JP4484022B2 - Storage stabilization method of amino composition - Google Patents
Storage stabilization method of amino composition Download PDFInfo
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- JP4484022B2 JP4484022B2 JP2003349545A JP2003349545A JP4484022B2 JP 4484022 B2 JP4484022 B2 JP 4484022B2 JP 2003349545 A JP2003349545 A JP 2003349545A JP 2003349545 A JP2003349545 A JP 2003349545A JP 4484022 B2 JP4484022 B2 JP 4484022B2
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- amino composition
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- 239000000203 mixture Substances 0.000 title claims description 131
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 title claims description 107
- 238000000034 method Methods 0.000 title claims description 27
- 230000006641 stabilisation Effects 0.000 title claims description 6
- 238000011105 stabilization Methods 0.000 title claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 74
- AFRJJFRNGGLMDW-UHFFFAOYSA-N lithium amide Chemical compound [Li+].[NH2-] AFRJJFRNGGLMDW-UHFFFAOYSA-N 0.000 claims description 59
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 52
- 238000001914 filtration Methods 0.000 claims description 40
- 238000003756 stirring Methods 0.000 claims description 40
- -1 alkenyl compound Chemical class 0.000 claims description 33
- 239000003463 adsorbent Substances 0.000 claims description 30
- 239000007788 liquid Substances 0.000 claims description 29
- 239000003513 alkali Substances 0.000 claims description 28
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 27
- 229910052744 lithium Inorganic materials 0.000 claims description 27
- 239000003054 catalyst Substances 0.000 claims description 26
- 229920000768 polyamine Polymers 0.000 claims description 26
- 229910052783 alkali metal Inorganic materials 0.000 claims description 22
- 150000001340 alkali metals Chemical class 0.000 claims description 20
- 238000007259 addition reaction Methods 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 10
- 150000004985 diamines Chemical class 0.000 claims description 9
- 230000000087 stabilizing effect Effects 0.000 claims description 6
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 claims description 5
- 229920001451 polypropylene glycol Polymers 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical compound CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 4
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical compound CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 claims description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 4
- MGNZXYYWBUKAII-UHFFFAOYSA-N cyclohexa-1,3-diene Chemical compound C1CC=CC=C1 MGNZXYYWBUKAII-UHFFFAOYSA-N 0.000 claims description 4
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 claims description 4
- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 claims description 4
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 claims description 4
- 230000003472 neutralizing effect Effects 0.000 claims description 4
- QMMOXUPEWRXHJS-UHFFFAOYSA-N pentene-2 Natural products CCC=CC QMMOXUPEWRXHJS-UHFFFAOYSA-N 0.000 claims description 4
- XMSVKICKONKVNM-UHFFFAOYSA-N bicyclo[2.2.1]heptane-3,4-diamine Chemical compound C1CC2(N)C(N)CC1C2 XMSVKICKONKVNM-UHFFFAOYSA-N 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 2
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 claims description 2
- IGSBHTZEJMPDSZ-UHFFFAOYSA-N 4-[(4-amino-3-methylcyclohexyl)methyl]-2-methylcyclohexan-1-amine Chemical compound C1CC(N)C(C)CC1CC1CC(C)C(N)CC1 IGSBHTZEJMPDSZ-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- KEIQPMUPONZJJH-UHFFFAOYSA-N dicyclohexylmethanediamine Chemical compound C1CCCCC1C(N)(N)C1CCCCC1 KEIQPMUPONZJJH-UHFFFAOYSA-N 0.000 claims description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 claims description 2
- 235000011180 diphosphates Nutrition 0.000 claims description 2
- 239000003456 ion exchange resin Substances 0.000 claims description 2
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 2
- JILPJDVXYVTZDQ-UHFFFAOYSA-N lithium methoxide Chemical compound [Li+].[O-]C JILPJDVXYVTZDQ-UHFFFAOYSA-N 0.000 claims description 2
- AZVCGYPLLBEUNV-UHFFFAOYSA-N lithium;ethanolate Chemical compound [Li+].CC[O-] AZVCGYPLLBEUNV-UHFFFAOYSA-N 0.000 claims description 2
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 claims description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 claims description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 2
- GHAIYFTVRRTBNG-UHFFFAOYSA-N piperazin-1-ylmethanamine Chemical compound NCN1CCNCC1 GHAIYFTVRRTBNG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 claims description 2
- RWMKSKOZLCXHOK-UHFFFAOYSA-M potassium;butanoate Chemical compound [K+].CCCC([O-])=O RWMKSKOZLCXHOK-UHFFFAOYSA-M 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 claims description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002594 sorbent Substances 0.000 claims 2
- 241000283984 Rodentia Species 0.000 claims 1
- 230000002378 acidificating effect Effects 0.000 claims 1
- 239000007864 aqueous solution Substances 0.000 claims 1
- CSFZOENQUCDFFR-UHFFFAOYSA-N bis(aminomethyl)tricyclo[5,2,1,02,6]decane Chemical compound C12CCCC2(CN)C2(CN)CC1CC2 CSFZOENQUCDFFR-UHFFFAOYSA-N 0.000 claims 1
- 235000019820 disodium diphosphate Nutrition 0.000 claims 1
- GYQBBRRVRKFJRG-UHFFFAOYSA-L disodium pyrophosphate Chemical compound [Na+].[Na+].OP([O-])(=O)OP(O)([O-])=O GYQBBRRVRKFJRG-UHFFFAOYSA-L 0.000 claims 1
- 150000004679 hydroxides Chemical class 0.000 claims 1
- VLPFTAMPNXLGLX-UHFFFAOYSA-N trioctanoin Chemical compound CCCCCCCC(=O)OCC(OC(=O)CCCCCCC)COC(=O)CCCCCCC VLPFTAMPNXLGLX-UHFFFAOYSA-N 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 54
- 229910052757 nitrogen Inorganic materials 0.000 description 27
- 238000013112 stability test Methods 0.000 description 25
- 239000012153 distilled water Substances 0.000 description 24
- 239000002244 precipitate Substances 0.000 description 24
- 238000004821 distillation Methods 0.000 description 22
- 230000001747 exhibiting effect Effects 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- QLBRROYTTDFLDX-UHFFFAOYSA-N [3-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCCC(CN)C1 QLBRROYTTDFLDX-UHFFFAOYSA-N 0.000 description 5
- 239000003822 epoxy resin Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229920000647 polyepoxide Polymers 0.000 description 5
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 4
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-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
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- BDYVWDMHYNGVGE-UHFFFAOYSA-N [2-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCCCC1CN BDYVWDMHYNGVGE-UHFFFAOYSA-N 0.000 description 1
- OXIKYYJDTWKERT-UHFFFAOYSA-N [4-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCC(CN)CC1 OXIKYYJDTWKERT-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004956 cyclohexylene group Chemical group 0.000 description 1
- AVKNGPAMCBSNSO-UHFFFAOYSA-N cyclohexylmethanamine Chemical compound NCC1CCCCC1 AVKNGPAMCBSNSO-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
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- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyethers (AREA)
Description
本発明はポリアミンとアルケニル化合物との付加反応により得られるアミノ組成物の貯蔵安定化方法に関する。 The present invention relates to a method for storage stabilization of an amino composition obtained by an addition reaction between a polyamine and an alkenyl compound.
強塩基性を呈する触媒を用い、ポリアミンとアルケニル化合物との付加反応により得られるアミノ組成物は、未反応ポリアミン含有量が比較的低く、低粘度であり、該アミノ組成物を含むエポキシ樹脂硬化剤を用いたエポキシ樹脂組成物は良好なエポキシ樹脂硬化物性能を与え、有用である。 An amino composition obtained by addition reaction of a polyamine and an alkenyl compound using a catalyst exhibiting strong basicity has a relatively low unreacted polyamine content and a low viscosity, and an epoxy resin curing agent containing the amino composition The epoxy resin composition using the resin gives good epoxy resin cured product performance and is useful.
該アミノ組成物は、製造直後は低粘度の透明液体であるが、経時的に変化（粘度上昇、および／または白色固体の生成）し、著しく商品価値を低下させてしまうのみならず、誘導されるエポキシ樹脂硬化物性能をも低下させる。 The amino composition is a transparent liquid having a low viscosity immediately after production, but it is not only induced to change over time (increased viscosity and / or production of a white solid) and significantly reduce the commercial value. This also reduces the performance of cured epoxy resin.
本発明の目的は、ポリアミンとアルケニル化合物との付加反応により得られるアミノ組成物の貯蔵安定化方法を提供することである。 An object of the present invention is to provide a storage stabilization method of an amino composition obtained by an addition reaction between a polyamine and an alkenyl compound.
本発明者らは、前記したような問題点を解決すべく、鋭意検討した結果、本発明に至ったものである。 As a result of intensive studies aimed at solving the above-described problems, the present inventors have arrived at the present invention.
即ち本発明は、ポリアミンとアルケニル化合物の付加反応により得られるアミノ組成物の貯蔵安定化方法であって、該アミノ組成物中のアルカリ金属含有量を１０ｐｐｍ以下にすることを特徴とするアミノ組成物の貯蔵安定化方法を提供するものである。 That is, the present invention relates to a storage stabilization method for an amino composition obtained by an addition reaction of a polyamine and an alkenyl compound, wherein the alkali composition content in the amino composition is 10 ppm or less. The method of stabilizing the storage of
以上の実施例から明らかなように、本発明のポリアミンとアルケニル化合物との付加反応により得られるアミノ組成物について、該組成物中のアルカリ金属含有量を１０ｐｐｍ以下にすることによって、アミノ組成物の貯蔵安定化が可能である。 As is clear from the above examples, with respect to the amino composition obtained by the addition reaction of the polyamine of the present invention and the alkenyl compound, by setting the alkali metal content in the composition to 10 ppm or less, Storage stability is possible.
本発明で使用されるポリアミンは、例えば、式（１）で示されるポリアミン、式（２）で示されるポリアミン、ポリアミンが分子内の炭素数が９以上で、分子内のアミノ基数が２以上であり、かつ該アミノ基に由来する活性水素数が３以上である環状脂肪族ポリアミン、ポリオキシアルキレンポリアミンなどが挙げられる。 The polyamine used in the present invention is, for example, a polyamine represented by the formula (1), a polyamine represented by the formula (2), or a polyamine having 9 or more carbon atoms in the molecule and 2 or more amino groups in the molecule. And cycloaliphatic polyamines and polyoxyalkylene polyamines having 3 or more active hydrogen atoms derived from the amino group.
本発明で使用される式（１）で示されるポリアミンとは、例えば、オルソキシリレンジアミン、メタキシリレンジアミン、パラキシリレンジアミン、１，２−ビス（アミノメチル）シクロヘキサン、１，３−ビス（アミノメチル）シクロヘキサン、１，４−ビス（アミノメチル）シクロヘキサンなどが挙げられる。 Examples of the polyamine represented by the formula (1) used in the present invention include orthoxylylenediamine, metaxylylenediamine, paraxylylenediamine, 1,2-bis (aminomethyl) cyclohexane, 1,3-bis. (Aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane and the like can be mentioned.
本発明で使用される式（２）で示されるポリアミンとは、例えば、エチレンジアミン、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ペンタエチレンヘキサミンなどが挙げられる。 Examples of the polyamine represented by the formula (2) used in the present invention include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine.
本発明で使用される分子内の炭素数が９以上で、分子内のアミノ基数が２以上であり、かつ該アミノ基に由来する活性水素数が３以上である環状脂肪族ポリアミンとは、例えば、メンセンジアミン、イソホロンジアミン、ジアミノジシクロヘキシルメタン、ビス（４−アミノ−３−メチルシクロヘキシル）メタン、Ｎ−アミノメチルピペラジン、ノルボルナンジアミン、ポリシクロヘキシルポリアミン、３（４），８（９）−ビス−（アミノメチル）−トリシクロ[５．２．１．０（２，６）]デカンなどが挙げられる。 The cycloaliphatic polyamine having 9 or more carbon atoms in the molecule, 2 or more amino groups in the molecule, and 3 or more active hydrogen atoms derived from the amino group used in the present invention is, for example, , Mensendiamine, isophoronediamine, diaminodicyclohexylmethane, bis (4-amino-3-methylcyclohexyl) methane, N-aminomethylpiperazine, norbornanediamine, polycyclohexylpolyamine, 3 (4), 8 (9) -bis- (Aminomethyl) -tricyclo [5.2.1.0 (2,6)] decane and the like.
本発明で使用されるポリオキシアルキレンポリアミンとは、例えば、ポリオキシエチレンジアミン、ポリオキシプロピレンジアミン、ポリオキシテトラメチレンジアミン、ポリ（オキシエチレン−オキシプロピレン）ジアミン等のポリオキシアルキレンジアミン、あるいはポリオキシエチレントリアミン、ポリオキシプロピレントリアミンなどが挙げられる。 The polyoxyalkylene polyamine used in the present invention is, for example, polyoxyalkylene diamine such as polyoxyethylene diamine, polyoxypropylene diamine, polyoxytetramethylene diamine, poly (oxyethylene-oxypropylene) diamine, or polyoxyethylene. Examples include triamine and polyoxypropylene triamine.
本発明で使用されるアルケニル化合物としては、あらゆるアルケニル化合物が挙げられるが、炭素数が２〜１０であるものが好ましい。例えば、エチレン、プロピレン、ブテン、ペンテン、ヘキセン、ヘプテン、オクテン、ノネン、デセン、イソブチレン、２−ペンテン、３−メチル−１−ブテン、２−メチル−２−ブテン、２，３−ジメチル−２−ブテン、シクロヘキセン、シクロヘキサジエン、スチレン、ジビニルベンゼンなどが挙げられる。 Examples of the alkenyl compound used in the present invention include all alkenyl compounds, but those having 2 to 10 carbon atoms are preferable. For example, ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, isobutylene, 2-pentene, 3-methyl-1-butene, 2-methyl-2-butene, 2,3-dimethyl-2- Examples include butene, cyclohexene, cyclohexadiene, styrene, and divinylbenzene.
本発明において、経時的に変化（粘度上昇、および／または白色固体の生成）しうる粗アミノ組成物は、ポリアミンとアルケニル化合物との付加反応により得られる。 In the present invention, a crude amino composition that can change over time (increased viscosity and / or formation of a white solid) is obtained by an addition reaction of a polyamine and an alkenyl compound.
本発明において、粗アミノ組成物を合成する際には、強塩基性を呈する触媒を使用することが好ましい。強塩基性を呈する触媒としては、例えば、アルカリ金属、アルカリ金属アミド、アルキル化アルカリ金属などが挙げられる。 In the present invention, when synthesizing a crude amino composition, it is preferable to use a catalyst exhibiting strong basicity. Examples of the catalyst exhibiting strong basicity include alkali metals, alkali metal amides, alkylated alkali metals, and the like.
アルカリ金属としては、例えば、金属リチウム、金属ナトリウム、金属カリウム、などが挙げられ、アルカリ金属アミドとしては、例えば、リチウムアミド、リチウムジイソプロピルアミド、ナトリウムアミド、などが挙げられ、アルキル化アルカリ金属としては、メチルリチウム、ブチルリチウムなどが挙げられ、その他の強塩基性を呈する触媒としては、リチウムメチラート、リチウムエチラート、ナトリウムメチラート、ナトリウムエチラート、カリウムメチラート、カリウムブチラートなどが挙げられる。 Examples of the alkali metal include metal lithium, metal sodium, and metal potassium. Examples of the alkali metal amide include lithium amide, lithium diisopropylamide, and sodium amide. Examples of the alkylated alkali metal include , Methyl lithium, butyl lithium and the like, and other strong basic catalysts include lithium methylate, lithium ethylate, sodium methylate, sodium ethylate, potassium methylate, potassium butyrate and the like.
触媒の使用量は、原料の種類や反応比率、反応温度等の条件により異なるが、通常は原料中０．０５〜５重量％であり、好ましくは０．１〜３重量％である。 The amount of the catalyst used varies depending on the type of raw material, reaction ratio, reaction temperature and the like, but is usually 0.05 to 5% by weight, preferably 0.1 to 3% by weight in the raw material.
粗アミノ組成物を合成する際の反応温度は、通常、５０〜１５０℃であり、好ましくは８０〜１００℃である。これより反応温度が低い場合は、ポリアミンとアルケニル化合物の付加反応速度が遅く、逆に反応温度が高い場合は、副生成物としてアルケニル化合物の重合物が生成するので好ましくない。 The reaction temperature for synthesizing the crude amino composition is usually 50 to 150 ° C, preferably 80 to 100 ° C. When the reaction temperature is lower than this, the addition reaction rate of the polyamine and the alkenyl compound is slow, and conversely, when the reaction temperature is high, a polymer of the alkenyl compound is formed as a by-product, which is not preferable.
反応終了後に得られる反応液中には、反応により生成したアミノ組成物と強塩基性を呈する触媒が含まれる。強塩基性を呈する触媒は、ろ過によりある程度の量は除去可能である。ろ過の場合は、塩酸、塩化水素ガス、酢酸などの酸、メタノール、エタノール等のアルコール、あるいは水等を加えて強塩基性を呈する触媒を除去容易な化合物に変えてからろ過することが可能である。例えば水を加えた場合には、強塩基性を呈する触媒が水酸化物となり、ろ過が容易となる。 The reaction solution obtained after completion of the reaction contains an amino composition produced by the reaction and a catalyst exhibiting strong basicity. A certain amount of the catalyst exhibiting strong basicity can be removed by filtration. In the case of filtration, it is possible to add a catalyst with strong basicity by adding hydrochloric acid, hydrogen chloride gas, an acid such as acetic acid, an alcohol such as methanol or ethanol, or water to make a compound that can be easily removed and then filtered. is there. For example, when water is added, the catalyst exhibiting strong basicity becomes a hydroxide, which facilitates filtration.
ところが、これらの強塩基性を呈する触媒の塩が一定量以上残存している粗アミノ組成物は、製造直後は低粘度の透明液体であるが、残存する強塩基性を呈する触媒を分解して生成したアルカリ金属化合物のために、経時的に変化（粘度上昇、および／または白色固体の生成）し、著しく商品価値を低下させてしまうのみならず、誘導されるエポキシ樹脂硬化物性能をも低下させるので、該組成物中のアルカリ金属含有量を１０ｐｐｍ以下、好ましくは５ｐｐｍ以下、特に好ましくは３ｐｐｍ以下とし、アミノ組成物の貯蔵安定化をはかる必要がある。 However, the crude amino composition in which a certain amount or more of the salt of the catalyst exhibiting strong basicity remains is a low-viscosity transparent liquid immediately after production, but the remaining catalyst exhibiting strong basicity is decomposed. Due to the alkali metal compound produced, it changes over time (increased viscosity and / or white solid), not only significantly reducing the commercial value, but also reducing the performance of the cured epoxy resin product. Therefore, the alkali metal content in the composition must be 10 ppm or less, preferably 5 ppm or less, particularly preferably 3 ppm or less, and storage stability of the amino composition must be achieved.
強塩基性を呈する触媒を除去する方法としては、（１）〜（７）が挙げられる。 Examples of a method for removing a catalyst exhibiting strong basicity include (1) to (7).
（１）アルカリ吸着剤を使用して除去する方法、（２）水洗することにより除去する方法、（３）酸で触媒を中和し、生じた塩をろ過することにより除去する方法、（４）イオン交換樹脂を用いて除去する方法、（５）アルカリ金属を炭酸ガスで中和して炭酸塩をろ過する方法、（６）酸水溶液を加え中和しろ過後、過剰の酸を酸吸着剤を使用して除去する方法、（７）酸性ピロリン酸塩、ピロリン酸２水素２ナトリウムを使用して除去する方法、などが挙げられるが、操作が簡便で経済的な（１）および（２）の方法が好ましい。これらの方法は、単独で行なっても良いし、併用しても良い。 (1) A method of removing using an alkali adsorbent, (2) A method of removing by washing with water, (3) A method of neutralizing the catalyst with an acid and removing the resulting salt by filtration, (4 ) Method of removing using ion exchange resin, (5) Method of neutralizing alkali metal with carbon dioxide and filtering carbonate, (6) Neutralizing by adding aqueous acid solution and filtering, then removing excess acid as acid adsorbent (7) Acid pyrophosphate, method using 2-sodium dihydrogen pyrophosphate, and the like (1) and (2) This method is preferred. These methods may be performed alone or in combination.
（１）アルカリ吸着剤を使用して除去する方法で用いるアルカリ吸着剤としては、あらゆるアルカリ吸着剤が挙げられるが、例えば、ＭｇＯ、Ａｌ（ＯＨ）３・ｘＨ２Ｏ、１．２５Ｍｇ（ＯＨ）２・Ａｌ（ＯＨ）３・ｘＣＯ３・ｙＨ２Ｏ、Ａｌ（ＯＨ）３・ＮａＨＣＯ３、Ｍｇ６Ａｌ２（ＯＨ）１６・ＣＯ３・４Ｈ２Ｏ、Ｍｇ４．５・Ａｌ２（ＯＨ）１３・ＣＯ３・３．５Ｈ２Ｏ、Ｍｇ０．７・Ａｌ０．３・Ｏ１．１５などが挙げられる。これらは単独で使用しても良いし、併用しても良い。 (1) Alkali adsorbents used in the removal method using an alkali adsorbent include all alkali adsorbents. For example, MgO, Al (OH) 3 xH 2 O, 1.25 Mg (OH) 2 · Al (OH) 3 · xCO 3 · yH 2 O, Al (OH) 3 · NaHCO 3 , Mg 6 Al 2 (OH) 16 · CO 3 · 4H 2 O, Mg 4.5 · Al 2 (OH) 13 · CO 3 · 3.5H 2 O , and the like Mg 0.7 · Al 0.3 · O 1.15 . These may be used alone or in combination.
アルカリ吸着剤の使用量は、強塩基性を呈する触媒１重量部に対して、１〜１０００重量部の割合で用いる。アルカリ吸着剤の使用量が、１重量部より少ないと、アミノ組成物中のアルカリ金属含有量を１０ｐｐｍ以下にすることができず、性状が安定しない。またアルカリ吸着剤の使用量が、１０００重量部より多いとアルカリ吸着剤を除去するための、ろ過操作の負荷が大きくなるばかりか、ろ過ケーク量が増加し経済的に好ましくない。 The amount of the alkali adsorbent used is 1 to 1000 parts by weight with respect to 1 part by weight of the catalyst exhibiting strong basicity. If the amount of the alkali adsorbent used is less than 1 part by weight, the alkali metal content in the amino composition cannot be reduced to 10 ppm or less, and the properties are not stable. On the other hand, when the amount of the alkali adsorbent used is more than 1000 parts by weight, not only does the load of the filtration operation for removing the alkali adsorbent increase, but the amount of the filter cake increases, which is not economically preferable.
アルカリ吸着剤による強塩基性を呈する触媒の除去は、ポリアミンとアルケニル化合物との付加反応終了後、塩酸、塩化水素ガス、酢酸などの酸、メタノール、エタノール等のアルコール、あるいは水等を加えて強塩基性を呈する触媒を除去容易な化合物に変えた後であればいつでも良く、例えば、付加反応終了後、水を加え強塩基性を呈する触媒を水酸化物とし、その後アルカリ吸着剤を加え、５０〜１５０℃で３０〜３００分撹拌した後、ろ過によってアルカリ吸着剤を除去する方法、付加反応終了後、水を加えて強塩基性を呈する触媒を水酸化物とし、水を除去、水酸化物をろ過したのち、アルカリ吸着剤を加え、５０〜１５０℃で３０〜３００分撹拌した後、ろ過によってアルカリ吸着剤を除去する方法などが挙げられる。撹拌温度が５０℃より低いとアルカリ吸着反応が進行しにくく好ましくない。また１５０℃より高いとアミノ組成物が着色するおそれがあるので好ましくない。撹拌時間は３０分より短いとアルカリ吸着反応が十分行えないので好ましくない。また３００分より長いと製造所要時間が長くなり好ましくない。 The removal of the strongly basic catalyst by the alkali adsorbent is performed by adding hydrochloric acid, hydrogen chloride gas, an acid such as acetic acid, an alcohol such as methanol or ethanol, or water after the addition reaction between the polyamine and the alkenyl compound. After the basic catalyst is changed to a compound that can be easily removed, for example, after completion of the addition reaction, water is added to form a strong basic catalyst as a hydroxide, and then an alkali adsorbent is added. After stirring at ˜150 ° C. for 30 to 300 minutes, the method of removing the alkali adsorbent by filtration, after completion of the addition reaction, water is added to make the catalyst exhibiting strong basicity into hydroxide and water is removed, hydroxide A method of removing the alkali adsorbent by filtration after adding an alkali adsorbent and stirring at 50 to 150 ° C. for 30 to 300 minutes can be mentioned. When the stirring temperature is lower than 50 ° C., the alkali adsorption reaction hardly proceeds, which is not preferable. Moreover, since there exists a possibility that an amino composition may color when it exceeds 150 degreeC, it is unpreferable. If the stirring time is shorter than 30 minutes, the alkali adsorption reaction cannot be sufficiently performed, which is not preferable. On the other hand, if it is longer than 300 minutes, the required production time becomes longer, which is not preferable.
（２）水洗することにより除去する方法で用いる水としては、例えば、工業用水、イオン交換水、蒸留水などが挙げられる。 (2) As water used by the method of removing by washing, industrial water, ion-exchange water, distilled water etc. are mentioned, for example.
水洗することによる強塩基性を呈する触媒の除去は、ポリアミンとアルケニル化合物との付加反応終了後であればいつ行なっても良く、例えば、付加反応終了後、水を加え、１０〜１００℃で５〜６０分撹拌した後、静置して、アミノ組成物層と水層に分液させ、この分液操作を該アミノ組成物中のアルカリ金属含有量が１０ｐｐｍ以下になるまで繰り返し行なう方法、付加反応終了後、水を加えて強塩基性を呈する触媒を水酸化物とし、水を除去、水酸化物をろ過したのち、水を加え、１０〜１００℃で５〜６０分撹拌した後、アミノ組成物層と水層に分液させ、この分液操作を該アミノ組成物中のアルカリ金属含有量が１０ｐｐｍ以下になるまで繰り返し行なう方法などが挙げられる。撹拌温度が１０℃より低いとアミノ組成物の粘度が比較的高く分液しづらく好ましくない。また１００℃より高いと水が気化するおそれがあるので好ましくない。さらに撹拌時間が５分より短いと水洗が十分行なえず好ましくない。また６０分より長くしても効果は変わらず製造所要時間が長くなり好ましくない。 The removal of the catalyst exhibiting strong basicity by washing with water may be performed at any time after the completion of the addition reaction between the polyamine and the alkenyl compound. After stirring for -60 minutes, let stand and separate into an amino composition layer and an aqueous layer, and repeat this separation operation until the alkali metal content in the amino composition is 10 ppm or less, addition After completion of the reaction, water is added to form a strongly basic catalyst as hydroxide, water is removed, the hydroxide is filtered, water is added, and the mixture is stirred at 10 to 100 ° C. for 5 to 60 minutes. Examples include a method in which the composition layer and the aqueous layer are separated, and this separation operation is repeated until the alkali metal content in the amino composition is 10 ppm or less. If the stirring temperature is lower than 10 ° C., the viscosity of the amino composition is relatively high and it is difficult to separate the liquid. Moreover, since there exists a possibility that water may vaporize when it exceeds 100 degreeC, it is unpreferable. Further, if the stirring time is shorter than 5 minutes, washing with water cannot be performed sufficiently, which is not preferable. Further, even if the time is longer than 60 minutes, the effect is not changed, and the time required for production is increased, which is not preferable.
水の使用量は、アミノ組成物１００重量部に対して、２０〜１０００重量部の割合で用いる。水の使用量が、２０重量部より少ないか、もしくは１０００重量部より多いと水とアミノ組成物が相溶し、分液できないので好ましくない。 The amount of water used is 20 to 1000 parts by weight with respect to 100 parts by weight of the amino composition. If the amount of water used is less than 20 parts by weight or more than 1000 parts by weight, it is not preferable because water and the amino composition are compatible and cannot be separated.
以上のとおり、本発明では、ポリアミンとアルケニル化合物との付加反応により得られるアミノ組成物の貯蔵安定化方法において、該組成物中のアルカリ金属含有量を１０ｐｐｍ以下にすることによりアミノ組成物を貯蔵安定化することができる。 As described above, in the present invention, in an amino composition storage stabilization method obtained by addition reaction of a polyamine and an alkenyl compound, the amino composition is stored by setting the alkali metal content in the composition to 10 ppm or less. Can be stabilized.
以下に、本発明を実施例によって具体的に説明するが、本発明はこれによって限定されるものではない。 EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.
＜実施例１＞
撹拌装置、温度計、窒素導入管、滴下漏斗、冷却管を備えた２リットルフラスコに、メタキシリレンジアミン（三菱ガス化学（株）製、ＭＸＤＡ（分子量１３６．２））８１７．２ｇ（６．０モル）とリチウムアミド（メルク社製、試薬）２．９ｇ（０．１３モル）を仕込み、窒素気流下、撹拌しながら８０℃に昇温した。８０℃に保ちながら、スチレン（和光純薬工業（株）製、試薬特級）６２５．２g（６．０モル）を２時間かけて滴下した。滴下終了後、８０℃で１時間保った。
その後、仕込んだリチウムアミドの１０倍モル量の蒸留水２３．４ｇ（１．３モル）、仕込んだリチウムアミドの１０倍重量部のアルカリ吸着剤として２ＭｇＯ６ＳｉＯ２／ｘＨ２Ｏ（協和化学工業（株）製、キョーワード６００ｓ）２９ｇを添加して１時間撹拌した。フラスコ内液中の沈殿物をろ過で分離後、減圧蒸留で水を留去し、アミノ組成物Ａ １３８２．５ｇを得た。アミノ組成物Ａのリチウム含有量は０．７ｐｐｍ、粘度は３７ｍＰａ・ｓ／２５℃であった。得られたアミノ組成物について、保存安定性試験を行なった。保存安定性試験方法は、各アミノ組成物２２５ｇを蓋付きガラス容器に入れ、窒素封入する。２５℃の環境試験室にて、１年間放置したのち、各アミノ組成物の外観を観察し、粘度を測定し、性状の変化を見るものとする。その結果を表１に示す。
<Example 1>
In a 2 liter flask equipped with a stirrer, a thermometer, a nitrogen introduction tube, a dropping funnel and a cooling tube, metaxylylenediamine (Mitsubishi Gas Chemical Co., Ltd., MXDA (molecular weight 136.2)) 817.2 g (6. 0 mol) and 2.9 g (0.13 mol) of lithium amide (manufactured by Merck & Co., Inc.) were charged, and the temperature was raised to 80 ° C. with stirring under a nitrogen stream. While maintaining the temperature at 80 ° C., 625.2 g (6.0 mol) of styrene (manufactured by Wako Pure Chemical Industries, Ltd., special grade reagent) was added dropwise over 2 hours. After completion of dropping, the mixture was kept at 80 ° C. for 1 hour.
Thereafter, 23.4 g (1.3 mol) of distilled water having a 10-fold molar amount of the charged lithium amide, and 2MgO 6 SiO 2 / xH 2 O (Kyowa Chemical Industry Co., Ltd.) as an alkali adsorbent having 10 times by weight of the charged lithium amide. 29 g (Kyoward 600s, manufactured by Co., Ltd.) was added and stirred for 1 hour. After separating the precipitate in the liquid in the flask by filtration, water was distilled off by distillation under reduced pressure to obtain 1382.5 g of amino composition A. Amino composition A had a lithium content of 0.7 ppm and a viscosity of 37 mPa · s / 25 ° C. The obtained amino composition was subjected to a storage stability test. In the storage stability test method, 225 g of each amino composition is placed in a glass container with a lid and sealed with nitrogen. After leaving for 1 year in an environmental test room at 25 ° C., the appearance of each amino composition is observed, the viscosity is measured, and the change in properties is observed. The results are shown in Table 1.
＜実施例２＞
実施例１と同様のフラスコにＭＸＤＡ ６８１．０ｇ（５．０モル）とリチウムアミド３．３ｇ（０．１４モル）を仕込み、窒素気流下、撹拌しながら８０℃に昇温した。８０℃に保ちながら、スチレン６５１．３g（６．２５モル）を２．５時間かけて滴下した。滴下終了後、８０℃で１時間保った。その後、仕込んだリチウムアミドの１０倍モル量の蒸留水２５．２ｇ（１．４モル）、仕込んだリチウムアミドの１０倍重量部のアルカリ吸着剤としてキョーワード６００ｓ ３３．０ｇをを添加して１時間撹拌した。フラスコ内液中の沈殿物をろ過で分離後、減圧蒸留で水を留去し、アミノ組成物Ｂ １２７３．３ｇを得た。アミノ組成物Ｂのリチウム含有量は０．８ｐｐｍ、粘度は５５ｍＰａ・ｓ／２５℃であった。得られたアミノ組成物について、保存安定性試験を行なった。その結果を表１に示す。
<Example 2>
MXDA 681.0g (5.0mol) and lithium amide 3.3g (0.14mol) were prepared to the same flask as Example 1, and it heated up at 80 degreeC, stirring under nitrogen stream. While maintaining the temperature at 80 ° C., 651.3 g (6.25 mol) of styrene was added dropwise over 2.5 hours. After completion of dropping, the mixture was kept at 80 ° C. for 1 hour. Thereafter, 25.2 g (1.4 mol) of distilled water having a 10-fold molar amount of the charged lithium amide, and 33.0 g of Kyoward 600s as an alkali adsorbent having 10-fold weight part of the charged lithium amide were added. Stir for hours. After the precipitate in the liquid in the flask was separated by filtration, water was removed by distillation under reduced pressure to obtain 1273.3 g of amino composition B. Amino composition B had a lithium content of 0.8 ppm and a viscosity of 55 mPa · s / 25 ° C. The obtained amino composition was subjected to a storage stability test. The results are shown in Table 1.
＜実施例３＞
実施例１と同様のフラスコに１，３−ビス（アミノメチル）シクロヘキサン（三菱ガス化学（株）製、１，３−ＢＡＣ（分子量１４２．２））８５３．２ｇ（６．０モル）とリチウムアミド３．０ｇ（０．１３モル）を仕込み、窒素気流下、撹拌しながら８０℃に昇温した。８０℃に保ちながら、スチレン６２５．２g（６．０モル）を２時間かけて滴下した。滴下終了後、８０℃で１時間保った。
その後、仕込んだリチウムアミドの１０倍モル量の蒸留水２３．４ｇ（１．３モル）、仕込んだリチウムアミドの１０倍重量部のアルカリ吸着剤としてキョーワード６００ｓ ３０．０ｇを添加して１時間撹拌した。フラスコ内液中の沈殿物をろ過で分離後、減圧蒸留で水を留去し、アミノ組成物Ｃ １４０９．６ｇを得た。アミノ組成物Ｃのリチウム含有量は１．２ｐｐｍ、粘度は３８ｍＰａ・ｓ／２５℃であった。
得られたアミノ組成物について、保存安定性試験を行なった。その結果を表１に示す。
<Example 3>
In the same flask as in Example 1, 853.2 g (6.0 mol) of 1,3-bis (aminomethyl) cyclohexane (Mitsubishi Gas Chemical Co., Ltd., 1,3-BAC (molecular weight 142.2)) and lithium The amide 3.0g (0.13mol) was prepared, and it heated up at 80 degreeC, stirring under nitrogen stream. While maintaining the temperature at 80 ° C., 625.2 g (6.0 mol) of styrene was added dropwise over 2 hours. After completion of dropping, the mixture was kept at 80 ° C. for 1 hour.
Thereafter, 23.4 g (1.3 mol) of distilled water having a 10-fold molar amount of the charged lithium amide and 30.0 g of Kyoward 600s as an alkali adsorbent having 10 times by weight of the charged lithium amide were added for 1 hour. Stir. After separating the precipitate in the liquid in the flask by filtration, water was distilled off by distillation under reduced pressure to obtain 1409.6 g of amino composition C. Amino composition C had a lithium content of 1.2 ppm and a viscosity of 38 mPa · s / 25 ° C.
The obtained amino composition was subjected to a storage stability test. The results are shown in Table 1.
＜実施例４＞
実施例１と同様のフラスコに１，３−ＢＡＣ ７１１．０ｇ（５．０モル）とリチウムアミド３．４ｇ（０．１５モル）を仕込み、窒素気流下、撹拌しながら８０℃に昇温した。８０℃に保ちながら、スチレン６５１．３g（６．２５モル）を２．５時間かけて滴下した。滴下終了後、８０℃で１時間保った。
その後、仕込んだリチウムアミドの１０倍モル量の蒸留水２７．０ｇ（１．５モル）、仕込んだリチウムアミドの１０倍重量部のアルカリ吸着剤としてキョーワード６００ｓ ３４．０ｇを添加して１時間撹拌した。フラスコ内液中の沈殿物をろ過で分離後、減圧蒸留で水を留去し、アミノ組成物Ｄ １３０８．８ｇを得た。アミノ組成物Ｄのリチウム含有量は０．９ｐｐｍ、粘度は５６ｍＰａ・ｓ／２５℃であった。得られたアミノ組成物について、保存安定性試験を行なった。その結果を表１に示す。
<Example 4>
In the same flask as in Example 1, 711.0 g (5.0 mol) of 1,3-BAC and 3.4 g (0.15 mol) of lithium amide were charged, and the temperature was raised to 80 ° C. with stirring in a nitrogen stream. . While maintaining the temperature at 80 ° C., 651.3 g (6.25 mol) of styrene was added dropwise over 2.5 hours. After completion of dropping, the mixture was kept at 80 ° C. for 1 hour.
Thereafter, 27.0 g (1.5 mol) of distilled water having a 10-fold molar amount of the charged lithium amide, and 34.0 g of Kyoward 600s as an alkali adsorbent having 10 times by weight of the charged lithium amide were added for 1 hour. Stir. After the precipitate in the liquid in the flask was separated by filtration, water was distilled off by distillation under reduced pressure to obtain 1308.8 g of amino composition D. Amino composition D had a lithium content of 0.9 ppm and a viscosity of 56 mPa · s / 25 ° C. The obtained amino composition was subjected to a storage stability test. The results are shown in Table 1.
＜実施例５＞
実施例１と同様のフラスコに、ジエチレントリアミン（関東化学（株）製、試薬特級、ＤＥＴＡ）４１２．７ｇ（４．０モル）とリチウムアミド２．５ｇ（０．１１モル）を仕込み、窒素気流下、撹拌しながら８０℃に昇温した。８０℃に保ちながら、スチレン６５１．３g（６．２５モル）を２．５時間かけて滴下した。滴下終了後、８０℃で０．５時間保った。その後、仕込んだリチウムアミドの１０倍モル量の蒸留水１９．８ｇ（１．１モル）、仕込んだリチウムアミドの１０倍重量部のアルカリ吸着剤としてキョーワード６００ｓ ２５．０ｇを添加して１時間撹拌した。フラスコ内液中の沈殿物をろ過で分離後、減圧蒸留で水を留去し、アミノ組成物Ｅ ７７８．１ｇを得た。アミノ組成物Ｅのリチウム含有量は１．５ｐｐｍ、粘度は２２ｍＰａ・ｓ／２５℃であった。得られたアミノ組成物について、保存安定性試験を行なった。その結果を表１に示す。
<Example 5>
In a flask similar to that in Example 1, 412.7 g (4.0 mol) of diethylenetriamine (manufactured by Kanto Chemical Co., Ltd., reagent grade, DETA) and 2.5 g (0.11 mol) of lithium amide were charged under a nitrogen stream. The temperature was raised to 80 ° C. with stirring. While maintaining the temperature at 80 ° C., 651.3 g (6.25 mol) of styrene was added dropwise over 2.5 hours. After completion of dropping, the temperature was kept at 80 ° C. for 0.5 hour. Thereafter, 19.8 g (1.1 mol) of distilled water having a 10-fold molar amount of the charged lithium amide and 25.0 g of Kyoward 600s as an alkali adsorbent having 10 times by weight of the charged lithium amide were added for 1 hour. Stir. After separating the precipitate in the liquid in the flask by filtration, water was distilled off by distillation under reduced pressure to obtain 778.1 g of amino composition E. Amino composition E had a lithium content of 1.5 ppm and a viscosity of 22 mPa · s / 25 ° C. The obtained amino composition was subjected to a storage stability test. The results are shown in Table 1.
＜実施例６＞
実施例１と同様のフラスコに、トリエチレンテトラミン（関東化学（株）製、試薬特級、ＴＥＴＡ）５８４．８ｇ（４．０モル）とリチウムアミド３．０ｇ（０．１３モル）を仕込み、窒素気流下、撹拌しながら８０℃に昇温した。８０℃に保ちながら、スチレン６５１．３g（６．２５モル）を２．５時間かけて滴下した。滴下終了後、８０℃で０．５時間保った。その後、仕込んだリチウムアミドの１０倍モル量の蒸留水２３．４ｇ（１．３モル）、仕込んだリチウムアミドの１０倍重量部のアルカリ吸着剤としてキョーワード６００ｓ ３０．０ｇを添加して１時間撹拌した。フラスコ内液中の沈殿物をろ過で分離後、減圧蒸留で水を留去し、アミノ組成物Ｆ ９９１ｇを得た。アミノ組成物Ｆのリチウム含有量は２．０ｐｐｍ、粘度は７７ｍＰａ・ｓ／２５℃であった。得られたアミノ組成物について、保存安定性試験を行なった。その結果を表１に示す。
<Example 6>
A flask similar to Example 1 was charged with 584.8 g (4.0 mol) of triethylenetetramine (manufactured by Kanto Chemical Co., Ltd., reagent special grade, TETA) and 3.0 g (0.13 mol) of lithium amide, and nitrogen. The temperature was raised to 80 ° C. with stirring under an air stream. While maintaining the temperature at 80 ° C., 651.3 g (6.25 mol) of styrene was added dropwise over 2.5 hours. After completion of dropping, the temperature was kept at 80 ° C. for 0.5 hour. Thereafter, 23.4 g (1.3 mol) of distilled water having a 10-fold molar amount of the charged lithium amide and 30.0 g of Kyoward 600s as an alkali adsorbent having 10 times by weight of the charged lithium amide were added for 1 hour. Stir. After the precipitate in the liquid in the flask was separated by filtration, water was distilled off by distillation under reduced pressure to obtain 991 g of amino composition F. Amino composition F had a lithium content of 2.0 ppm and a viscosity of 77 mPa · s / 25 ° C. The obtained amino composition was subjected to a storage stability test. The results are shown in Table 1.
＜実施例７＞
実施例１と同様のフラスコに、イソホロンジアミン（デグッサ社製、ＩＰＤＡ）６８１．２ｇ（４．０モル）とリチウムアミド３．３ｇ（０．１４モル）を仕込み、窒素気流下、撹拌しながら８０℃に昇温した。８０℃に保ちながら、スチレン４１６．８g（４．０モル）を２．５時間かけて滴下した。滴下終了後、８０℃で１時間保った。その後、仕込んだリチウムアミドの１０倍モル量の蒸留水２５．２ｇ（１．４モル）、仕込んだリチウムアミドの１０倍重量部のアルカリ吸着剤としてキョーワード６００ｓ ３３．０ｇを添加して１時間撹拌した。フラスコ内液中の沈殿物をろ過で分離後、減圧蒸留で水を留去し、アミノ組成物Ｇ １０３２．７ｇを得た。アミノ組成物Ｇのリチウム含有量は１．８ｐｐｍ、粘度は９０ｍＰａ・ｓ／２５℃であった。得られたアミノ組成物について、保存安定性試験を行なった。その結果を表１に示す。
<Example 7>
In a flask similar to that of Example 1, 681.2 g (4.0 mol) of isophoronediamine (manufactured by Degussa, IPDA) and 3.3 g (0.14 mol) of lithium amide were charged with stirring under a nitrogen stream. The temperature was raised to ° C. While maintaining the temperature at 80 ° C., 416.8 g (4.0 mol) of styrene was added dropwise over 2.5 hours. After completion of dropping, the mixture was kept at 80 ° C. for 1 hour. Thereafter, 25.2 g (1.4 mol) of distilled water having a 10-fold molar amount of the charged lithium amide and 33.0 g of Kyoward 600s as an alkali adsorbent having 10 times by weight of the charged lithium amide were added for 1 hour. Stir. After the precipitate in the liquid in the flask was separated by filtration, water was distilled off by distillation under reduced pressure to obtain 1032.7 g of amino composition G. Amino composition G had a lithium content of 1.8 ppm and a viscosity of 90 mPa · s / 25 ° C. The obtained amino composition was subjected to a storage stability test. The results are shown in Table 1.
＜実施例８＞
実施例１と同様のフラスコに、ノルボルナンジアミン（三井化学（株）製、ＮＢＤＡ）６１７．２ｇ（４．０モル）とリチウムアミド３．１ｇ（０．１４モル）を仕込み、窒素気流下、撹拌しながら８０℃に昇温した。８０℃に保ちながら、スチレン４１６．８g（４．０モル）を２．５時間かけて滴下した。滴下終了後、８０℃で１時間保った。その後、仕込んだリチウムアミドの１０倍モル量の蒸留水２５．２ｇ（１．４モル）、仕込んだリチウムアミドの１０倍重量部のアルカリ吸着剤としてキョーワード６００ｓ ３１．０ｇを添加して１時間撹拌した。フラスコ内液中の沈殿物をろ過で分離後、減圧蒸留で水を留去し、アミノ組成物Ｈ ９７２．２ｇを得た。アミノ組成物Ｈのリチウム含有量は２．２ｐｐｍ、粘度は６４ｍＰａ・ｓ／２５℃であった。得られたアミノ組成物について、保存安定性試験を行なった。その結果を表２に示す。
<Example 8>
In a flask similar to that in Example 1, 617.2 g (4.0 mol) of norbornanediamine (manufactured by Mitsui Chemicals, Inc., NBDA) and 3.1 g (0.14 mol) of lithium amide were stirred under a nitrogen stream. The temperature was raised to 80 ° C. While maintaining the temperature at 80 ° C., 416.8 g (4.0 mol) of styrene was added dropwise over 2.5 hours. After completion of dropping, the mixture was kept at 80 ° C. for 1 hour. Thereafter, 25.2 g (1.4 moles) of distilled water having a 10-fold molar amount of the charged lithium amide and 101.0 parts by weight of an alkaline adsorbent of 10 parts by weight of the charged lithium amide were added, and 31.0 g of Kyoward 600s was added for 1 hour Stir. After the precipitate in the liquid in the flask was separated by filtration, water was removed by distillation under reduced pressure to obtain 972.2 g of amino composition H. Amino composition H had a lithium content of 2.2 ppm and a viscosity of 64 mPa · s / 25 ° C. The obtained amino composition was subjected to a storage stability test. The results are shown in Table 2.
＜実施例９＞
実施例１と同様のフラスコに、ポリオキシプロピレンジアミン（ハンツマン・コーポレーション社製、ジェファーミンＤ−２３０（分子量２３０））４６０．０ｇ（２．０モル）とリチウムアミド２１．３ｇ（０．９３モル）を仕込み、窒素気流下、撹拌しながら１００℃に昇温した。１００℃に保ちながら、スチレン２０８．４g（２．０モル）を４時間かけて滴下した。滴下終了後、１００℃で４時間保った。その後、仕込んだリチウムアミドの１０倍モル量の蒸留水１６７．７ｇ（９．３モル）、仕込んだリチウムアミドの１０倍重量部のアルカリ吸着剤としてキョーワード６００ｓ２１３．０ｇを添加して１時間撹拌した。フラスコ内液中の沈殿物をろ過で分離後、減圧蒸留で水を留去し、アミノ組成物Ｉ ６３５．１ｇを得た。アミノ組成物Ｉのリチウム含有量は２．２ｐｐｍ、粘度は３０ｍＰａ・ｓ／２５℃であった。得られたアミノ組成物について、保存安定性試験を行なった。その結果を表２に示す。
<Example 9>
In a flask similar to that in Example 1, 460.0 g (2.0 mol) of polyoxypropylenediamine (manufactured by Huntsman Corporation, Jeffamine D-230 (molecular weight 230)) and 21.3 g (0.93 mol) of lithium amide were used. And heated to 100 ° C. with stirring under a nitrogen stream. While maintaining the temperature at 100 ° C., 208.4 g (2.0 mol) of styrene was added dropwise over 4 hours. After completion of dropping, the temperature was kept at 100 ° C. for 4 hours. Then, 167.7 g (9.3 mol) of distilled water having a 10-fold molar amount of the charged lithium amide, and 103.0 parts by weight of Kyoward 600s 213.0 g as an alkaline adsorbent were added and stirred for 1 hour. did. After the precipitate in the liquid in the flask was separated by filtration, water was distilled off by distillation under reduced pressure to obtain 635.1 g of amino composition I. Amino composition I had a lithium content of 2.2 ppm and a viscosity of 30 mPa · s / 25 ° C. The obtained amino composition was subjected to a storage stability test. The results are shown in Table 2.
＜実施例１０＞
実施例１と同様のフラスコに、ポリオキシエチレンジアミン（ハンツマン・コーポレーション社製、ジェファーミンＥＤＲ−１４８（分子量１４８））２９６．０ｇ（２．０モル）とリチウムアミド１．５ｇ（０．０６５モル）を仕込み、窒素気流下、撹拌しながら１００℃に昇温した。１００℃に保ちながら、スチレン２０８．４g（２．０モル）を４時間かけて滴下した。滴下終了後、１００℃で４時間保った。
その後、仕込んだリチウムアミドの１０倍モル量の蒸留水１１．７ｇ（０．６５モル）、仕込んだリチウムアミドの１０倍重量部のアルカリ吸着剤としてキョーワード６００ｓ １５．０ｇを添加して１時間撹拌した。フラスコ内液中の沈殿物をろ過で分離後、減圧蒸留で水を留去し、アミノ組成物Ｊ ４７９．０ｇを得た。アミノ組成物Ｊのリチウム含有量は０．９ｐｐｍ、粘度は３０ｍＰａ・ｓ／２５℃であった。得られたアミノ組成物について、保存安定性試験を行なった。その結果を表２に示す。
<Example 10>
In a flask similar to that of Example 1, 296.0 g (2.0 mol) of polyoxyethylenediamine (manufactured by Huntsman Corporation, Jeffamine EDR-148 (molecular weight 148)) and 1.5 g (0.065 mol) of lithium amide Was heated to 100 ° C. with stirring under a nitrogen stream. While maintaining the temperature at 100 ° C., 208.4 g (2.0 mol) of styrene was added dropwise over 4 hours. After completion of dropping, the temperature was kept at 100 ° C. for 4 hours.
Thereafter, 11.7 g (0.65 mol) of distilled water having a 10-fold molar amount of the charged lithium amide and 15.0 g of Kyoward 600s as an alkali adsorbent having 10 times by weight of the charged lithium amide were added for 1 hour. Stir. The precipitate in the liquid in the flask was separated by filtration, and then water was removed by distillation under reduced pressure to obtain 479.0 g of amino composition J. Amino composition J had a lithium content of 0.9 ppm and a viscosity of 30 mPa · s / 25 ° C. The obtained amino composition was subjected to a storage stability test. The results are shown in Table 2.
＜実施例１１＞
実施例１と同様のフラスコに、ポリオキシプロピレントリアミン（ハンツマン・コーポレーション社製、ジェファーミンＴ−４０３（分子量４０３））８０６．０ｇ（２．０モル）とリチウムアミド３５．０g（１．５モル）を仕込み、窒素気流下、撹拌しながら１００℃に昇温した。１００℃に保ちながら、スチレン３１２．６ｇ（３．０モル）を６時間かけて滴下した。滴下終了後、１００℃で４時間保った。その後、仕込んだリチウムアミドの１０倍モル量の水２７０．０ｇ（１５．０モル）、仕込んだリチウムアミドの１０倍重量部のアルカリ吸着剤としてキョーワード６００ｓ ３５０．０ｇを添加して１時間撹拌した。フラスコ内液中の沈殿物をろ過で分離後、減圧蒸留で水を留去し、アミノ組成物Ｋ １０５２．９ｇを得た。
アミノ組成物Ｋのリチウム含有量は１．５ｐｐｍ、粘度は５８０ｍＰａ・ｓ／２５℃であった。得られたアミノ組成物について、保存安定性試験を行なった。その結果を表２に示す。
<Example 11>
In a flask similar to that in Example 1, 806.0 g (2.0 mol) of polyoxypropylene triamine (manufactured by Huntsman Corporation, Jeffamine T-403 (molecular weight 403)) and 35.0 g (1.5 mol) of lithium amide And heated to 100 ° C. with stirring under a nitrogen stream. While maintaining the temperature at 100 ° C., 312.6 g (3.0 mol) of styrene was added dropwise over 6 hours. After completion of dropping, the temperature was kept at 100 ° C. for 4 hours. Then, 270.0 g (15.0 mol) of water in a 10-fold molar amount of the charged lithium amide, and 350.0 g of Kyoward 600s as an alkali adsorbent in 10 times by weight of the charged lithium amide were added and stirred for 1 hour. did. After separating the precipitate in the liquid in the flask by filtration, water was distilled off by distillation under reduced pressure to obtain 1052.9 g of amino composition K.
Amino composition K had a lithium content of 1.5 ppm and a viscosity of 580 mPa · s / 25 ° C. The obtained amino composition was subjected to a storage stability test. The results are shown in Table 2.
＜実施例１２＞
実施例１と同様のフラスコに、ＭＸＤＡ ８１７．２ｇ（６．０モル）とリチウムアミド２．９ｇ（０．１３モル）を仕込み、窒素気流下、撹拌しながら８０℃に昇温した。８０℃に保ちながら、スチレン６２５．２g（６．０モル）を２時間かけて滴下した。滴下終了後、８０℃で１時間保った。
その後、仕込んだリチウムアミドの１０倍モル量の蒸留水２３．４ｇ（１．３モル）を添加して１時間撹拌した。フラスコ内液中の沈殿物をろ過で分離後、減圧蒸留で水を留去し、粗アミノ組成物を得た。その後、仕込んだリチウムアミドの１０倍重量部のアルカリ吸着剤としてキョーワード６００ｓ ２９ｇを添加して１時間撹拌した。フラスコ内液中の沈殿物をろ過で分離し、アミノ組成物Ｌ １３３０．０ｇを得た。アミノ組成物Ｌのリチウム含有量は０．３ｐｐｍ、粘度は３７ｍＰａ・ｓ／２５℃であった。得られたアミノ組成物について、保存安定性試験を行なった。その結果を表２に示す。
<Example 12>
In a flask similar to that in Example 1, 817.2 g (6.0 mol) of MXDA and 2.9 g (0.13 mol) of lithium amide were charged and heated to 80 ° C. with stirring under a nitrogen stream. While maintaining the temperature at 80 ° C., 625.2 g (6.0 mol) of styrene was added dropwise over 2 hours. After completion of dropping, the mixture was kept at 80 ° C. for 1 hour.
Thereafter, 23.4 g (1.3 mol) of distilled water having a 10-fold molar amount of the charged lithium amide was added and stirred for 1 hour. After the precipitate in the liquid in the flask was separated by filtration, water was distilled off under reduced pressure to obtain a crude amino composition. Thereafter, 29 g of Kyoward 600s was added as an alkali adsorbent of 10 times by weight of the charged lithium amide and stirred for 1 hour. The precipitate in the liquid in the flask was separated by filtration to obtain 1330.0 g of an amino composition L. Amino composition L had a lithium content of 0.3 ppm and a viscosity of 37 mPa · s / 25 ° C. The obtained amino composition was subjected to a storage stability test. The results are shown in Table 2.
＜実施例１３＞
実施例１と同様のフラスコに、ＭＸＤＡ ８１７．２ｇ（６．０モル）とリチウムアミド２．９ｇ（０．１３モル）を仕込み、窒素気流下、撹拌しながら８０℃に昇温した。８０℃に保ちながら、スチレン６２５．２g（６．０モル）を２時間かけて滴下した。滴下終了後、８０℃で１時間保った。
その後、８０℃の蒸留水６１８．２ｇを添加し、１０分間撹拌後、５分間静置した。２層に分離したフラスコ内液の下層を別のフラスコに移し、同様の操作を７回繰り返したのち、下層に溶解した蒸留水を減圧蒸留で留去し、アミノ組成物Ｍ １３８２．５ｇを得た。アミノ組成物Ｍのリチウム含有量は０．８ｐｐｍ、粘度は６６ｍＰａ・ｓ／２５℃であった。得られたアミノ組成物について、保存安定性試験を行なった。その結果を表２に示す。
<Example 13>
In a flask similar to that in Example 1, 817.2 g (6.0 mol) of MXDA and 2.9 g (0.13 mol) of lithium amide were charged and heated to 80 ° C. with stirring under a nitrogen stream. While maintaining the temperature at 80 ° C., 625.2 g (6.0 mol) of styrene was added dropwise over 2 hours. After completion of dropping, the mixture was kept at 80 ° C. for 1 hour.
Thereafter, 618.2 g of distilled water at 80 ° C. was added, stirred for 10 minutes, and allowed to stand for 5 minutes. The lower layer of the liquid in the flask separated into two layers was transferred to another flask and the same operation was repeated seven times, and then distilled water dissolved in the lower layer was distilled off under reduced pressure to obtain 1382.5 g of amino composition M. It was. Amino composition M had a lithium content of 0.8 ppm and a viscosity of 66 mPa · s / 25 ° C. The obtained amino composition was subjected to a storage stability test. The results are shown in Table 2.
＜比較例１＞
撹拌装置、温度計、窒素導入管、滴下漏斗、冷却管を備えた２リットルフラスコに、活性水素当量が３４のＭＸＤＡ ８１７．２ｇ（６．０モル）とリチウムアミド２．９ｇ（０．１３モル）を仕込み、窒素気流下、撹拌しながら８０℃に昇温した。８０℃に保ちながら、スチレン６２５．２g（６．０モル）を２時間かけて滴下した。滴下終了後、８０℃で１時間保った。
その後、仕込んだリチウムアミドの１０倍モル量の蒸留水２３．４ｇ（１．３モル）を添加して撹拌した。フラスコ内液中の沈殿物をろ過で分離後、減圧蒸留で水を留去し、アミノ組成物Ｎ １３８０．７ｇを得た。アミノ組成物Ｎのリチウム含有量は２６．３ｐｐｍ、粘度は３７ｍＰａ・ｓ／２５℃であった。得られたアミノ組成物について、保存安定性試験を行なった。その結果を表３に示す。
<Comparative Example 1>
In a 2 liter flask equipped with a stirrer, thermometer, nitrogen inlet tube, dropping funnel, and condenser tube, 817.2 g (6.0 mol) of MXDA having an active hydrogen equivalent weight of 34 and 2.9 g (0.13 mol) of lithium amide were added. And heated to 80 ° C. with stirring under a nitrogen stream. While maintaining the temperature at 80 ° C., 625.2 g (6.0 mol) of styrene was added dropwise over 2 hours. After completion of dropping, the mixture was kept at 80 ° C. for 1 hour.
Thereafter, 23.4 g (1.3 mol) of distilled water having a molar amount 10 times that of the charged lithium amide was added and stirred. After the precipitate in the liquid in the flask was separated by filtration, water was removed by distillation under reduced pressure to obtain 1380.7 g of amino composition N. The lithium content of amino composition N was 26.3 ppm, and the viscosity was 37 mPa · s / 25 ° C. The obtained amino composition was subjected to a storage stability test. The results are shown in Table 3.
＜比較例２＞
実施例１と同様のフラスコにＭＸＤＡ ６８１．０ｇ（５．０モル）とリチウムアミド３．３ｇ（０．１４モル）を仕込み、窒素気流下、撹拌しながら８０℃に昇温した。８０℃に保ちながら、スチレン６５１．３g（６．２５モル）を２．５時間かけて滴下した。滴下終了後、８０℃で１時間保った。
その後、仕込んだリチウムアミドの１０倍モル量の蒸留水２５．２ｇ（１．４モル）を添加して撹拌した。フラスコ内液中の沈殿物をろ過で分離後、減圧蒸留で水を留去し、アミノ組成物Ｐ １２７０．９ｇを得た。アミノ組成物Ｐのリチウム含有量は２４．４ｐｐｍ、粘度は５５ｍＰａ・ｓ／２５℃であった。得られたアミノ組成物について、保存安定性試験を行なった。その結果を表３に示す。
<Comparative example 2>
MXDA 681.0g (5.0mol) and lithium amide 3.3g (0.14mol) were prepared to the same flask as Example 1, and it heated up at 80 degreeC, stirring under nitrogen stream. While maintaining the temperature at 80 ° C., 651.3 g (6.25 mol) of styrene was added dropwise over 2.5 hours. After completion of dropping, the mixture was kept at 80 ° C. for 1 hour.
Thereafter, 25.2 g (1.4 mol) of distilled water having a molar amount 10 times that of the charged lithium amide was added and stirred. After the precipitate in the liquid in the flask was separated by filtration, water was distilled off by distillation under reduced pressure to obtain 1270.9 g of amino composition P. Amino composition P had a lithium content of 24.4 ppm and a viscosity of 55 mPa · s / 25 ° C. The obtained amino composition was subjected to a storage stability test. The results are shown in Table 3.
＜比較例３＞
実施例１と同様のフラスコに１，３−ＢＡＣ ８５３．２ｇ（６．０モル）とリチウムアミド３．０ｇ（０．１３モル）を仕込み、窒素気流下、撹拌しながら８０℃に昇温した。８０℃に保ちながら、スチレン６２５．２g（６．０モル）を２時間かけて滴下した。滴下終了後、８０℃で１時間保った。
その後、仕込んだリチウムアミドの１０倍モル量の蒸留水２３．４ｇ（１．３モル）を添加して撹拌した。フラスコ内液中の沈殿物をろ過で分離後、減圧蒸留で水を留去し、アミノ組成物Ｑ １４０９．３ｇを得た。アミノ組成物Ｑのリチウム含有量は３３．２ｐｐｍ、粘度は３８ｍＰａ・ｓ／２５℃であった。得られたアミノ組成物について、保存安定性試験を行なった。その結果を表３に示す。
<Comparative Example 3>
A flask similar to Example 1 was charged with 853.2 g (6.0 mol) of 1,3-BAC and 3.0 g (0.13 mol) of lithium amide, and the temperature was raised to 80 ° C. with stirring in a nitrogen stream. . While maintaining the temperature at 80 ° C., 625.2 g (6.0 mol) of styrene was added dropwise over 2 hours. After completion of dropping, the mixture was kept at 80 ° C. for 1 hour.
Thereafter, 23.4 g (1.3 mol) of distilled water having a molar amount 10 times that of the charged lithium amide was added and stirred. After separating the precipitate in the liquid in the flask by filtration, water was removed by distillation under reduced pressure to obtain 1409.3 g of amino composition Q. Amino composition Q had a lithium content of 33.2 ppm and a viscosity of 38 mPa · s / 25 ° C. The obtained amino composition was subjected to a storage stability test. The results are shown in Table 3.
＜比較例４＞
実施例１と同様のフラスコに１，３−ＢＡＣ ７１１．０ｇ（５．０モル）とリチウムアミド３．４ｇ（０．１５モル）を仕込み、窒素気流下、撹拌しながら８０℃に昇温した。８０℃に保ちながら、スチレン６５１．３g（６．２５モル）を２．５時間かけて滴下した。滴下終了後、８０℃で１時間保った。
その後、仕込んだリチウムアミドの１０倍モル量の蒸留水２７．０ｇ（１．５モル）を添加して撹拌した。フラスコ内液中の沈殿物をろ過で分離後、減圧蒸留で水を留去し、アミノ組成物Ｒ １３０５．８ｇを得た。アミノ組成物Ｒのリチウム含有量は２９．８ｐｐｍ、粘度は５６ｍＰａ・ｓ／２５℃であった。得られたアミノ組成物について、保存安定性試験を行なった。その結果を表３に示す。
<Comparative example 4>
In the same flask as in Example 1, 711.0 g (5.0 mol) of 1,3-BAC and 3.4 g (0.15 mol) of lithium amide were charged, and the temperature was raised to 80 ° C. with stirring in a nitrogen stream. . While maintaining the temperature at 80 ° C., 651.3 g (6.25 mol) of styrene was added dropwise over 2.5 hours. After completion of dropping, the mixture was kept at 80 ° C. for 1 hour.
Thereafter, 27.0 g (1.5 mol) of distilled water having a 10-fold molar amount of the charged lithium amide was added and stirred. After separating the precipitate in the liquid in the flask by filtration, water was distilled off by distillation under reduced pressure to obtain 1305.8 g of amino composition R. Amino composition R had a lithium content of 29.8 ppm and a viscosity of 56 mPa · s / 25 ° C. The obtained amino composition was subjected to a storage stability test. The results are shown in Table 3.
＜比較例５＞
実施例１と同様のフラスコに、ＤＥＴＡ ４１２．７ｇ（４．０モル）とリチウムアミド（メルク社製、試薬）２．５ｇ（０．１１モル）を仕込み、窒素気流下、撹拌しながら８０℃に昇温した。８０℃に保ちながら、スチレン６５１．３g（６．２５モル）を２．５時間かけて滴下した。滴下終了後、８０℃で０．５時間保った。その後、仕込んだリチウムアミドの１０倍モル量の蒸留水１９．８ｇ（１．１モル）を添加して撹拌した。フラスコ内液中の沈殿物をろ過で分離後、減圧蒸留で水を留去し、アミノ組成物Ｓ ７７７．０ｇを得た。アミノ組成物Ｓのリチウム含有量は３３．１ｐｐｍ、粘度は２２ｍＰａ・ｓ／２５℃であった。得られたアミノ組成物について、保存安定性試験を行なった。その結果を表３に示す。
<Comparative Example 5>
In a flask similar to that in Example 1, 412.7 g (4.0 mol) of DETA and 2.5 g (0.11 mol) of lithium amide (manufactured by Merck & Co., Inc.) were charged, and the mixture was stirred at 80 ° C. in a nitrogen stream. The temperature was raised to. While maintaining the temperature at 80 ° C., 651.3 g (6.25 mol) of styrene was added dropwise over 2.5 hours. After completion of dropping, the temperature was kept at 80 ° C. for 0.5 hour. Thereafter, 19.8 g (1.1 mol) of distilled water having a 10-fold molar amount of the charged lithium amide was added and stirred. After the precipitate in the liquid in the flask was separated by filtration, water was removed by distillation under reduced pressure to obtain 777.0 g of amino composition S. Amino composition S had a lithium content of 33.1 ppm and a viscosity of 22 mPa · s / 25 ° C. The obtained amino composition was subjected to a storage stability test. The results are shown in Table 3.
＜比較例６＞
実施例１と同様のフラスコに、ＴＥＴＡ ５８４．８ｇ（４．０モル）とリチウムアミド３．０ｇ（０．１３モル）を仕込み、窒素気流下、撹拌しながら８０℃に昇温した。８０℃に保ちながら、スチレン６５１．３g（６．２５モル）を２．５時間かけて滴下した。滴下終了後、８０℃で０．５時間保った。
その後、仕込んだリチウムアミドの１０倍モル量の蒸留水２３．４ｇ（１．３モル）を添加して撹拌した。フラスコ内液中の沈殿物をろ過で分離後、減圧蒸留で水を留去し、アミノ組成物Ｔ ９９０ｇを得た。アミノ組成物Ｔのリチウム含有量は３０．０ｐｐｍ、粘度は７７ｍＰａ・ｓ／２５℃であった。得られたアミノ組成物について、保存安定性試験を行なった。その結果を表３に示す。
<Comparative Example 6>
In the same flask as in Example 1, 584.8 g (4.0 mol) of TETA and 3.0 g (0.13 mol) of lithium amide were charged, and the temperature was raised to 80 ° C. with stirring in a nitrogen stream. While maintaining the temperature at 80 ° C., 651.3 g (6.25 mol) of styrene was added dropwise over 2.5 hours. After completion of dropping, the temperature was kept at 80 ° C. for 0.5 hour.
Thereafter, 23.4 g (1.3 mol) of distilled water having a molar amount 10 times that of the charged lithium amide was added and stirred. After the precipitate in the liquid in the flask was separated by filtration, water was removed by distillation under reduced pressure to obtain 990 g of amino composition T. Amino composition T had a lithium content of 30.0 ppm and a viscosity of 77 mPa · s / 25 ° C. The obtained amino composition was subjected to a storage stability test. The results are shown in Table 3.
＜比較例７＞
実施例１と同様のフラスコに、ＩＰＤＡ ６８１．２ｇ（４．０モル）とリチウムアミド３．３ｇ（０．１４モル）を仕込み、窒素気流下、撹拌しながら８０℃に昇温した。８０℃に保ちながら、スチレン４１６．８g（４．０モル）を２．５時間かけて滴下した。滴下終了後、８０℃で１時間保った。その後、仕込んだリチウムアミドの１０倍モル量の蒸留水２５．２ｇ（１．４モル）を添加して撹拌した。フラスコ内液中の沈殿物をろ過で分離後、減圧蒸留で水を留去し、アミノ組成物Ｕ １０３２．７ｇを得た。アミノ組成物Ｕのリチウム含有量は４１．０ｐｐｍ、粘度は９０ｍＰａ・ｓ／２５℃であった。得られたアミノ組成物について、保存安定性試験を行なった。その結果を表４に示す。
<Comparative Example 7>
In the same flask as in Example 1, 681.2 g (4.0 mol) of IPDA and 3.3 g (0.14 mol) of lithium amide were charged, and the temperature was raised to 80 ° C. with stirring in a nitrogen stream. While maintaining the temperature at 80 ° C., 416.8 g (4.0 mol) of styrene was added dropwise over 2.5 hours. After completion of dropping, the mixture was kept at 80 ° C. for 1 hour. Thereafter, 25.2 g (1.4 mol) of distilled water having a molar amount 10 times that of the charged lithium amide was added and stirred. After the precipitate in the liquid in the flask was separated by filtration, water was distilled off by distillation under reduced pressure to obtain 1032.7 g of amino composition U. The lithium content of amino composition U was 41.0 ppm, and the viscosity was 90 mPa · s / 25 ° C. The obtained amino composition was subjected to a storage stability test. The results are shown in Table 4.
＜比較例８＞
実施例１と同様のフラスコに、ＮＢＤＡ ６１７．２ｇ（４．０モル）とリチウムアミド３．１ｇ（０．１４モル）を仕込み、窒素気流下、撹拌しながら８０℃に昇温した。８０℃に保ちながら、スチレン４１６．８g（４．０モル）を２．５時間かけて滴下した。滴下終了後、８０℃で１時間保った。その後、仕込んだリチウムアミドの１０倍モル量の蒸留水２５．２ｇ（１．４モル）を添加して撹拌した。フラスコ内液中の沈殿物をろ過で分離後、減圧蒸留で水を留去し、アミノ組成物Ｖ ９６９．３ｇを得た。アミノ組成物Ｖのリチウム含有量は４０．５ｐｐｍ、粘度は６４ｍＰａ・ｓ／２５℃であった。得られたアミノ組成物について、保存安定性試験を行なった。その結果を表４に示す。
<Comparative Example 8>
In the same flask as in Example 1, 617.2 g (4.0 mol) of NBDA and 3.1 g (0.14 mol) of lithium amide were charged, and the temperature was raised to 80 ° C. with stirring in a nitrogen stream. While maintaining the temperature at 80 ° C., 416.8 g (4.0 mol) of styrene was added dropwise over 2.5 hours. After completion of dropping, the mixture was kept at 80 ° C. for 1 hour. Thereafter, 25.2 g (1.4 mol) of distilled water having a molar amount 10 times that of the charged lithium amide was added and stirred. The precipitate in the liquid in the flask was separated by filtration, and then water was removed by distillation under reduced pressure to obtain 969.3 g of amino composition V. Amino composition V had a lithium content of 40.5 ppm and a viscosity of 64 mPa · s / 25 ° C. The obtained amino composition was subjected to a storage stability test. The results are shown in Table 4.
＜比較例９＞
実施例１と同様のフラスコに、ジェファーミンＤ−２３０ ４６０．０ｇ（２．０モル）とリチウムアミド２１．３ｇ（０．９３モル）を仕込み、窒素気流下、撹拌しながら１００℃に昇温した。１００℃に保ちながら、スチレン２０８．４g（２．０モル）を４時間かけて滴下した。滴下終了後、１００℃で４時間保った。
その後、仕込んだリチウムアミドの１０倍モル量の蒸留水１６７．７ｇ（９．３モル）を添加して撹拌した。フラスコ内液中の沈殿物をろ過で分離後、減圧蒸留で水を留去し、アミノ組成物Ｗ ６３５．０ｇを得た。アミノ組成物Ｗのリチウム含有量は３０ｐｐｍ、粘度は８６．６ｍＰａ・ｓ／２５℃であった。得られたアミノ組成物について、保存安定性試験を行なった。その結果を表４に示す。
<Comparative Example 9>
Into the same flask as in Example 1, 460.0 g (2.0 mol) of Jeffamine D-230 and 21.3 g (0.93 mol) of lithium amide were charged, and the temperature was raised to 100 ° C. with stirring in a nitrogen stream. did. While maintaining the temperature at 100 ° C., 208.4 g (2.0 mol) of styrene was added dropwise over 4 hours. After completion of dropping, the temperature was kept at 100 ° C. for 4 hours.
Thereafter, 167.7 g (9.3 mol) of distilled water having a 10-fold molar amount of the charged lithium amide was added and stirred. After the precipitate in the liquid in the flask was separated by filtration, water was distilled off by distillation under reduced pressure to obtain 635.0 g of amino composition W. Amino composition W had a lithium content of 30 ppm and a viscosity of 86.6 mPa · s / 25 ° C. The obtained amino composition was subjected to a storage stability test. The results are shown in Table 4.
＜比較例１０＞
実施例１と同様のフラスコに、ジェファーミンＥＤＲ−１４８ ２９６．０ｇ（２．０モル）とリチウムアミド１．５ｇ（０．０６５モル）を仕込み、窒素気流下、撹拌しながら１００℃に昇温した。１００℃に保ちながら、スチレン２０８．４g（２．０モル）を４時間かけて滴下した。滴下終了後、１００℃で４時間保った。その後、仕込んだリチウムアミドの１０倍モル量の蒸留水水１１．７ｇ（０．６５モル）を添加して撹拌した。フラスコ内液中の沈殿物をろ過で分離後、減圧蒸留で水を留去し、アミノ組成物Ｘ ４７８．８ｇを得た。アミノ組成物Ｘのリチウム含有量は３０ｐｐｍ、粘度は５１．０ｍＰａ・ｓ／２５℃であった。得られたアミノ組成物について、保存安定性試験を行なった。その結果を表４に示す。
<Comparative Example 10>
Into the same flask as in Example 1, 296.0 g (2.0 mol) of Jeffermine EDR-148 and 1.5 g (0.065 mol) of lithium amide were charged, and the temperature was raised to 100 ° C. with stirring in a nitrogen stream. did. While maintaining the temperature at 100 ° C., 208.4 g (2.0 mol) of styrene was added dropwise over 4 hours. After completion of dropping, the temperature was kept at 100 ° C. for 4 hours. Thereafter, 11.7 g (0.65 mol) of distilled water having a 10-fold molar amount of the charged lithium amide was added and stirred. The precipitate in the liquid in the flask was separated by filtration, and then water was removed by distillation under reduced pressure to obtain 478.8 g of amino composition X. Amino composition X had a lithium content of 30 ppm and a viscosity of 51.0 mPa · s / 25 ° C. The obtained amino composition was subjected to a storage stability test. The results are shown in Table 4.
＜比較例１１＞
実施例１と同様のフラスコに、ジェファーミンＴ−４０３ ８０６．０ｇ（２．０モル）とリチウムアミド３５．０g（１．５モル）を仕込み、窒素気流下、撹拌しながら１００℃に昇温した。１００℃に保ちながら、スチレン３１２．６ｇ（３．０モル）を６時間かけて滴下した。滴下終了後、１００℃で４時間保った。
その後、仕込んだリチウムアミドの１０倍モル量の水２７０．０ｇ（１５．０モル）を添加して撹拌した。フラスコ内液中の沈殿物をろ過で分離後、減圧蒸留で水を留去し、アミノ組成物Ｙ １０５１．５ｇを得た。アミノ組成物Ｙのリチウム含有量は９１．１ｐｐｍ、粘度は５８０ｍＰａ・ｓ／２５℃であった。得られたアミノ組成物について、保存安定性試験を行なった。その結果を表４に示す。
<Comparative Example 11>
Into the same flask as in Example 1, 806.0 g (2.0 mol) of Jeffermine T-403 and 35.0 g (1.5 mol) of lithium amide were added, and the temperature was raised to 100 ° C. with stirring in a nitrogen stream. did. While maintaining the temperature at 100 ° C., 312.6 g (3.0 mol) of styrene was added dropwise over 6 hours. After completion of dropping, the temperature was kept at 100 ° C. for 4 hours.
Thereafter, 270.0 g (15.0 mol) of water having a 10-fold molar amount of the charged lithium amide was added and stirred. After separating the precipitate in the liquid in the flask by filtration, water was distilled off by distillation under reduced pressure to obtain 1051.5 g of amino composition Y. The lithium content of amino composition Y was 91.1 ppm, and the viscosity was 580 mPa · s / 25 ° C. The obtained amino composition was subjected to a storage stability test. The results are shown in Table 4.
Claims (5)
（Ａ） 式（１）で示されるポリアミン、
（Ｄ）ポリオキシエチレンジアミン、ポリオキシプロピレンジアミン、ポリオキシテトラメチレンジアミン、ポリ（オキシエチレン−オキシプロピレン）ジアミン、ポリオキシエチレントリアミンおよびポリオキシプロピレントリアミンからなる群より選ばれるポリオキシアルキレンポリアミン、
（Ｅ）エチレン、プロピレン、ブテン、ペンテン、ヘキセン、ヘプテン、オクテン、ノネン、デセン、イソブチレン、２−ペンテン、３−メチル−１−ブテン、２−メチル−２−ブテン、２，３−ジメチル−２−ブテン、シクロヘキセン、シクロヘキサジエン、スチレンおよびジビニルベンゼンからなる群より選ばれるアルケニル化合物、
（Ｆ）金属リチウム、金属ナトリウム、金属カリウム、リチウムアミド、リチウムジイソプロピルアミド、ナトリウムアミド、メチルリチウム、ブチルリチウム、リチウムメチラート、リチウムエチラート、ナトリウムメチラート、ナトリウムエチラート、カリウムメチラートおよびカリウムブチラートからなる群より選ばれる触媒、
（１）アルカリ吸着剤を使用してアルカリ金属を除去する、
（２）水洗することによりアルカリ金属を除去する、
（３）酸で該触媒を中和し、生じた塩をろ過することによりアルカリ金属を除去する、
（４）イオン交換樹脂を用いてアルカリ金属を除去する、
（５）アルカリ金属を炭酸ガスで中和して炭酸塩をろ過することによりアルカリ金属を除去する、
（６）酸水溶液を加え中和しろ過後、過剰の酸を酸吸着剤を使用してアルカリ金属を除去する、
（７）酸性ピロリン酸塩、ピロリン酸２水素２ナトリウムを使用してアルカリ金属を除去する。 By subjecting any of the polyamines shown in the following (A) to (D) and the alkenyl compound shown in the following (E) to an addition reaction at 50 to 150 ° C. in the presence of a catalyst having a strong basicity shown in the following (F). A method for stabilizing the storage of an amino composition obtained, wherein the alkali metal content in the amino composition is reduced to 10 ppm or less by any of the operations (1) to (7) below: A method for storage stabilization of a composition.
(A) a polyamine represented by the formula (1),
(D) polyoxyalkylene polyamine selected from the group consisting of polyoxyethylene diamine, polyoxypropylene diamine, polyoxytetramethylene diamine, poly (oxyethylene-oxypropylene) diamine, polyoxyethylene triamine and polyoxypropylene triamine,
(E) Ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, isobutylene, 2-pentene, 3-methyl-1-butene, 2-methyl-2-butene, 2,3-dimethyl-2 An alkenyl compound selected from the group consisting of butene, cyclohexene, cyclohexadiene, styrene and divinylbenzene,
(F) metallic lithium, metallic sodium, metallic potassium, lithium amide, lithium diisopropylamide, sodium amide, methyl lithium, butyl lithium, lithium methylate, lithium ethylate, sodium methylate, sodium ethylate, potassium methylate and potassium butyrate A catalyst selected from the group consisting of Rato,
(1) Use an alkali adsorbent to remove alkali metals.
(2) The alkali metal is removed by washing with water.
(3) neutralize the catalyst with an acid and remove the alkali metal by filtering the resulting salt;
(4) removing an alkali metal using an ion exchange resin;
(5) The alkali metal is removed by neutralizing the alkali metal with carbon dioxide and filtering the carbonate.
(6) After adding an acid aqueous solution to neutralize and filtering, excess acid is removed from the alkali metal using an acid adsorbent.
(7) The alkali metal is removed using acidic pyrophosphate and disodium dihydrogen pyrophosphate.
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