JPH0776197B2 - Method for producing long-chain unsaturated aliphatic secondary amine - Google Patents
Method for producing long-chain unsaturated aliphatic secondary amineInfo
- Publication number
- JPH0776197B2 JPH0776197B2 JP3283845A JP28384591A JPH0776197B2 JP H0776197 B2 JPH0776197 B2 JP H0776197B2 JP 3283845 A JP3283845 A JP 3283845A JP 28384591 A JP28384591 A JP 28384591A JP H0776197 B2 JPH0776197 B2 JP H0776197B2
- Authority
- JP
- Japan
- Prior art keywords
- unsaturated aliphatic
- long
- nitrile
- secondary amine
- reaction
- 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 - Lifetime
Links
- -1 unsaturated aliphatic secondary amine Chemical class 0.000 title claims description 31
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 150000002825 nitriles Chemical class 0.000 claims description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- 238000005984 hydrogenation reaction Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 150000001408 amides Chemical class 0.000 claims 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 9
- 238000006722 reduction reaction Methods 0.000 description 8
- 235000014113 dietary fatty acids Nutrition 0.000 description 7
- 239000000194 fatty acid Substances 0.000 description 7
- 229930195729 fatty acid Natural products 0.000 description 7
- 150000004665 fatty acids Chemical class 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 150000003335 secondary amines Chemical class 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 125000002560 nitrile group Chemical group 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000005909 Kieselgur Substances 0.000 description 2
- 239000004902 Softening Agent Substances 0.000 description 2
- GXDVEXJTVGRLNW-UHFFFAOYSA-N [Cr].[Cu] Chemical compound [Cr].[Cu] GXDVEXJTVGRLNW-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000003760 tallow Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LTHNHFOGQMKPOV-UHFFFAOYSA-N 2-ethylhexan-1-amine Chemical compound CCCCC(CC)CN LTHNHFOGQMKPOV-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 description 1
- URXZXNYJPAJJOQ-UHFFFAOYSA-N Erucic acid Natural products CCCCCCC=CCCCCCCCCCCCC(O)=O URXZXNYJPAJJOQ-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 235000019482 Palm oil Nutrition 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 1
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- ILRSCQWREDREME-UHFFFAOYSA-N dodecanamide Chemical compound CCCCCCCCCCCC(N)=O ILRSCQWREDREME-UHFFFAOYSA-N 0.000 description 1
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 1
- DPUOLQHDNGRHBS-KTKRTIGZSA-N erucic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 235000019197 fats Nutrition 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000026045 iodination Effects 0.000 description 1
- 238000006192 iodination reaction Methods 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- UIAMCVSNZQYIQS-KTKRTIGZSA-N oleonitrile Chemical compound CCCCCCCC\C=C/CCCCCCCC#N UIAMCVSNZQYIQS-KTKRTIGZSA-N 0.000 description 1
- 229940113162 oleylamide Drugs 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【０００１】[0001]
【技術分野】本発明は、長鎖不飽和脂肪族ニトリルを水
素還元して長鎖不飽和脂肪族第2級アミンを製造する方
法の改良に関する。TECHNICAL FIELD The present invention relates to an improvement in a method for producing a long-chain unsaturated aliphatic secondary amine by hydrogen reduction of a long-chain unsaturated aliphatic nitrile.
【０００２】[0002]
【従来技術及びその問題点】一般に、長鎖アルキル基を
有するアミン類は、天然油脂類から誘導される長鎖脂肪
族ニトリルを水素環元することにより製造されている。
この長鎖脂肪族ニトリルを水素還元する場合、第1級〜
第3級アミンの混合物が得られるが、これらの中、長鎖
不飽和脂肪族第2級アミンは、これを4級化することによ
り、各種衣料あるいは毛髪に対して柔軟性と帯電防止性
を付与することができ、しかも吸水性に優れ、また、取
扱い易いという利点を有する柔軟剤とすることができる
ため、その利用価値が極めて高いことから、このものを
選択性よく高収率で製造することが望まれていた。従
来、この種の長鎖不飽和脂肪族第2級アミンを製造する
方法として、長鎖不飽和脂肪族ニトリル等を、銅−クロ
ム触媒の存在下で水素還元する方法(英国特許第773,432
号明細書)、あるいはニッケル系水素化触媒の存在下で
水素還元する方法(米国特許第2,355,356号明細書、米国
特許第2,784,232号明細書、英国特許第759,291号明細
書、特開昭55−9018号公報等)等が知られているが、前
者の方法は、使用する銅−クロム触媒の活性が低いため
に反応時間が長くかかるという欠点を有し、また後者の
方法では、ニトリル基がアミノ基に転換される間に炭化
水素鎖中の不飽和結合の大部分が水素添加されてしま
い、長鎖不飽和脂肪族第2級アミンへの選択率が悪いと
いう欠点があった。2. Description of the Related Art In general, amines having a long-chain alkyl group are produced by hydrogenating a long-chain aliphatic nitrile derived from natural fats and oils.
When reducing this long-chain aliphatic nitrile with hydrogen,
A mixture of tertiary amines can be obtained. Among these, long-chain unsaturated aliphatic secondary amines are quaternized to give flexibility and antistatic properties to various clothing or hair. Since it is possible to provide a softening agent which has the advantages of being excellent in water absorption and being easy to handle, it has a very high utility value. Therefore, this softening agent is produced with high selectivity and high yield. Was desired. Conventionally, as a method for producing this type of long-chain unsaturated aliphatic secondary amine, long-chain unsaturated aliphatic nitrile, etc., a method of hydrogen reduction in the presence of copper-chromium catalyst (UK Patent No. 773,432
No.) or a method of hydrogen reduction in the presence of a nickel-based hydrogenation catalyst (U.S. Pat.No. 2,355,356, U.S. Pat.No. 2,784,232, British Patent 759,291, JP-A-55-9018). However, the former method has a drawback that the reaction time is long due to the low activity of the copper-chromium catalyst used, and in the latter method, the nitrile group has an amino group. Most of the unsaturated bonds in the hydrocarbon chain are hydrogenated during conversion to a group, and there is a drawback that the selectivity to long-chain unsaturated aliphatic secondary amine is poor.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、前記従来技
術の欠点を克服し、長鎖不飽和脂肪族ニトリルまたはこ
れらのニトリルを含むニトリル混合物から、選択性よく
かつ高収率で長鎖不飽和脂肪族第2級アミンを製造する
方法を提供することをその課題とする。SUMMARY OF THE INVENTION The present invention overcomes the above-mentioned drawbacks of the prior art and provides long-chain unsaturation with high selectivity and high yield from long-chain unsaturated aliphatic nitriles or nitrile mixtures containing these nitriles. It is an object of the present invention to provide a method for producing a saturated aliphatic secondary amine.
【０００４】[0004]
【課題を解決するための手段】本発明によれば、ニッケ
ル系水素化触媒を用い、炭素数８〜２２の不飽和脂肪族
ニトリルまたはこれらのニトリルを含むニトリル混合物
を水素還元反応させて長鎖不飽和脂肪族第２級アミンを
製造する方法において、反応系に炭素数８〜２２の脂肪
族カルボン酸アミドを炭素数８〜２２の不飽和脂肪族ニ
トリルに対して０．０３〜３モル％添加し、反応温度１
６０〜２００℃の条件下で行うことを特徴とする長鎖不
飽和脂肪族第２級アミンの製造方法が提供される。According to the present invention, an unsaturated aliphatic nitrile having 8 to 22 carbon atoms or a nitrile mixture containing these nitriles is subjected to hydrogen reduction reaction using a nickel-based hydrogenation catalyst to effect long-chain reaction. In the method for producing an unsaturated aliphatic secondary amine, an aliphatic carboxylic acid amide having 8 to 22 carbon atoms is added to the reaction system in an amount of 0.03 to 3 mol% based on the unsaturated aliphatic nitrile having 8 to 22 carbon atoms. Add, reaction temperature 1
Provided is a method for producing a long-chain unsaturated aliphatic secondary amine, which is carried out under the conditions of 60 to 200 ° C.
【０００５】一般に、ニッケル系水素化触媒を用いて長
鎖不飽和脂肪族ニトリルを第2級アミンに変える反応に
おいては、ニトリル基のアミノ基への還元反応を促進す
ると、炭化水素鎖の不飽和結合の水添速度も増大し、長
鎖不飽和脂肪族第2級アミンの他に長鎖飽和脂肪族第2級
アミンも副生し、長鎖不飽和脂肪族第2級アミンを高選
択率で得ることができず、また、逆に、該炭化水素鎖の
不飽和結合の水添速度を抑制する条件下では、長鎖不飽
和脂肪族第2級アミンの生成速度が遅くなり、長鎖不飽
和脂肪族第2級アミンを高収率で得ることが困難であっ
た。本発明は、上記したように、ニッケル系水素化触媒
を用いる長鎖不飽和脂肪族ニトリルの水素還元反応を、
反応系にカルボン酸アミドを添加し、160〜200℃の反応
温度で行うものであるが、このような条件下では、炭化
水素鎖の不飽和結合の水添反応が抑制される上、かつニ
トリル基のアミノ基への転換反応は促進されるため、長
鎖不飽和脂肪族第2級アミンを選択性よくしかも、高収
率で得ることができる。Generally, in the reaction of converting a long-chain unsaturated aliphatic nitrile into a secondary amine using a nickel-based hydrogenation catalyst, if the reduction reaction of a nitrile group to an amino group is promoted, the unsaturated hydrocarbon chain becomes unsaturated. The hydrogenation rate of the bond also increases, and long-chain unsaturated aliphatic secondary amines are by-produced in addition to the long-chain unsaturated aliphatic secondary amines, and the long-chain unsaturated aliphatic secondary amines have high selectivity. On the contrary, under the condition that the hydrogenation rate of the unsaturated bond of the hydrocarbon chain is suppressed, the production rate of the long-chain unsaturated aliphatic secondary amine becomes slow, It was difficult to obtain unsaturated aliphatic secondary amines in high yield. The present invention, as described above, the hydrogen reduction reaction of a long-chain unsaturated aliphatic nitrile using a nickel-based hydrogenation catalyst,
Carboxylic acid amide is added to the reaction system, which is carried out at a reaction temperature of 160 to 200 ° C. Under such conditions, hydrogenation reaction of unsaturated bond of hydrocarbon chain is suppressed, and nitrile Since the conversion reaction of a group into an amino group is promoted, a long-chain unsaturated aliphatic secondary amine can be obtained with high selectivity and in high yield.
【０００６】本発明において原料として使用する長鎖不
飽和脂肪族ニトリルは、炭素数8〜22の長鎖不飽和脂肪
族ニトリルまたはこれらのニトリルを含むニトリル混合
物であり、このようなニトリルとしては、たとえば、オ
レイン酸、リノール酸、リノレン酸、エルカ酸、牛脂脂
肪酸、大豆油脂肪酸、パーム油脂肪酸、トール油脂肪酸
又は、ナタネ油脂肪酸等から製造されるニトリル等を挙
げることができる。また、本発明においては、触媒とし
て、ニッケル系水素化触媒、殊に、ケイ藻土、アルミ
ナ、シリカアルミナ、その他の担体に担持されたニッケ
ル触媒が使用される。この触媒使用量は、原料ニトリル
100重量部に対し、0.1〜0.5重量部が適当である。The long-chain unsaturated aliphatic nitrile used as a raw material in the present invention is a long-chain unsaturated aliphatic nitrile having 8 to 22 carbon atoms or a nitrile mixture containing these nitriles. Examples thereof include oleic acid, linoleic acid, linolenic acid, erucic acid, tallow fatty acid, soybean oil fatty acid, palm oil fatty acid, tall oil fatty acid, and nitrile produced from rapeseed oil fatty acid. Further, in the present invention, a nickel-based hydrogenation catalyst, in particular, a diatomaceous earth, alumina, silica-alumina, or other nickel catalyst supported on a carrier is used as the catalyst. The amount of this catalyst used is the raw material nitrile.
0.1 to 0.5 parts by weight is suitable for 100 parts by weight.
【０００７】本発明において用いる脂肪族カルボン酸ア
ミドは、炭素数８〜２２の飽和または不飽和脂肪族カル
ボン酸アミドであり、これらは各々単独あるいは2種以
上混合して使用することもできる。本発明で用いられる
飽和もしくは不飽和脂肪族カルボン酸アミドの具体例と
しては2−エチルヘキシルアミド、ラウリルアミド、ス
テアリルアミド、オレイルアミド、エルカアミド、ヤシ
脂肪酸アミド、牛脂脂肪酸アミド等が挙げられる。脂肪
族カルボン酸アミドの添加量は、原料ニトリルに対し、
0.03〜3モル％、好ましくは0.3〜3モル％である。脂肪
族カルボン酸アミドの添加量が少なすぎると炭化水素鎖
の不飽和結合の水添防止に充分な効果が得られず、また
多すぎるとニトリルの環元反応が進みにくくなり、第2
級アミンの収率が低下する。The aliphatic carboxylic acid amide used in the present invention is a saturated or unsaturated aliphatic carboxylic acid amide having 8 to 22 carbon atoms, and these can be used alone or in admixture of two or more. Specific examples of the saturated or unsaturated aliphatic carboxylic acid amide used in the present invention include 2-ethylhexylamide, laurylamide, stearylamide, oleylamide, erucamide, coconut fatty acid amide, and tallow fatty acid amide. The amount of the aliphatic carboxylic acid amide added is based on the raw material nitrile.
It is 0.03 to 3 mol%, preferably 0.3 to 3 mol%. If the addition amount of the aliphatic carboxylic acid amide is too small, a sufficient effect for preventing hydrogenation of unsaturated bonds in the hydrocarbon chain cannot be obtained, and if it is too large, the nitrile ring reaction is difficult to proceed,
The yield of primary amine is reduced.
【０００８】更に、本発明においては、炭化水素鎖の不
飽和結合残存率の高い第2級アミンを高収率で得るに
は、反応温度を160〜200℃という限定された範囲に選定
する必要がある。反応温度が200℃を越えると炭化水素
鎖の不飽和結合の水添反応が速まり、得られる第2級ア
ミンの不飽和結合残存率が低くなり、また反応温度がこ
れより低いと、ニトリル基のアミノ基への転換反応が遅
くなり、第2級アミンの収率が低下する。しかしなが
ら、本発明においては、内容物を加熱し、所定反応温度
に上昇させる場合、触媒の活性化と急激な還元反応を避
けるために、160℃以下の温度から水素を流通させるこ
とを除外するものではなく、実質的反応が160〜200℃の
温度で実施されればよい。本発明の方法における水素圧
は、大気圧以上であればよいが、経済的観点からいっ
て、ゲージ圧10kg/cm2以下の範囲で選定するのが適当で
ある。本発明の方法は、反応容器に前記した原料ニトリ
ル、触媒およびカルボン酸アミドを充填し、内容物をか
きまぜながら、水素を反応容器内に流通させ、反応温度
を160〜200℃に維持させることにより実施される。Further, in the present invention, the reaction temperature must be selected within a limited range of 160 to 200 ° C. in order to obtain a secondary amine having a high unsaturated bond residual ratio of the hydrocarbon chain in a high yield. There is. If the reaction temperature exceeds 200 ° C, the hydrogenation reaction of the unsaturated bond of the hydrocarbon chain will be accelerated, and the residual ratio of the unsaturated bond of the obtained secondary amine will be low. If the reaction temperature is lower than this, the nitrile group The conversion reaction of the amino acid to the amino group becomes slow, and the yield of the secondary amine decreases. However, in the present invention, when the contents are heated and raised to a predetermined reaction temperature, in order to avoid activation of the catalyst and rapid reduction reaction, the passage of hydrogen from a temperature of 160 ° C. or lower is excluded. Instead, the substantial reaction may be carried out at a temperature of 160-200 ° C. The hydrogen pressure in the method of the present invention may be atmospheric pressure or higher, but from an economical point of view, it is suitable to select within a gauge pressure of 10 kg / cm 2 or less. The method of the present invention, by filling the reaction vessel with the above-mentioned raw material nitrile, catalyst and carboxylic acid amide, stirring the content, flowing hydrogen into the reaction vessel, and maintaining the reaction temperature at 160 to 200 ° C. Be implemented.
【０００９】[0009]
【発明の効果】本発明においては、前記したように、ニ
ッケル系水素化触媒を用いる長鎖不飽和脂肪族ニトリル
の水素還元反応を、炭素数８〜２２の脂肪族カルボン酸
アミドを反応系に特定量添加し、反応温度160〜200℃の
条件下で行うことから、原料ニトリルの炭化水素鎖中に
存在する不飽和結合の80％以上が残存され、かつ第2級
アミンへの選択率が85％以上であるとともに、原料ニト
リルの90％以上がアミンに転換された、長鎖不飽和脂肪
族第2級アミンを主体とする混合物を得ることができ
る。INDUSTRIAL APPLICABILITY In the present invention, as described above, the hydrogen reduction reaction of a long-chain unsaturated aliphatic nitrile using a nickel-based hydrogenation catalyst is carried out using an aliphatic carboxylic acid amide having 8 to 22 carbon atoms as a reaction system. Since a specific amount is added and the reaction is carried out at a reaction temperature of 160 to 200 ° C, 80% or more of the unsaturated bonds present in the hydrocarbon chain of the raw material nitrile remain, and the selectivity to the secondary amine is high. It is possible to obtain a mixture mainly composed of a long-chain unsaturated aliphatic secondary amine, which is 85% or more and 90% or more of the raw material nitrile is converted to an amine.
【００１０】[0010]
【実施例】つぎに、本発明を実施例により更に詳細に説
明する。EXAMPLES Next, the present invention will be described in more detail with reference to Examples.
【００１１】実施例１ １リットルの誘導回転式オートクレーブにオレオニトリ
ル500ｇ、ニッケル−ケイソウ土触媒１ｇ、および表１
に示す脂肪族カルボン酸アミドを充填し、水素圧を3ｋ
ｇ／ｃｍ2(ゲージ圧)に維持しながら水素を流通させ、
撹拌下加熱し、温度が170℃に達した時点を反応開始時
点とし、この時点から2時間、温度を180℃、水素圧を3
ｋｇ／ｃｍ2(ゲージ圧)に維持して、水素を流通させな
がら撹拌を続けた。 反応終了後100℃に冷却し、触媒
を濾別して、第1級アミン、第2級アミン、第3級アミン
からなるアミン混合物を得た。表１にその反応結果と、
生成したアミン混合物のヨウ素価を示す。このヨウ素化
は、理論ヨウ素価(原料ニトリルがすべて第2級アミンに
転換し、かつ炭化水素鎖の不飽和結合がまったく水添さ
れない場合のヨウ素価。以下の実施例および比較例にお
いても同じ)に対する割合で示した。Example 1 500 g of oleonitrile, 1 g of nickel-diatomaceous earth catalyst, and Table 1 in a 1-liter induction rotary autoclave.
Filled with the aliphatic carboxylic acid amide shown in, and set the hydrogen pressure to 3k.
Flow hydrogen while maintaining g / cm 2 (gauge pressure),
The reaction is started when the temperature of the mixture reaches 170 ° C when heated under stirring. From this point, the temperature is 180 ° C and the hydrogen pressure is 3 ° C.
While maintaining the pressure at kg / cm 2 (gauge pressure), stirring was continued while flowing hydrogen. After completion of the reaction, the mixture was cooled to 100 ° C. and the catalyst was filtered off to obtain an amine mixture consisting of primary amine, secondary amine and tertiary amine. Table 1 shows the reaction results,
The iodine value of the produced amine mixture is shown. This iodination is a theoretical iodine value (the iodine value when all the raw material nitriles are converted to secondary amines and the unsaturated bonds of the hydrocarbon chain are not hydrogenated at all. The same applies to the following Examples and Comparative Examples). It was shown as a ratio to.
【００１２】[0012]
【表１】 [Table 1]
Claims (1)
〜２２の不飽和脂肪族ニトリルまたはこれらのニトリル
を含むニトリル混合物を水素還元反応させて長鎖不飽和
脂肪族第２級アミンを製造する方法において、反応系に
炭素数８〜２２の脂肪族カルボン酸アミドを炭素数８〜
２２の不飽和脂肪族ニトリルに対して０．０３〜３モル
％添加し、反応温度１６０〜２００℃の条件下で行うこ
とを特徴とする長鎖不飽和脂肪族第２級アミンの製造方
法。1. A nickel-based hydrogenation catalyst is used, which has 8 carbon atoms.
~ 22 unsaturated aliphatic nitrile or a nitrile mixture containing these nitriles is hydrogen-reduced to produce a long-chain unsaturated aliphatic secondary amine, wherein the reaction system contains an aliphatic carboxylic acid having 8 to 22 carbon atoms. Acid amide with 8 to 8 carbon atoms
22. The method for producing a long-chain unsaturated aliphatic secondary amine, which comprises adding 0.03 to 3 mol% to the unsaturated aliphatic nitrile of No. 22 and conducting the reaction at a reaction temperature of 160 to 200 ° C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3283845A JPH0776197B2 (en) | 1991-10-04 | 1991-10-04 | Method for producing long-chain unsaturated aliphatic secondary amine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3283845A JPH0776197B2 (en) | 1991-10-04 | 1991-10-04 | Method for producing long-chain unsaturated aliphatic secondary amine |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61015255A Division JPS62175445A (en) | 1986-01-27 | 1986-01-27 | Production of long-chain saturated aliphatic secondary amine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0517415A JPH0517415A (en) | 1993-01-26 |
| JPH0776197B2 true JPH0776197B2 (en) | 1995-08-16 |
Family
ID=17670911
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3283845A Expired - Lifetime JPH0776197B2 (en) | 1991-10-04 | 1991-10-04 | Method for producing long-chain unsaturated aliphatic secondary amine |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0776197B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2799953B2 (en) * | 1993-07-06 | 1998-09-21 | 山下ゴム株式会社 | Liquid ring vibration isolator |
| US5772189A (en) * | 1995-06-15 | 1998-06-30 | Yamashita Rubber Kabuskiki Kaisha | Antivibration rubber device |
| JP5191734B2 (en) * | 2005-09-06 | 2013-05-08 | ライオン・アクゾ株式会社 | Process for producing unsaturated aliphatic primary amine |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2784232A (en) | 1951-07-05 | 1957-03-05 | Gen Mills Inc | Hydrogenation of fatty nitriles using a nickel borate catalyst |
| US3299117A (en) | 1964-10-05 | 1967-01-17 | Armour & Co | Stepwise preparation of fatty acid nitriles |
| US3850974A (en) | 1973-05-23 | 1974-11-26 | Akzona Inc | Production of nitriles |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62175445A (en) * | 1986-01-27 | 1987-08-01 | Lion Akzo Kk | Production of long-chain saturated aliphatic secondary amine |
-
1991
- 1991-10-04 JP JP3283845A patent/JPH0776197B2/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2784232A (en) | 1951-07-05 | 1957-03-05 | Gen Mills Inc | Hydrogenation of fatty nitriles using a nickel borate catalyst |
| US3299117A (en) | 1964-10-05 | 1967-01-17 | Armour & Co | Stepwise preparation of fatty acid nitriles |
| US3850974A (en) | 1973-05-23 | 1974-11-26 | Akzona Inc | Production of nitriles |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0517415A (en) | 1993-01-26 |
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