經濟部智慧財產局B工消费合作社印製 附件2 :第85103895號專利申請案中文說明書修正頁 民國88年10月呈Printed by the B Cooperative Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Annex 2: Revised Chinese Manual of Patent Application No. 85103895
五、發明說明（2 ) j ' 1 J 本發明之目標係提供一種對聚醯胺類化合物之單體組 份可產生較佳選擇率的方法* 若解聚合反應係在0 . 5至5 a tm壓力下發生時， •則此一目標便可達成。較佳地，解聚合反應係在〇 . 9與 3 atm之間的壓力下發生。 根據本發明之方法，不僅可獲得較高選擇率，同時也 可避免高壓解聚合所需設備的額外投資成本》若從經濟觀 點來看，此舉將使本發明之方法更具吸引力。對照下，在 美國專利US-A—5.302.756案號中，解聚合 反應係在至少7 a tm壓力下進行·其實施例則描述了壓 力係從30至300a tm變化。但在該專利申請案中卻 都沒有任何指示在低壓下進行解聚合是否可行，及可否產 生此高選擇率。US — A — 5 · 302 . 756案號之揭 示內容係與本發明背離的。US — A— 5 . 302 . 7 5 6案號之表3是解說較高壓力爲較佳的，因爲壓力愈 高，總產量愈高。 舉例之適於解聚合反應之含氮化合物有NH3，（環） 脂肪族胺，（環）脂肪族二胺、（環）脂肪族多元胺，而 該脂肪族基含有1 一 2 0個碳原子；芳族胺、芳族二胺及 /或芳族多元胺。此類化合物之實例爲胺基甲烷、胺基乙 烷、胺基丙烷、胺基丁烷、胺基戊烷、胺基己烷、胺基十 二烷、1 ，2_二胺基乙胺、1 ，3 —二胺基丙烷、1， 3 —二胺基丁烷、1 ，4 —二胺基丁烷（DAB) 、1 ， 4 —二胺基己烷（HDA) 、1 ，6 —二胺基己烷（ 本紙張尺度適用中國國家標準（CNS)A4規格（210x297公釐）_ b _ ----------I yi Μ. · I--I —I — ^-illlll!^J^ (靖先閱讀背面之注意事項再填寫本頁) A7 _B7___ 五、發明説明（1 ) 本發明係關於一種藉在至少一個含氮化合物存在下使 一或多個聚醯胺類化合物解聚合之方法。 此一方法可從美國專利U S — A — 5 . 3 0 2 . 7 5 6案號中得知。該專利申請案係掲示在 高壓下藉助於氨，或者在磷酸塩觸媒存在下使耐龍6，6 或耐龍6與耐龍6，6之混合物解聚合，結果可生成單體 組份。 此已知方法的缺點係對聚醯胺類化合物之單體組份有 較低的選擇率。對耐龍6而言，有己內醯胺及己內醯胺前 驅物。前聚物乃推定爲那些無需先接受轉化即可用來製備 聚醢胺類化合物者，例如胺基己酸。 經濟部中央揉準局属工消费合作社印製 (請先閱讀背面之注$項再填寫本頁) 聚醯胺類化合物（舉例之，如生產廢料）已被再循環 長達約4 0年。此舉乃特別會在聚醯胺生產者及聚醢胺纖 維紡絲者身上發生。在過去幾年內產品再循環也已渐增此 發生在地毯製造商身上。一般而言，聚醢胺類化合物之解 聚合方法係與那'些聚醢胺類化合物需經特別加工之聚醢胺 製品及地毯相關聯。在未來，以具經濟效應方法再循環地 毯廢料（工業用地毯廢料及所謂消耗後地毯廢料）將渐漸 地增加其重要性，原因是塡土掩埋的容納力快接近最大的 利用效果。當然，地毯廢料再循環之商業可行性乃直接依 視將這些地毯之聚醢胺部份轉化成單體組份的經濟性/技 術性能力而定，其單體組份較佳地係可立即再使用，亦即 無需進一步的轉化反應。基於此一理由，則需要有關地毯 廢料再循環的進一步改良方法。 本紙張尺度逋用中國國家梯準（CNS)A4規格（210Χ297公釐〉-4 - 經濟部智慧財產局B工消费合作社印製 附件2 :第85103895號專利申請案中文說明書修正頁 民國88年10月呈V. Description of the invention (2) j '1 J The object of the present invention is to provide a method that can produce a better selectivity for the monomer component of polyamidine compounds. * If the depolymerization reaction is in the range of 0.5 to 5 a When it occurs under tm pressure, then this goal can be achieved. Preferably, the depolymerization reaction occurs under a pressure between 0.9 and 3 atm. According to the method of the present invention, not only a higher selectivity can be obtained, but also the additional investment cost of equipment required for high-pressure depolymerization can be avoided. "From an economic point of view, this will make the method of the present invention more attractive. In contrast, in US-A-5.302.756, the depolymerization reaction is performed at a pressure of at least 7 a tm. The examples describe the pressure system from 30 to 300 a tm. However, there is no indication in this patent application whether the depolymerization at low pressure is feasible and whether this high selectivity can be produced. The disclosure content of US-A-5.302.756 is a departure from the present invention. US — A — 5.302. 7 5 6 Table 3 illustrates that higher pressure is better, because the higher the pressure, the higher the total output. Examples of nitrogen-containing compounds suitable for depolymerization are NH3, (cyclic) aliphatic amines, (cyclic) aliphatic diamines, (cyclic) aliphatic polyamines, and the aliphatic group contains 1 to 20 carbon atoms. ; Aromatic amines, aromatic diamines, and / or aromatic polyamines. Examples of such compounds are aminomethane, aminoethane, aminopropane, aminobutane, aminopentane, aminohexane, aminododecane, 1,2-diaminoethylamine, 1,3-diaminopropane, 1,3-diaminobutane, 1,4-diaminobutane (DAB), 1,4-diaminohexane (HDA), 1,6-di Amine hexane (This paper size applies Chinese National Standard (CNS) A4 specification (210x297 mm) _ b _ ---------- I yi Μ. · I--I —I — ^ -illlll ! ^ J ^ (Jing first read the notes on the back before filling out this page) A7 _B7___ V. Description of the invention (1) The present invention relates to a method in which one or more polyamine compounds are prepared by the presence of at least one nitrogen-containing compound Depolymerization method. This method can be known from the US patent US-A-5.302.756. This patent application shows the use of ammonia under high pressure, or a catalyst of phosphoric acid. In the presence of Nylon 6,6 or a mixture of Nylon 6 and Nylon 6,6, the monomer component can be formed as a result. The disadvantage of this known method is that the monomer component of the polyamine compound has lower Selectivity. For Nylon 6, there are caprolactam and caprolactam precursors. Prepolymers are presumed to be those that can be used to prepare polyamidoamine compounds without first undergoing conversion, such as aminocaproic acid. Printed by the Central Bureau of the Ministry of Economic Affairs of the Industrial and Consumer Cooperatives (please read the note on the back before filling this page) Polyamines (for example, production waste) have been recycled for about 40 years. This is particularly true for polyamide producers and polyamide fiber spinners. Product recycling has also increased in the past few years for carpet manufacturers. In general, polyamides The method of depolymerization of compounds is related to those polyamide products and carpets that require special processing. In the future, carpet waste (industrial carpet waste and so-called post-consumer Carpet waste) will gradually increase its importance, because the capacity of burial burial is approaching the maximum utilization effect. Of course, the commercial feasibility of carpet waste recycling is directly dependent on the polyamide portion of these carpets. Depending on the economic / technical ability to convert into monomer components, the monomer components are preferably reusable immediately, that is, no further conversion reaction is required. For this reason, the relevant carpet waste recycling is required This paper standard uses the Chinese National Standard (CNS) A4 specification (210 × 297 mm) -4-Printed by the B Intellectual Property Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, Amendment 2: Amendment to Chinese Specification of Patent Application No. 85103895 The Republic of China presented in October 88
五、發明說明（2 ) j ' 1 J 本發明之目標係提供一種對聚醯胺類化合物之單體組 份可產生較佳選擇率的方法* 若解聚合反應係在0 . 5至5 a tm壓力下發生時， •則此一目標便可達成。較佳地，解聚合反應係在〇 . 9與 3 atm之間的壓力下發生。 根據本發明之方法，不僅可獲得較高選擇率，同時也 可避免高壓解聚合所需設備的額外投資成本》若從經濟觀 點來看，此舉將使本發明之方法更具吸引力。對照下，在 美國專利US-A—5.302.756案號中，解聚合 反應係在至少7 a tm壓力下進行·其實施例則描述了壓 力係從30至300a tm變化。但在該專利申請案中卻 都沒有任何指示在低壓下進行解聚合是否可行，及可否產 生此高選擇率。US — A — 5 · 302 . 756案號之揭 示內容係與本發明背離的。US — A— 5 . 302 . 7 5 6案號之表3是解說較高壓力爲較佳的，因爲壓力愈 高，總產量愈高。 舉例之適於解聚合反應之含氮化合物有NH3，（環） 脂肪族胺，（環）脂肪族二胺、（環）脂肪族多元胺，而 該脂肪族基含有1 一 2 0個碳原子；芳族胺、芳族二胺及 /或芳族多元胺。此類化合物之實例爲胺基甲烷、胺基乙 烷、胺基丙烷、胺基丁烷、胺基戊烷、胺基己烷、胺基十 二烷、1 ，2_二胺基乙胺、1 ，3 —二胺基丙烷、1， 3 —二胺基丁烷、1 ，4 —二胺基丁烷（DAB) 、1 ， 4 —二胺基己烷（HDA) 、1 ，6 —二胺基己烷（ 本紙張尺度適用中國國家標準（CNS)A4規格（210x297公釐）_ b _ ----------I yi Μ. · I--I —I — ^-illlll!^J^ (靖先閱讀背面之注意事項再填寫本頁) 經濟部中央橾準局貝工消费合作杜印装 A7 _B7___ 五、發明説明（3 ) HMDA)、二甲基胺、二乙基胺、二丙基胺、三甲基胺 、三乙基胺、三丙基胺、（二）環己基胺、（二）胺基環 己垸、4 一胺基甲基一 1 ’ 8 —二胺基辛焼、3—胺基乙 基一 1，6 -二胺基己烷、雙乙撑三胺、雙丁撑三胺、雙 己撑三胺、經胺基（烷基）取代之哌啶、經胺基（烷基） 取代之芳族化合物。較佳地係使用具有沸點低於己內醯胺 (27 0 °C)之含氮化合物。特定言之，可使用NH3、 胺基乙烷、胺基丙烷、二胺基乙烷、二胺基丙烷、二胺基 丁烷或二胺基己烷做爲含氮化合物。 含氮化合物之量通常係爲至少1莫耳每莫耳欲解聚合 之聚醢胺中的胺基。較佳地爲大於2莫耳每莫耳所用胺基 。一般而言，該量可爲小於2 5 0莫耳含氮化合物每莫耳 胺基，較佳地是小於1 Q 〇。 爲了影響反應速度及選擇¥，解聚合反應較佳地係在 路易士酸（亦即Ai?2〇3或S i 〇3) 、Br0nsted酸（如 H3P〇4或H3B〇3)、或彼等之塩（例如銨塩、耐龍6 或耐龍6，6之寡聚物）存在下進行。這些化合物係以 0 . l — 2 0wt%，相對於含氮化合物：較佳地1 一 1 0 w t %之量存在。藉由含氮化合物與金屬化合物（ 如銅塩、鈷塩）之錯合以影響反應速度及選擇率亦是可行 的。該金屬化合物之存在量係爲〇 · 1一1 〇wt%，相 對於含氮化合物，較佳地爲〇 · 5 — 5wt%。緊接於含 氮化合物的存在，解聚合反應也可在水存在下進行。水量 是至少5 Owt%，相對於聚醯胺，較佳地係至多2 0 本紙張尺度適用中國國家標準（CNS ) A4規格（2丨0X297公釐）-6 _ '~~ I------........Ji— -·ID -....... I (請先Η·讀背面之注意事項再填寫本頁) 訂 經濟部中央揉準扃貝工消费合作社印裝 A7 _B7_ 五、發明説明（4 ) wt%，更佳地至多1Owt%。聚醯胺經常含有一些水 :所以該方法通常係在大於1 w t %水存在下進行。雖然 ，從日本專利JP - A _4 6 — 3 1 5 4 1案號中可知悉 ，聚醯胺類化合物係在氨及水存在下解聚合，但根據此日 本專利說明害中所揭示之方法，該解聚合反應係在非常高 的壓力下操作。 根據本發明之解聚合方法的溫度係在2 0 0與4 0 0 °C之間，較佳地，該溫度係在25 0至3 5 0 °C之間。 解聚合反應之進行係藉令含氮化合物與先行熔化之聚 醯胺接觸，然後，再將聚醯胺分裂成其單體組份。這些單 體組份較佳地係經由氣相，與該含氮化合物一起除去。 藉使用本身已知之技巧將含氮化合物與單體組份分離 。此類技巧之實例有汽餾法及眞空蒸餾法。蒸餾可以一或 多個步驟進行。然後，這些含氮化合物可直接返回解聚合 反應器內，再使用。隨後，單體組份及彼等之前驅物可藉 由蒸餾（汽餾或眞空蒸餾）、再結晶，或其他常用之純化 技巧來純化。 根據本發明之方法可傑出地用於聚醯胺、由聚醯胺類 化合物製造或含有聚醯胺類化合物之製品（特別是工業用 地毯廢料及消耗後地毯廢料）之加工處理上。較佳地，地 毯應先進行機械式尺寸減小步驟，舉例之，可藉由碾磨、 砍碎及/或切碎。地毯中較大部份之非聚醯胺組份，例如 乳膠（其可能以CaC〇3填充）、黃麻及/或聚丙烯， 可以一或多個分離步驟而與地毯中之聚醯胺部份分開。然 本紙張尺度適用中國國家橾準（CNS)A4规格（ 210X297公釐）_ 7 _ (请A.S讀背面之注f項再填寫本買) -裝· 訂 經濟部中央揉準局貝工消费合作社印装 A7 ____B7__ 五、發明説明（5 ) 而，地毯碎片也可依此送進反應器內。根據本發明之方法 ，縱使反應器內之聚醯胺量如1 %般低，且還與其他組份 一起時，也可達到良好結果。V. Description of the invention (2) j '1 J The object of the present invention is to provide a method that can produce a better selectivity for the monomer component of polyamidine compounds. * If the depolymerization reaction is in the range of 0.5 to 5 a When it occurs under tm pressure, then this goal can be achieved. Preferably, the depolymerization reaction occurs under a pressure between 0.9 and 3 atm. According to the method of the present invention, not only a higher selectivity can be obtained, but also the additional investment cost of equipment required for high-pressure depolymerization can be avoided. "From an economic point of view, this will make the method of the present invention more attractive. In contrast, in US-A-5.302.756, the depolymerization reaction is performed at a pressure of at least 7 a tm. The examples describe the pressure system from 30 to 300 a tm. However, there is no indication in this patent application whether the depolymerization at low pressure is feasible and whether this high selectivity can be produced. The disclosure content of US-A-5.302.756 is a departure from the present invention. US — A — 5.302. 7 5 6 Table 3 illustrates that higher pressure is better, because the higher the pressure, the higher the total output. Examples of nitrogen-containing compounds suitable for depolymerization are NH3, (cyclic) aliphatic amines, (cyclic) aliphatic diamines, (cyclic) aliphatic polyamines, and the aliphatic group contains 1 to 20 carbon atoms. ; Aromatic amines, aromatic diamines, and / or aromatic polyamines. Examples of such compounds are aminomethane, aminoethane, aminopropane, aminobutane, aminopentane, aminohexane, aminododecane, 1,2-diaminoethylamine, 1,3-diaminopropane, 1,3-diaminobutane, 1,4-diaminobutane (DAB), 1,4-diaminohexane (HDA), 1,6-di Amine hexane (This paper size applies Chinese National Standard (CNS) A4 specification (210x297 mm) _ b _ ---------- I yi Μ. · I--I —I — ^ -illlll ! ^ J ^ (Jing first read the notes on the back and then fill out this page) DuPont Packing A7 _B7___ DuPont Packing Cooperative Work of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of Invention (3) HMDA), Dimethylamine, Diethyl Amine, dipropylamine, trimethylamine, triethylamine, tripropylamine, (di) cyclohexylamine, (di) aminocyclohexylamine, 4-monoaminomethyl-1 '8-diamine Aminooctamidine, 3-aminoethyl-1,6-diaminohexane, diethylenetriamine, dibutyltriamine, dihexyltriamine, piperidine substituted with amine (alkyl) Pyrimidine, aromatic compounds substituted with amine (alkyl). It is preferred to use a nitrogen-containing compound having a boiling point lower than caprolactam (270 ° C). Specifically, as the nitrogen-containing compound, NH3, aminoethane, aminopropane, diaminoethane, diaminopropane, diaminobutane, or diaminohexane can be used. The amount of the nitrogen-containing compound is usually at least 1 mol per amine of the polyamine to be depolymerized. Preferably it is greater than 2 moles per amine. In general, the amount may be less than 250 moles of nitrogen-containing compound per mole of amine groups, preferably less than 1 Q0. In order to influence the reaction speed and select ¥, the depolymerization reaction is preferably based on Lewis acid (ie, Ai? 203 or Sio3), Bronsted acid (such as H3P04 or H3B03), or the like Tritium (such as ammonium tritium, Nylon 6, or an oligomer of Nylon 6,6) is performed. These compounds are present in an amount of 0.1 to 20 wt% relative to the nitrogen-containing compound: preferably 1 to 10 wt%. It is also feasible to influence the reaction speed and selectivity by the combination of nitrogen-containing compounds and metal compounds (such as copper rhenium and cobalt rhenium). The metal compound is present in an amount of 0.1 to 10 wt%, and preferably 0.5 to 5 wt% relative to the nitrogen-containing compound. Immediately after the presence of the nitrogen-containing compound, the depolymerization reaction can also be performed in the presence of water. The amount of water is at least 5 Owt%. Relative to polyamide, it is preferably at most 20. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (2 丨 0X297 mm) -6 _ '~~ I ---- --........ Ji—-· ID -....... I (please read the notes on the back before filling out this page) Order the Central Ministry of Economic Affairs, Zhunbei Cooperative Consumer Cooperative Printing A7 _B7_ V. Description of the invention (4) wt%, more preferably at most 10 wt%. Polyamide often contains some water: so this method is usually performed in the presence of more than 1 wt% water. Although it can be known from the Japanese patent JP-A _4 6 — 3 1 5 4 1 that polyamine compounds are depolymerized in the presence of ammonia and water, according to the method disclosed in this Japanese patent specification, The depolymerization reaction is operated under a very high pressure. The temperature of the depolymerization method according to the present invention is between 200 and 400 ° C, and preferably, the temperature is between 250 and 350 ° C. The depolymerization is carried out by contacting the nitrogen-containing compound with the previously melted polyamide, and then splitting the polyamide into its monomer components. These monomer components are preferably removed together with the nitrogen-containing compound via the gas phase. The nitrogen-containing compounds are separated from the monomer components by techniques known per se. Examples of such techniques are steam distillation and air distillation. Distillation can be performed in one or more steps. These nitrogen-containing compounds can then be returned directly to the depolymerization reactor for reuse. Subsequently, the monomer components and their precursors can be purified by distillation (vapor distillation or air distillation), recrystallization, or other commonly used purification techniques. The method according to the invention can be used outstandingly for the processing of polyamides, products made from polyamides or products containing polyamides (especially industrial carpet waste and post-consumer carpet waste). Preferably, the carpet is first subjected to a mechanical size reduction step. For example, the carpet can be milled, chopped, and / or chopped. Larger portions of non-polyamide components in carpets, such as latex (which may be filled with CaCO3), jute, and / or polypropylene, can be separated from the polyamine portion of the carpet in one or more separation steps Separate. However, the paper size is applicable to China National Standards (CNS) A4 (210X297 mm) _ 7 _ (Please read the note f on the back of the AS and fill in this purchase) Printing A7 ____B7__ 5. Description of the invention (5) Moreover, carpet fragments can also be sent into the reactor accordingly. According to the method of the present invention, good results can be achieved even when the amount of polyamide in the reactor is as low as 1% and also with other components.
實施例I 將40 . 0克耐龍6放入一2升CrNi鋼製反應器 內，同時在2 9 0 X：下使少置氮氣流通過。約2分鐘後， 開始供應氨氣（2 8 5毫微升/小時）。此舉係經由螺旋 管線卸料入一位於反應器底部之中心處的進料開□而完成 。藉由一在3 5 0 °C之塩浴來加熱氣體進料管線及反應器 。在3 3 0 °C下進行解聚合反應。壓力爲1 a tm。 一霧狀廢氣會形成（氣溶膠），其需立刻地從反應器 中卸下。在較冷的地點，冷凝液會與氣溶膠分離而沈積在 卸料管壁上。 氣溶膠，從氣溶膠中分離出之冷凝液及沈稹物都可被 收集在水中。因此，2小時後可於水中回收到總置爲 8 . 3克之產物，其含有： 83 . 3wt%己內醯胺 1 2 . 9 w t %胺基己酸 2.0wt%胺基己醯胺 4 . 3 w t %胺基己腈 反應器內之殘留物爲白色，其表示沒有焦油形生或表 本紙張尺度遑用中國國家標準（CNS ) A4規格（210X297公釐）· § _ <請先鬩讀背面之注$項再填寫本頁) • J— · '\ 裝· 訂 經濟部中央標準局負工消费合作社印袈 A7 ________B7__五、發明説明（6 ) 示沒有發生降解作用。此乃意味著殘留物可再接受解聚合 反應。對耐龍6單體之選擇率經計算如下： 毫莫耳己內醯胺+毫莫耳胺基己酸 選擇率= ------ -毫莫耳回收產物 此解聚合反應之選擇率爲9 7 %。純化後，己內醯胺 及胺基己酸可直接再使用。胺基己醯胺及胺基己腈可藉由 水解及環化反應而轉化成己內醯胺及胺基甲酸。 窗施例I I 將4 5克耐龍6及4 . 5克磷酸二氫銨導入一攪拌著 之2升雙壁CrN i鋼製反應器內*同時在3 1 OeC下讓 少量氮氣流通過。約2分鐘後，開始供應氨氣（1 9 4毫 微升/小時）。此舉係經由套層進料管線卸料入一位於反 應器底部之中心處的進料開口而完成。進料管線及反應器 二者皆係藉由溫度爲3 3 0°C之油來加熱。在3 1 5°C下 進行解聚合反應。壓力爲1大氣壓。 —霧狀廢氣會形成（氣溶膠），其須立即地從反應器 中卸下。 在2 5 0 °C下加熱反應器（油熱式）之雙壁封蓋以及 氣體卸料管線。 藉助於加熱至8 0°C之螺旋冷凝器來冷凝該所得之氣 (請先閲讀背面之注f項再填寫本頁) 一裝. 訂 本紙張尺度適用中國國家揉準（CNS > A4规格（210X 297公釐> -9 - 經濟部中央搮準局員工消费合作社印装 A7 ___B7_五、發明説明（7 ) 髏流。依此，1小時後即可回收總置爲3 8 · 4克之產物 ，其包含： 8 3 . 4wt%己內醯胺 < 0 . 1 w t %胺基己酸 0.8wt%胺基己醢胺 1 1 . 8 w t %胺基己睛 反應器內之殘留物是澄清的，但爲淺棕色，其表示僅 有微量之焦油形成及/或降解發生。 選擇率爲8 7 %。 比鲛件眚驗A 在1 . 3克磷酸氫二銨存在下於2升壓熱器中使4 0 克酎龍6解聚合。在3 2 0 °C溫度下將1 1毫升/分鐘之 液態氨送入壓熱器內。使用壓力閥來控制壓熱器之壓力， 使其在6 8 atm下。 揮發性反應產物將藉由廢氣離開壓熱器。 單體產量乃如下列： 3 7 w t %己內醢胺 0 w t %胺基己酸 5 0 %胺基己醯胺 1 %胺基己腈 (請先聞讀背面之注意事項再填寫本頁) 本紙張尺度適用中國Η家楳率（CNS)A4规格（2丨0X297公釐）-1〇 - A7 ___B7_ 五、發明説明（8 ) 選擇率爲4 5 %。 眚施例I I L A部份 此實施例係如實施例I I般進行，而現在只是使用1 .5克磷酸二氫銨。 1小f後，可以5次餾份方式回收到總量爲3 0 . 5 克之產物，這些餾份是在1 0，2 0 ，3 0，4 0及6 0 分鏟後收集的。此30.5克包含： 79.6wt%己內醯胺 〇 _ 5 w t %胺基己酸 〇 · 4 w t %胺基己醯胺 1 5 · 〇 w t %胺基己腈 選擇率爲8 4 %。 每~餾份之重量及組成份乃如表1所示。 I M I 訂 c (請先M'讀背面之注$項再填寫本頁) 經濟部中央揉準局員工消費合作杜印製 本紙 )A4规格（210X 297公釐）_ ^ 1 Β7 五、發明说明（9 ) 表 1 皤份 重置 己內醯 胺基己 胺基己 胺基己 (編 胺（毫 醯胺（ 酸（毫 腈（毫 號） (克） 莫耳） 毫莫耳） 莫耳） 莫耳） 1 12.0 91.6 0.2 0.3 7.0 2 8.5 61.5 0.2 0.3 11.8 3 5 . 6 38 . 0 0.2 0.3 10.0 4 2 . 7 16.3 0.2 0 . 2 6 . 1 5 1 . 7 7.6 0.2 0.1 5.9 ---J--------'>装-- (請^-聞讀背面之注意事項再填寫本頁) 訂 經濟部中央揉率局員工消费合作社印装 B部份 在A部份所述之解聚合後，立即此重複解聚合反應而 無需將殘留物從反應器內卸下。再次地將4 5克耐龍6放 入反應器內，同時在3 1 0T下使少董氮氣流通過，但並 不再添加新鮮之額外的磷酸二氫銨。 5 0分鐘後，以4次餾份方式回收總量3 9 . 1克之 本紙ft尺度逋用中國國家標準（CNS)A4规格（210Χ297公釐）_ 12 - A7 B7 五、發明説明（l〇 ) 產物，這些餾份係在1 0、2 0、3 0及5 0分鐘後收集 的。此3 9 · 1克含有： 7 6 . 7wt%己內酿胺 0 . 4 w t %胺基己酸 0 . 4 w t %胺基己醯胺 1 5 . 0 w t %胺基己腈 選擇率爲8 4 %。 每一餾份之重量及組成份係列於表2中。 (請先W·讀背面之注意事項再填寫本頁) I - - - -- —-4 經濟部中央揉準局貝工消费合作社印製 本紙張尺度適用中國國家棵準（CNS ) A4規格（210X297公釐）_Example I 40.0 grams of Nylon 6 was placed in a 2 liter CrNi steel reactor while passing a small amount of nitrogen gas flow through at 2900X :. After about 2 minutes, ammonia gas supply (285 nanoliters / hour) was started. This is accomplished by unloading the spiral line into a feed opening located at the center of the bottom of the reactor. The gas feed line and reactor were heated by a simmering bath at 350 ° C. Depolymerization was carried out at 3 3 0 ° C. The pressure is 1 a tm. A mist-like exhaust gas (aerosol) is formed, which needs to be immediately removed from the reactor. In colder locations, the condensate separates from the aerosol and deposits on the discharge tube wall. Aerosols, condensate and sediments separated from aerosols can be collected in water. Therefore, a total of 8.3 grams of the product can be recovered in water after 2 hours, which contains: 83.3% by weight caprolactam 12.9% by weight aminocaproic acid 2.0% by weight aminocaproamide 4. The residue in the 3 wt% amine caprocarbonitrile reactor is white, which means that there is no tar-shaped raw or surface paper size. Chinese National Standard (CNS) A4 specification (210X297 mm) · § _ < Please first Read the note at the back of the page and fill in this page.) • J— · '\ Binding · Binding A7 of the Central Standards Bureau of the Ministry of Economic Affairs and Consumer Cooperatives 袈 A7 ________B7__ 5. The description of the invention (6) shows that no degradation has occurred. This means that the residue is ready for depolymerization. The selectivity for Nylon 6 monomers is calculated as follows: Selectivity of millimolar caprolactam + millimolide aminohexanoic acid = -------Selectivity of the depolymerization reaction of recovered millimolar products It is 97%. After purification, caprolactam and aminocaproic acid can be reused directly. Aminocaproxamine and aminocapronitrile can be converted into caprolactam and aminoformic acid through hydrolysis and cyclization reactions. Window Example I I Introduced 45 grams of Nylon 6 and 4.5 grams of ammonium dihydrogen phosphate into a stirred 2 liter double-walled CrN i steel reactor * while passing a small amount of nitrogen at 3 1 OeC. After about 2 minutes, ammonia gas supply (194 nanoliters / hour) was started. This is accomplished by unloading the jacketed feed line into a feed opening located at the center of the bottom of the reactor. Both the feed line and the reactor are heated by oil at a temperature of 330 ° C. Depolymerization was carried out at 3 1 5 ° C. The pressure is 1 atmosphere. -Misty exhaust gases (aerosols) are formed which must be removed immediately from the reactor. Heat the double-walled lid of the reactor (oil-heated) and the gas discharge line at 250 ° C. The obtained gas is condensed by means of a spiral condenser heated to 80 ° C (please read the note f on the back before filling out this page). One pack. The size of the paper is applicable to the Chinese national standard (CNS > A4 size) (210X 297mm > -9-Printed as A7 _B7_ by the Consumer Cooperatives of the Central Government Bureau of the Ministry of Economic Affairs Ⅴ. Invention Description (7) Cross-border flow. According to this, the total amount can be recovered after 1 hour to 3 8 · 4 Grams of product, which contains: 8 3.4% by weight caprolactam < 0.1% by weight aminocaproic acid 0.8% by weight aminocaproxamine 1 1.8% by weight amine residue in the reactor It is clear, but light brown, which means that only a small amount of tar formation and / or degradation occurs. The selectivity is 87.%. Test A is in the presence of 1.3 g of diammonium hydrogen phosphate in 2 liters. Decompose 40 grams of Nine Dragons 6 in an autoclave. At a temperature of 320 ° C, send 11 ml / min of liquid ammonia into the autoclave. Use a pressure valve to control the pressure of the autoclave so that It is at 6 8 atm. The volatile reaction product will leave the autoclave through the exhaust gas. The monomer yield is as follows: 37 wt% caprolactam 0 wt% aminocaproic acid 50% amine Hexylamine 1% amine capronitrile (please read the precautions on the back before filling in this page) This paper size is applicable to China's Household Standards (CNS) A4 specification (2 丨 0X297 mm) -1〇- A7 ___B7_ 5. Description of the invention (8) The selectivity is 45%. 眚 Example IILA part This example is carried out as in Example II, but now only 1.5 grams of ammonium dihydrogen phosphate is used. After a small f, you can A total of 30.5 grams of product was recovered in five fractions, and these fractions were collected after 1, 20, 30, 40, and 60 minutes of scooping. This 30.5 grams contained: 79.6wt% Caprolactam 〇 5 wt% Aminocaproic acid 0.4 wt% Aminocaproamide 15 50 wt% Aminocapronitrile selectivity is 84%. The weight and composition of each distillate is As shown in Table 1. IMI order (please read M's note on the back before filling in this page) Central Government Bureau of the Ministry of Economic Affairs, Consumer Co-operation, Du printed paper) A4 size (210X 297 mm) _ ^ 1 Β7 V. Description of the invention (9) Table 1 Partial reset of caprolactamylaminohexylaminohexylaminohexyl (formamide (milliamine) (acid (millinitrile (milli)) (g) Moore) Momo Ear Mol) 1 12.0 91.6 0.2 0.3 7.0 2 8.5 61.5 0.2 0.3 11.8 3 5. 6 38. 0 0.2 0.3 10.0 4 2. 7 16.3 0.2 0. 2 6. 1 5 1. 7 7.6 0.2 0.1 5.9 --- J- ------- '> Packing-(please ^-read the notes on the back and fill in this page) Order the printed part B of the Consumer Cooperatives of the Central Rubbing Bureau of the Ministry of Economic Affairs as described in Part A Immediately after depolymerization, this depolymerization reaction was repeated without removing the residue from the reactor. Once again, 45 grams of Nylon 6 was placed in the reactor while passing a nitrogen stream at 3 10 T, but no additional fresh ammonium dihydrogen phosphate was added. After 50 minutes, a total of 39.1 grams of the paper ft size was recovered in 4 fractions, using Chinese National Standard (CNS) A4 specifications (210 × 297 mm) _ 12-A7 B7 V. Description of the invention (10) Product, these fractions were collected after 10, 20, 30 and 50 minutes. This 39 · 1 gram contains: 76.7 wt% caprolactam 0.4 wt% aminohexanoic acid 0.4 wt% aminohexamidine 15.0 wt% aminocapronitrile selectivity 8 4%. The weight and composition series of each fraction are shown in Table 2. (Please read the precautions on the back before filling this page) I------- 4 The paper size printed by the Central Government Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperatives, is printed on paper that is applicable to China National Standard (CNS) A4 specifications ( 210X297 mm) _
7 7 A B 五、發明説明（11 ) 表 2 餾份 重量 己內醯 胺基己 胺基己 胺基己 (編 胺（毫 醢胺（ 酸（毫 腈（毫 號） (克） 莫耳） 毫莫耳） 莫耳） 莫耳） 1 15 . 4 114:8 .0.4 0.4 12 . 4 2 10.6 75 . 4 0 . 3 0.3 15.5 3 6.9 44.6 0.2 0.2 12.8 4 6 . 2 34 . 6 0.3 0.3 12.5 I----- -----' 裝 1111-—訂. * (請it.»讀背面之注意Ϋ項再填寫本頁) 經濟部中央標準局負工消费合作社印氧 從此資施例之A部份及B部份中可清礎知悉，單體之 製造及對單體之選擇率並無顯著的不同。此乃解說了碟酸 塩化合物可再循環。從此實施例之A部份及B部份之選擇 率結果來自，此乃清晰可見。 再者，表1及表2二者也解說了，在第一次餾份與最 後一次餾份比較時，其對耐龍6·單嫌之解聚合反應速度及 選擇率將顯著地更佳。此意味著若連績操作如本發明之解 聚合方法時，將可顯著地增進對耐龍6單體之總選擇率。 本紙張尺度適用中國國家揉準（CNS)A4规格（210X297公釐）_ 14 _ 經濟部中央揉準局貝工消费合作社印装 389778 at _B7_五、發明説明（12 ) 眚施例I V 此實施例係如實施例II般進行。但欲使用胺基丙烷 (1 3 2克/小時）取代氨以做爲含氮化合物。該胺基丙 烷係在套層進料管線中藉使液體胺基丙烷蒸發而摻混入位 於反應器底部處之進料開口內。 4小時後，可回收397.4克產物，其含有： 1 . 6 w t %己內醯胺 <0.1wt%胺基己酸 <0 . lwt%胺基己醯胺 <0.1wt%胺基己睛 反應器之殘留物爲白色。 選擇率是> 9 5 %。 從此實‘施例中可推論出使用胺基丙烷時可獏得高選擇 率〇 窗施例V 此實施例係如實施例I I般進行。但欲使用1 3 2克 /小時胺基•丙烷取代氨，且係如實施例I V般進行摻混 0 2小時後，可回收到2次飽份形式之2 0 7 . 7克產 物，這些餾份係在每一小時終了時收集的。該2 0 7 . 7 克含有 (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度遑用中圉國家搞準（CNS)A4規格（ 210X297公釐）-15 - 389776 A7 B7 五、發明説明（13 ) 15.lwt%己內醯胺 < 0 . 1 w t %胺基己酸 < 0 . 1 w t %胺基__’己酿胺 0 . 5wt%胺基己睛 反應P中之殘留物是澄清的，且爲淡棕色，並且只有 微置的焦油形成及/或降解發生。 選擇率是9 6 %。 毎一餹份之重量及組合物乃示於表3中。 (請先閱讀背面之注f項再填寫本頁) 經濟部中央橾準局貝工消費合作社印装 表 3 皤份 重量 己內醯 胺基己 胺基己 胺基己 (編 胺（毫 醯胺（ 酸（毫 腈（毫 號） (克） 莫耳） 毫莫耳） 莫耳） 莫耳） 1 120.2 271.2 <1 1.2 7.3 2 87.5 6.0 <1 <1 2.6 從表3中可清晰得知，在第一小時內可生成超過9 5 %之耐龍6單體。再次地，如實施例I I I般，可推論出 本紙張尺度逋用中國國家標準（CNS) A4規格U10X297公釐）-16- 389776 at B7 "五、發明説明（14 )連績操作如本發明之解聚合方法時，可導致非常高的選擇 率結果。 flan—· n ^^^^1 ^^—^1 n^i —^n mV * mV - (請先聞讀背面之注意事項再填寫本頁) 訂 經濟部中央橾準局負工消费合作社印製 本紙張尺度逋用中國國家揉率（CNS)A4规格（ 210X297公釐）· 17 -7 7 AB V. Description of the invention (11) Table 2 Distillate weight Caprolactamylhexylaminohexylaminohexyl (Amine (milliamine) (acid (millinitrile (milli)) (g) Moore) Milli Moore) Moore) Moore) 1 15. 4 114: 8 .0.4 0.4 12. 4 2 10.6 75. 4 0. 3 0.3 15.5 3 6.9 44.6 0.2 0.2 12.8 4 6. 2 34. 6 0.3 0.3 12.5 I- ---- ----- '装 1111-—Order. * (Please it. »Read the note on the back and fill in this page again.) The Central Standards Bureau of the Ministry of Economic Affairs, the Consumers Cooperatives, printed oxygen, from the A It is clear from Part B and Part B that there is no significant difference between the manufacture of monomers and the selectivity of monomers. This illustrates the recyclability of the phosphonium sulfonium compound. From the selection results of part A and part B of this embodiment, this is clearly visible. In addition, Tables 1 and 2 also explain that when the first distillate is compared with the last distillate, its depolymerization reaction speed and selectivity to Nailong 6 · Danxian will be significantly better. This means that if the continuous operation is performed as in the solution polymerization method of the present invention, the total selection rate of Nylon 6 monomer can be significantly improved. This paper size applies to the Chinese National Standard (CNS) A4 (210X297 mm) _ 14 _ Printed by the Central Consumers Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperative, 389778 at _B7_ V. Description of the Invention (12) 眚 Example IV This implementation The examples were performed as in Example II. However, it is intended to use aminopropane (132 g / h) instead of ammonia as a nitrogen-containing compound. The amine propane is blended into the feed opening at the bottom of the reactor by evaporating liquid amine propane in the jacketed feed line. After 4 hours, 397.4 grams of product can be recovered, which contains: 1.6 wt% caprolactam < 0.1 wt% amine caproic acid < 0.1 wt% amine caproylamine < 0.1 wt% amine caprole The residue in the eye reactor was white. The selectivity is> 95%. From this example, it can be inferred that a high selectivity can be obtained when using aminopropane. Window Example V This example is performed as in Example II. However, if 132 gram / hour of amine • propane is used instead of ammonia, and after blending for 0.2 hours as in Example IV, 207.7 grams of the product can be recovered in two saturated forms. Copies were collected at the end of each hour. The 2 0 7 gram contains (please read the precautions on the back before filling this page) This paper size is in accordance with the standard of China and China (CNS) A4 (210X297 mm) -15-389776 A7 B7 V. Invention Explanation (13) 15.1 wt% caprolactam < 0.1 wt% amine caproic acid < 0.1 wt% amine group _'hexanylamine 0.5 wt% amine group The residue is clear and light brown, and only tar formation and / or degradation occurs. The selection rate is 96%. The weight and composition of each part are shown in Table 3. (Please read the note f on the back before filling out this page) Printed by the Central Bureau of Standards, Ministry of Economic Affairs, Shellfish Consumer Cooperatives, Form 3 Table weight, caprolactamylhexylaminohexylaminohexyl (hexamidine) (Acid (millonitrile (milligrams) (g) Moore) Moore) Moore) Moore) 1 120.2 271.2 < 1 1.2 7.3 2 87.5 6.0 < 1 < 1 2.6 It is clear from Table 3 It is known that more than 95% of Nylon 6 monomer can be produced in the first hour. Again, as in Example III, it can be inferred that this paper size uses the Chinese National Standard (CNS) A4 specification U10X297 mm) -16- 389776 at B7 " V. Description of the invention (14) Continuous operation as in the present invention Depolymerization methods can lead to very high selectivity results. flan— · n ^^^^ 1 ^^ — ^ 1 n ^ i — ^ n mV * mV-(Please read the precautions on the reverse side before filling out this page) Order by the Ministry of Economic Affairs, Central Bureau of Quasi-Bureau Consumers Cooperative Paper sizes for paper use: China National Kneading Rate (CNS) A4 (210X297 mm) · 17-