JPH10298148A - Production of butylated diphenylamines - Google Patents
Production of butylated diphenylaminesInfo
- Publication number
- JPH10298148A JPH10298148A JP10626697A JP10626697A JPH10298148A JP H10298148 A JPH10298148 A JP H10298148A JP 10626697 A JP10626697 A JP 10626697A JP 10626697 A JP10626697 A JP 10626697A JP H10298148 A JPH10298148 A JP H10298148A
- Authority
- JP
- Japan
- Prior art keywords
- diphenylamines
- diphenylamine
- reaction
- butyldiphenylamine
- butylated
- 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.)
- Withdrawn
Links
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000001257 hydrogen Substances 0.000 claims abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 16
- 239000004927 clay Substances 0.000 abstract description 14
- 239000002994 raw material Substances 0.000 abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 8
- 239000003963 antioxidant agent Substances 0.000 abstract description 3
- 239000011368 organic material Substances 0.000 abstract description 3
- JTMODJXOTWYBOZ-UHFFFAOYSA-N 2-methyl-n-phenylaniline Chemical compound CC1=CC=CC=C1NC1=CC=CC=C1 JTMODJXOTWYBOZ-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract description 2
- 230000003078 antioxidant effect Effects 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 2
- 238000007599 discharging Methods 0.000 abstract 1
- 239000010891 toxic waste Substances 0.000 abstract 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 24
- 239000000203 mixture Substances 0.000 description 15
- OPEKHRGERHDLRK-UHFFFAOYSA-N 4-tert-butyl-n-(4-tert-butylphenyl)aniline Chemical compound C1=CC(C(C)(C)C)=CC=C1NC1=CC=C(C(C)(C)C)C=C1 OPEKHRGERHDLRK-UHFFFAOYSA-N 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000004821 distillation Methods 0.000 description 7
- 229910001385 heavy metal Inorganic materials 0.000 description 7
- 239000002351 wastewater Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000002699 waste material Substances 0.000 description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 6
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical group CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- SVMHJGGEHKZZCC-UHFFFAOYSA-N C(C)(C)(C)C=1C(=C(C=CC1)NC1=CC=CC=C1)C(C)(C)C Chemical compound C(C)(C)(C)C=1C(=C(C=CC1)NC1=CC=CC=C1)C(C)(C)C SVMHJGGEHKZZCC-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- IMXRBCGZTVENAC-UHFFFAOYSA-N n-phenyl-n-(2,4,4-trimethylpentan-2-yl)aniline Chemical compound C=1C=CC=CC=1N(C(C)(C)CC(C)(C)C)C1=CC=CC=C1 IMXRBCGZTVENAC-UHFFFAOYSA-N 0.000 description 3
- MHJCZOMOUCUAOI-UHFFFAOYSA-N n-tert-butyl-n-phenylaniline Chemical compound C=1C=CC=CC=1N(C(C)(C)C)C1=CC=CC=C1 MHJCZOMOUCUAOI-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 235000005074 zinc chloride Nutrition 0.000 description 3
- 239000011592 zinc chloride Substances 0.000 description 3
- WRDWWAVNELMWAM-UHFFFAOYSA-N 4-tert-butylaniline Chemical compound CC(C)(C)C1=CC=C(N)C=C1 WRDWWAVNELMWAM-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- SRENRFDRXNVMKN-UHFFFAOYSA-N n-butyl-n-phenylaniline Chemical compound C=1C=CC=CC=1N(CCCC)C1=CC=CC=C1 SRENRFDRXNVMKN-UHFFFAOYSA-N 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- -1 such as 2% Chemical compound 0.000 description 2
- XHCAGOVGSDHHNP-UHFFFAOYSA-N 1-bromo-4-tert-butylbenzene Chemical compound CC(C)(C)C1=CC=C(Br)C=C1 XHCAGOVGSDHHNP-UHFFFAOYSA-N 0.000 description 1
- RZFNPHWOOGJMQE-UHFFFAOYSA-N 2-ethyl-n-(2-ethylphenyl)aniline Chemical compound CCC1=CC=CC=C1NC1=CC=CC=C1CC RZFNPHWOOGJMQE-UHFFFAOYSA-N 0.000 description 1
- JWXNJZPOYUARDX-UHFFFAOYSA-N 2-tert-butyl-n-phenyl-n-(2,4,4-trimethylpentan-2-yl)aniline Chemical compound C=1C=CC=C(C(C)(C)C)C=1N(C(C)(C)CC(C)(C)C)C1=CC=CC=C1 JWXNJZPOYUARDX-UHFFFAOYSA-N 0.000 description 1
- MKASXAGBWHIGCF-UHFFFAOYSA-N 3-methoxy-n-phenylaniline Chemical compound COC1=CC=CC(NC=2C=CC=CC=2)=C1 MKASXAGBWHIGCF-UHFFFAOYSA-N 0.000 description 1
- QCQCHGYLTSGIGX-GHXANHINSA-N 4-[[(3ar,5ar,5br,7ar,9s,11ar,11br,13as)-5a,5b,8,8,11a-pentamethyl-3a-[(5-methylpyridine-3-carbonyl)amino]-2-oxo-1-propan-2-yl-4,5,6,7,7a,9,10,11,11b,12,13,13a-dodecahydro-3h-cyclopenta[a]chrysen-9-yl]oxy]-2,2-dimethyl-4-oxobutanoic acid Chemical compound N([C@@]12CC[C@@]3(C)[C@]4(C)CC[C@H]5C(C)(C)[C@@H](OC(=O)CC(C)(C)C(O)=O)CC[C@]5(C)[C@H]4CC[C@@H]3C1=C(C(C2)=O)C(C)C)C(=O)C1=CN=CC(C)=C1 QCQCHGYLTSGIGX-GHXANHINSA-N 0.000 description 1
- OBHGSIGHEBGGFS-UHFFFAOYSA-N 4-methoxy-n-phenylaniline Chemical compound C1=CC(OC)=CC=C1NC1=CC=CC=C1 OBHGSIGHEBGGFS-UHFFFAOYSA-N 0.000 description 1
- DMLLDZGHGNLZNW-UHFFFAOYSA-N 4-octyl-n-phenylaniline Chemical compound C1=CC(CCCCCCCC)=CC=C1NC1=CC=CC=C1 DMLLDZGHGNLZNW-UHFFFAOYSA-N 0.000 description 1
- GVETWXKNKJJNST-UHFFFAOYSA-N N-phenyl-2,3-bis(2,4,4-trimethylpentan-2-yl)aniline Chemical compound CC(CC(C)(C)C)(C)C=1C(=C(C=CC1)NC1=CC=CC=C1)C(CC(C)(C)C)(C)C GVETWXKNKJJNST-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000006210 debutylation Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- QUSSPXNPULRXKG-UHFFFAOYSA-N galleon Natural products O1C(=CC=2)C(OC)=CC=2CCCCC(=O)CCC2=CC=C(O)C1=C2 QUSSPXNPULRXKG-UHFFFAOYSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- ZJHJWUVWYXNFLY-UHFFFAOYSA-N n-methoxy-n-phenylaniline Chemical compound C=1C=CC=CC=1N(OC)C1=CC=CC=C1 ZJHJWUVWYXNFLY-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ブチル化ジフェニ
ルアミン類の製造方法に関する。詳しくは、有機材料の
酸化防止剤として、また電子写真用の有機光導電性材料
の原料として、極めて有用なブチル化ジフェニルアミン
類を、安価な原料から、簡単なプロセスで、収率良く製
造する方法に関する。[0001] The present invention relates to a method for producing butylated diphenylamines. More specifically, a method for producing butylated diphenylamines, which are extremely useful as antioxidants for organic materials and as raw materials for organic photoconductive materials for electrophotography, from inexpensive raw materials in a simple process with high yield. About.
【０００２】[0002]
【従来の技術】従来、ブチル化ジフェニルアミン類を製
造する方法は、いくつかの公知文献に開示されている。
例えば、Journal of the American Chemical Society,
57(1935) 195〜197 には、4-アミノ-t-ブチルベンゼン
を、その塩酸塩と共に、還流することによる、4,4'-ジ-
t-ブチルジフェニルアミンを製造する方法が開示されて
いる。しかし、この方法では、高価な原料を使用するの
で、製造費が高くなること、及びグラスライニング等の
特殊な反応装置を使用しなければならないこと等、工業
化の為には欠点がある。2. Description of the Related Art Conventionally, methods for producing butylated diphenylamines have been disclosed in several known documents.
For example, Journal of the American Chemical Society,
57 (1935) 195-197 discloses that 4,4'-di- by refluxing 4-amino-t-butylbenzene with its hydrochloride salt.
A method for producing t-butyldiphenylamine is disclosed. However, this method has disadvantages for industrialization, such as high production costs due to the use of expensive raw materials and the necessity of using special reaction equipment such as glass lining.
【０００３】Izvestiia Akademii Nauk SSSR.Seriia Kh
imicheskaia.25(1976)2217には、ジフェニルアミンとイ
ソブチレンとを塩化亜鉛触媒で、オートクレーブ中で、
１７０℃で反応させ、4,4'-ジ-t-ブチルジフェニルアミ
ンを製造する方法が開示されている。しかし、この方法
は、触媒が劇物であり取扱に注意を要し、さらにオート
クレーブという特殊な反応装置を使用する。収率も再結
晶品で約２５％と低かった。また重金属を含む廃棄物又
は廃水が多量に出るので、工業的に適した方法とは言い
がたい。[0003] Izvestiia Akademii Nauk SSSR. Seriia Kh
imicheskaia.25 (1976) 2217, diphenylamine and isobutylene with zinc chloride catalyst in an autoclave,
A method for producing 4,4′-di-t-butyldiphenylamine by reacting at 170 ° C. is disclosed. However, in this method, the catalyst is a harmful substance, requires careful handling, and uses a special reaction apparatus called an autoclave. The yield was as low as about 25% for the recrystallized product. In addition, since a large amount of waste or wastewater containing heavy metals is generated, it cannot be said that the method is industrially suitable.
【０００４】特開平３−１１４０６８号、特開平３−１
２７７６５号、及び特開平７−１２６２２５号には4-t-
ブチルアニリンをまず無水酢酸と反応させ4-t-ブチルア
セトアニリドを合成し、次にその4-t-ブチルアセトアニ
リドと4-t-ブチルブロムベンゼンとを無水炭酸カリウム
と銅粉等を触媒として１８０〜２２０℃で反応させ、そ
の後アルカリ性下で加水分解することにより、4,4'-ジ-
t-ブチルジフェニルアミンを製造する方法が開示されて
いる。収率は、メタノール洗浄品で６０％であり、前記
の文献より改善されている。しかし、この方法は、高価
な原料を使用する上に工程数が多い為に、製造費が高く
なってしまうという欠点がある。さらに廃水が多量に出
てしまい、また重金属を含む廃棄物が出る為に、環境保
護上も好ましくない。[0004] JP-A-3-114068 and JP-A-3-13-1
No. 27765 and JP-A-7-126225 disclose 4-t-
Butyl aniline is first reacted with acetic anhydride to synthesize 4-t-butyl acetanilide, and then the 4-t-butyl acetanilide and 4-t-butyl bromobenzene are reacted for 180- By reacting at 220 ° C. and then hydrolyzing under alkaline conditions, 4,4′-di-
A method for producing t-butyldiphenylamine is disclosed. The yield is 60% for the methanol-washed product, which is an improvement over the above-mentioned literature. However, this method has a drawback that the production cost is increased because expensive raw materials are used and the number of steps is large. Further, a large amount of wastewater is discharged, and waste containing heavy metals is discharged, which is not preferable in terms of environmental protection.
【０００５】特公平１−５８２３５号、及び特開平３−
２１５５９６号には、ジフェニルアミンとジイソブチレ
ンとを活性白土触媒で反応させた結果、生成物の一部と
してブチル化ジフェニルアミン類が含まれる方法が開示
されている。しかし、その生成物はジフェニルアミン3.
5％、モノ-t-ブチルジフェニルアミン13.2％、モノ-t-
オクチルジフェニルアミン＋ジ-t-ブチルジフェニルア
ミン25.3％、t-ブチル-t-オクチルジフェニルアミン24.
2％、ジ-t-オクチルジフェニルアミン＋高級アルキル化
ジフェニルアミン24.3％という様にオクチル化ジフェニ
ルアミンを主体とした各種混合物であり、ブチル化ジフ
ェニルアミンを選択的に製造する方法ではない。また、
モノ-t-オクチルジフェニルアミンとジ-t-ブチルジフェ
ニルアミンは、沸点が非常に近接している。従って、こ
の反応生成物から、例えばジ-t-ブチルジフェニルアミ
ンを、蒸留や再結晶等の常法により取り出すことは、非
常に困難であり、事実上不可能である。[0005] Japanese Patent Publication No. 1-58235 and Japanese Unexamined Patent Publication No.
No. 215596 discloses a method in which diphenylamine and diisobutylene are reacted with an activated clay catalyst, and as a result, butylated diphenylamines are contained as a part of the product. However, the product is diphenylamine 3.
5%, mono-t-butyldiphenylamine 13.2%, mono-t-
Octyl diphenylamine + di-t-butyldiphenylamine 25.3%, t-butyl-t-octyldiphenylamine 24.
Various mixtures mainly composed of octylated diphenylamine, such as 2%, di-t-octyldiphenylamine + 24.3% of higher alkylated diphenylamine, are not a method for selectively producing butylated diphenylamine. Also,
Mono-t-octyldiphenylamine and di-t-butyldiphenylamine have very close boiling points. Therefore, it is very difficult and practically impossible to remove di-t-butyldiphenylamine from the reaction product by a conventional method such as distillation or recrystallization.
【０００６】[0006]
【発明が解決しようとする課題】本発明は、このような
従来技術が有する欠点を克服し、安価な原料から、簡単
なプロセスで、重金属を含む有害な廃水や廃棄物を出す
こと無く、ブチル化ジフェニルアミン類を選択的に収率
良く製造する方法を提供することを目的とする。DISCLOSURE OF THE INVENTION The present invention overcomes the disadvantages of the prior art, and uses a simple process from inexpensive raw materials to produce harmful wastewater and waste containing heavy metals without butyl. It is an object of the present invention to provide a method for selectively producing diphenylamines in good yield.
【０００７】[0007]
【課題を解決するための手段】本発明者らは、前記目的
を達成する為に鋭意研究を重ねた結果、ジフェニルアミ
ン類とイソブチレンという安価な原料から、シリカ−ア
ルミナ系触媒を用いて１４０℃以上２３０℃以下の温度
で反応させることにより、ブチル化ジフェニルアミン類
を、簡単なプロセスで選択的に収率良く製造できること
を見出した。この方法は、グラスライニングやオートク
レーブ等の特殊な装置を必要とせず、触媒は毒劇物では
ない為取扱いが容易で、しかも、反応後、触媒を濾過で
簡単に除去でき、その後、蒸留や再結晶等の常法によっ
てブチル化ジフェニルアミン類を容易に取り出すことが
できる。しかも重金属を含む廃水や廃棄物も出ない為、
工業的に極めて有利な方法である。Means for Solving the Problems The inventors of the present invention have conducted intensive studies in order to achieve the above-mentioned object. As a result, the inexpensive raw materials of diphenylamines and isobutylene were used at a temperature of 140 ° C. or more using a silica-alumina catalyst. By reacting at a temperature of 230 ° C. or lower, it has been found that butylated diphenylamines can be selectively produced in a simple process with a high yield. This method does not require special equipment such as glass lining and autoclave, and is easy to handle because the catalyst is not a poisonous substance.Furthermore, after the reaction, the catalyst can be easily removed by filtration, and then distilled or recycled. Butylated diphenylamines can be easily removed by a conventional method such as crystallization. Moreover, since no wastewater or waste containing heavy metals is produced,
This is a very industrially advantageous method.
【０００８】原料のジフェニルアミン類としては、[0008] Diphenylamines as raw materials include:
【化２】 （式中、Ｒ1、Ｒ2は、同一でも異なっても良く、水素、
アルキル基、シクロアルキル基、アリール基、アリール
アルキル基、アルコキシ基から選ばれる基を示し、ジフ
ェニルアミン骨格の4-又は4'-位の少なくとも一方は、
水素である。）で示されるジフェニルアミン類が用いら
れる。この例としては、ジフェニルアミン、2-メチルジ
フェニルアミン、2,2'-ジエチルジフェニルアミン、4-
ブチルジフェニルアミン、4-オクチルジフェニルアミ
ン、4-ノニルジフェニルアミン、4-（メチルシクロヘキ
シル）ジフェニルアミン、4-(α-メチルベンジル）ジフ
ェニルアミン、4-(α,α-ジメチルベンジル）ジフェニ
ルアミン、3-メトキシジフェニルアミン、4-メトキシジ
フェニルアミン等が挙げられるが、式（ＩＩ）で示され
る範囲であれば、特に限定されるものではない。Embedded image (Wherein, R 1 and R 2 may be the same or different, and hydrogen,
Alkyl group, cycloalkyl group, aryl group, arylalkyl group, represents a group selected from an alkoxy group, at least one of the 4- or 4'-position of the diphenylamine skeleton,
Hydrogen. ) Are used. Examples of this are diphenylamine, 2-methyldiphenylamine, 2,2'-diethyldiphenylamine,
Butyldiphenylamine, 4-octyldiphenylamine, 4-nonyldiphenylamine, 4- (methylcyclohexyl) diphenylamine, 4- (α-methylbenzyl) diphenylamine, 4- (α, α-dimethylbenzyl) diphenylamine, 3-methoxydiphenylamine, 4-methoxydiphenylamine Examples thereof include methoxydiphenylamine, but are not particularly limited as long as they are in the range represented by the formula (II).
【０００９】本発明で使用されるシリカ−アルミナ系触
媒は、酸性白土、活性白土、及びシリカ−アルミナから
選ばれる一種又は二種以上である。The silica-alumina catalyst used in the present invention is one or more selected from acidic clay, activated clay and silica-alumina.
【００１０】触媒量は、必要に応じ任意に設定できる。
目安として、ジフェニルアミン類に対して0.1〜50重量
％の間で使用できる。The amount of the catalyst can be arbitrarily set as required.
As a guide, it can be used between 0.1 and 50% by weight based on the diphenylamines.
【００１１】反応は、１４０℃以上２３０℃以下、好ま
しくは１６５℃以上２２０℃以下の温度で実施される。
１４０℃未満の温度では反応が殆ど進まないか又は進ん
でも副生物が多い。また２３０℃を越える温度では脱ブ
チル化が激しく起こり、ブチル化ＤＰＡの収率が低くな
る。いずれの場合も経済的に不利になってしまう。１４
０℃以上２３０℃以下の温度で反応を行なうことによ
り、選択的に収率良くモノブチルＤＰＡやジブチルＤＰ
Ａを得ることができる。更に、１６５℃以上２２０℃以
下の温度で反応を行なえば、反応は一層効率良く進み、
ジブチルＤＰＡを５０重量％以上の好収率で得ることが
できる。[0011] The reaction is carried out at a temperature of 140 ° C to 230 ° C, preferably 165 ° C to 220 ° C.
At a temperature lower than 140 ° C., the reaction hardly proceeds or even if the reaction proceeds, there are many by-products. If the temperature exceeds 230 ° C., debutylation occurs violently, and the yield of butylated DPA decreases. Either case is economically disadvantageous. 14
By conducting the reaction at a temperature of 0 ° C. or more and 230 ° C. or less, monobutyl DPA or dibutyl DP
A can be obtained. Further, if the reaction is carried out at a temperature of 165 ° C. or more and 220 ° C. or less, the reaction proceeds more efficiently,
Dibutyl DPA can be obtained in a good yield of 50% by weight or more.
【００１２】ジフェニルアミン類対イソブチレンのモル
比は、必要に応じいかなる比率でも良いが、一般的に１
対０．２〜１対２．５で反応が行われる。The molar ratio of diphenylamines to isobutylene may be any ratio if necessary, but is generally 1
The reaction is performed at a ratio of 0.2 to 1: 2.5.
【００１３】反応は大気圧を含めた様々な圧力で、回分
式又は連続式いずれでも実施し得る。The reaction can be carried out at various pressures including atmospheric pressure, either batchwise or continuously.
【００１４】反応は無溶媒下又は適切な溶媒の存在下い
ずれでも実施し得る。The reaction can be carried out without solvent or in the presence of a suitable solvent.
【００１５】本発明の反応を行なった後、必要に応じ他
の反応を行なうことができる。また、本発明の反応を行
なうと同時に、他の反応を行なうこともできる。例え
ば、ジフェニルアミン類とイソブチレンを反応させた
後、ジイソブチレン等を反応させることができるし、ま
た、ジフェニルアミン類とイソブチレンとジイソブチレ
ン等を同時に反応させることもできる。After carrying out the reaction of the present invention, other reactions can be carried out if necessary. At the same time as performing the reaction of the present invention, another reaction can be performed. For example, after reacting diphenylamines with isobutylene, diisobutylene or the like can be reacted, or diphenylamines, isobutylene, diisobutylene, or the like can be simultaneously reacted.
【００１６】以上の様に反応を行った後、触媒を濾別
し、そのまま、あるいは必要に応じその後蒸留や再結晶
等の常法の操作を行ない、ブチル化ジフェニルアミン類
を取り出すことができる。After the reaction as described above, the catalyst is separated by filtration and, as it is, or after that, if necessary, ordinary operations such as distillation and recrystallization can be carried out to obtain the butylated diphenylamines.
【００１７】[0017]
【実施例】次に実施例により本発明をさらに詳細に説明
するが、本発明はこれらの例によってなんら限定される
ものではない。Next, the present invention will be described in more detail by way of examples, which should not be construed as limiting the present invention.
【００１８】実施例１ 攪拌装置、温度計、還流冷却器、水分離器、イソブチレ
ン導入管を備えた３００mlの４つ口フラスコにジフェニ
ルアミン１５０ｇ（０．８８７モル）、活性白土（水澤
化学工業株式会社製ガレオンアースＮＦ−２）３０ｇ、
及びヘプタン８mlを仕込み、内部空間を窒素置換した。
加熱昇温しヘプタンを還流して活性白土に含まれる水を
除去した。１８３℃にて導入管よりイソブチレン８５ｇ
（１．５１５モル）を８時間にわたって導入し、その後
同温度にて２時間反応を続けた。反応後、冷却してヘプ
タン１００mlを加えて希釈し、活性白土を濾別した。ヘ
プタンを蒸留除去することにより、蒸留残分として4-t-
ブチルジフェニルアミンと4,4'-ジ-t-ブチルジフェニル
アミンを主成分とする混合物２３０ｇを得た。それから
さらに、4-t-ブチルジフェニルアミンを蒸留除去するこ
とにより、蒸留残分として、4,4'-ジ-t-ブチルジフェニ
ルアミンを主成分とする白色固体１８０ｇを得た。この
白色固体はこのまま、有機材料の酸化防止剤として使用
できる。この白色固体をメタノールから再結晶すること
により、融点１０７〜１０８℃の白色の4,4'-ジ-t-ブチ
ルジフェニルアミン１５０ｇ（０．５３３モル、収率６
０％対ジフェニルアミン）を得た。Example 1 In a 300 ml four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a water separator, and an isobutylene inlet tube, 150 g (0.887 mol) of diphenylamine, activated clay (Mizusawa Chemical Industry Co., Ltd.) Galeon Earth NF-2) 30g,
And 8 ml of heptane, and the internal space was replaced with nitrogen.
Heating was carried out and the heptane was refluxed to remove water contained in the activated clay. 85 g of isobutylene from the inlet tube at 183 ° C
(1.515 mol) was introduced over 8 hours, and the reaction was continued at the same temperature for 2 hours. After the reaction, the mixture was cooled and diluted with 100 ml of heptane, and the activated clay was filtered off. By removing the heptane by distillation, 4-t-
230 g of a mixture containing butyldiphenylamine and 4,4′-di-t-butyldiphenylamine as main components were obtained. Thereafter, 4-t-butyldiphenylamine was further distilled off to obtain 180 g of a white solid mainly composed of 4,4′-di-t-butyldiphenylamine as a distillation residue. This white solid can be used as it is as an antioxidant for organic materials. By recrystallizing this white solid from methanol, 150 g of white 4,4′-di-t-butyldiphenylamine having a melting point of 107 to 108 ° C. (0.533 mol, yield 6)
0% vs. diphenylamine).
【００１９】実施例２〜１２、比較例１〜３ 実施例１の触媒、触媒量、反応温度等を変えてブチル化
ジフェニルアミン類を合成した。結果を表１に示す。Examples 2 to 12, Comparative Examples 1 to 3 Butylated diphenylamines were synthesized by changing the catalyst, the amount of the catalyst, the reaction temperature and the like of Example 1. Table 1 shows the results.
【００２０】[0020]
【表１】 [Table 1]
【００２１】なお、これらの実施例及び比較例に用いた
活性白土ガレオンアースＮＦ−２は水澤化学工業株式会
社製の活性白土であり、ニッカナイトＧ３６は日本活性
白土株式会社製の活性白土であり、ニッカナイトＳ２０
０は日本活性白土株式会社製の酸性白土でありまたシリ
カアルミナＨ６３３ＨＮは日揮化学株式会社製のシリカ
アルミナでありそれぞれの組成は以下の通りであった。The activated clay earthen NF-2 used in these Examples and Comparative Examples is activated clay manufactured by Mizusawa Chemical Industry Co., Ltd., and Nikkanite G36 is activated clay manufactured by Japan Activated Clay Co., Ltd. , Nikka Knight S20
Numeral 0 is an acid clay made by Nippon Activated Clay Co., Ltd., and silica alumina H633HN was a silica alumina made by JGC Chemical Co., Ltd., and their compositions were as follows.
【００２２】ガレオンアースＮＦ−２の組成 ＳｉＯ2 ７８．３重量％ Ａｌ2Ｏ3 １０．７重量％ Ｆｅ2Ｏ3 ２．１重量％ ＭｇＯ ２．３重量％ ＣａＯ ０．６重量％以下 強熱減量 ５．０重量％The Galleon Earth composition of NF-2 SiO 2 78.3 wt% Al 2 O 3 10.7 wt% Fe 2 O 3 2.1 wt% MgO 2.3 wt% CaO 0.6 wt% or less ignition Weight loss 5.0% by weight
【００２３】ニッカナイトＧ３６の組成 ＳｉＯ2 ７５〜８５重量％ Ａｌ2Ｏ3 ９〜１３重量％ Ｆｅ2Ｏ3 １〜２重量％ ＭｇＯ １〜３重量％ ＣａＯ １重量％以下 Ｎａ2Ｏ＋Ｋ2Ｏ １重量％以下 強熱減量 ５〜９重量％The composition of SiO 2 Nikka night G36 75-85 wt% Al 2 O 3 9 to 13 wt% Fe 2 O 3 1 to 2 wt% MgO 1 to 3 weight percent CaO 1 wt% or less Na 2 O + K 2 O 1 Less than 5% by weight Ignition loss 5-9% by weight
【００２４】ニッカナイトＳ２００の組成 ＳｉＯ2 ７２．９重量％ Ａｌ2Ｏ3 １２．５重量％ Ｆｅ2Ｏ3 １．８重量％ ＭｇＯ １．６重量％ ＣａＯ ３．０重量％以下 Ｎａ2Ｏ＋Ｋ2Ｏ ０．６重量％以下 強熱減量 ７．５重量％The composition of SiO 2 Nikka Night S200 72.9 wt% Al 2 O 3 12.5 wt% Fe 2 O 3 1.8 wt% MgO 1.6 wt% CaO 3.0 wt% Na 2 O + K 2 O 0.6% by weight or less Ignition loss 7.5% by weight
【００２５】シリカアルミナＨ６３３ＨＮの組成 ＳｉＯ2 ６６．５重量％ Ａｌ2Ｏ3 ２５．１重量％ Ｆｅ2Ｏ3 ０．０４重量％ Ｎａ2Ｏ ０．０２重量％The composition SiO 2 66.5 silica-alumina H633HN wt% Al 2 O 3 25.1 wt% Fe 2 O 3 0.04 wt% Na 2 O 0.02 wt%
【００２６】比較例４ 攪拌装置、温度計、還流冷却器、水分離器，イソブチレ
ン導入管を備えた３００mlの４つ口フラスコにジフェニ
ルアミン１５０ｇ（０．８８７モル）、塩化亜鉛１８ｇ
を仕込み、内部空間を窒素置換した。加熱昇温し１７０
℃にて、導入管よりイソブチレン８５ｇ（１．５１５モ
ル）を８時間にわたって導入し、その後同温度にて２時
間反応を続けた。反応後、冷却してヘプタン１００mlを
加えて希釈し、さらに水１００mlを加えて塩化亜鉛を水
層側に溶解した。水層を分離除去後、ヘプタン層に炭酸
水素ナトリウム水溶液を加えて中和した。さらに水層を
分離除去後、ヘプタン層を水洗した。ヘプタンを蒸留除
去することにより、蒸留残分として4-t-ブチルジフェニ
ルアミンと4,4'-ジ-t-ブチルジフェニルアミンを主成分
とする混合物２３０ｇを得た。それからさらに、4-t-ブ
チルジフェニルアミンを蒸留除去することにより、蒸留
残分として、4,4'-ジ-t-ブチルジフェニルアミンを主成
分とする褐色固体１７５ｇを得た。この褐色固体をメタ
ノールから再結晶したところ、融点１０７〜１０８℃の
微黄色の4,4'-ジ-t-ブチルジフェニルアミンを１４０ｇ
（０．４９７モル、収率５６％対ジフェニルアミン）得
た。収率としては実施例１とほぼ同様だったが、得られ
た物が着色していた上に、処理に困る重金属を多量に含
む廃水が出た。反応液の組成を表２に示す。Comparative Example 4 150 g (0.887 mol) of diphenylamine and 18 g of zinc chloride were placed in a 300 ml four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a water separator and an isobutylene inlet tube.
And the internal space was purged with nitrogen. 170
At 85 ° C., 85 g (1.515 mol) of isobutylene were introduced from an inlet tube over 8 hours, and the reaction was continued at the same temperature for 2 hours. After the reaction, the mixture was cooled and diluted by adding 100 ml of heptane, and 100 ml of water was further added to dissolve zinc chloride in the aqueous layer. After separating and removing the aqueous layer, the heptane layer was neutralized by adding an aqueous solution of sodium hydrogen carbonate. After separating and removing the aqueous layer, the heptane layer was washed with water. By removing heptane by distillation, 230 g of a mixture containing 4-t-butyldiphenylamine and 4,4′-di-t-butyldiphenylamine as main components was obtained as a distillation residue. Then, 4-t-butyldiphenylamine was further distilled off to obtain 175 g of a brown solid mainly composed of 4,4′-di-t-butyldiphenylamine as a distillation residue. When this brown solid was recrystallized from methanol, 140 g of slightly yellow 4,4′-di-t-butyldiphenylamine having a melting point of 107 to 108 ° C.
(0.497 mol, 56% yield vs. diphenylamine). The yield was almost the same as that of Example 1, but the obtained product was colored and wastewater containing a large amount of heavy metal which was difficult to treat was obtained. Table 2 shows the composition of the reaction solution.
【００２７】[0027]
【表２】 [Table 2]
【００２８】比較例５ 攪拌装置、温度計、還流冷却器、水分離器を備えた３０
０mlの４つ口フラスコにジフェニルアミン１５０ｇ
（０．８８７モル）、活性白土（水澤化学工業株式会社
製ガレオンアースＮＦ−２）３０ｇ、ヘプタン８mlを仕
込み、内部空間を窒素置換した。加熱昇温しヘプタンを
還流し、活性白土に含まれる水を除去した。１７０℃に
て、ジイソブチレン１５５ｇ（１．３８１モル）を１６
時間にわたって滴下し、その後同温度にて３２時間反応
を続けた。反応後、冷却しヘプタン１００mlを加えて希
釈し、活性白土を濾別した。ヘプタンとジイソブチレン
を蒸留除去することにより、蒸留残分としてジフェニル
アミン、4-t-ブチルジフェニルアミン、4-t-オクチルジ
フェニルアミン、4,4'-ジ-t-ブチルジフェニルアミン、
4-t-ブチル-4'-t-オクチルジフェニルアミン、4,4'-ジ-
t-オクチルジフェニルアミン及びその他の成分の混合物
２６０ｇを得た。この混合物よりブチル化ジフェニルア
ミンのみを取り出す事は、不可能だった。反応液の組成
を表３に示す。Comparative Example 5 30 equipped with a stirrer, a thermometer, a reflux condenser, and a water separator
150 g of diphenylamine in a 0 ml four-necked flask
(0.887 mol), 30 g of activated clay (Galeon Earth NF-2 manufactured by Mizusawa Chemical Industry Co., Ltd.) and 8 ml of heptane were charged, and the internal space was purged with nitrogen. Heptane was refluxed by heating to remove the water contained in the activated clay. At 170 ° C., 155 g (1.381 mol) of diisobutylene was added to 16
The reaction was continued at the same temperature for 32 hours. After the reaction, the mixture was cooled and diluted with 100 ml of heptane, and the activated clay was separated by filtration. By distilling off heptane and diisobutylene, diphenylamine, 4-t-butyldiphenylamine, 4-t-octyldiphenylamine, 4,4′-di-t-butyldiphenylamine,
4-t-butyl-4'-t-octyldiphenylamine, 4,4'-di-
260 g of a mixture of t-octyldiphenylamine and other components was obtained. It was not possible to remove only the butylated diphenylamine from this mixture. Table 3 shows the composition of the reaction solution.
【００２９】[0029]
【表３】 [Table 3]
【００３０】実施例１〜12、比較例１〜５から判るよう
に、本発明の方法で反応させることにより、ブチル化ジ
フェニルアミン類を、重金属等の有害な物質を含む廃水
や廃棄物を出さずに、選択的に収率良く製造することが
できる。As can be seen from Examples 1 to 12 and Comparative Examples 1 to 5, by reacting with the method of the present invention, butylated diphenylamines can be converted into wastewater and waste containing harmful substances such as heavy metals. In addition, it can be selectively produced at a high yield.
【００３１】[0031]
【発明の効果】本発明により、ブチル化ジフェニルアミ
ン類を、安価な原料から、簡単なプロセスで、選択的に
収率良く製造することができる。また重金属等の有害な
物質を含む廃水や廃棄物が出ない為、工業的に有利な製
造方法である。According to the present invention, butylated diphenylamines can be selectively produced at a high yield from inexpensive raw materials by a simple process. Further, since no wastewater or waste containing harmful substances such as heavy metals is produced, this is an industrially advantageous production method.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 有田 修 埼玉県川口市柳崎一丁目15番33号 精工化 学株式会社内 (72)発明者 古木 正昭 埼玉県川口市柳崎一丁目15番33号 精工化 学株式会社内 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Osamu Arita 1-115-33 Yanagizaki, Kawaguchi City, Saitama Prefecture Inside Seiko Kagaku Co., Ltd. Chemical Co., Ltd.
Claims (2)
アルキル基、シクロアルキル基、アリール基、アリール
アルキル基、アルコキシ基から選ばれる基を示し、ジフ
ェニルアミン骨格の4-又は4'-位の少なくとも一方は、
水素である。）で示されるジフェニルアミン類を、シリ
カ−アルミナ系触媒の存在下で、１４０℃以上２３０℃
以下の温度で、イソブチレンと反応させることからなる
ブチル化ジフェニルアミン類の製造方法。[Claim 1] (Wherein, R 1 and R 2 may be the same or different, and hydrogen,
Alkyl group, cycloalkyl group, aryl group, arylalkyl group, represents a group selected from an alkoxy group, at least one of the 4- or 4'-position of the diphenylamine skeleton,
Hydrogen. ) In the presence of a silica-alumina-based catalyst at 140 ° C to 230 ° C.
A method for producing butylated diphenylamines, which comprises reacting with isobutylene at the following temperature.
℃以下である請求項１に記載のブチル化ジフェニルアミ
ン類の製造方法。2. The reaction temperature is 165.degree.
The method for producing butylated diphenylamines according to claim 1, wherein the temperature is lower than or equal to ° C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10626697A JPH10298148A (en) | 1997-04-23 | 1997-04-23 | Production of butylated diphenylamines |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10626697A JPH10298148A (en) | 1997-04-23 | 1997-04-23 | Production of butylated diphenylamines |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH10298148A true JPH10298148A (en) | 1998-11-10 |
Family
ID=14429293
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10626697A Withdrawn JPH10298148A (en) | 1997-04-23 | 1997-04-23 | Production of butylated diphenylamines |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH10298148A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001316336A (en) * | 2000-02-25 | 2001-11-13 | Hodogaya Chem Co Ltd | Manufacturing method of electronic product materials |
| JP2007512409A (en) * | 2003-11-25 | 2007-05-17 | デュスロ エイエス | Antioxidant composition of octylated diphenylamine and process for its preparation |
| CN106478428A (en) * | 2016-09-30 | 2017-03-08 | 武汉材料保护研究所 | A kind of method using ionic liquid-catalyzed synthesis of alkyl diphenylamines antioxidant |
-
1997
- 1997-04-23 JP JP10626697A patent/JPH10298148A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001316336A (en) * | 2000-02-25 | 2001-11-13 | Hodogaya Chem Co Ltd | Manufacturing method of electronic product materials |
| JP2007512409A (en) * | 2003-11-25 | 2007-05-17 | デュスロ エイエス | Antioxidant composition of octylated diphenylamine and process for its preparation |
| CN106478428A (en) * | 2016-09-30 | 2017-03-08 | 武汉材料保护研究所 | A kind of method using ionic liquid-catalyzed synthesis of alkyl diphenylamines antioxidant |
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