JPH02127425A - Production of polyoxyalkylenepolyamine having secondary amino group at molecular end - Google Patents
Production of polyoxyalkylenepolyamine having secondary amino group at molecular endInfo
- Publication number
- JPH02127425A JPH02127425A JP27946988A JP27946988A JPH02127425A JP H02127425 A JPH02127425 A JP H02127425A JP 27946988 A JP27946988 A JP 27946988A JP 27946988 A JP27946988 A JP 27946988A JP H02127425 A JPH02127425 A JP H02127425A
- Authority
- JP
- Japan
- Prior art keywords
- polyol
- reaction
- polyoxyalkylene
- manufacturing
- hydrogenation
- 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.)
- Pending
Links
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 title claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 229920005862 polyol Polymers 0.000 claims abstract description 27
- 150000003077 polyols Chemical class 0.000 claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- -1 secondary amine compound Chemical class 0.000 claims abstract description 20
- 229920000768 polyamine Polymers 0.000 claims abstract description 12
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 9
- 229920001451 polypropylene glycol Polymers 0.000 claims abstract description 5
- 229920000909 polytetrahydrofuran Polymers 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000005909 Kieselgur Substances 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 229910052759 nickel Inorganic materials 0.000 abstract description 3
- 239000004033 plastic Substances 0.000 abstract description 3
- 229920003023 plastic Polymers 0.000 abstract description 3
- 239000000377 silicon dioxide Substances 0.000 abstract description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract 1
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 24
- 229940043279 diisopropylamine Drugs 0.000 description 8
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229920002396 Polyurea Polymers 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- BWLUMTFWVZZZND-UHFFFAOYSA-N Dibenzylamine Chemical compound C=1C=CC=CC=1CNCC1=CC=CC=C1 BWLUMTFWVZZZND-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-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
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- LIWAQLJGPBVORC-UHFFFAOYSA-N ethylmethylamine Chemical compound CCNC LIWAQLJGPBVORC-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- QPKNFEVLZVJGBM-UHFFFAOYSA-N 2-aminonaphthalen-1-ol Chemical compound C1=CC=CC2=C(O)C(N)=CC=C21 QPKNFEVLZVJGBM-UHFFFAOYSA-N 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- XBPCUCUWBYBCDP-UHFFFAOYSA-N Dicyclohexylamine Chemical compound C1CCCCC1NC1CCCCC1 XBPCUCUWBYBCDP-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- GXDVEXJTVGRLNW-UHFFFAOYSA-N [Cr].[Cu] Chemical compound [Cr].[Cu] GXDVEXJTVGRLNW-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- IMHDGJOMLMDPJN-UHFFFAOYSA-N dihydroxybiphenyl Natural products OC1=CC=CC=C1C1=CC=CC=C1O IMHDGJOMLMDPJN-UHFFFAOYSA-N 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- TZMQHOJDDMFGQX-UHFFFAOYSA-N hexane-1,1,1-triol Chemical compound CCCCCC(O)(O)O TZMQHOJDDMFGQX-UHFFFAOYSA-N 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- ISGXOWLMGOPVPB-UHFFFAOYSA-N n,n-dibenzylaniline Chemical compound C=1C=CC=CC=1CN(C=1C=CC=CC=1)CC1=CC=CC=C1 ISGXOWLMGOPVPB-UHFFFAOYSA-N 0.000 description 1
- XCVNDBIXFPGMIW-UHFFFAOYSA-N n-ethylpropan-1-amine Chemical compound CCCNCC XCVNDBIXFPGMIW-UHFFFAOYSA-N 0.000 description 1
- RIVIDPPYRINTTH-UHFFFAOYSA-N n-ethylpropan-2-amine Chemical compound CCNC(C)C RIVIDPPYRINTTH-UHFFFAOYSA-N 0.000 description 1
- OMEMQVZNTDHENJ-UHFFFAOYSA-N n-methyldodecan-1-amine Chemical compound CCCCCCCCCCCCNC OMEMQVZNTDHENJ-UHFFFAOYSA-N 0.000 description 1
- NTNWKDHZTDQSST-UHFFFAOYSA-N naphthalene-1,2-diamine Chemical compound C1=CC=CC2=C(N)C(N)=CC=C21 NTNWKDHZTDQSST-UHFFFAOYSA-N 0.000 description 1
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 229960001553 phloroglucinol Drugs 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- VOZKAJLKRJDJLL-UHFFFAOYSA-N tolylenediamine group Chemical group CC1=C(C=C(C=C1)N)N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
- C08G18/5024—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino groups
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyethers (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、分子末端に２級アミノ基を有するポリオキシ
アルキレンポリアミンの製造方法に関し、さらに詳しく
は、水素化−脱水素触媒の存在下、ポリオキシアルキレ
ンポリオールと２級アミン化合物とを反応させることを
特徴とする、分子末端に２級アミノ基を有するポリオキ
シアルキレンポリアミンを製造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 producing a polyoxyalkylene polyamine having a secondary amino group at the end of the molecule, and more specifically, in the presence of a hydrogenation-dehydrogenation catalyst, The present invention relates to a method for producing a polyoxyalkylene polyamine having a secondary amino group at the end of the molecule, which is characterized by reacting a polyoxyalkylene polyol and a secondary amine compound.
末端にアミノ基を有するポリエーテルはポリイソシアナ
ートとの重付加反応によりポリウレアを提供し、ポリウ
レア系のＲＩＭ 、エラストマー、軟質フオーム、硬質
フオーム等の原料として用いられる。また、エポキシ樹
脂、ポリアミド、ポリイミド等の各種プラスチック原料
としても有用な化金物である。A polyether having an amino group at the terminal provides polyurea through a polyaddition reaction with a polyisocyanate, and is used as a raw material for polyurea-based RIM, elastomer, soft foam, hard foam, etc. It is also a chemical compound useful as a raw material for various plastics such as epoxy resins, polyamides, and polyimides.
ポリオキシアルキレンポリオールと１級アミン化合物を
反応させて、末端に２級アミノ基を有するポリオキシア
ルキレンポリアミンを得る方法は公知である０例えば、
特公昭４５−７２８９号公報では、ポリオキシアルキレ
ンポリオールの末端水酸基をラネー金属触媒を用いて、
高温高圧下に、１級アミンと反応させて製造する方法が
提案されている。A method for obtaining a polyoxyalkylene polyamine having a secondary amino group at the terminal by reacting a polyoxyalkylene polyol with a primary amine compound is known. For example,
In Japanese Patent Publication No. 45-7289, the terminal hydroxyl group of a polyoxyalkylene polyol is converted using a Raney metal catalyst,
A method of manufacturing by reacting with a primary amine under high temperature and high pressure has been proposed.
しかし、これに基づき本発明者らが実験したところ、ポ
リオキシアルキレンポリアミンの２級アミン含量は低く
、用途によっては、満足なものではない。However, based on this, the inventors conducted experiments and found that the secondary amine content of polyoxyalkylene polyamines is low, which is not satisfactory for some uses.
本発明の目的は、水素化−脱水素触媒の存在下、ポリオ
キシアルキレンポリオールと稀アミン化るポリオキシア
ルキレンポリアミンを製造する方法において、２級アミ
ン含量の高いポリオキシアルキレンポリアミンを得る方
法を提供することにある。An object of the present invention is to provide a method for producing a polyoxyalkylene polyamine having a high secondary amine content in a method for producing a polyoxyalkylene polyamine which undergoes dilute amination with a polyoxyalkylene polyol in the presence of a hydrogenation-dehydrogenation catalyst. It's about doing.
本発明者らは、上記目的を達成するため鋭意検討し、遂
に本発明に至った。The present inventors have made extensive studies to achieve the above object, and have finally arrived at the present invention.
即ち、本発明は、水素化−脱水素触媒の存在下、ポリオ
キシアルキレンポリオールと２級アミン化合物とを反応
させることを特徴とする、分子末端に２級アミノ基を有
するポリオキシアルキレンポリアミンの製造方法である
。That is, the present invention is a method for producing a polyoxyalkylene polyamine having a secondary amino group at the end of the molecule, which is characterized by reacting a polyoxyalkylene polyol and a secondary amine compound in the presence of a hydrogenation-dehydrogenation catalyst. It's a method.
本発明で用いるポリオキシアルキレンポリオールとは、
２〜８官能性で、平均分子１４００以上のものが適当で
ある０例えば、エチレングリコール、ジエチレングリコ
ール、プロピレングリコール、１．４−ブチレングリコ
ール、ビスフェノールＡ、グリセリン、ヘキサントリオ
ール、トリメチロールプロパン、ペンタエリスリトール
、ソルビトール、スクロース、ジプロピレングリコール
、ビスフェノールＦ１ジヒドロキシジフエニルエーテル
、ジヒドロキシビフェニル、ハイドロキノン、レゾルシ
ン、ナフタレンジオール、アミノフェノール、アミノナ
フトール、フェノールホルムアルデヒド縮合物、フロロ
グルシン、メチルジェタノールアミン、エチルジイソプ
ロパノールアミン、トリエタノールアミン、エチレンジ
アミン、ヘキサメチレンジアミン、ビス（ρ−アミノシ
クロへキシル）メタン、トリレンジアミン、ジフェニル
メタンジアミン、ナフタレンジアミンなどに、エチレン
オキシド、プロピレンオキシド、ブチレンオキシド、ス
チレンオキシドなどを１種または２種以上付加せしめて
得られるポリオキシアルキレンポリオールである０以上
のほか、テトラヒドロフランの開環重合によって得られ
るポリテトラメチレンエーテルグリコールなども例に挙
げられる。The polyoxyalkylene polyol used in the present invention is
Those with 2-8 functionality and an average molecular weight of 1400 or more are suitable.For example, ethylene glycol, diethylene glycol, propylene glycol, 1,4-butylene glycol, bisphenol A, glycerin, hexanetriol, trimethylolpropane, pentaerythritol, Sorbitol, sucrose, dipropylene glycol, bisphenol F1 dihydroxydiphenyl ether, dihydroxybiphenyl, hydroquinone, resorcinol, naphthalene diol, aminophenol, aminonaphthol, phenol formaldehyde condensate, phloroglucin, methyljetanolamine, ethyldiisopropanolamine, triethanol One or more types of ethylene oxide, propylene oxide, butylene oxide, styrene oxide, etc. are added to amines, ethylene diamine, hexamethylene diamine, bis(ρ-aminocyclohexyl) methane, tolylene diamine, diphenylmethane diamine, naphthalene diamine, etc. Examples include 0 or more, which are polyoxyalkylene polyols obtained at least, and polytetramethylene ether glycol obtained by ring-opening polymerization of tetrahydrofuran.
本発明で用いる水素化−脱水素触媒としては、従来公知
の触媒を使用することができ、例えばニッケル、コバル
ト等をケイソウ土、アルミナ、シリカのような担体に担
持させた担体型触媒、ニッケル、コバルト系のラネー型
触媒、銅−クロム系触媒、銅−亜鉛系触媒等が代表的な
例である。中でも担体型触媒は特に好適な触媒の一つで
ある。As the hydrogenation-dehydrogenation catalyst used in the present invention, conventionally known catalysts can be used, such as a carrier type catalyst in which nickel, cobalt, etc. are supported on a carrier such as diatomaceous earth, alumina, or silica; Representative examples include cobalt-based Raney type catalysts, copper-chromium-based catalysts, and copper-zinc-based catalysts. Among these, a carrier type catalyst is one of the particularly suitable catalysts.
本発明で用いる２級アミン化合物としては、ジメチルア
ミン、ジエチルアミン、ジプロピルアミン、ジイソプロ
ピルアミン、ジブチルアミン、シアミルアミン、ジエチ
ルアミン、メチルエチルアミン、メチルプロとルアミン
、メチノ？イソプロピルアミン、エチルプロピルアミン
、エチルイソプロピルアミン、Ｎ−メチルドデシルアミ
ン、Ｎ−メチルアニリン、トエチルアニリン、ジベンジ
ルアニリン、ジフェニルアミン等が例に挙げられる。The secondary amine compounds used in the present invention include dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, cyamylamine, diethylamine, methylethylamine, methylpro-ruamine, methino? Examples include isopropylamine, ethylpropylamine, ethylisopropylamine, N-methyldodecylamine, N-methylaniline, toethylaniline, dibenzylaniline, diphenylamine, and the like.
本発明で使用されるアミン化合物の量は、用途に応じて
決められるが、通常、水酸基に対して、０．２〜５０当
量、好ましくは０．５〜２０当量が使用される。The amount of the amine compound used in the present invention is determined depending on the intended use, but is usually 0.2 to 50 equivalents, preferably 0.5 to 20 equivalents, based on the hydroxyl group.
本発明の反応条件は、特に限定されるものではないが、
−ｍには、反応温度１５０〜２８０℃、好ましくは１８
０〜２５０℃、反応圧力２０〜１５０ｋｇ／ｅｄＧ 。Although the reaction conditions of the present invention are not particularly limited,
-m includes a reaction temperature of 150 to 280°C, preferably 18°C.
0 to 250°C, reaction pressure 20 to 150 kg/edG.
好ましくは３０〜１００ｋｇ／ｃｊＧ 、反応時間１〜
２０時間、好ましくは５〜１０時間で行う０反応系内に
、水素を共存させてもよいし、させなくてもよい９反応
塩度が低いほど、反応速度が小さ（、また高すぎるとポ
リオキシアルキレンポリオールが分解してしまうので好
ましくない。Preferably 30-100 kg/cjG, reaction time 1-
Hydrogen may or may not coexist in the reaction system, which is carried out for 20 hours, preferably 5 to 10 hours.9 The lower the salinity, the lower the reaction rate (and if it is too high, the polymer This is not preferable because the oxyalkylene polyol decomposes.
反応終了後は、未反応アミン化合物の蒸発による回収、
触媒濾別、水洗、乾燥等の方法を適宜組み合わせること
により、目的物である、分子末端に２級アミノ基を有す
るポリオキシアルキレンポリアミンを得ることができる
。After the reaction is completed, the unreacted amine compound is recovered by evaporation,
By appropriately combining methods such as catalyst filtration, water washing, and drying, it is possible to obtain the desired polyoxyalkylene polyamine having a secondary amino group at the end of the molecule.
以下、実施例により本発明を説明する。 The present invention will be explained below with reference to Examples.
実施例１
２００＋ｗｌの高圧オートクレーブに、ニッケルケイソ
ウ土触媒にッケル含有率５０％）５ｇ、グリセリンにプ
ロピレンオキシドを付加重合させて得られるポリオキシ
プロピレントリオール（水酸基価３３．４ｍｇＫＯＲ／
ｇ 、平均分子量５０４０ ；以下ポリオールＰと略称
する。）１００ｇ、ジイソプロピルアミン３０．４ｇを
、この順で仕込み、窒素置換を５回（１０ｋｇ／ｅｄＧ
）行った後、水素を初期圧力５０ｋｇ／ｄＣで仕込んだ
、攪拌しなから２２０’Ｃまで昇温し、８時間反応を行
った。このとき圧力は６３ｋｇ／ｃｄＧであった。Example 1 In a 200+wl high-pressure autoclave, 5 g of nickel diatomaceous earth catalyst (Kickel content 50%), polyoxypropylene triol obtained by addition polymerizing propylene oxide to glycerin (hydroxyl value 33.4 mg KOR/
g, average molecular weight 5040; hereinafter abbreviated as polyol P. ), 30.4 g of diisopropylamine were charged in this order, and nitrogen substitution was performed 5 times (10 kg/edG
), hydrogen was charged at an initial pressure of 50 kg/dC, the temperature was raised to 220'C without stirring, and the reaction was carried out for 8 hours. At this time, the pressure was 63 kg/cdG.
反応終了後、触媒濾別、減圧乾燥により分子末端に２級
アミノ基を有するポリオキシアルキレンポリアミンを精
製した。結果を第１表に示す。After the reaction was completed, the polyoxyalkylene polyamine having a secondary amino group at the end of the molecule was purified by filtering off the catalyst and drying under reduced pressure. The results are shown in Table 1.
実施例２
実施例１において、ポリオールＰ／ジイソプロピルアミ
ンの当量比を１／１０、反応時間を１２時間にかえた以
外は実施例１と同一条件で反応を行った。結果を第１表
に示す。Example 2 A reaction was carried out under the same conditions as in Example 1 except that the equivalent ratio of polyol P/diisopropylamine was changed to 1/10 and the reaction time was changed to 12 hours. The results are shown in Table 1.
実施例３
実施例２において、反応温度を１８０℃、反応時間８時
間にかえた以外は、実施例２と同一条件で反応を行った
。結果を第１表に示す。Example 3 The reaction was carried out under the same conditions as in Example 2, except that the reaction temperature was changed to 180° C. and the reaction time was changed to 8 hours. The results are shown in Table 1.
実施例４
実施例１において、ポリオールＰのかわりに、グリセリ
ンにプロピレンオキシド、次いでエチレンオキシドを付
加重合さセて得られるポリオキシプロピレンポリオキシ
エチレントリオール（エチレンオキシド含量１５−ｔχ
、水酸基価３３．０ｍｇにＯＨ／ｇ。Example 4 In Example 1, instead of polyol P, polyoxypropylene polyoxyethylene triol (ethylene oxide content 15-tχ
, OH/g with a hydroxyl value of 33.0 mg.
平均分子量５１００ ；以下ポリオールＱと略称する）
を用いた以外は、実施例１と同一条件で反応を行った。Average molecular weight 5100; hereinafter abbreviated as polyol Q)
The reaction was carried out under the same conditions as in Example 1 except that .
結果を第１表に示す。The results are shown in Table 1.
実施例５
実施例１において、ポリオールＰのかわりに、テトラヒ
ドロフランの開環重合によって得られるポリテトラメチ
レンエーテルグリコール（水酸基価１１２糟ｇにｏｌ！
／ｇ 、平均分子量１０００ ｉ以下ポリオールＲと略
称する）を用いた以外は、実施例１と同一条件で反応を
行った。結果を第１表に示す。Example 5 In Example 1, instead of polyol P, polytetramethylene ether glycol (ol! with a hydroxyl value of 112 g) obtained by ring-opening polymerization of tetrahydrofuran was used.
The reaction was carried out under the same conditions as in Example 1, except that polyol R (abbreviated as polyol R) having an average molecular weight of 1000 i or less was used. The results are shown in Table 1.
実施例６
実施例１において、ジイソプロピルアミンのかわりに、
ジベンジルアミンを用いた以外は、実施例１と同一・条
件で反応を行った。結果を第１表に示す。Example 6 In Example 1, instead of diisopropylamine,
The reaction was carried out under the same conditions as in Example 1 except that dibenzylamine was used. The results are shown in Table 1.
実施例７
実施例１において、ジイソプロピルアミンのかわりに、
ジメチルアミンを用いた以外は、実施例１と同一条件で
反応を行った。但し、触媒、ポリオールＰを仕込み、窒
素置換を行った後、ジメチルアミンを仕込んだ、結果を
第１表に示す。Example 7 In Example 1, instead of diisopropylamine,
The reaction was carried out under the same conditions as in Example 1 except that dimethylamine was used. However, after charging the catalyst and polyol P and performing nitrogen substitution, dimethylamine was charged. The results are shown in Table 1.
実施例８
実施例１において、ジイソプロピルアミンのかわりに、
ジベンジルアミンを用いた以外は、実施例１と同一条件
で反応を行った。結果を第１表に示す。Example 8 In Example 1, instead of diisopropylamine,
The reaction was carried out under the same conditions as in Example 1 except that dibenzylamine was used. The results are shown in Table 1.
実施例９
実施例１において、ジイソプロピルアミンのかわりに、
ジシクロヘキシルアミンを用いた以外は、実施例１と同
一条件で反応を行った。結果を第１表に示す。Example 9 In Example 1, instead of diisopropylamine,
The reaction was carried out under the same conditions as in Example 1 except that dicyclohexylamine was used. The results are shown in Table 1.
比較例１
実施例１において、ジイソプロピルアミンのかわりに、
イソプロピルアミンを用いた以外は、実施例１と同一条
件で反応を行った。結果を第１表に示す。Comparative Example 1 In Example 1, instead of diisopropylamine,
The reaction was carried out under the same conditions as in Example 1 except that isopropylamine was used. The results are shown in Table 1.
比較例２
比較例１において、ポリオールＰ／イソプロピルアミン
の当量比を１ ／１．２にかえた以外は、比較例１と同
一条件で反応を行った。結果を第１表に示す。Comparative Example 2 A reaction was carried out under the same conditions as in Comparative Example 1, except that the equivalent ratio of polyol P/isopropylamine was changed to 1/1.2. The results are shown in Table 1.
〔発明の効果］
水素化−脱水素触媒の存在下、ポリオキシアルキレンポ
リオールと、２級アミン化合物を反応させることによっ
て、従来よりも２級アミノ基含量の高いポリオキシアル
キレンポリアミンを得ることが可能となる。[Effect of the invention] By reacting a polyoxyalkylene polyol with a secondary amine compound in the presence of a hydrogenation-dehydrogenation catalyst, it is possible to obtain a polyoxyalkylene polyamine with a higher content of secondary amino groups than before. becomes.
本発明の方法によって得られる化合物は、イソシアナー
トと反応してウレア結合によるポリウレア樹脂を得る等
の、プラスチック原材料として有効に利用できる。The compound obtained by the method of the present invention can be effectively used as a raw material for plastics, such as by reacting with isocyanate to obtain a polyurea resin with urea bonds.
特許出願人 三井東圧化学株式会社Patent applicant Mitsui Toatsu Chemical Co., Ltd.
Claims (1)
ンポリオールと２級アミン化合物とを反応させることを
特徴とする、分子末端に２級アミノ基を有するポリオキ
シアルキレンポリアミンの製造方法。 ２、ポリオキシアルキレンポリオールが、ポリオキシプ
ロピレンポリオールである請求項１記載の製造方法。 ３、ポリオキシアルキレンポリオールが、ポリオキシプ
ロピレンポリオキシエチレンポリオールである請求項１
記載の製造方法。 ４、ポリオキシアルキレンポリオールが、ポリテトラメ
チレンエーテルグリコールである請求項１記載の製造方
法。 ５、２級アミン化合物が炭素数２〜２０個を有するアミ
ンである請求項１記載の製造方法。 ６、水素化−脱水素触媒が、ニッケル触媒である請求項
１記載の製造方法。 ７、１５０〜２８０℃の温度で反応を行う請求項１記載
の製造方法。[Claims] 1. A polyoxyalkylene polyamine having a secondary amino group at the end of the molecule, which is characterized by reacting a polyoxyalkylene polyol with a secondary amine compound in the presence of a hydrogenation-dehydrogenation catalyst. manufacturing method. 2. The manufacturing method according to claim 1, wherein the polyoxyalkylene polyol is a polyoxypropylene polyol. 3. Claim 1 wherein the polyoxyalkylene polyol is polyoxypropylene polyoxyethylene polyol.
Manufacturing method described. 4. The manufacturing method according to claim 1, wherein the polyoxyalkylene polyol is polytetramethylene ether glycol. 5. The manufacturing method according to claim 1, wherein the secondary amine compound is an amine having 2 to 20 carbon atoms. 6. The manufacturing method according to claim 1, wherein the hydrogenation-dehydrogenation catalyst is a nickel catalyst. 7. The manufacturing method according to claim 1, wherein the reaction is carried out at a temperature of 150 to 280°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27946988A JPH02127425A (en) | 1988-11-07 | 1988-11-07 | Production of polyoxyalkylenepolyamine having secondary amino group at molecular end |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27946988A JPH02127425A (en) | 1988-11-07 | 1988-11-07 | Production of polyoxyalkylenepolyamine having secondary amino group at molecular end |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02127425A true JPH02127425A (en) | 1990-05-16 |
Family
ID=17611494
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27946988A Pending JPH02127425A (en) | 1988-11-07 | 1988-11-07 | Production of polyoxyalkylenepolyamine having secondary amino group at molecular end |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02127425A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5015774A (en) * | 1988-11-16 | 1991-05-14 | Mitsui Toatsu Chemicals, Inc. | Preparation process of polyoxyalkylene polyamine having terminal secondary amino group |
-
1988
- 1988-11-07 JP JP27946988A patent/JPH02127425A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5015774A (en) * | 1988-11-16 | 1991-05-14 | Mitsui Toatsu Chemicals, Inc. | Preparation process of polyoxyalkylene polyamine having terminal secondary amino group |
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