200844078 九、發明說明： 【發明所屬之技術領域】 本發明關於由一級二胺製備二級二胺。 【先前技術】 有許多種多官能基化合物，包括二醇及二胺，可在聚 胺基甲酸酯、聚脲、及聚胺基甲酸酯-脲聚合物之製備中作 爲鏈延長劑及/或作爲環氧樹脂用硬化劑。這些化合物均不 具有使其普遍理想之反應性，而且在使用其製造之產物中 大多無法提供令人滿意之性質。因此仍有發現可作爲鏈延 長劑或硬化劑之新穎化合物的需求。美國專利第4,806,6 1 6 號教示特定之N，N’ -二烷基苯二胺在製備聚胺基甲酸酯與 聚脲中作爲鏈延長劑之用法。關於此點亦參見例如美國專 利第4，5 2 8，3 6 3號，其教示二級脂族二胺作爲樹脂黏合劑之 一部分的用法，及美國專利第6,2 1 8,480 B1號，其揭示芳 族二胺作爲聚胺基甲酸酯用硬化劑之用法。二級脂族二胺 亦已作爲橡膠用抗降解劑；參見美國專利第4,900,868號。 亞胺經常由一級胺與醛或酮之組合形成。此亞胺可作 爲調味劑（參見美國專利第3,625,7 1 0號）或香料（參見 EP 1 067 1 1 6 號專利）。 現在對硬化速率較慢之鏈延長劑漸有需求，希望其爲 具有呈現較慢硬化速率之二胺。因此進一步希望爲二級二 胺路線，特別是在溫和條件下進行此方法時。 【發明內容】 本發明提供在溫和條件下製備脂族二級二胺之方法。 200844078 用於本發明方法之相當溫和壓力及溫度條件的一個 可使用一般方法裝置，所以不需要如高壓反應所需 設備。 本發明之一個具體實施例爲一種用於形成二級 方法。此方法包括使〇至少一種脂族環形酮，Η)至 脂族一級二胺，i i i)氫，及i ν)氫化觸媒在一起。脂 二胺爲異佛爾酮二胺或脂族一級α，ω -二胺，而且氫 係選自鉑碳、鈀碳、硫化鉑碳、硫化鈀碳、及以上 混合物。此方法係在約20 °C至約75 °C範圍之溫度及 方英吋量規爲約1至約95磅（1·08χ105至7.56xl05 圍之氫壓進行，使得形成二級二胺。 本發明之這些及其他具體實施例及特點由以下 所附申請專利範圍而更爲顯而易知。 【實施方式】 此技藝常用之名詞可用於指稱本發明之各態樣 胺（一級二胺與羰基化合物之反應產物）有時稱爲 ，而且此二亞胺係藉至少某些本發明方法形成。在 成二亞胺之羰基化合物爲酮時，此二亞胺偶而稱爲 或二酮亞胺。由一級二胺與酮形成二級二胺經常稱 性烷化或還原性胺化，而且名詞「還原性烷化」及 性胺化」可用於敘述本發明之方法。 在全部此文件中，名詞「每平方英吋量規之膀 簡稱爲p s i g，指大於大氣壓力之壓力，即其等於每 吋之磅數小於大氣壓力之壓力値。 優點爲 之特殊 二胺之 少一種 族一級 化觸媒 任二之 在每平 Pa)範 敘述及 。二亞 希夫鹼 用於形 酮亞胺 爲還原 「還原 數」， 平方英 200844078 本發明之方法在單一步驟中經由使酮、脂族一級二胺 、氫、與氫化觸媒在一起而製備脂族二級二胺。酮爲至少 一種脂族環形酮，脂族一級二胺爲異佛爾酮二胺或脂族一 級α，ω-二胺之至少一種脂族一級二胺，而且氫化觸媒係選 自鉑碳、鈀碳、及其混合物。此方法係在約20。(：至約75 °C 範圍之溫度及在每平方英吋量規爲約1至約95磅（1.0 8 xlO5 至7.5 6 x105 pa)範圍之氫壓進行。 本發明之方法使用脂族環形烴酮；這些酮包括單酮、 二酮及多酮。酮之烴部分爲環，此環可爲二環，而且環上 可有一或多個取代基。用於本發明實務之酮較佳爲具有5 至約20個碳原子。更佳爲具有5至約15個碳原子之酮。 環上之取代基爲脂族，及可爲環形、分支或直鏈，而且較 佳爲分支或直鏈。較佳取代基具有1至約6個碳原子。合 適取代基包括甲基、乙基、丙基、異丙基、1,1-二甲基丙基 、正丁基、二級丁基、環丁基、2-乙基丁基、正戊基、2-戊基、2-甲基戊基、環戊基、己基、環己基、甲基環己基 、孟基、八乙基己基、庚基、環辛基、5·壬基、癸基、十 ~~*碳基％。 合適之單酮包括環丁酮、2-十二碳基環丁酮、3-異丙 基環丁酮、環戊酮、2-甲基環戊酮、3-乙基環戊酮、3-二級 丁基環戊酮、2,5-二甲基環戊酮、2-戊基環戊酮、環己酮、 2-甲基環己酮、3-正丙基環己酮、3-環丁基環己酮、4-乙基 環己酮、3-異丙基-1-環己酮、4-三級丁基環己酮、2-(2-甲基戊基）環己酮、2-(2-乙基己基）環己酮、4-(1,1-二 200844078 、2,4-貳（1,1-二甲 S環己酮）、2,2,6-、3,3,5,5·四甲基環 4 -環己基環己酮、 丨、環辛酮、2 -甲基 案酮（十氫-1-萘酮 二環[3 · 3 · 1 ]壬-9 -酮 然較佳爲使用一種 使用酮之混合物可 種二酮或多酮。可 基-1,3-環丁二酮、 ，3-環戊二酮、1，4-、5-甲基-1，3-環己 基-1，3-環己二酮、 2,6-二酮、1,5-二甲 多種二酮或多酮可 形式。對於某些酮 此條件，則可使用 甲基丙基）環己酮、2,6 -二甲基環己酮’ 基丙基）環己酮、孟酮（5-甲基-2-異丙-三乙基環己酮、3，3,5-三正戊基環己酮’ 己酮、2-環己基環己酮（二環己酮）' 環庚酮、2_乙基環庚酮、2-正丁基環庚_ 環辛酮、2-(2-戊基）環辛酮、卜十氫1 )、2-十氫萘酮、二環[3·2· 1]辛-2-酮、 等。較佳之酮包括環戊酮與環己酮。雖 酮，其可使用二或更多種酮之混合物。 生成產物之混合物。 代替或除了單酮，其可使用一或多 用於本發明實務之二酮的實例包括四甲 1，3-環戊二酮、1,3 _環己二酮、2-甲基-1 環己二酮、1，3-環庚二酮、1，4-環庚二酮 二酮、4，4-二甲基-1，3-環己二酮、5-異丙 二環[3.3.1]壬-3,7-二酮、二環[3.3.1]壬-基二環[3.3.0]辛-3,7 -二酮等。使用一或 產生寡聚或聚合產物。 酮在用於本發明方法時通常爲液體 ，高溫及/或增加將酮液化。如果不使用 溶劑提供液體形式之酮。 用於本發明方法之脂族一級二胺爲異佛爾酮二胺或脂 族一級α，ω-二胺。脂族一級α，ω-二胺爲直鏈形式之一級二 胺’其2個終端碳原子各鍵結一級胺基。直鏈爲烴直鏈或 200844078 二級胺基直鏈，其中「二級胺基直鏈」表示其中烴直鏈中 -CH”部分之一被-NH-部分代替之直鏈。月旨族一級二胺之此 二級胺基在本發明之方法中不變成三級。較佳爲脂族一級 α，ω -二胺具有約3至約20個碳原子；更佳爲脂族一級 α，ω -二胺具有約4至約10個碳原子。 合適之脂族一級二胺包括但不限於異佛爾酮二胺及脂 族一級α，ω ·二胺，如1，3 -二胺基丙烷、1，4 -二胺基丁烷、 1，5-二胺基戊烷、1，6-二胺基己烷、1，7-二胺基庚烷、1,8-二胺基辛烷、1，10-二胺基癸烷、1，12-二胺基十二烷、二伸 乙三胺（Ν- ( 2-胺基乙基）-1，2-乙二胺）、降精脒、精脒 、貳（伸己基）三胺、Ν- ( 3-胺基丙基）屍胺、Ν- ( 3-胺 基丙基）-1，7 -庚二胺、三伸乙四胺、與四伸乙五胺。較佳 之脂族一級二胺包括1，6-二胺基己烷、異佛爾酮二胺與二 伸乙三胺。本發明方法中之較佳組合爲使用異佛爾酮二胺 與環己酮、使用1, 6 -二胺基己烷與環己酮、及使用二伸乙 三胺與環己酮。 脂族一級二胺在用於本發明方法時通常爲液體形式。 對於某些一級二胺，高溫及/或增加將一級二胺液化。如果 不使用此條件，則可使用大量酮或溶劑提供液體形式之一 級二胺。 對於單酮，酮對脂族一級二胺之莫耳比例通常爲每莫 耳胺基爲至少約1莫耳酮，即每莫耳二胺爲至少約2莫耳 單酮。其較佳爲使用過量酮，較佳爲使用相對一級二胺爲 至少約1 0 %莫耳過量酮。約2.2 :丨至約1 〇 : 1範圍之單酮對 200844078 脂族一級二胺之莫耳比例爲有效的，因此較佳； 2.5:1至約6:1範圍之單酮對脂族一級二胺之莫耳 爲過量之酮在本發明實務中爲可接受的；酮可（ 較佳爲）以足以亦作爲溶劑之量存在。事實上’ 之酮經常視爲有益的，因爲如此技藝所已知，二 本發明之方法中據信爲二級二胺形成之中間物） 現平衡，而且過量之酮經常有助於使平衡偏向利 形成。 ^ 類似地，對於二酮，酮對脂族一級二胺之莫 常爲每莫耳胺基爲至少約1莫耳酮基，即每莫耳 少約1莫耳二酮。其較佳爲使用過量酮，較佳爲 一級二胺爲至少約1 〇 %莫耳過量酮。約1.1:1至約 之二酮對脂族一級二胺之莫耳比例爲有效的，因 更佳爲約1 · 2 :1至約3 :1範圍之二酮對脂族一級二 比例。這些比例可按多酮（例如三酮）所需而調 發明實務中，二酮或多酮可以足以亦作爲溶劑之 I i V 本發明之方法較佳爲在氫氈下之操作。在氫 存在通常不利，因爲據信氧至少促成氫化觸媒破 在氫大氣下操作時，含一或多種惰氣（例如氮、 之惰性大氣之存在經常較佳。 用於本發明之氫化觸媒爲鈾碳、鈀碳、硫化 化鈀碳、或以上任二之混合物。其較佳爲使用一 非觸媒混合物。在本發明實務中，鉑碳及鈀碳爲 化觸媒。強酸隨鈾碳或鈀碳存在通常爲不必要的 更佳爲約 比例。大 而且單酮 大爲過量 亞胺（在 之形成表 於二亞胺 耳比例通 二胺爲至 使用相對 5 : 1範圍 此較佳； 胺之莫耳 整。在本 量存在。 化期間氧 壞。在不 氨或氬） 鉑碳、硫 型觸媒而 較佳之氫 。在使用 -10- 200844078 鉑碳或鈀碳時，其可爲粉末形式或爲粒狀形式。 合適量之氫化觸媒可爲相當低，即相對一級二胺爲約 1重量％至約1 0重量％之範圍。更合適爲可使用相對一級二 胺爲約3重量％至約5重量％之氫化觸媒。 不希望受理論限制，在本發明之方法中’據信其形成 二亞胺作爲中間物，產生水作爲副產物’此水據信使平衡 偏向酮與一級二胺；因此在此方法中通常不希望有大量水 。雖然已發現反應中產生之水之存在未如本發明方法先前 據信有害，在至少某些情形，其可能希望使反應混合物中 之水量最少。一種使反應混合物中之水量最少的方法爲使 用水去除劑。水去除劑可包括於反應混合物以去除在方法 中產生之水。唯一之要求爲水去除劑不負面地影響反應或 其產物。合適之水去除劑包括分子篩、矽膠、氯化鈣等。 在本發明實務中，分子篩爲較佳之水去除劑。 使用水去除劑之一個替代方案爲包括溶劑或足夠過量 之酮作爲溶劑以有效地稀釋水，其受推薦且較佳。在使用 溶劑時，可與水共沸因而去除在方法期間產生之水的溶劑 爲一種較佳操作方式。使用溶劑時之另一種較佳操作方式 爲使用將水溶入與發生反應之相分離之相中的溶劑；用於 此操作方式之較佳溶劑包括甲苯與二氯甲烷。包括溶劑或 足夠過量之酮作爲溶劑及使用水去除劑可用於使水量最小 。一種特佳操作方式爲使用足夠過量之酮稀釋水。 一般而言，在本發明方法中’方法開始時水不存在作 爲成分，除了偶然存在之水（例如相對反應團塊之總重量 -11- 200844078 爲小於約1重量％之水）。關於此點應注意，無水條件未必 成功地進行本發明之方法。 其經常較佳爲使用大爲過量之酮，使得酮在本發明之 方法中作爲溶劑，特別是單酮；然而在本發明之方法期間 可存在一或多種溶劑。選擇溶劑之重要考量爲其不干擾氫 化觸媒；例如選擇之溶劑應不破壞氫化觸媒。可用於本發 明方法之溶劑型式包括但不限於液態芳族烴、液態脂族烴 '液態鹵化脂族烴、液態鹵化芳族烴、醚、酯、醇、及二 f : 或更多種溶劑之混合物。關於此點已觀察到，至少在特定 情形’在醇存在下反應顯然較快速地結束。因此在一個較 佳具體實施例中，其在方法期間存在醇，特別是CV4醇。 此醇一般爲反應混合物總重量之約2 5重量％至約7 5重量％ :較佳爲醇爲反應混合物總重量之4 5重量％至約6 5重量％ 〇 合適之液態烴包括苯、甲苯、二甲苯、莱、異丙苯、 異丙甲苯、戊烷、己烷、異己烷、環己烷、甲基環己烷、 I 庚烷、辛烷、環辛烷、壬烷等。可使用之液態鹵化脂族烴 包括二氯甲烷、三氯甲烷、1,2-二氯乙烷、1-溴-2-氯乙烷 、（氯甲基）環丙烷、1 -溴丁烷、氯環丁烷、氯新戊烷、 1-溴-5-氯戊烷、溴環戊烷、1，6-二溴己烷、反·1，2-二氯環 己烷、1-氯庚烷、1，8 -二氯辛烷等。適合用於本發明之醚包 括二乙醚、二正丙醚、二異丙醚、二正丁醚、丁基乙基醚 、環己基甲基醚、四氫呋喃、1，3-二噁烷、1，3-二氧戊環、 二甘醇二乙醚（乙二醇之二甲醚）、2-甲氧基乙基醚（二 -12- 200844078 甘二甲醚）等。合適之液態鹵化芳族烴包括氯苯。可使用 之酯的實例包括乙酸乙酯、乙酸異丙酯、乙酸正丁酯、乙 酸異丁酯、乙酸第三丁酯、乙酸正戊酯、乙酸異戊酯、乙 酸己酯、丙酸甲酯、丙酸乙酯、丁酸乙酯等。可用於本發 明實務之醇包括甲醇、乙醇、1 -丙醇、2 -丙醇、1 - 丁醇、2 -甲基-1-丙醇、1-甲基-丨_丙醇、環丙基甲醇、環丁醇、環戊 醇、順-2 -甲基環己醇等。較佳之溶劑包括二氯甲烷、乙酸 乙酯、甲苯、及特別是甲醇及/或乙醇。 本發明之方法係在約20°C至約75 °C範圍之溫度及在 每平方央吋量規爲約1至約95榜（1.08xl05至7.56xl05 Pa )範圍之氫壓進行。較佳爲溫度爲約4 0 °C至約7 5 °C之範圍 ’及壓力爲每平方英吋量規約50至約95膀（4·46χ105至 7.56xl05 Pa )之範圍。 酮、一級二胺、觸媒、及氫可以任何次序在一起。據 信爲了以較佳產率及/或在短時間內得到二級二胺，氫化觸 媒爲必要的。一種用於製備二級二胺之特佳方法爲將一級 二胺、氫化觸媒與溶劑置於反應容器中，然後在氫氣壓力 下將反應容器密封。然後如所需將容器加熱同時攪拌反應 混合物。在實驗室規模，反應時間一般爲約5小時至約20 小時。 在本發明實務中，此方法產生主要爲二級二胺。在觀 察到時，三級二胺爲約5 %或更小之量，而且經常爲約3 % 或更小之量，其中百分比爲本發明方法製造之未純化產物 混合物的氣相層析術（GC)面積百分比。在此（包括申請專 -13· 200844078 利範圍）使用且除非另有明確地指示，名詞「未純化產物 混合物」指摻有使脂族環形酮、脂族一級二胺、氫、與氫 化觸媒（選自鉑碳、鈀碳及其混合物）在一起之製備生成 之共產物及/或雜質的二級脂族二胺。因此對於未純化產物 混合物，產物之組成物係由方法決定，而非使用可影響產 物混合物之化學組成物的下游純化技術（如再結晶、層析 、蒸餾等步驟）之結果。 本發明方法製造之二級二胺通常爲液體。其可使用此 f 技藝已知之分離液體的方法分離至少一部分二胺與反應混 合物之其他組分。此方法包括例如再結晶、層析及蒸餾。 蒸餾爲較佳之分離方法。在製造之二級二胺爲固體時，其 可使用標準固-液分離方法（如離心、過濾或再結晶）分離 至少一部分產物與反應混合物之液體部分。如果需要，則 二級二胺可以未隔離形式使用。 回收及再循環過量之酮通常具經濟性，特別是在使用 大爲過量之酮作爲反應混合物之溶劑時。酮與反應混合物 之分離可藉蒸餾、分離任何共沸物之水性部分、或傾析水 層繼而蒸餾酮層而實行。一旦已將至少一部分之產物二胺 或二級二胺自反應混合物去除，其可將未反應原料再循環 至反應器形成進料之一部分。 本發明方法之產物爲脂族二級二胺，其包括但不限於 Ν,Ν’ -二環戊基異佛爾酮二胺、N，N，-二環己基異佛爾酮 二胺、N，N，-二（4-乙基環己基）異佛爾酮二胺、n，N，-二環丁 -1，3-二胺基丙烷、N，N，-二（3-異丙基環丁基）-1,4- -14- 200844078 二胺基丁烷、N，N’ -二（2,5-二甲基環戊基）-1,4-二胺基丁 烷、N，N，-二環戊基-1，5 -二胺基戊烷、N，N’ -二（3 -乙基 環戊基）-1，5-二胺基戊烷、N，N’ ·二環己基-1，5-二胺基戊 烷、N，N’ -二（4-第三丁基環己基）-1，5-二胺基戊烷、N，N’ -二（3-環丁基環己基）-1，6-二胺基己烷、N，N’ -二環戊基 -1,6-二胺基己烷、Ν,Ν’ -二（2-甲基環戊基）-1，6-二胺基 己烷、N，N，-二環己基·1，6·二胺基環己烷、N，N，-二[2-( 2-乙基己基）環己基]-1，6-二胺基己烷、N，N’ -二（3-異丙 ( ' 基-1-環己基）-1，6-二胺基己烷、N，N’ -二（4-第三丁基環 己基）-1,6-二胺基己烷、N，N，-二孟基-1,6-二胺基己烷、 N，N’ -二（2,2,6-三乙基環己基）-1，6-二胺基己烷、1^川’-二（3,3,5,5-四甲基環己基）-1，6-二胺基己烷、N，N’ -二（ 2-正丁基環庚基）-1,6-二胺基己烷、N，N’ -二（2-甲基環辛 基）-1，6-二胺基己烷、N，N，-二（環辛基）-1,6-二胺基己 烷、N，N’ -二[4- ( 1，1-二甲基丙基）環己基]-1,7·二胺基庚 烷、N，N’ -二（2,6-二甲基環己基）-1，7-二胺基庚烷、Ν,Ν’ -、 二（3-乙基環戊基）-1,8-二胺基辛烷、Ν，Ν’ -二（環己基 )-1,8-二胺基辛烷、Ν，Ν’ -二（4-第三丁基環己基）-1，8-二胺基辛烷、Ν，Ν’ -二環戊基-1，10-二胺基癸烷、Ν，Ν’ -二孟基-1，10 -二胺基癸烷、Ν，Ν’ -二（2 -十二碳基環丁基） -1，12 -二胺基十二烷、Ν，Ν，-二環己基-1，12 -二胺基十二烷 、一*[2- (Ν -環己胺基）乙基]胺、一*[3- (Ν -環戊Η女基）丙 基]胺、[3- (Ν-環辛胺基）丙基][4- (Ν -環辛胺基）丁基] 胺、[3-(Ν·2-甲基環戊胺基）丙基][5-(Ν-2·甲基環戊胺基 -15- 200844078 )戊基]胺、與[3-(N-環丁胺基）丙基][7_(N-環丁胺基） 庚基]胺。 以下實例係爲了例證目的而提出，及不意圖對本發明 之範圍施加限制。 實例1 N，N，-二環己基-1，6 -二胺基瓌己烷之合成 將1，6-二胺基環己烷（23.2克，0.2莫耳）、環己酮（ 49克，0.5莫耳）、及Pd/C (5重量％鈀碳，1.16克’相對 P： 1，6 -二胺基環己烷爲5重量％)裝至100毫升熱壓器。將熱 壓器在22-25 °C以95 psig之Hh (7·56χ105 Pa)攪拌沖洗3次 。在攪拌時開始將混合物加熱；在52°C觀察到H2散逸。將 混合物在75°C於95 psig之H2下加熱及攪拌19小時’然後 將混合物冷卻及脫氣。氣相層析術（GC; ( 100°C/5分鐘/10 。(：-分鐘速率/2 80 °(：))顯示產率爲96.7%之^4川’-二環己 基-1，6 -二胺基己烷，及3 . 3 %之中間物。未發現三級胺或過 烷化副產物。 I 實例2 N，N’ ·二環己基-1，6-二胺基環己烷之合成 將1,6-二胺基環己烷（8.12克，0.07莫耳）、環己酮 (54.9克，0.56莫耳）、及Pt/C (3重量％鉑碳，0.81克， 相對1,6-二胺基環己烷爲10重量％)裝至100毫升熱壓器 。將熱壓器在22-24°C以95 psig之H2 (7.56xl05 Pa)攪拌沖 洗3次。在攪拌時開始將混合物加熱。將混合物在7 5 t於 9 5 psig之H2下加熱及攪拌10小時，然後將混合物冷卻及 -16- 200844078 脫氣。GC顯示產率爲至少98%之N，N’ ·二環己基-1，6-二胺 基己烷，小於1 %之中間物，及小於1 %之過烷化副產物。 未發現三級胺。 實例3 N，N，-二（環己基）-異佛爾酮二胺之合成 將異佛爾酮二胺（IPDA，17克，0.1莫耳）、環己酮 (49克，0.5莫耳）、及Pd/C ( 0.85克，相對IPDA爲5重 量％)裝至100毫升熱壓器。將熱壓器在22 °C以95 psig之 f H2 (7.56xl05 Pa)攪拌沖洗3次。在攪拌時開始將混合物加 熱；在45 -5 0°C觀察到H2散逸。將混合物在75 °C於95 psig 之H2下加熱及攪拌1 2小時’然後將混合物冷卻及脫氣。 GC ( 100°C/5 分鐘/10°C -分鐘速率 /2 80°C ; GC-MS 證實 2 種 異構物）顯示產率爲至少98%之N，N’ -二環己基異佛爾酮 二胺。未發現中間物、三級胺或過烷化副產物。 實例4 N，N’ -二（環己基）-異佛爾酮二胺之合成 I 將異佛爾酮二胺（IPDA，12.75克，0.075莫耳）、環 己酮（58.8克，0.6莫耳）、及Pt/C ( 0.64克，相對IPDA 爲5重量％ )裝至1〇〇毫升熱壓器。將熱壓器在22 °C以95 psig之H2 (7.5 6x 1 05 Pa)攪拌沖洗3次。在攪拌時開始將混 合物加熱；在50°C觀察到H2散逸。將混合物在75°C於95 psig之H2下加熱及攪拌12小時，然後將混合物冷卻及脫 氣。GC顯示產率爲96.82%之N，N’ -二環己基異佛爾酮二 胺（總共2種異構物）及3 · 1 8 %之中間物。未發現三級胺或 -17- 200844078 過烷化副產物。 實例5 N，N’ -二環己基-1，6-二胺基環己烷之合成 將1,6-二胺基環己烷（8.12克，0.07莫耳）、環己酮 (20.6克，0.21莫耳）、無水乙醇（35克）、及Pd/C (0.41 克，相對1,6-二胺基環己烷爲5重量％ )裝至1〇〇毫升熱壓 器。將熱壓器在22°C以95 psig之PL· (7.56xl05 Pa)攪拌沖 洗3次。在攪拌時開始將混合物加熱；在4 5 °C觀察到H2 f 散逸。將混合物在76°C於95 pS1g之H2下加熱及攪拌4小 時，然後將混合物冷卻及脫氣。GC顯示轉化率爲100%之 1，6-二胺基己烷，產率爲99%之N，N’ -二環己基-1，6-二胺 基己烷，及小於1 %之過烷化副產物與雜質。 應了解，在本文件任意處之化學名稱或化學式所指之 反應物及組分，不論指單數或複數，均以其在接觸以化學 名稱或化學型式所指之其他物質（例如其他反應物、溶劑 等）前存在而證驗。在所得混合物或溶液或反應介質中發 " 生之預備化學變化、轉變及/或反應（若有）均無關，因爲 此變化、轉變及/或反應爲在依照本揭示之條件下使指定反 應物及/或組分在一起之自然結果。因此反應物及組分係證 驗爲關於實行所需化學操作或反應、或形成用於進行所需 操作或反應之混合物而在一起之成分。又即使具體實施例 可能以現在式（「包括」、「包含」等）指稱物質、組分 及/或成分，此指稱爲其恰在依照本揭示最先接觸、摻合或 混合一或多種其他物質、組分及/或成分前存在之物質或成 -18- 200844078 分。 又即使申請專利範圍可能以現在式（例如「包括」、 「是」等）指稱物質，此指稱爲其恰在依照本揭示最先接 觸、摻合或混合一或多種其他物質前存在之物質。 上述各專利、專利公告及出版刊物在此依法全部倂入 作爲參考。 除了另有明確地表示，在此使用之名詞” a”或” an” 不意圖限制，而且不應視爲將說明或申請專利範圍限制爲 f 名詞所指之單一元素。而是在此使用之名詞” a”或” an，，> 意圖涵蓋一或多種此元素，除了另有明確地表示。 本發明在所附申請專利範圍之精神及範圍內可大幅變 動。 -19-200844078 IX. Description of the invention: [Technical field to which the invention pertains] The present invention relates to the preparation of a secondary diamine from a primary diamine. [Prior Art] There are many kinds of polyfunctional compounds, including diols and diamines, which can be used as chain extenders in the preparation of polyurethanes, polyureas, and polyurethane-urea polymers. / or as a hardener for epoxy resins. None of these compounds have reactivity which is generally desirable, and most of the products produced using them do not provide satisfactory properties. Therefore, there is still a need to find novel compounds that can act as chain extenders or hardeners. U.S. Patent No. 4,806,601 teaches the use of specific N,N'-dialkylphenylenediamines as chain extenders in the preparation of polyurethanes and polyureas. See also, for example, U.S. Patent No. 4,520,336, which teaches the use of a secondary aliphatic diamine as part of a resin binder, and U.S. Patent No. 6,2,8,480 B1, The use of aromatic diamines as hardeners for polyurethanes is disclosed. Secondary aliphatic diamines have also been used as antidegradants for rubber; see U.S. Patent No. 4,900,868. Imines are often formed from a combination of a primary amine and an aldehyde or ketone. This imine can be used as a flavoring agent (see U.S. Patent No. 3,625,7 1 0) or a fragrance (see EP 1 067 1 16). There is an increasing demand for chain extenders which have a slower rate of hardening, and it is desirable to have a diamine which exhibits a slower rate of hardening. It is therefore further desirable to have a secondary diamine route, especially when subjected to this process under mild conditions. SUMMARY OF THE INVENTION The present invention provides a process for preparing an aliphatic secondary diamine under mild conditions. 200844078 One of the relatively mild pressure and temperature conditions used in the process of the present invention can be operated using conventional methods, so that equipment such as high pressure reaction is not required. One embodiment of the invention is a method for forming a secondary method. The process comprises bringing at least one aliphatic cyclic ketone, hydrazine, to an aliphatic primary diamine, i i i hydrogen, and i ν) a hydrogenation catalyst. The lipodiamine is isophoronediamine or an aliphatic first-grade α,ω-diamine, and the hydrogen is selected from the group consisting of platinum carbon, palladium carbon, platinum sulfide carbon, palladium sulfide carbon, and the like. The process is carried out at a temperature in the range of from about 20 ° C to about 75 ° C and a ferrule gauge of from about 1 to about 95 lbs (1. 08 χ 105 to 7.56 x 105) to form a secondary diamine. These and other specific embodiments and features of the invention are more apparent from the following claims. [Embodiment] The term "common" in the art can be used to refer to the various amines of the invention (primary diamine and carbonyl) The reaction product of the compound is sometimes referred to, and the diimine is formed by at least some of the processes of the invention. When the carbonyl compound of the diimine is a ketone, the diimine is occasionally referred to as a diketimine. The formation of secondary diamines from primary diamines and ketones is often referred to as reductive or reductive amination, and the terms "reductive alkylation" and amination are used to describe the process of the invention. The head of the gauge per square inch is referred to as psig, which refers to the pressure greater than atmospheric pressure, that is, it is equal to the pressure of each pound less than atmospheric pressure. The advantage is that the special diamine is less than one kind of primary catalyst. In every flat Pa) The succinimide is used in the reduction of the "reduction number", and the method of the present invention is carried out in a single step via a ketone, an aliphatic primary diamine, hydrogen, and a hydrogenation catalyst. An aliphatic secondary diamine is prepared. The ketone is at least one aliphatic cyclic ketone, the aliphatic primary diamine is isophorone diamine or at least one aliphatic primary diamine of the aliphatic primary alpha, omega-diamine, and the hydrogenation catalyst is selected from platinum carbon, Palladium carbon, and mixtures thereof. This method is at about 20. (: to a temperature in the range of about 75 ° C and a hydrogen pressure in the range of from about 1 to about 95 pounds per square inch (1.0 8 x 10 5 to 7.5 6 x 105 pa). The method of the invention uses an aliphatic cyclic hydrocarbon Ketones; these ketones include monoketones, diketones and polyketones. The hydrocarbon moiety of the ketone is a ring which may be a bicyclic ring and may have one or more substituents on the ring. The ketone useful in the practice of the invention preferably has 5 to about 20 carbon atoms. More preferably, it is a ketone having 5 to about 15 carbon atoms. The substituent on the ring is aliphatic, and may be cyclic, branched or linear, and is preferably branched or linear. Preferred substituents have from 1 to about 6 carbon atoms. Suitable substituents include methyl, ethyl, propyl, isopropyl, 1,1-dimethylpropyl, n-butyl, secondary butyl, cyclic Butyl, 2-ethylbutyl, n-pentyl, 2-pentyl, 2-methylpentyl, cyclopentyl, hexyl, cyclohexyl, methylcyclohexyl, montyl, octaethylhexyl, heptyl , cyclooctyl, 5·fluorenyl, fluorenyl, ten~~*carbyl%. Suitable monoketones include cyclobutanone, 2-dodecylcyclobutanone, 3-isopropylcyclobutanone, and rings. Pentanone, 2-methylcyclopentanone 3-ethylcyclopentanone, 3-secondylcyclopentanone, 2,5-dimethylcyclopentanone, 2-pentylcyclopentanone, cyclohexanone, 2-methylcyclohexanone, 3 - n-propylcyclohexanone, 3-cyclobutylcyclohexanone, 4-ethylcyclohexanone, 3-isopropyl-1-cyclohexanone, 4-tert-butylcyclohexanone, 2-( 2-methylpentyl)cyclohexanone, 2-(2-ethylhexyl)cyclohexanone, 4-(1,1-di 200844078, 2,4-indole (1,1-dimethylscyclohexanone) ), 2,2,6-,3,3,5,5·tetramethylcyclo-4-cyclohexylcyclohexanone, anthracene, cyclooctanone, 2-methyl-n-one (decahydro-1-naphthalenone) The ring [3 · 3 · 1 ] -9-ketone is preferably a diketone or a polyketone using a mixture of ketones. Keki-1,3-cyclobutanedione, 3-cyclopentadione , 1,4-, 5-methyl-1,3-cyclohexyl-1,3-cyclohexanedione, 2,6-dione, 1,5-dimethyldione or diketone form. For certain ketone conditions, methylpropyl)cyclohexanone, 2,6-dimethylcyclohexanone'propyl)cyclohexanone, and mennone (5-methyl-2-isopropyl-) can be used. Triethylcyclohexanone, 3,3,5-tri-n-pentylcyclohexanone 'hexanone, 2-cyclohexylcyclohexanone (dicyclohexanone)' Ketone, 2-ethylcycloheptanone, 2-n-butylcycloheptan-cyclooctanone, 2-(2-pentyl)cyclooctanone, b-hydrogen 1 ), 2-decahydronaphthalone, bicyclo [ 3·2·1] oct-2-one, etc. Preferred ketones include cyclopentanone and cyclohexanone. Although ketones, it is possible to use a mixture of two or more ketones to form a mixture of products. Examples of ketones which may be used in one or more of the diketones useful in the practice of the invention include tetramethyl1,3-pentanedione, 1,3-cyclohexanedione, 2-methyl-1 cyclohexanedione, 1 , 3-cycloheptanedione, 1,4-cycloheptanedione, 4,4-dimethyl-1,3-cyclohexanedione, 5-isopropylbicyclo[3.3.1]壬-3 , 7-diketone, bicyclo [3.3.1] fluorenyl-bicyclo[3.3.0] oct-3,7-dione, and the like. Use one to produce oligomeric or polymeric products. Ketones are typically liquid, high temperature and/or increased in liquefying the ketone when used in the process of the invention. If the solvent is not used, the ketone is supplied in liquid form. The aliphatic primary diamine used in the process of the present invention is isophoronediamine or an aliphatic primary alpha, omega-diamine. The aliphatic primary alpha, omega-diamine is a linear form of a primary diamine. The two terminal carbon atoms each bond a primary amine group. The straight chain is a hydrocarbon straight chain or a 200844078 secondary amine-based straight chain, wherein the "secondary amine-based straight chain" means a straight chain in which one of the -CH" portions of the hydrocarbon straight chain is replaced by a -NH- moiety. The secondary amine group of the diamine does not become tertiary in the process of the invention. Preferably, the aliphatic primary alpha, omega-diamine has from about 3 to about 20 carbon atoms; more preferably the aliphatic primary alpha, - The diamine has from about 4 to about 10 carbon atoms. Suitable aliphatic primary diamines include, but are not limited to, isophorone diamine and aliphatic primary alpha, omega diamines such as 1,3 -diaminopropane 1,4 -Diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane 1,10-Diaminodecane, 1,12-diaminododecane, diethylenetriamine (Ν-(2-aminoethyl)-1,2-ethanediamine),脒, 脒, 贰 (extension) triamine, Ν-(3-aminopropyl) cadaverine, Ν-(3-aminopropyl)-1,7-heptanediamine, triamethylenetetramine And tetraethylamine. Preferred aliphatic primary diamines include 1,6-diaminohexane, isophorone diamine and diamethylene A preferred combination of the methods of the invention is the use of isophoronediamine and cyclohexanone, the use of 1,6-diaminohexane and cyclohexanone, and the use of diethylenetriamine and cyclohexanone. Group 1 diamines are generally in liquid form when used in the process of the invention. For certain primary diamines, high temperature and/or increased liquefaction of the primary diamine. If this condition is not used, a large amount of ketone or solvent may be used to provide the liquid form. A mono-diamine. For monoketones, the molar ratio of ketone to aliphatic primary diamine is typically at least about 1 mole per mole of amine group, i.e., at least about 2 moles per mole of diamine. It is preferred to use an excess of ketone, preferably at least about 10% molar excess ketone using a relative primary diamine. About 2.2: 丨 to about 1 〇: a range of monoketone pairs 200844078 aliphatic primary diamine The ratio of ears is effective and therefore preferred; the monoketone in the range of from 2.5:1 to about 6:1 is an excess of the ketone of the aliphatic primary diamine in the practice of the invention; the ketone is preferred. Is present in an amount sufficient to also act as a solvent. In fact, the ketone is often considered beneficial because of this It is known in the art that the intermediate of the second invention is believed to be in equilibrium in the process of the invention, and that excess ketone often helps to favor equilibrium formation. ^ Similarly, for diketones, ketone pairs The aliphatic primary diamine is usually at least about 1 mole per methoxyl group, i.e., about 1 mole of diketone per mole. It is preferred to use an excess of a ketone, preferably a primary diamine. At least about 1% by mole of ketone. A molar ratio of about 1.1:1 to about ketone to the aliphatic primary diamine is effective, more preferably from about 1 · 2 : 1 to about 3 : 1 The ratio of diketone to aliphatic first order. These ratios may be practiced as required for polyketones (e.g., triketones), and diketones or polyketones may be sufficient as solvent I i V. The method of the present invention is preferably The operation under the hydrogen felt. The presence of hydrogen is generally disadvantageous because it is believed that the presence of an inert atmosphere containing one or more inert gases (e.g., nitrogen) is often preferred when oxygen is at least caused to operate under hydrogen atmosphere. Hydrogenation catalysts useful in the present invention. It is uranium carbon, palladium carbon, palladium sulfide carbon, or a mixture of the above two. It preferably uses a non-catalytic mixture. In the practice of the present invention, platinum carbon and palladium carbon are catalytic vehicles. Strong acid with uranium carbon Or the presence of palladium carbon is generally unnecessarily more preferably in proportion. Large and monoketone is a large excess of imine (the formation of the diimine in the ratio of diamine to the use of the relative 5: 1 range is preferred; Amine of the amine. In the presence of this amount, the oxygen is bad during the oxidation. In the case of ammonia or argon, platinum or sulfur catalyst is preferred. When using -10 200844078 platinum carbon or palladium carbon, it can be In powder form or in granular form, a suitable amount of hydrogenation catalyst can be relatively low, i.e., in the range of from about 1% by weight to about 10% by weight relative to the primary diamine. More suitably, a relative primary diamine can be used at about 3 From about 5% by weight to about 5% by weight of hydrogenation catalyst. Theoretically, in the process of the invention 'it is believed that it forms a diimine as an intermediate, producing water as a by-product' which is believed to bias the equilibrium towards the ketone and the primary diamine; therefore, a large amount of water is generally undesirable in this process. Although it has been found that the presence of water produced in the reaction is not previously believed to be detrimental to the process of the invention, in at least some instances it may be desirable to minimize the amount of water in the reaction mixture. One method of minimizing the amount of water in the reaction mixture is to use Water remover. A water remover may be included in the reaction mixture to remove water produced in the process. The only requirement is that the water remover does not negatively affect the reaction or its product. Suitable water removers include molecular sieves, silica gel, calcium chloride. In the practice of the present invention, molecular sieves are preferred water removers. An alternative to using a water remover is to include a solvent or a sufficient excess of ketone as a solvent to effectively dilute water, which is recommended and preferred. When a solvent which azeotropes with water and thus removes water produced during the process is a preferred mode of operation, when a solvent is used A preferred mode of operation is to use a solvent which dissolves water in the phase separated from the phase in which the reaction takes place; preferred solvents for this mode of operation include toluene and methylene chloride, including solvents or a sufficient excess of ketone as solvent and water. A remover can be used to minimize the amount of water. A particularly preferred mode of operation is to use a sufficient excess of ketone to dilute water. In general, in the process of the invention, water is not present as a component at the beginning of the process, except for occasional water (eg relative reaction) The total weight of the masses is from -11 to 200844078, which is less than about 1% by weight of water. It should be noted in this regard that the anhydrous conditions are not necessarily successful in carrying out the process of the invention. It is often preferred to use a large excess of ketone to make the ketone In the process of the invention as a solvent, in particular a monoketone; however, one or more solvents may be present during the process of the invention. The important consideration in selecting a solvent is that it does not interfere with the hydrogenation catalyst; for example, the solvent selected should not destroy the hydrogenation contact Media. Solvent versions useful in the process of the invention include, but are not limited to, liquid aromatic hydrocarbons, liquid aliphatic hydrocarbons, liquid halogenated aliphatic hydrocarbons, liquid halogenated aromatic hydrocarbons, ethers, esters, alcohols, and di- or more solvents. mixture. It has been observed in this regard that the reaction apparently ends relatively quickly, at least in the particular case' in the presence of an alcohol. Thus in a preferred embodiment, it is present during the process of alcohol, particularly CV4 alcohol. The alcohol is generally from about 25 wt% to about 75 wt% of the total weight of the reaction mixture: preferably the alcohol is from 45 wt% to about 65 wt% of the total weight of the reaction mixture. Suitable liquid hydrocarbons include benzene, toluene. , xylene, lyon, cumene, isopropyl toluene, pentane, hexane, isohexane, cyclohexane, methylcyclohexane, I heptane, octane, cyclooctane, decane, and the like. Liquid halogenated aliphatic hydrocarbons which may be used include dichloromethane, chloroform, 1,2-dichloroethane, 1-bromo-2-chloroethane, (chloromethyl)cyclopropane, 1-bromobutane, Chlorocyclobutane, chloropentane, 1-bromo-5-chloropentane, bromocyclopentane, 1,6-dibromohexane, trans-1,2-dichlorocyclohexane, 1-chloroglycan Alkane, 1,8-dichlorooctane, and the like. Ethers suitable for use in the present invention include diethyl ether, di-n-propyl ether, diisopropyl ether, di-n-butyl ether, butyl ethyl ether, cyclohexyl methyl ether, tetrahydrofuran, 1,3-dioxane, 1, 3-dioxolane, diethylene glycol diethyl ether (dimethyl ether of ethylene glycol), 2-methoxyethyl ether (di-12-200844078 glyme), and the like. Suitable liquid halogenated aromatic hydrocarbons include chlorobenzene. Examples of esters which may be used include ethyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, tert-butyl acetate, n-amyl acetate, isoamyl acetate, hexyl acetate, methyl propionate. , ethyl propionate, ethyl butyrate and the like. Alcohols useful in the practice of the invention include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-1-propanol, 1-methyl-indole-propanol, cyclopropyl Methanol, cyclobutanol, cyclopentanol, cis-2-methylcyclohexanol, and the like. Preferred solvents include dichloromethane, ethyl acetate, toluene, and especially methanol and/or ethanol. The process of the present invention is carried out at a temperature in the range of from about 20 ° C to about 75 ° C and at a hydrogen pressure in the range of from about 1 to about 95 gauges per square centimeter gauge (1.08 x 105 to 7.56 x 105 Pa). Preferably, the temperature ranges from about 40 ° C to about 75 ° C and the pressure ranges from about 50 to about 95 bladders per square inch of gauge (4·46 χ 105 to 7.56 x 105 Pa). Ketones, primary diamines, catalysts, and hydrogen can be combined in any order. It is believed that a hydrogenation catalyst is necessary in order to obtain a secondary diamine in a preferred yield and/or in a short period of time. A particularly preferred method for preparing the secondary diamine is to place the primary diamine, hydrogenation catalyst and solvent in a reaction vessel and then to seal the reaction vessel under hydrogen pressure. The vessel is then heated as needed while stirring the reaction mixture. On a laboratory scale, the reaction time is generally from about 5 hours to about 20 hours. In the practice of the invention, this process produces predominantly secondary diamines. When observed, the tertiary diamine is present in an amount of about 5% or less, and often in an amount of about 3% or less, wherein the percentage is a gas chromatograph of the unpurified product mixture produced by the method of the invention ( GC) Area percentage. The term "unpurified product mixture" is used herein to include an aliphatic cyclic ketone, an aliphatic primary diamine, hydrogen, and a hydrogenation catalyst, unless otherwise explicitly indicated. (Secondary aliphatic diamines selected from the group consisting of platinum carbon, palladium carbon, and mixtures thereof) to produce co-products and/or impurities. Thus, for an unpurified product mixture, the composition of the product is determined by the method, rather than the results of downstream purification techniques (e.g., recrystallization, chromatography, distillation, etc.) that can affect the chemical composition of the product mixture. The secondary diamine produced by the process of the invention is typically a liquid. It is possible to separate at least a portion of the diamine from the other components of the reaction mixture using methods known in the art for separating liquids. This method includes, for example, recrystallization, chromatography, and distillation. Distillation is the preferred separation method. Where the secondary diamine produced is a solid, it can be separated from at least a portion of the product and the liquid portion of the reaction mixture using standard solid-liquid separation methods such as centrifugation, filtration or recrystallization. If desired, the secondary diamine can be used in unisolated form. It is generally economical to recover and recycle excess ketone, especially when using a large excess of ketone as a solvent for the reaction mixture. Separation of the ketone from the reaction mixture can be carried out by distillation, separation of the aqueous portion of any azeotrope, or decantation of the aqueous layer followed by distillation of the ketone layer. Once at least a portion of the product diamine or secondary diamine has been removed from the reaction mixture, it can recycle the unreacted feed to the reactor to form a portion of the feed. The product of the process of the invention is an aliphatic secondary diamine including, but not limited to, fluorene, Ν'-dicyclopentylisophorone diamine, N,N,-dicyclohexylisophorone diamine, N ,N,-bis(4-ethylcyclohexyl)isophorone diamine, n,N,-bicyclobutane-1,3-diaminopropane, N,N,-di(3-isopropyl Cyclobutyl)-1,4- -14- 200844078 diaminobutane, N,N'-bis(2,5-dimethylcyclopentyl)-1,4-diaminobutane, N, N,-dicyclopentyl-1,5-diaminopentane, N,N'-bis(3-ethylcyclopentyl)-1,5-diaminopentane, N,N' Cyclohexyl-1,5-diaminopentane, N,N'-bis(4-tert-butylcyclohexyl)-1,5-diaminopentane, N,N'-di(3-ring Butylcyclohexyl)-1,6-diaminohexane, N,N'-dicyclopentyl-1,6-diaminohexane, hydrazine, Ν'-bis(2-methylcyclopentyl) -1,6-diaminohexane, N,N,-dicyclohexyl-1,6-diaminocyclohexane, N,N,-bis[2-(2-ethylhexyl)cyclohexyl -1,6-diaminohexane, N,N'-bis(3-isopropyl('-yl-1-cyclohexyl)-1,6-diaminohexane, N,N' - (4-tert-butylcyclohexyl)-1,6-diaminohexane, N,N,-dimenityl-1,6-diaminohexane, N,N'-di(2,2 ,6-triethylcyclohexyl)-1,6-diaminohexane, 1^chuan '-bis(3,3,5,5-tetramethylcyclohexyl)-1,6-diamine Alkane, N,N'-bis(2-n-butylcycloheptyl)-1,6-diaminohexane, N,N'-bis(2-methylcyclooctyl)-1,6-di Aminohexane, N,N,-bis(cyclooctyl)-1,6-diaminohexane, N,N'-bis[4-(1,1-dimethylpropyl)cyclohexyl] -1,7·diaminoheptane, N,N'-bis(2,6-dimethylcyclohexyl)-1,7-diaminoheptane, hydrazine, Ν'-, two (3-ethyl Cyclopentyl)-1,8-diaminooctane, anthracene, Ν'-di(cyclohexyl)-1,8-diaminooctane, anthracene, Ν'-di(4-tert-butyl Cyclohexyl)-1,8-diaminooctane, anthracene, Ν'-dicyclopentyl-1,10-diaminodecane, hydrazine, Ν'-dimenityl-1,10-diamino Decane, hydrazine, Ν'-bis(2-dodecylcyclobutyl)-1,12-diaminododecane, anthracene, fluorene,-dicyclohexyl-1,12-diamino-12 Alkane, mono-[2-(indolyl-cyclohexyl)ethyl] Amine, mono-[3-(indolyl-cyclopentanyl)propyl]amine, [3-(indolyl-cyclooctyl)propyl][4-(indolyl-cyclooctylamino)butyl]amine , [3-(Ν·2-methylcyclopentylamino)propyl][5-(Ν-2·methylcyclopentylamino-15-200844078)pentyl]amine, and [3-(N- Cyclobutyryl)propyl][7-(N-cyclobutylamino)heptyl]amine. The following examples are presented for illustrative purposes and are not intended to limit the scope of the invention. Example 1 Synthesis of N,N,-dicyclohexyl-1,6-diaminopyridinium 1,6-diaminocyclohexane (23.2 g, 0.2 mol), cyclohexanone (49 g, 0.5 mol), and Pd/C (5 wt% palladium carbon, 1.16 g 'relative P: 1,6-diaminocyclohexane 5% by weight) were charged to a 100 ml autoclave. The autoclave was rinsed 3 times at 22-25 ° C with 95 h psig Hh (7·56 χ 105 Pa). The mixture was heated while stirring; H2 dissipation was observed at 52 °C. The mixture was heated and stirred at 95 ° C under 95 psig of H2 for 19 hours' then the mixture was cooled and degassed. Gas Chromatography (GC; (100 ° C / 5 min / 10 ° (: - minute rate / 80 ° (:)) shows a yield of 96.7% of ^ 4 Chuan '-dicyclohexyl-1,6 -diaminohexane, and 3.3% of intermediate. No tertiary amine or peralkylation by-product was found. I Example 2 N,N' Dicyclohexyl-1,6-diaminocyclohexane Synthesis of 1,6-diaminocyclohexane (8.12 g, 0.07 mol), cyclohexanone (54.9 g, 0.56 mol), and Pt/C (3 wt% platinum carbon, 0.81 g, relative to 1 , 6-diaminocyclohexane (10% by weight) was charged to a 100 ml autoclave. The autoclave was rinsed 3 times at 95-24 psi with 95 psig of H2 (7.56 x 105 Pa). The mixture was initially heated. The mixture was heated and stirred at 75 Torr at 9 5 psig for 1 hour, then the mixture was cooled and degassed from -16 to 200844078. GC showed a yield of at least 98% N, N'. Dicyclohexyl-1,6-diaminohexane, less than 1% of the intermediate, and less than 1% of the alkylation by-product. No tertiary amine was found. Example 3 N,N,-di(cyclohexyl) - Synthesis of isophorone diamine will be isophorone diamine (IPDA, 17 g, 0.1 mol), cyclohexyl (49 g, 0.5 mol), and Pd/C (0.85 g, 5% by weight relative to IPDA) were charged to a 100 ml autoclave. The autoclave was at 95 psig f H2 at 22 °C (7.56 x 105 Pa) The mixture was stirred 3 times. The mixture was heated while stirring; H2 was observed to escape at 45 - 50 ° C. The mixture was heated and stirred at 95 ° C under 95 psig of H 2 for 12 hours' and then the mixture was cooled and Degassing. GC (100 ° C / 5 min / 10 ° C - min rate / 80 ° C; GC-MS confirmed 2 isomers) showed a yield of at least 98% of N, N'-dicyclohexyl Isophorone diamine. No intermediates, tertiary amines or peralkylation by-products were found. Example 4 Synthesis of N,N'-bis(cyclohexyl)-isophoronediamine I Isophorone II Amine (IPDA, 12.75 g, 0.075 mol), cyclohexanone (58.8 g, 0.6 mol), and Pt/C (0.64 g, 5% by weight relative to IPDA) were charged to a 1 cc autoclave. The autoclave was rinsed 3 times with H2 (7.5 6 x 1 05 Pa) at 95 psig at 22 ° C. The mixture was heated while stirring; H2 dissipation was observed at 50 ° C. The mixture was at 95 ° C at 95 ° C. Heating and stirring for 12 hours under H2 The mixture was then cooled and degassed .GC display yield of 96.82% N, N '- dicyclohexyl isophorone diamine (a total of two kinds of isomers) and 3 · 18% of the intermediate. No tertiary amine or -17- 200844078 peralkylation by-product was found. Example 5 Synthesis of N,N'-Dicyclohexyl-1,6-diaminocyclohexane 1,6-Diaminocyclohexane (8.12 g, 0.07 mol), cyclohexanone (20.6 g, 0.21 mol), absolute ethanol (35 g), and Pd/C (0.41 g, 5% by weight relative to 1,6-diaminocyclohexane) were charged to a 1 cc autoclave. The autoclave was washed 3 times at 22 ° C with 95 psig of PL· (7.56 x 105 Pa). The mixture was heated while stirring; H2f dissipation was observed at 45 °C. The mixture was heated and stirred at 95 ° C under 1 g of H 2 at 76 ° C for 4 hours, then the mixture was cooled and degassed. GC showed 100% conversion of 1,6-diaminohexane, 99% yield of N,N'-dicyclohexyl-1,6-diaminohexane, and less than 1% para-alkane By-products and impurities. It should be understood that the reactants and components referred to in the chemical names or chemical formulas in any part of this document, whether singular or plural, are in contact with other substances referred to by chemical names or chemical formulas (eg other reactants, Solvents, etc. exist before the test. The preparatory chemical changes, transformations, and/or reactions, if any, in the resulting mixture or solution or reaction medium are irrelevant, as such changes, transformations, and/or reactions are such that the specified reaction is carried out under the conditions of the present disclosure. The natural result of the substance and / or components together. Thus, the reactants and components are tested together as ingredients for performing the desired chemical manipulation or reaction, or forming a mixture for carrying out the desired operation or reaction. In addition, even though the specific embodiments may refer to substances, components, and/or components in the present formula ("including", "comprising", etc.), this refers to the first contact, blending, or mixing of one or more other in accordance with the present disclosure. Substances in the presence of substances, components and/or ingredients or in the form of -18-200844078. Even if the scope of the patent application may refer to a substance in its current form (for example, "including", "yes", etc.), it refers to a substance that exists just before the first contact, blending, or mixing of one or more other substances in accordance with the present disclosure. The above-mentioned patents, patent announcements and publications are hereby incorporated by reference in their entirety. The term "a" or "an" as used herein is not intended to be limiting, and is not to be construed as limiting the scope of the description or the application. Rather, the term "a" or "an," is used herein to cover one or more of the elements, unless otherwise explicitly indicated. The invention may vary widely within the spirit and scope of the appended claims. 19-