Sirrus, Inc. | Solution polymers including one or more 1,1-disubstituted alkene compounds, solution polymerization methods, and polymer compositions |
| US9249265B1 (en) | 2014-09-08 | 2016-02-02 | Sirrus, Inc. | Emulsion polymers including one or more 1,1-disubstituted alkene compounds, emulsion methods, and polymer compositions |
| EP2831185B1 (en) * | 2012-03-30 | 2019-09-25 | Sirrus, Inc. | Ink and coating formulations and polymerizable systems for producing the same |
| WO2013149168A1 (en) | 2012-03-30 | 2013-10-03 | Bioformix, Inc. | Composite and laminate articles and polymerizable systems for producing the same |
| US10047192B2 (en) | 2012-06-01 | 2018-08-14 | Sirrus, Inc. | Optical material and articles formed therefrom |
| WO2014078689A1 (en) | 2012-11-16 | 2014-05-22 | Bioformix Inc. | Plastics bonding systems and methods |
| CN105164797B (en) | 2012-11-30 | 2019-04-19 | 瑟拉斯公司 | Complex composition for electronic application |
| US9315597B2 (en) | 2014-09-08 | 2016-04-19 | Sirrus, Inc. | Compositions containing 1,1-disubstituted alkene compounds for preparing polymers having enhanced glass transition temperatures |
| US9334430B1 (en) | 2015-05-29 | 2016-05-10 | Sirrus, Inc. | Encapsulated polymerization initiators, polymerization systems and methods using the same |
| US9617377B1 (en) | 2016-06-03 | 2017-04-11 | Sirrus, Inc. | Polyester macromers containing 1,1-dicarbonyl-substituted 1 alkenes |
| US10196481B2 (en) | 2016-06-03 | 2019-02-05 | Sirrus, Inc. | Polymer and other compounds functionalized with terminal 1,1-disubstituted alkene monomer(s) and methods thereof |
| US9567475B1 (en) | 2016-06-03 | 2017-02-14 | Sirrus, Inc. | Coatings containing polyester macromers containing 1,1-dicarbonyl-substituted 1 alkenes |
-
1979
- 1979-12-06 JP JP15835979A patent/JPS5681537A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63254247A (en) * | 1987-04-09 | 1988-10-20 | Kajima Corp | Pendulum type dynamic vibration absorber |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5681537A (en) | 1981-07-03 |
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