JPH0312057B2 - - Google Patents
Info
- Publication number
- JPH0312057B2 JPH0312057B2 JP26614685A JP26614685A JPH0312057B2 JP H0312057 B2 JPH0312057 B2 JP H0312057B2 JP 26614685 A JP26614685 A JP 26614685A JP 26614685 A JP26614685 A JP 26614685A JP H0312057 B2 JPH0312057 B2 JP H0312057B2
- Authority
- JP
- Japan
- Prior art keywords
- acrylonitrile
- maleimides
- solution
- weight
- maleimide
- 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
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 33
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 31
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 14
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- 238000006116 polymerization reaction Methods 0.000 description 13
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 10
- 239000013078 crystal Substances 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- 238000004128 high performance liquid chromatography Methods 0.000 description 7
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 7
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000003112 inhibitor Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- KPQOXMCRYWDRSB-UHFFFAOYSA-N 1-(2-chlorophenyl)pyrrole-2,5-dione Chemical compound ClC1=CC=CC=C1N1C(=O)C=CC1=O KPQOXMCRYWDRSB-UHFFFAOYSA-N 0.000 description 3
- QYOJZFBQEAZNEW-UHFFFAOYSA-N 1-(2-methylphenyl)pyrrole-2,5-dione Chemical compound CC1=CC=CC=C1N1C(=O)C=CC1=O QYOJZFBQEAZNEW-UHFFFAOYSA-N 0.000 description 3
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- IYMZEPRSPLASMS-UHFFFAOYSA-N 3-phenylpyrrole-2,5-dione Chemical compound O=C1NC(=O)C(C=2C=CC=CC=2)=C1 IYMZEPRSPLASMS-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- -1 flakes Substances 0.000 description 2
- 150000002431 hydrogen 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
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- MKRBAPNEJMFMHU-UHFFFAOYSA-N 1-benzylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1CC1=CC=CC=C1 MKRBAPNEJMFMHU-UHFFFAOYSA-N 0.000 description 1
- FPDOHAABWLBAKE-UHFFFAOYSA-N 1-bromo-3-phenylpyrrole-2,5-dione Chemical compound O=C1N(Br)C(=O)C=C1C1=CC=CC=C1 FPDOHAABWLBAKE-UHFFFAOYSA-N 0.000 description 1
- SXTILEHINBCKSS-UHFFFAOYSA-N 1-chloro-3-phenylpyrrole-2,5-dione Chemical compound O=C1N(Cl)C(=O)C=C1C1=CC=CC=C1 SXTILEHINBCKSS-UHFFFAOYSA-N 0.000 description 1
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 description 1
- SJLLJZNSZJHXQN-UHFFFAOYSA-N 1-dodecylpyrrole-2,5-dione Chemical compound CCCCCCCCCCCCN1C(=O)C=CC1=O SJLLJZNSZJHXQN-UHFFFAOYSA-N 0.000 description 1
- FBPVUBVZRPURIU-UHFFFAOYSA-N 1-hexylpyrrole-2,5-dione Chemical compound CCCCCCN1C(=O)C=CC1=O FBPVUBVZRPURIU-UHFFFAOYSA-N 0.000 description 1
- HHVCCCZZVQMAMT-UHFFFAOYSA-N 1-hydroxy-3-phenylpyrrole-2,5-dione Chemical compound O=C1N(O)C(=O)C=C1C1=CC=CC=C1 HHVCCCZZVQMAMT-UHFFFAOYSA-N 0.000 description 1
- QCOLXFOZKYRROA-UHFFFAOYSA-N 1-methoxy-3-phenylpyrrole-2,5-dione Chemical compound O=C1N(OC)C(=O)C=C1C1=CC=CC=C1 QCOLXFOZKYRROA-UHFFFAOYSA-N 0.000 description 1
- IYBPIDAYDPNCTP-UHFFFAOYSA-N 1-methyl-3-phenylpyrrole-2,5-dione Chemical compound O=C1N(C)C(=O)C=C1C1=CC=CC=C1 IYBPIDAYDPNCTP-UHFFFAOYSA-N 0.000 description 1
- PSKLSRMDQQEEGQ-UHFFFAOYSA-N 1-nitro-3-phenylpyrrole-2,5-dione Chemical compound O=C1N([N+](=O)[O-])C(=O)C=C1C1=CC=CC=C1 PSKLSRMDQQEEGQ-UHFFFAOYSA-N 0.000 description 1
- KIKBJYQCJJXCBZ-UHFFFAOYSA-N 1-octylpyrrole-2,5-dione Chemical compound CCCCCCCCN1C(=O)C=CC1=O KIKBJYQCJJXCBZ-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- WAXBZQUSTLNLPU-UHFFFAOYSA-N 2,5-dioxo-3-phenylpyrrole-1-carboxylic acid Chemical compound O=C1N(C(=O)O)C(=O)C=C1C1=CC=CC=C1 WAXBZQUSTLNLPU-UHFFFAOYSA-N 0.000 description 1
- ZJKWJHONFFKJHG-UHFFFAOYSA-N 2-Methoxy-1,4-benzoquinone Chemical compound COC1=CC(=O)C=CC1=O ZJKWJHONFFKJHG-UHFFFAOYSA-N 0.000 description 1
- ODJQKYXPKWQWNK-UHFFFAOYSA-N 3,3'-Thiobispropanoic acid Chemical class OC(=O)CCSCCC(O)=O ODJQKYXPKWQWNK-UHFFFAOYSA-N 0.000 description 1
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 1
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 description 1
- 206010011224 Cough Diseases 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- GHAZCVNUKKZTLG-UHFFFAOYSA-N N-ethyl-succinimide Natural products CCN1C(=O)CCC1=O GHAZCVNUKKZTLG-UHFFFAOYSA-N 0.000 description 1
- HDFGOPSGAURCEO-UHFFFAOYSA-N N-ethylmaleimide Chemical compound CCN1C(=O)C=CC1=O HDFGOPSGAURCEO-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000003905 agrochemical Substances 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- CMRVDFLZXRTMTH-UHFFFAOYSA-L copper;2-carboxyphenolate Chemical compound [Cu+2].OC1=CC=CC=C1C([O-])=O.OC1=CC=CC=C1C([O-])=O CMRVDFLZXRTMTH-UHFFFAOYSA-L 0.000 description 1
- IXPUJMULXNNEHS-UHFFFAOYSA-L copper;n,n-dibutylcarbamodithioate Chemical compound [Cu+2].CCCCN(C([S-])=S)CCCC.CCCCN(C([S-])=S)CCCC IXPUJMULXNNEHS-UHFFFAOYSA-L 0.000 description 1
- ZOUQIAGHKFLHIA-UHFFFAOYSA-L copper;n,n-dimethylcarbamodithioate Chemical compound [Cu+2].CN(C)C([S-])=S.CN(C)C([S-])=S ZOUQIAGHKFLHIA-UHFFFAOYSA-L 0.000 description 1
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000011978 dissolution method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000005722 itchiness Effects 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- SEEYREPSKCQBBF-UHFFFAOYSA-N n-methylmaleimide Chemical compound CN1C(=O)C=CC1=O SEEYREPSKCQBBF-UHFFFAOYSA-N 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- JHLVQVPUILZTNX-UHFFFAOYSA-N prop-2-enenitrile;pyrrole-2,5-dione Chemical compound C=CC#N.O=C1NC(=O)C=C1 JHLVQVPUILZTNX-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004250 tert-Butylhydroquinone Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 235000019281 tert-butylhydroquinone Nutrition 0.000 description 1
- DUBNHZYBDBBJHD-UHFFFAOYSA-L ziram Chemical compound [Zn+2].CN(C)C([S-])=S.CN(C)C([S-])=S DUBNHZYBDBBJHD-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Pyrrole Compounds (AREA)
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明はマレイミド類をアクリロニトリルの溶
液として移送ないし貯蔵する方法に関するもので
ある。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for transporting or storing maleimides as a solution of acrylonitrile.
マレイミド類は樹脂、医薬、農薬などの原料と
して有用な化合物であるが、本発明は取扱いが容
易で安全かつ簡単なマレイミド類の移送ならびに
貯蔵方法を提供するものである。 Maleimides are compounds useful as raw materials for resins, medicines, agricultural chemicals, etc., and the present invention provides a method for transporting and storing maleimides that is easy to handle, safe, and simple.
［従来の技術］
従来、常温で固体のマレイミド類は粉体、フレ
ーク、タブレツトなどの形状で取扱われているの
が一般的である。しかしながら、このような形態
のマレイミド類中にはマレイミド類の微粉末が含
まれている。[Prior Art] Maleimides, which are solid at room temperature, have conventionally been generally handled in the form of powder, flakes, tablets, and the like. However, such a form of maleimide contains fine powder of maleimide.
とくにこのような固体状のマレイミド類の移送
中、マレイミド類の粉化が進み、マレイミド類の
微粉末が多量に発生する。 In particular, during the transfer of such solid maleimides, the maleimides are pulverized and a large amount of fine powder of maleimides is generated.
マレイミド類そのものは人体に対して刺激性が
あり、特に微粉末を吸入すると鼻腔、咽喉を刺激
し、咳、くしやみが出、また皮膚に付着したまま
放置すると炎症をおこすなど好ましくない性質を
有している。それゆえ、このような微粉末を含有
しているマレイミド類を取扱う場合には、できる
かぎり皮膚への接触をさけるよう厳重な注意を払
う必要がある。 Maleimides themselves are irritating to the human body, and have undesirable properties such as irritating the nasal passages and throat, causing coughing and itchiness when inhaled, especially when finely powdered, and causing inflammation when left on the skin. are doing. Therefore, when handling maleimides containing such fine powder, strict care must be taken to avoid contact with the skin as much as possible.
したがつて、マレイミド類の移送に際してでき
るだけ微粉末を発生しないようにしたり、また移
送後のマレイミド類から微粉末を除去するために
多大の労力を要している。 Therefore, a great deal of effort is required to prevent the generation of fine powder as much as possible during the transfer of maleimide, and to remove fine powder from the maleimide after transfer.
さらに、固体物質の移送は、多くの場合、紙
袋、ドラム缶、コンテナなどに固体物質を充てん
し移送されるが、これらの場合どうしてもマレイ
ミド類と人体との接触がさけられず、人体にマレ
イミド類の微粉末が付着することは不可避であ
る。 Furthermore, in many cases, solid substances are transported by filling paper bags, drums, containers, etc., but in these cases, contact between maleimides and the human body is unavoidable, and maleimides may come into contact with the human body. Adhesion of fine powder is inevitable.
加えて、人体と接触しないようにするために固
体物質の配管による移送は基本的にむつかしく配
管移送中に管内を閉塞したりするために、これら
固体物質を安定に移送するために、固体の形、大
きさ、比重などにきびしい制約が課せられる。 In addition, in order to avoid contact with the human body, it is difficult to transfer solid substances through piping, and the inside of the pipe may become clogged during piping transfer. Strict restrictions are imposed on size, specific gravity, etc.
このように、常温で固体のマレイミド類の移送
方法には数々の困難な問題があると言わざるをえ
ない。同様のことは、その貯蔵時についてもいえ
る。 As described above, it must be said that there are many difficult problems in the method of transporting maleimides which are solid at room temperature. The same thing can be said about the time of storage.
［発明が解決しようとする問題点］
このように現存するマレイミド類の移送ならび
に貯蔵方法は多くの問題点を有しており、特に工
業的に多量に取扱うに際して種々の不都合を生じ
ている。[Problems to be Solved by the Invention] As described above, the existing methods for transporting and storing maleimides have many problems, and in particular, various inconveniences occur when handling large quantities industrially.
そこで、本発明の目的は移送において微粉末の
発生の心配がなく、配管、タンクのバルブ、ノズ
ル等の閉塞を起こさないようなマレイミド類の安
全かつ簡単な移送方法ならびに貯蔵方法を提供す
ることにある。 Therefore, an object of the present invention is to provide a safe and simple method for transferring and storing maleimides that does not cause the generation of fine powder during transfer and does not cause clogging of pipes, tank valves, nozzles, etc. be.
［問題点を解決するための手段］
かかる目的を達成するために、本発明者等は鋭
意検討した結果、マレイミド類はアクリロニトリ
ルへ溶解し易く、かつ、溶解度が高いために、容
易に高濃度の溶液を得ることができ、加えて、溶
液の過飽和領域が著るしく広く、広い温度範囲に
わたつて溶液を安定に取扱えること、さらに、予
期せざることではあるが、マレイミド類は常温よ
り比較的高い温度でも重合禁止剤の存在下アクリ
ロニトリル中において重合せず安定であることを
発見した。その結果、マレイミド類をアクリロニ
トリル溶液となしこの形態で移送することによ
り、全く微粉末の発生もなく容易に取扱えること
を見出し、本発明を完成するにいたつたものであ
る。[Means for Solving the Problems] In order to achieve the above object, the present inventors have made extensive studies and found that maleimides are easily soluble in acrylonitrile, and because of their high solubility, they can be easily dissolved in high concentrations. In addition, the supersaturation region of the solution is significantly wide, and the solution can be stably handled over a wide temperature range.Also, unexpectedly, maleimides are We have discovered that it does not polymerize and is stable in acrylonitrile in the presence of a polymerization inhibitor, even at extremely high temperatures. As a result, the inventors discovered that by converting maleimides into acrylonitrile solutions and transferring them in this form, they could be easily handled without generating any fine powder, leading to the completion of the present invention.
マレイミド類はABS樹脂、AAS樹脂、AS樹
脂、ACS樹脂などの耐熱向上剤として広く使用
されており、多くの場合アクリロニトリル、スチ
レンなどのモノマーと共重合させることにより用
いられる。 Maleimides are widely used as heat resistance improvers for ABS resins, AAS resins, AS resins, ACS resins, etc., and are often used by copolymerizing with monomers such as acrylonitrile and styrene.
ところが、マレイミド類はスチレンには溶解し
にくいばかりでなく、スチレン中で重合禁止剤の
存在下で常温においてさえ、容易に重合してしま
う。それに対して、アクリロニトリルに対するマ
レイミド類の高い溶解性、およびアクリロニトリ
ル中でのマレイミド類の重合に対する安定性など
を考えると、マレイミド類をアクリロニトリルの
溶液として取扱うことによつて、人体へ直接接触
することもなく、液体として取扱えることから、
容易に移送もでき、貯蔵も安全にでき、微粉末の
発生もなく、樹脂合成時においてもアクリロニト
リルがマレイミド類以外の共重合組成の１種類で
あることから、重合反応にマレイミドのアクリロ
ニトリル溶液をそのまま用いることができるな
ど、多くの利点が得られる。 However, maleimides are not only difficult to dissolve in styrene, but also easily polymerize in styrene even at room temperature in the presence of a polymerization inhibitor. On the other hand, considering the high solubility of maleimides in acrylonitrile and the stability of maleimides against polymerization in acrylonitrile, direct contact with the human body is possible by handling maleimides as a solution of acrylonitrile. Because it can be handled as a liquid,
It is easy to transport, can be stored safely, does not generate fine powder, and since acrylonitrile is one type of copolymer composition other than maleimides during resin synthesis, a solution of maleimide in acrylonitrile can be directly used in the polymerization reaction. There are many advantages, such as the ability to use
この様に、マレイミド類を移送するにあたり、
アクリロニトリル溶液として取扱う方法はまさに
理想的な方法であると言わざるをえない。 In this way, when transferring maleimides,
It must be said that the method of handling it as an acrylonitrile solution is truly an ideal method.
すなわち、本発明はマレイミド類を重合禁止剤
の存在下アクリロニトリルに溶解させ溶液として
取扱うことを特徴とするマレイミド類の移送なら
びに貯蔵方法である。 That is, the present invention is a method for transporting and storing maleimides, which is characterized in that maleimides are dissolved in acrylonitrile in the presence of a polymerization inhibitor and handled as a solution.
本発明の方法により移送ならびに貯蔵できるマ
レイミド類としては、例えば、Ｎ−メチルマレイ
ミド、Ｎ−エチルマレイミド、Ｎ−ヘキシルマレ
イミド、Ｎ−オクチルマレイミド、Ｎ−ドデシル
マレイミド、Ｎ−ベンジルマレイミド、Ｎ−シク
ロヘキシルマレイミド、Ｎ−フエニルマレイミ
ド、Ｎ−ニトロフエニルマレイミド、Ｎ−メトキ
シフエニルマレイミド、Ｎ−メチルフエニルマレ
イミド、Ｎ−カルボキシフエニルマレイミド、Ｎ
−ヒドロキシフエニルマレイミド、Ｎ−クロルフ
エニルマレイミド、Ｎ−ジメチルフエニルマレイ
ミド、Ｎ−ジクロルフエニルマレイミド、Ｎ−ブ
ロムフエニルマレイミド、Ｎ−ジブロムフエニル
マレイミド、Ｎ−トリクロルフエニルマレイミ
ド、Ｎ−トリブロムフエニルマレイミドなどが挙
げられるが、これらに限定されるものではない。 Examples of maleimides that can be transported and stored by the method of the present invention include N-methylmaleimide, N-ethylmaleimide, N-hexylmaleimide, N-octylmaleimide, N-dodecylmaleimide, N-benzylmaleimide, and N-cyclohexylmaleimide. , N-phenylmaleimide, N-nitrophenylmaleimide, N-methoxyphenylmaleimide, N-methylphenylmaleimide, N-carboxyphenylmaleimide, N
-Hydroxyphenylmaleimide, N-chlorophenylmaleimide, N-dimethylphenylmaleimide, N-dichlorophenylmaleimide, N-bromphenylmaleimide, N-dibromphenylmaleimide, N-trichlorophenylmaleimide, N- Examples include, but are not limited to, -tribromphenylmaleimide and the like.
また、固体状のマレイミド類をアクリロニトリ
ルに溶解させるに際し用いられる重合禁止剤とし
ては例えば、メトキシベンゾキノン、ｐ−メトキ
シフエノール、フエノチアジン、ハイドロキノ
ン、アルキル化ジフエニルアミン類、メチレンブ
ルー、tert−ブチルカテコール、tert−ブチルハ
イドロキノン、ジメチルジチオカルバミン酸亜
鉛、ジメチルジチオカルバミン酸銅、ジブチルジ
チオカルバミン酸銅、サリチル酸銅、チオジプロ
ピオン酸エステル類、メルカプトベンズイミダゾ
ール、トリフエニルホスフアイト、アルキルフエ
ノール類、アルキルビスフエノール類などが挙げ
られるが、これらに限定されるものではない。そ
の使用量はマレイミド類のアクリロニトリル溶液
に対して0.0001〜0.5重量％、好ましくは0.001〜
0.1重量％である。尚、重合禁止剤の種類につい
ては、製造する重合体の種類、重合の方法、使用
する開始剤などを勘案して選択される。 Examples of polymerization inhibitors used when dissolving solid maleimides in acrylonitrile include methoxybenzoquinone, p-methoxyphenol, phenothiazine, hydroquinone, alkylated diphenylamines, methylene blue, tert-butylcatechol, and tert-butylhydroquinone. , zinc dimethyldithiocarbamate, copper dimethyldithiocarbamate, copper dibutyldithiocarbamate, copper salicylate, thiodipropionic acid esters, mercaptobenzimidazole, triphenylphosphite, alkylphenols, alkylbisphenols, etc. It is not limited to. The amount used is 0.0001 to 0.5% by weight, preferably 0.001 to 0.5% by weight based on the acrylonitrile solution of maleimides.
It is 0.1% by weight. The type of polymerization inhibitor is selected in consideration of the type of polymer to be produced, the polymerization method, the initiator to be used, and the like.
マレイミド類のアクリロニトリルへ溶解させる
温度は、アクリロニトリルの沸点以下であること
が好ましく、アクリロニトリルが高い蒸気圧を有
するところから通常40〜60℃で溶解が行なわれ
る。 The temperature at which the maleimide is dissolved in acrylonitrile is preferably below the boiling point of acrylonitrile, and since acrylonitrile has a high vapor pressure, the dissolution is usually carried out at 40 to 60°C.
なお、溶解方法については基本的にいずれの方
法も採用できるが、マレイミド類にアクリロニト
リルを投入してもよいし、アクリロニトリル中に
マレイミド類を投入することもできる。マレイミ
ド類のアクリロニトリル溶液の濃度は、溶液を取
扱う温度によつて決められるが、通常マレイミド
類の溶液が常温で取扱われることから、50重量％
程度の濃度が好んで用いられる。しかしながら、
最終樹脂製品としてマレイミド含有量の高いもの
を必要とする場合には該溶液を保温してマレイミ
ド類の高濃度溶液として取扱われる。かかる場合
には、50〜80重量％のマレイミド類濃度が用いら
れる。 As for the dissolution method, basically any method can be adopted, but acrylonitrile may be added to maleimide, or maleimide may be added to acrylonitrile. The concentration of maleimide acrylonitrile solution is determined by the temperature at which the solution is handled, but since maleimide solutions are usually handled at room temperature, it is 50% by weight.
Concentrations of about 10% are preferred. however,
When a final resin product with a high maleimide content is required, the solution is kept warm and handled as a high concentration solution of maleimides. In such cases, maleimides concentrations of 50 to 80% by weight are used.
以下、本発明を実施例によつてさらに詳しく説
明する。 Hereinafter, the present invention will be explained in more detail with reference to Examples.
実施例 １
撹拌機と冷却管を取付けた500mlのフラスコに
アクリロニトリル100ｇとｐ−メトキシフエノー
ル10mgを入れた。水浴温度を調整し、内温を30℃
とした。次に撹拌しながら純度99.5重量％のＮ−
フエニルマレイミドの結晶を100ｇ加えたところ、
Ｎ−フエニルマレイミドの結晶はすみやかに溶解
し、完全に澄明な黄色のアクリロニトリル溶液が
えられた。Example 1 100 g of acrylonitrile and 10 mg of p-methoxyphenol were placed in a 500 ml flask equipped with a stirrer and a condenser. Adjust the water bath temperature to bring the internal temperature to 30℃
And so. Next, while stirring, N- with a purity of 99.5% by weight was added.
When 100g of phenylmaleimide crystals were added,
The N-phenylmaleimide crystals dissolved quickly, giving a completely clear yellow acrylonitrile solution.
なお、この溶液を−５℃まで冷却してもＮ−フ
エニルマレイミドの析出は見られず、安定した溶
液状態で取扱えるものであつた。次に、内温を50
℃にして30日間保持した。30日後も液の澄明さは
変わらず、この溶液からアクリロニトリルを蒸発
せしめたところ、彩やかな黄色の結晶をえた。こ
のもののＮ−フエニルマレイミド含有量を高速液
体クロマトグラフイーで測定したところ、99.5重
量％であり、全く重合は見られなかつた。 Incidentally, even when this solution was cooled to -5°C, no precipitation of N-phenylmaleimide was observed, and the solution could be handled in a stable solution state. Next, increase the internal temperature to 50
℃ and kept for 30 days. After 30 days, the liquid remained clear, and when acrylonitrile was evaporated from this solution, bright yellow crystals were obtained. When the N-phenylmaleimide content of this product was measured by high performance liquid chromatography, it was 99.5% by weight, and no polymerization was observed.
実施例 ２
実施例１においてｐ−メトキシフエノール10mg
の代わりにｐ−tert−ブチルカテコール50mgを加
えた以外は実施例１と同じ操作をし、完全に澄明
な黄色のアクリロニトリル溶液をえた。Example 2 10 mg of p-methoxyphenol in Example 1
The same procedure as in Example 1 was carried out except that 50 mg of p-tert-butylcatechol was added instead of , to obtain a completely clear yellow acrylonitrile solution.
次に内温を50℃にして30日間保持した。30日後
も液の澄明さは全く変わらず、この溶液からアク
リロニトリルを蒸発せしめたところ、彩やかな黄
色の結晶をえた。このもののＮ−フエニルマレイ
ミド含有量を高速液体クロマトグラフイーで測定
したところ、99.5重量％であり、全く重合は見ら
れなかつた。 Next, the internal temperature was raised to 50°C and maintained for 30 days. After 30 days, the clarity of the liquid remained unchanged, and when acrylonitrile was evaporated from this solution, bright yellow crystals were obtained. When the N-phenylmaleimide content of this product was measured by high performance liquid chromatography, it was 99.5% by weight, and no polymerization was observed.
比較例 １
実施例１で用いたと同じフラスコにスチレン
100ｇを入れ、内温を30℃に調整した。続いて撹
拌しながら純度99.5重量％のＮ−フエニルマレイ
ミドの結晶と、ｐ−tert−ブチルカテコール50mg
を加えたところ、溶解し完全に澄明な黄色のスチ
レン溶液がえられた。Comparative Example 1 Styrene was added to the same flask used in Example 1.
100g was added and the internal temperature was adjusted to 30°C. Next, while stirring, crystals of N-phenylmaleimide with a purity of 99.5% by weight and 50 mg of p-tert-butylcatechol were added.
was added, resulting in a completely clear yellow styrene solution.
次に、このものの内温を40℃にして保持したと
ころ３日後に溶液は著しく白だくした。この溶液
からスチレンを減圧下で留去したところ粘着性の
ある黄白色の物質がえられた。このもののＮ−フ
エニルマレイミド含有量を高速液体クロマトグラ
フイーにて測定したところ75.5重量％であり、明
らかに重合していることがわかつた。 Next, the internal temperature of this solution was kept at 40°C, and after 3 days, the solution turned white significantly. When styrene was distilled off from this solution under reduced pressure, a sticky yellow-white substance was obtained. The N-phenylmaleimide content of this product was measured by high performance liquid chromatography and was found to be 75.5% by weight, indicating that it was clearly polymerized.
比較例 ２
比較例１において、ｐ−tert−ブチルカテコー
ルの代わりにｐ−メトキシフエノールを用い、保
持した温度を20℃にした以外は比較例１と同様の
操作をしたところ、７日後に溶液は白だくした。Comparative Example 2 The same procedure as in Comparative Example 1 was performed except that p-methoxyphenol was used instead of p-tert-butylcatechol and the temperature was maintained at 20°C. After 7 days, the solution It was white.
この溶液からスチレンを減圧下で留去したとこ
ろ粘着性のある黄白色の物質がえられた。このも
ののＮ−フエニルマレイミド含有量を高速液体ク
ロマトグラフイーにて測定したところ90重量％で
あり、明らかに重合していることがわかつた。 When styrene was distilled off from this solution under reduced pressure, a sticky yellow-white substance was obtained. The N-phenylmaleimide content of this product was measured by high performance liquid chromatography and was found to be 90% by weight, indicating that it was clearly polymerized.
実施例 ３
実施例１において、Ｎ−フエニルマレイミドの
代わりに純度99.5重量％のＮ−（ｏ−メチルフエ
ニル）マレイミドを用い、ｐ−メトキシフエノー
ルの代わりに２，４−ジメチル−６−tert−ブチ
ルフエノール100mgを用いた以外は同様の操作を
行ない、澄明な淡黄色のＮ−（ｏ−メチルフエニ
ル）マレイミドの50重量％のアクリロニトリル溶
液をえた。Example 3 In Example 1, N-(o-methylphenyl)maleimide with a purity of 99.5% by weight was used instead of N-phenylmaleimide, and 2,4-dimethyl-6-tert-butyl was used instead of p-methoxyphenol. The same operation was carried out except that 100 mg of phenol was used to obtain a clear pale yellow 50% by weight acrylonitrile solution of N-(o-methylphenyl)maleimide.
この溶液の内温を50℃にして30日間保持した。
30日後、アクリロニトリルを蒸発せしめたところ
彩やかな淡黄色の結晶をえた。次にこのものの中
のＮ−（ｏ−メチルフエニル）マレイミドの含有
量を高速液体クロマトグラフイーにて測定したと
ころ99.5重量％であり全く重合による変化は見ら
れなかつた。 The internal temperature of this solution was brought to 50°C and maintained for 30 days.
After 30 days, when the acrylonitrile was evaporated, bright yellow crystals were obtained. Next, the content of N-(o-methylphenyl)maleimide in this product was measured by high performance liquid chromatography and was found to be 99.5% by weight, with no change at all due to polymerization.
実施例 ４
実施例１においてＮ−フエニルマレイミドの代
わりに純度99.0重量％のＮ−（ｏ−クロルフエニ
ル）マレイミドを用い、ｐ−メトキシフエノール
の量を30mgとした以外は同様の操作を行ない澄明
な淡黄色のＮ−（ｏ−クロルフエニル）マレイミ
ドの50重量％のアクリロニトリル溶液をえた。Example 4 The same operation as in Example 1 was performed except that N-(o-chlorophenyl)maleimide with a purity of 99.0% by weight was used instead of N-phenylmaleimide, and the amount of p-methoxyphenol was changed to 30 mg. A pale yellow 50% by weight solution of N-(o-chlorophenyl)maleimide in acrylonitrile was obtained.
この溶液の内温を50℃にして30日間保持した。
30日後アクリロニトリルを蒸発せしめたところ彩
やかな淡黄色の結晶をえた。次にこのものの中の
Ｎ−（ｏ−クロルフエニル）マレイミドの含有量
を高速液体クロマトグラフイーにて測定したとこ
ろ99.0重量％であり、全く重合による変化は見ら
れなかつた。 The internal temperature of this solution was brought to 50°C and maintained for 30 days.
After 30 days, when the acrylonitrile was evaporated, colorful pale yellow crystals were obtained. Next, the content of N-(o-chlorophenyl)maleimide in this product was measured by high performance liquid chromatography and was found to be 99.0% by weight, with no change at all due to polymerization observed.
実施例 ５
撹拌機と冷却管を取付けた500mlのフラスコに
アクリロニトリル60ｇとｐ−メトキシフエノール
0.6mgを入れた。水浴温度を調整し内温を50℃と
した。Example 5 60 g of acrylonitrile and p-methoxyphenol were placed in a 500 ml flask equipped with a stirrer and condenser.
I added 0.6 mg. The water bath temperature was adjusted to bring the internal temperature to 50°C.
次に撹拌しながら純度99.5重量％のＮ−フエニ
ルマレイミドの結晶を140ｇ加えたところ、Ｎ−
フエニルマレイミドの結晶はすみやかに溶解し、
完全に澄明な黄色のアクリロニトリル溶液がえら
れた。 Next, 140g of N-phenylmaleimide crystals with a purity of 99.5% by weight were added while stirring.
Phenylmaleimide crystals dissolve quickly,
A completely clear yellow acrylonitrile solution was obtained.
次にこの溶液の内温を70℃にして30日間保持し
た。30日後も液の澄明さは変わらず、この溶液か
らアクリロニトリルを蒸発せしめたところ彩やか
な黄色の結晶をえた。 Next, the internal temperature of this solution was brought to 70°C and maintained for 30 days. After 30 days, the liquid remained clear, and when acrylonitrile was evaporated from this solution, bright yellow crystals were obtained.
このもののＮ−フエニルマレイミドの含有量を
高速液体クロマトグラフイーで測定したところ
99.5重量％であり、全く重合は見られなかつた。 The content of N-phenylmaleimide in this product was measured using high performance liquid chromatography.
It was 99.5% by weight, and no polymerization was observed.
参考例 １
Ｎ−フエニルマレイミドのアクリロニトリルに
対する溶解度を測定した。えられた溶解度曲線を
第１図に示した。Reference Example 1 The solubility of N-phenylmaleimide in acrylonitrile was measured. The solubility curve obtained is shown in FIG.
第１図は参考例１でえられたＮ−フエニルマレ
イミドのアクリロニトリルに対する溶解度曲線で
ある。
FIG. 1 is a solubility curve of N-phenylmaleimide obtained in Reference Example 1 in acrylonitrile.
１ 式
［式中、Ｚは水素または−COR基（基中、Ｒは
水素、C1-4−アルキル、C1-4−アルコキシ、C1-4
−ハロゲンアルキル、C2-4−アルケニル、ベンジ
ルまたはフエニル基を表わす。）を表わし、Ｘお
よびＹは互に独立したものであつて、各々水素、
ハロゲン原子、C1-4−アルキル、ハロゲンメチル
またはフエニル基を表わすか、または一緒になつ
て−CH＝CH−CH＝CH−を表わすか、または
Ｘは７位に結合してＲと一緒になつて−CH2CH2
−を表わす。］
で示される化合物を製造するにあたり、式
［式中、Ｒ，ＸおよびＹは前記と同じ意味を表わ
1 formula [Wherein, Z is hydrogen or -COR group (in the group, R is hydrogen, C 1-4 -alkyl, C 1-4 -alkoxy, C 1-4
- represents a halogenalkyl, C 2-4 -alkenyl, benzyl or phenyl group. ), where X and Y are independent of each other, and each represents hydrogen,
represents a halogen atom, C 1-4 -alkyl, halogenmethyl or phenyl group, or together represents -CH=CH-CH=CH-, or X is bonded to the 7-position and together with R Natsute－CH 2 CH 2
- represents. ] In producing the compound represented by the formula [In the formula, R, X and Y represent the same meanings as above.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26614685A JPS62126167A (en) | 1985-11-28 | 1985-11-28 | Transfer and storage of maleimide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26614685A JPS62126167A (en) | 1985-11-28 | 1985-11-28 | Transfer and storage of maleimide |
Related Child Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3339117A Division JPH0791267B2 (en) | 1991-12-20 | 1991-12-20 | Acrylonitrile solution for transfer or storage of maleimides |
| JP4291813A Division JPH0794433B2 (en) | 1992-10-29 | 1992-10-29 | Method for storing maleimides |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62126167A JPS62126167A (en) | 1987-06-08 |
| JPH0312057B2 true JPH0312057B2 (en) | 1991-02-19 |
Family
ID=17426942
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26614685A Granted JPS62126167A (en) | 1985-11-28 | 1985-11-28 | Transfer and storage of maleimide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62126167A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0768300A1 (en) * | 1995-08-29 | 1997-04-16 | Nippon Shokubai Co., Ltd. | Acrylonitrile solutions of maleimides, method for preparation thereof, and acrylonitrile based copolymers obtained by use of the solutions |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62145062A (en) * | 1985-12-19 | 1987-06-29 | Nippon Shokubai Kagaku Kogyo Co Ltd | Prevention of maleimide against polymerization |
| JPH0688971B2 (en) * | 1987-06-18 | 1994-11-09 | 株式会社日本触媒 | Method for preventing polymerization of maleimides |
| JPH0676374B2 (en) * | 1987-09-02 | 1994-09-28 | 株式会社日本触媒 | Method for transporting and storing acrylonitrile solution of maleimides |
| JP2732798B2 (en) * | 1987-09-02 | 1998-03-30 | 株式会社日本触媒 | Method for transporting and storing solutions of maleimides in acrylonitrile |
| JPH0670009B2 (en) * | 1988-08-18 | 1994-09-07 | 株式会社日本触媒 | Method for producing acrylonitrile solution of maleimides |
| US5128484A (en) * | 1987-12-28 | 1992-07-07 | Sokubai Kagaku Kogyo, Co., Ltd. | Acrylonitrile maleimides solution composition of improved shelf life and method for production thereof |
| JPH0672133B2 (en) * | 1987-12-28 | 1994-09-14 | 株式会社日本触媒 | Method for transporting and storing acrylonitrile solution of maleimides |
| JPH0670008B2 (en) * | 1988-08-18 | 1994-09-07 | 株式会社日本触媒 | Method for producing acrylonitrile solution of maleimides |
| JPH0672134B2 (en) * | 1987-12-28 | 1994-09-14 | 株式会社日本触媒 | Method for transporting and storing acrylonitrile solution of maleimides |
| JPH0672135B2 (en) * | 1987-12-28 | 1994-09-14 | 株式会社日本触媒 | Method for transporting and storing acrylonitrile solution of maleimides |
| JPH0678306B2 (en) * | 1988-12-13 | 1994-10-05 | 株式会社日本触媒 | Method for producing acrylonitrile solution of maleimides |
| JP2599197B2 (en) * | 1989-05-11 | 1997-04-09 | 大八化学工業株式会社 | Stabilizer for acrylonitrile solution of N-phenylmaleimide compound |
| US5149827A (en) * | 1990-01-10 | 1992-09-22 | Nippon Shokubai Kagaku Kogyo Co., Ltd. | Method for handling maleimides |
| JPH0774200B2 (en) * | 1990-08-22 | 1995-08-09 | 大八化学工業株式会社 | Process for producing N-substituted maleimides |
| JP3085914B2 (en) * | 1996-12-27 | 2000-09-11 | 株式会社日本触媒 | Method for preparing color-stabilized basic monomers |
-
1985
- 1985-11-28 JP JP26614685A patent/JPS62126167A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0768300A1 (en) * | 1995-08-29 | 1997-04-16 | Nippon Shokubai Co., Ltd. | Acrylonitrile solutions of maleimides, method for preparation thereof, and acrylonitrile based copolymers obtained by use of the solutions |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62126167A (en) | 1987-06-08 |
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