JPS62167733A - Method for preventing formation of polymeric by-product - Google Patents
Method for preventing formation of polymeric by-productInfo
- Publication number
- JPS62167733A JPS62167733A JP860486A JP860486A JPS62167733A JP S62167733 A JPS62167733 A JP S62167733A JP 860486 A JP860486 A JP 860486A JP 860486 A JP860486 A JP 860486A JP S62167733 A JPS62167733 A JP S62167733A
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- compound
- polymer
- formation
- conjugated diolefin
- 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.)
- Granted
Links
- 239000006227 byproduct Substances 0.000 title claims abstract description 17
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 11
- 238000000034 method Methods 0.000 title claims description 11
- -1 diolefin compound Chemical class 0.000 claims abstract description 32
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 17
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000005698 Diels-Alder reaction Methods 0.000 claims abstract description 11
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 10
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 5
- VMESOKCXSYNAKD-UHFFFAOYSA-N n,n-dimethylhydroxylamine Chemical compound CN(C)O VMESOKCXSYNAKD-UHFFFAOYSA-N 0.000 claims abstract description 3
- 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 abstract 2
- 229920000642 polymer Polymers 0.000 claims description 17
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 150000001993 dienes Chemical class 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- OQAIUHLITJGRMM-UHFFFAOYSA-N n,n-di(propan-2-yl)hydroxylamine Chemical compound CC(C)N(O)C(C)C OQAIUHLITJGRMM-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 238000004581 coalescence Methods 0.000 claims 1
- PAZXUKOJTOTKBK-UHFFFAOYSA-N n,n-dibutylhydroxylamine Chemical compound CCCCN(O)CCCC PAZXUKOJTOTKBK-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 28
- 230000000694 effects Effects 0.000 abstract description 3
- 239000011541 reaction mixture Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 5
- 229920001174 Diethylhydroxylamine Polymers 0.000 description 4
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical compound CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000002252 acyl group Chemical group 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- AYOOGWWGECJQPI-NSHDSACASA-N n-[(1s)-1-(5-fluoropyrimidin-2-yl)ethyl]-3-(3-propan-2-yloxy-1h-pyrazol-5-yl)imidazo[4,5-b]pyridin-5-amine Chemical compound N1C(OC(C)C)=CC(N2C3=NC(N[C@@H](C)C=4N=CC(F)=CN=4)=CC=C3N=C2)=N1 AYOOGWWGECJQPI-NSHDSACASA-N 0.000 description 3
- 229920006254 polymer film Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000003172 aldehyde group Chemical group 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- FUSUHKVFWTUUBE-UHFFFAOYSA-N buten-2-one Chemical compound CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 150000002443 hydroxylamines Chemical class 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- OJOWICOBYCXEKR-APPZFPTMSA-N (1S,4R)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound CC=C1C[C@@H]2C[C@@H]1C=C2 OJOWICOBYCXEKR-APPZFPTMSA-N 0.000 description 1
- APPOKADJQUIAHP-GGWOSOGESA-N (2e,4e)-hexa-2,4-diene Chemical compound C\C=C\C=C\C APPOKADJQUIAHP-GGWOSOGESA-N 0.000 description 1
- QIVUCLWGARAQIO-OLIXTKCUSA-N (3s)-n-[(3s,5s,6r)-6-methyl-2-oxo-1-(2,2,2-trifluoroethyl)-5-(2,3,6-trifluorophenyl)piperidin-3-yl]-2-oxospiro[1h-pyrrolo[2,3-b]pyridine-3,6'-5,7-dihydrocyclopenta[b]pyridine]-3'-carboxamide Chemical compound C1([C@H]2[C@H](N(C(=O)[C@@H](NC(=O)C=3C=C4C[C@]5(CC4=NC=3)C3=CC=CN=C3NC5=O)C2)CC(F)(F)F)C)=C(F)C=CC(F)=C1F QIVUCLWGARAQIO-OLIXTKCUSA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes 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
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 1
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- NFWSQSCIDYBUOU-UHFFFAOYSA-N methylcyclopentadiene Chemical compound CC1=CC=CC1 NFWSQSCIDYBUOU-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- WJDXUULXUDFDGA-UHFFFAOYSA-N n-hexyl-n-methylhydroxylamine Chemical compound CCCCCCN(C)O WJDXUULXUDFDGA-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- XULSCZPZVQIMFM-IPZQJPLYSA-N odevixibat Chemical compound C12=CC(SC)=C(OCC(=O)N[C@@H](C(=O)N[C@@H](CC)C(O)=O)C=3C=CC(O)=CC=3)C=C2S(=O)(=O)NC(CCCC)(CCCC)CN1C1=CC=CC=C1 XULSCZPZVQIMFM-IPZQJPLYSA-N 0.000 description 1
- 125000005740 oxycarbonyl group Chemical group [*:1]OC([*:2])=O 0.000 description 1
- 150000004989 p-phenylenediamines Chemical class 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 238000000710 polymer precipitation Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000002747 voluntary effect Effects 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は一般式（Ｉ）
（Ｒ１は水素原子、又は炭素数１〜８のアルキル基、
Ｒ２は炭素数１〜８のアルキル基ヲ示す。又Ｒ１とＲ２
は同一でありても別種であってもよい。）
で表わされる化合物の存在下ディールス・アルダー反応
を行なうことを特徴とする重合体副生成物の生成防止法
に関するものである。Detailed Description of the Invention <Industrial Application Field> The present invention relates to compounds of the general formula (I) (R1 is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,
R2 represents an alkyl group having 1 to 8 carbon atoms. Also R1 and R2
may be the same or different types. ) This invention relates to a method for preventing the formation of polymer by-products, which is characterized by carrying out a Diels-Alder reaction in the presence of a compound represented by:
ディールス・アルダー反応は工業的に非常に有用な反応
であって、たとえばＥＰＤＭの第３成分として使用され
る５−エチリデン−２−ノルボルネンの原料として有用
な５−ビニル−２−ノルボルネンの製造等に利用されて
いる。The Diels-Alder reaction is an industrially very useful reaction, for example in the production of 5-vinyl-2-norbornene, which is useful as a raw material for 5-ethylidene-2-norbornene, which is used as the third component of EPDM. It's being used.
〈従来の技術〉
ディールス・アルダー反応は共役ジオレフィンにオレフ
ィン化合物が１．４−付加する反応である。この反応は
熱的に進行するため反応温度を比較的高温、たとえば７
０〜２５０℃をこして行なうことが望ましいか、この様
な高温反応では、原料である共役ジオレフィン化合物お
よび／又はオレフィン化合物、およヒ反応生成物である
環状オレフィン類の重合がおこり易＜、ｉｉ重合物析出
、付着による装置の閉塞、装置内壁面における重合体被
膜の形成などの障害を生じる。この為長時間の連続操業
が実際上困難となる。従来、比較的高温でのディールス
・アルダー反応において反応物ニッケル化合物を添加す
る方法が知られているが、これらの化合物は空気中で不
安定であり取扱いが煩雑となるために実際にディールス
・アルダー反応を実施する場合には不適当である。又特
公昭５７−７１３１号公報番こはｐ−フェニレンジアミ
ン類を添加剤として用いることが示されているが２本願
表−１実施例および比較例−３，４に示す様にその効果
は十分とはいえない。<Prior Art> The Diels-Alder reaction is a reaction in which an olefin compound is 1,4-added to a conjugated diolefin. Since this reaction proceeds thermally, the reaction temperature is set to a relatively high temperature, e.g.
It is preferable to carry out the reaction at 0 to 250°C; however, in such a high temperature reaction, polymerization of the conjugated diolefin compound and/or olefin compound as a raw material and the cyclic olefin as a reaction product is likely to occur. , ii. Problems such as polymer precipitation, clogging of the device due to adhesion, and formation of a polymer film on the inner wall surface of the device occur. This makes continuous operation for a long time practically difficult. Conventionally, a method of adding a reactant nickel compound in the Diels-Alder reaction at a relatively high temperature has been known, but these compounds are unstable in air and are complicated to handle, so it is actually difficult to use the Diels-Alder reaction. It is unsuitable for carrying out reactions. In addition, Japanese Patent Publication No. 57-7131 discloses the use of p-phenylenediamines as additives, but as shown in Table 1 of this application, Examples and Comparative Examples 3 and 4, the effect is sufficient. I can't say that.
〈発明が解決しようとする問題点〉
本発明は、これら従来の技術の欠点、即ち共役ジオレフ
ィン化合物とオレフィン化合物とのディールス・アルダ
ー反応における重合物の析出、付着による装置の閉塞、
装置内壁面における重合体被膜の形成などの障害を防止
し、ディールス・７〜グ一反応を長時間支障なく行なう
方法を提供するものである。<Problems to be Solved by the Invention> The present invention addresses the drawbacks of these conventional techniques, namely, the precipitation of polymers in the Diels-Alder reaction between a conjugated diolefin compound and an olefin compound, clogging of the apparatus due to deposition,
The object of the present invention is to provide a method that prevents problems such as the formation of a polymer film on the inner wall surface of the apparatus and allows the Diels-7-G reaction to be carried out for a long time without any trouble.
〈問題点を解決する為の手段〉
本発明は兵役ジオレフィン化合物とオレフィン化合物と
を反応させるディールス・アルダー反応において一般式
（Ｉ）
（Ｒ，は水素原子、又は炭素数１〜８のアルキル基、
Ｒ２は炭素数１〜８のアルキル基を示す。又Ｒ＋とＲ
２は同一であっても別種であっても良い。）
で表わされるヒドロキシルアミンを反応物の全量に対し
て１０−１００００ ｐｐｍ存在させて共役ジオレフィ
ン化合物とオレフィン化合物とを反応させることを特徴
とする重合体副生成物の生成防止法に関するものである
。<Means for Solving the Problems> The present invention relates to a Diels-Alder reaction in which a military diolefin compound and an olefin compound are reacted. ,
R2 represents an alkyl group having 1 to 8 carbon atoms. Also R+ and R
2 may be the same or different types. ) A conjugated diolefin compound and an olefin compound are reacted in the presence of 10 to 10,000 ppm of hydroxylamine represented by the total amount of reactants. .
これらのヒドロキシルアミンの具体例としては、 Ｎ、
Ｎ−ジメチルヒドロキシルアミン。Specific examples of these hydroxylamines include N,
N-dimethylhydroxylamine.
Ｎ、Ｎ−ジエチルヒドロキシルアミン、Ｎ、Ｎ−ジイソ
プロピルヒドロキシルアミン、Ｎ、Ｎ−ジーｎ−ブチル
ヒドロ午ジルアミン、Ｎ−メチルヒドロ午ジルアミン、
Ｎ−メチル−Ｎ−ヘキシルヒドロキシルアミン等が例示
できる。N,N-diethylhydroxylamine, N,N-diisopropylhydroxylamine, N,N-di-n-butylhydrozylamine, N-methylhydrozylamine,
Examples include N-methyl-N-hexylhydroxylamine.
これらのヒドロキシノンアミンは通常供給原料の全重量
に対してｌＯ−１１００００ｐｐ好ましくは１００−５
０００ ｐｐｍの範囲で添加される。これらのヒドロキ
シルアミンは単独あるいは２種以上混合して使用される
。These hydroxynonamines usually contain lO-110,000 pp, preferably 100-5, based on the total weight of the feedstock.
000 ppm. These hydroxylamines may be used alone or in combination of two or more.
本発明蚤こおいて使用される共役ジオレフィンは兵役二
重結合を有する鎖状および環状共役ジオレフィン化合物
の全てである。化学式で示せば１例えば一般式の）で例
示される。The conjugated diolefins used in the flea of the present invention are all linear and cyclic conjugated diolefin compounds having a military double bond. In terms of a chemical formula, 1 is exemplified by (for example, the general formula).
（ここでＲ４，Ｒｓ、 Ｒａ、 Ｒｙ、 ＲａおよびＲ
９は水素、メチル基、エチル基、ｎ−プロピル基。(Here R4, Rs, Ra, Ry, Ra and R
9 is hydrogen, methyl group, ethyl group, n-propyl group.
１ｓｏ−プロピル基、ｎ−ペンチル基、 ｉｓ。1so-propyl group, n-pentyl group, is.
−ペンチル基、ヘキシル基、ヘプチル基等のようなアル
キル基；フェニル基、ナフチル基、アラルキル基等のよ
うなアリール基：アルコキシ基、アシル基、オキシカル
ボニル基、あるいはその池重合防止剤と反応しない基で
ある。Ｒ＝、 Ｒｓ、 ＲＡ、 Ｒｙ、 Ｒａｔ６
よびＲ９は同じであっても、また異なっていても差しつ
かえない。またＲ４−Ｒ９が適当に組合さって環を形成
していてもよい。）
この様な共役ジオレフィンとしては、ｌ、３−ブタジェ
ン、イソプレン、１，３−ペンタジェン、２．４−へキ
サジエン、２．３−ジメチルブタジェン、ｌ−フェニル
ブタジェン、あるいはシクロペンタジェン、メチルシク
ロペンタジェン等の環状ジオレフィン等がある。- Alkyl groups such as pentyl, hexyl, heptyl, etc.; aryl groups such as phenyl, naphthyl, aralkyl, etc.; do not react with alkoxy, acyl, oxycarbonyl, or other polymerization inhibitors; It is the basis. R=, Rs, RA, Ry, Rat6
and R9 may be the same or different. Further, R4-R9 may be appropriately combined to form a ring. ) Such conjugated diolefins include l,3-butadiene, isoprene, 1,3-pentadiene, 2,4-hexadiene, 2,3-dimethylbutadiene, l-phenylbutadiene, or cyclopentadiene, Examples include cyclic diolefins such as methylcyclopentadiene.
本発明において使用されるオレフィン化合物は一般式（
■））こよりて表わされる。The olefin compound used in the present invention has the general formula (
■)) Expressed by this.
ＲｃＣ＝Ｃ−Ｒじ
（ここでゐは水素もしくは炭素数１〜２０のアルキル基
、アルケニル基、アルコキシ基。RcC=C-R (here, i is hydrogen or an alkyl group having 1 to 20 carbon atoms, an alkenyl group, or an alkoxy group.
アルデヒド基、アシル基またはシアノ基でアルか、フェ
ニル、ナフチル等の７リール基またはベンジル等の７ラ
ルキル基である。It is an aldehyde group, an acyl group, or a cyano group, or a heptalyl group such as phenyl or naphthyl, or a heptaralkyl group such as benzyl.
Ｒ１１，Ｒ１２およびＲＩＳは水素、炭素数１〜６の低
級アルケニル基、アルコキシ基、アルデヒド基、アシル
基、シアノ基、アリール基およびアラルキル基のいずれ
かである。勿論Ｒｅ、 ＲＩｔ、 Ｒ）およびＲｕは同
じであってもよく、また異なっていても差しつかえない
。R11, R12 and RIS are hydrogen, a lower alkenyl group having 1 to 6 carbon atoms, an alkoxy group, an aldehyde group, an acyl group, a cyano group, an aryl group, or an aralkyl group. Of course, Re, RIt, R) and Ru may be the same or different.
さらにＲＩｔまたーはＲ＋ＩとＲＩｔまたはシとがなん
らかの形で結合した環状化合物であつてもよい。）
この様なオレフィン化合物としては、エチレン、プロピ
レン、ブテン、１．３−７’タジエン。Furthermore, it may be a cyclic compound in which RIt or R+I and RIt or C are combined in some form. ) Such olefin compounds include ethylene, propylene, butene, and 1,3-7'tadiene.
１．３−ペンタジェン、イソプレン、ヘキセン。1.3-Pentadiene, isoprene, hexene.
スチレン、メチルビニルエーテル、メチルビニルケトン
、クロトンアルデヒド、熱水マレイン酸、メチルメタク
リレート、アクリロニトリルさらにはシクロペンタジェ
ン、ビニルシクロへ午セン、ビニルノルボルネン等のよ
うな環状オレフィンなどが含まれる。Included are styrene, methyl vinyl ether, methyl vinyl ketone, crotonaldehyde, hydrothermal maleic acid, methyl methacrylate, acrylonitrile, and cyclic olefins such as cyclopentadiene, vinyl cyclobenzene, vinyl norbornene, and the like.
デ（−ルス・アルダ−反応における共役ジオレフィンの
オレフィンに対するモル比は。What is the molar ratio of conjugated diolefin to olefin in the Delus-Alder reaction?
目的生成物として何を得るかによっても異なるが、一般
にｌ：１０からｌｏ：１までの範囲が適当である。反応
には一般にｎ−へブタンやベンゼン等のような不活性溶
媒が使用されるが、これらの溶媒は必ずしも使う必要が
ない。Although it varies depending on the desired product to be obtained, a range of 1:10 to 1:1 is generally suitable. Inert solvents such as n-hebutane, benzene, etc. are generally used in the reaction, but these solvents do not necessarily need to be used.
反応温度は９反応基質の反応性に応じて一１Ｏ℃〜１８
０℃あるいはそれ以上の温度が選ばれる。The reaction temperature ranges from -10°C to 18°C depending on the reactivity of the reaction substrate.
A temperature of 0°C or higher is selected.
反応時間は反応基質の性質により５分〜５時間あるいは
それ以上であるが１反応温度によりて適当に変えること
ができる。とりわけ本発明法では高温反応が支障な〈実
施可能である乃で比較的短時間、たとえば５〜３０分の
反応時間で充分に反応率をあげることができて説明する
が本発明はこれらに限定されるものではない。The reaction time ranges from 5 minutes to 5 hours or more depending on the nature of the reaction substrate, but can be changed appropriately depending on the reaction temperature. In particular, in the method of the present invention, high-temperature reactions are a problem (we will explain that the reaction rate can be sufficiently increased in a relatively short time, for example, 5 to 30 minutes, but the present invention is limited to these). It is not something that will be done.
実施例１〜３および比較例１〜４
１．３−ブタジェンあるいはイソプレンとシクロペンタ
ジェンをモル比Ｌ３：Ｉで混合し１表−１に示す種々の
添加物を５０００ｐｐｍ加工て内容積１００ｃｃのステ
ンレス製オートクレーブに入れ１３０℃で３時間反応さ
せた。反応終了後反応液を９２℃、２ｍｍＨｇの条件で
減圧処理し残った重合体忠ＩＩ生成物の量を計算し全反
応液（二対する重量割合で比較した。結果を表−１に示
す。（重合体副生成物については従来メタノールあるい
はアセトンを加えて白濁物の析出により観察されていた
が巾広い分子量分布をもつ重合体副生成物の生成量を定
量化するため上記方法を用いた。）
実施例−４
１，３−ゲタジエンとシクロペンタジェンをモル比１．
３：１で混合し、 Ｎ、Ｎ−ジエチルヒドロキシルアミ
ンを１５００ｐｐｍ加えて内容積１００ｃｃのステンレ
ス製オートクレーブに入れ１３０℃で３時間処理した。Examples 1 to 3 and Comparative Examples 1 to 4 1.3-Butadiene or isoprene and cyclopentadiene were mixed at a molar ratio of L3:I and processed with 5000 ppm of various additives shown in Table 1 to produce stainless steel with an internal volume of 100 cc. The mixture was placed in a manufactured autoclave and reacted at 130°C for 3 hours. After the reaction was completed, the reaction solution was treated under reduced pressure at 92°C and 2 mmHg, and the amount of the remaining Polymer Chu II product was calculated and compared in terms of weight ratio to the total reaction solution (2 mmHg).The results are shown in Table 1. Polymer by-products have traditionally been observed by adding methanol or acetone and precipitating white turbidity, but the above method was used to quantify the amount of polymer by-products with a wide molecular weight distribution.) Example-4 1,3-getadiene and cyclopentadiene were mixed at a molar ratio of 1.
The mixture was mixed at a ratio of 3:1, 1500 ppm of N,N-diethylhydroxylamine was added, and the mixture was placed in a stainless steel autoclave with an internal volume of 100 cc and treated at 130°C for 3 hours.
その結果重合体副生成物の量は１．６％であった。As a result, the amount of polymer by-product was 1.6%.
比較例−５
１，３−ブタジェンとシクロペンタジェンを■：１のモ
ル比で滞留時間１０分になる様にフィードし１反応温度
１６０℃で１００時間連続運転を実施した。反応停止後
オートクレーブ内は析出した重合体副生成物で一杯にな
っていた。尚この時反応液中の重合体副生成物は２．６
％であった。Comparative Example-5 1,3-butadiene and cyclopentadiene were fed at a molar ratio of 1:1 so that the residence time was 10 minutes, and continuous operation was carried out for 100 hours at a reaction temperature of 160°C. After the reaction was stopped, the autoclave was filled with precipitated polymer by-products. At this time, the polymer by-product in the reaction solution was 2.6
%Met.
実施例−５
比較例−５と同一条件で、 Ｎ、Ｎ−ジエチルヒドロキ
シルアミン２５００１）ｐｍ添加し実験を行なりなとこ
ろ反応停止後オートクレーブ内に析出した重合体副生成
物はなくきれいであった。尚この時反応液中の重合体副
生成物は０．０５％であった。Example 5 An experiment was conducted under the same conditions as Comparative Example 5, with the addition of 25,001 pm of N,N-diethylhydroxylamine, and the autoclave was clean with no polymer by-product precipitated after the reaction was stopped. . At this time, the amount of polymer by-products in the reaction solution was 0.05%.
実施例−６ Ｎ、Ｎ−ジエチルヒドロキシルアミンｓｏｏ。Example-6 N,N-diethylhydroxylamine soo.
ｐｐｍヲ含むブタジェンとヘキセンの混合液（フタジエ
ン／４−メチル−１−ペンテン＝１．２（モル比））を
１００ｃｃのステンレス製オートクレーブにて１３０℃
で３時間処理した。その結果重合体副生成物は０．６４
％であった。A mixed solution of butadiene and hexene containing ppm (phtadiene/4-methyl-1-pentene = 1.2 (molar ratio)) was heated at 130°C in a 100cc stainless steel autoclave.
It was treated for 3 hours. As a result, the polymer by-product is 0.64
%Met.
比較例−６
実施例−６と同一条件で重合防止剤を添加せずＧこ実験
を行なった。その結果重合体副生成物は９．１％であや
だ。Comparative Example-6 An experiment was conducted under the same conditions as in Example-6 without adding a polymerization inhibitor. As a result, the polymer by-product was 9.1%.
〈発明の効果〉
兵役ジオレフィン化合物とオレフィン化合物とを反応さ
せるディールス・アルダー反応において、一般式（Ｉ）
（Ｒ，は水素原子、又は炭素数ｌ〜８のアルキル基、
Ｒ２は炭素数１〜８のアルキル示す。又Ｒ１とＲ２は
同一であっても号１１＠であってもよい。）
で表わされるヒドロキシルアミンを反応物の全量に対し
て１０ − １００００ｐｐｍ存在させて兵役ジオレフ
ィン化合物とオレフィン化合物とを反応させることによ
り，重合物の析出・付着による装置の閉塞，装置の内壁
面Ｇこおける重合体被膜の形成などの障害を生じること
なく良好な選択率で，長時間反応させること力；できた
。<Effect of the invention> In the Diels-Alder reaction in which a military diolefin compound and an olefin compound are reacted, general formula (I) (R is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,
R2 represents alkyl having 1 to 8 carbon atoms. Further, R1 and R2 may be the same or may be number 11@. ) By reacting the military diolefin compound with the olefin compound in the presence of 10 to 10,000 ppm of hydroxylamine represented by It was possible to carry out the reaction for a long time with good selectivity without causing problems such as the formation of a polymer film.
手続補正書（自発） 昭和６１年５月１ζ日Procedural amendment (voluntary) May 1ζ, 1985
Claims (5)
反応させるディールス・アルダー反応において、一般式
（ I ） （ I ）▲数式、化学式、表等があります▼ （Ｒ＿１は水素原子、又は炭素数１〜８のアルキル基、
Ｒ＿２は炭素数１〜８のアルキル基を示す。又Ｒ＿１と
Ｒ＿２は同一であっても別種であってもよい。） で表わされるヒドロキシルアミンを反応物の全量に対し
て１０〜１００００ｐｐｍ存在させて共役ジオレフィン
化合物とオレフィン化合物とを反応させることを特徴と
する重合体副生成物の生成防止方法。(1) In the Diels-Alder reaction in which a conjugated diolefin compound and an olefin compound are reacted, the general formula (I) (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (R_1 is a hydrogen atom or has a carbon number of 1 to 8 an alkyl group,
R_2 represents an alkyl group having 1 to 8 carbon atoms. Further, R_1 and R_2 may be the same or different types. 1. A method for preventing the formation of polymer by-products, which comprises reacting a conjugated diolefin compound and an olefin compound in the presence of 10 to 10,000 ppm of hydroxylamine represented by the following formula based on the total amount of the reactants.
プレン、オレフィン化合物がシクロペンタジエンである
、特許請求の範囲第１項記載の重合体副生成物の生成防
止法。(2) The method for preventing the formation of polymer by-products according to claim 1, wherein the conjugated diolefin is 1,3-butadiene or isoprene, and the olefin compound is cyclopentadiene.
プレン、オレフィン化合物がシクロペンタジエンとジシ
クロペンタジエンの混合物である特許請求の範囲第１項
記載の重合体副生成物の生成防止法。(3) The method for preventing the formation of polymer by-products according to claim 1, wherein the conjugated diolefin is 1,3-butadiene or isoprene, and the olefin compound is a mixture of cyclopentadiene and dicyclopentadiene.
キシルアミン、Ｎ，Ｎ−ジイソプロピルヒドロキシルア
ミン、Ｎ，Ｎ−ジ−ｎ−ブチルヒドロキシルアミンから
選ばれる化合物である特許請求の範囲第１項記載の重合
体副生成物の生成防止法。(4) The polymer according to claim 1, wherein the hydroxylamine is a compound selected from N,N-dimethylhydroxylamine, N,N-diisopropylhydroxylamine, and N,N-di-n-butylhydroxylamine. Method for preventing the formation of coalescence by-products.
量が１００〜５０００ｐｐｍである、特許請求の範囲第
１項記載の重合体副生成物の生成防止方法。(5) The method for preventing the formation of polymer by-products according to claim 1, wherein the amount of hydroxylamine added to the total amount of the reactants is 100 to 5000 ppm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP860486A JPS62167733A (en) | 1986-01-18 | 1986-01-18 | Method for preventing formation of polymeric by-product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP860486A JPS62167733A (en) | 1986-01-18 | 1986-01-18 | Method for preventing formation of polymeric by-product |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62167733A true JPS62167733A (en) | 1987-07-24 |
| JPH0344056B2 JPH0344056B2 (en) | 1991-07-04 |
Family
ID=11697563
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP860486A Granted JPS62167733A (en) | 1986-01-18 | 1986-01-18 | Method for preventing formation of polymeric by-product |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62167733A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0317211A2 (en) * | 1987-11-13 | 1989-05-24 | Dow Corning Corporation | Method for stabilizing unsaturated organosilicone compositions |
| EP0785186A1 (en) | 1996-01-22 | 1997-07-23 | Mitsui Toatsu Chemicals, Inc. | Process for preparing diels-alder addition product from conjugated diolefin and acrylonitrile |
| US5767635A (en) * | 1993-06-04 | 1998-06-16 | Sihi Gmbh & Co. Kg | Displacement machine with electronic motor synchronization |
| JP2012530144A (en) * | 2009-06-16 | 2012-11-29 | アミリス， インコーポレイテッド | Cyclohexene 1,4-carboxylate |
| EP2781496A1 (en) | 2013-03-20 | 2014-09-24 | Evonik Industries AG | Method and composition for inhibiting the polymerisation of cyclopentadiene compounds |
| CN117567227A (en) * | 2023-11-16 | 2024-02-20 | 广东新华粤石化集团股份公司 | Preparation method of high-purity dicyclopentadiene and derivatives |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4926619A (en) * | 1972-07-05 | 1974-03-09 | ||
| JPS59167524A (en) * | 1983-03-03 | 1984-09-21 | ブナウエルケ・ヒユ−ルス・ゲゼルシヤフト・ミト・ベシユレンクテル・ハフツング | Method of preventing polymer by-products on manufacturing diels-alder adducts |
-
1986
- 1986-01-18 JP JP860486A patent/JPS62167733A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4926619A (en) * | 1972-07-05 | 1974-03-09 | ||
| JPS59167524A (en) * | 1983-03-03 | 1984-09-21 | ブナウエルケ・ヒユ−ルス・ゲゼルシヤフト・ミト・ベシユレンクテル・ハフツング | Method of preventing polymer by-products on manufacturing diels-alder adducts |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0317211A2 (en) * | 1987-11-13 | 1989-05-24 | Dow Corning Corporation | Method for stabilizing unsaturated organosilicone compositions |
| US5767635A (en) * | 1993-06-04 | 1998-06-16 | Sihi Gmbh & Co. Kg | Displacement machine with electronic motor synchronization |
| EP0785186A1 (en) | 1996-01-22 | 1997-07-23 | Mitsui Toatsu Chemicals, Inc. | Process for preparing diels-alder addition product from conjugated diolefin and acrylonitrile |
| US5861528A (en) * | 1996-01-22 | 1999-01-19 | Mitsui Chemicals, Inc. | Process for preparing diels-alder addition product from conjugated diolefin and acrylonitrile |
| JP2012530144A (en) * | 2009-06-16 | 2012-11-29 | アミリス， インコーポレイテッド | Cyclohexene 1,4-carboxylate |
| EP2781496A1 (en) | 2013-03-20 | 2014-09-24 | Evonik Industries AG | Method and composition for inhibiting the polymerisation of cyclopentadiene compounds |
| DE102013204950A1 (en) | 2013-03-20 | 2014-09-25 | Evonik Industries Ag | Process and composition for inhibiting the polymerization of cyclopentadiene compounds |
| CN117567227A (en) * | 2023-11-16 | 2024-02-20 | 广东新华粤石化集团股份公司 | Preparation method of high-purity dicyclopentadiene and derivatives |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0344056B2 (en) | 1991-07-04 |
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