申請者已廣泛研究在用於服裝應用之尼龍紗線中的親水性，包括檢查隨氧乙烯(-OCH2
CH2
-)重複單元向聚醯胺中之納入變化之親水性改良。用於服裝應用中之尼龍紗線中之柔軟性的期望性質可經由納入醚(-OR-)重複單元(其中R係(例如但不限於) CH2
CH2
或CH2
CHMe或CH2
CH2
CH2
CH2
)而顯現。業內已實施實質性研究來尋找氧乙烯重複單元在聚醯胺聚合物主鏈中之適當平衡。因此，已發現該經修飾聚合物可能需要改變之聚合條件且紡紗條件不易預測或不易適用於習用紡織業。本文揭示適於使用習用熔融紡絲設備紡成服裝纖維之合成聚醯胺組合物及其產生方法。 揭示主鏈中含有聚(醚二醇) [一個該類別闡述為聚(烷基化氧)]組分之聚醯胺產物，其中醚(即，聚(醚二醇))官能基源自聚縮合反應之羧酸組分而非源自胺。 在一種所揭示聚醯胺組合物中，醚官能基可存於二胺之至少一部分中，以及存於二羧酸之至少一部分中。 適宜二羧酸包括PEG (聚(乙烯)二醇)源之二羧酸。 亦揭示聚縮合製程以產生含醚之聚醯胺。亦揭示與二羧酸組分中無醚之類似組合物相比具有增強之較高水分保持/親水性的纖維及織物(包括針織、織造及直接鋪列非織物)。 所揭示聚醯胺可包含尼龍及聚(醚二醇)二羧酸，其中聚(醚二醇)二羧酸之數目平均分子量為≥250 Da，例如≥600 Da及≥1500 Da及≥2500 Da及≥5000 Da。該聚醯胺之回潮率可介於≥5重量%至≤35重量%之範圍內。除非另外陳述，否則數目平均分子量係以道爾頓(Da)之單位給出。 所揭示聚醯胺充分適於製備親水聚醯胺組合物。因此，本文之揭示內容亦係關於經改良之合成聚醯胺(尼龍)聚合物組合物。所揭示聚醯胺可包含尼龍及聚(醚二醇)二羧酸及視情況聚醚胺。所揭示組合物可適用於製造紗線或纖維以及含有該等紗線或纖維之紡織品或織物或衣裝。 所揭示聚醯胺包含尼龍及聚(醚二醇)二羧酸且可具有介於約5%至約35%、例如約10至約25%、例如約15%至約20%範圍內之回潮率(如本文所述量測)；所有回潮率值皆係以重量計。該回潮率可改良本發明聚醯胺組合物之後續處理期間之可處理性。舉例而言，聚醯胺在紡成紗線時可具有20%至90%之斷裂伸長率。如本文所論述，聚醯胺組合物可係可酸(陰離子)或鹼(陽離子)染色聚合物。在一個實施例中，至少85%之聚合物主鏈(介於醯胺單元之間)可包含脂肪族基團。本文所論述之尼龍可係(例如但不限於)聚六亞甲基己二醯胺(尼龍6,6)、聚己醯胺(尼龍6)或該等尼龍中任一者之共聚物。在一個實施例中，尼龍可為尼龍6,6。尼龍可以介於約50重量%至99重量%範圍內之量存在於聚醯胺中。 聚(醚二醇)二羧酸可藉由使聚(醚二醇)與有機鹼(例如第三丁醇鉀)及烷基化劑(例如溴乙酸乙酯)反應來製得(但不限於該方法)。Greenwald, R. B.等人，J. Med. Chem.
,1996
,39
, 424-431。此向聚(醚二醇)之羥基添加酯官能基。隨後使用適當水性鹼(例如氫氧化鈉)皂化酯基團。可藉由用礦物酸(例如鹽酸水溶液)酸化混合物並用有機溶劑(例如二氯甲烷)催化來分離二羧酸產物。隨後蒸發溶液以形成濃縮溶液並藉由將溶液緩慢添加至經攪拌反溶劑(例如第三丁基甲醚)中使聚合物沈澱。 或者，低分子量聚(醚二醇)二羧酸(例如聚(乙二醇))可自諸如Sigma-Aldrich company等供應商購得。 適宜聚(醚二醇)二羧酸之非限制性實例可包括聚丙二醇二羧酸、聚四甲醛二羧酸、包含聚乙二醇(PEG)、聚丙二醇(PPG)及聚四甲二醇(PTMG)之嵌段之嵌段共聚物，例如：(PEG)-b-(PPG)；或(PEG)-b-(PPG)-b-(PEG)；或(PPG)-b-(PEG)-b-(PPG)。 如本文所論述，聚(醚二醇)二羧酸可用於尼龍單體之聚合以形成可紡成展現優良親水性之尼龍紗線之聚醯胺。該等性質可賦予自該等紗線製造之服飾商品高度期望之觸覺美感及穿著舒適度。 此外，聚(醚二醇)二羧酸可存在於聚醯胺中且可具有多個分子量，此端視所得聚合物之期望性質(包括如本文所論述之可處理性)而定。在一個實施例中，聚(醚二醇)二羧酸之數目平均分子量(Mn
，以道爾頓Da量測)為至少250 Da。在其他態樣中，聚(醚二醇)二羧酸之數目平均分子量可為至少600 Da或至少1500 Da、或至少2500 Da或甚至至少5000 Da。另外，聚(醚二醇)二羧酸可以介於佔聚醯胺約1 wt.%至約50 wt.%之範圍內之量存在。在一態樣中，聚(醚二醇)二羧酸可以介於約5 wt.%至約25 wt.%、例如約8 wt.%至約25 wt.%範圍內之量存在。在另一實施例中，聚(醚二醇)二羧酸係以約8 wt.%至約20 wt.%之量存在。 本文所述聚醯胺包含脂肪族二胺。在一實例中，二胺可為含有6至12個碳原子之脂肪族二胺。在一態樣中，二胺可為六亞甲基二胺。二胺之部分可以產生實質上等莫耳比例之胺基團對聚(醚二醇)二羧酸之酸基團之量存於聚合物中。本文所述之聚醯胺可具有多種物理性質。在一個實施例中，聚醯胺可具有25至130胺端基克當量/1000公斤聚合物。此外，聚醯胺可具有介於約20至約80範圍內之相對黏度。在另一實施例中，相對黏度可基於甲酸測試方法根據在美國專利商標局(United States Patent and Trademark Office)申請本發明時已知之ASTM D789-86來計算。所揭示聚醯胺可具有約25至約45之黃度指數[YI]。所揭示聚醯胺之特徵可在於以下中之一或多者：L*色坐標為約75至約85；a*色坐標為約-5至約5且b*色坐標為約5至約25。 所揭示聚醯胺可進一步包含一或多種如上文所述之聚(醚二醇)二羧酸。在一個實施例中，聚(醚二醇)二羧酸之數目平均分子量(Mn
)可為≥250道爾頓(Da)，例如≥500 Da、≥600 Da及≥1500 Da。在其他態樣中，聚(醚二醇)二羧酸之Mn
可為≥2500 Da或甚至≥5000 Da。 所揭示聚醯胺可進一步包含一或多種聚醚胺，如已公開PCT申請案WO 2014/057363中所述。 可使用與CIE白度等級一致之測試方法來測定每一樣品之白度。可使用GRETAG MACBETH 「COLOR EYE」反射式分光光度計個別量測樣品之白度(W)及黃度(Y)。首先，測定CIELAB色坐標L、a*及b*；及然後，藉助業內已知方式計算W及Y (參見：ASTM方法E313-1996Standard Practice for Calculating Whiteness and Yellowness Indices from Instrumentally Measured Color Coordinates
)。此量測之詳情參見Color Technology in the Textile Industry
第2版，由Committee RA 36, AATCC (1997)公開；參見此卷：Harold及Hunter，Special Scales for White Colors
，第140-146頁及其中之參考文獻，所有該等文獻之全文皆以引用方式併入本文中。 此外，本發明聚醯胺可進一步包含觸媒。在一個實施例中，觸媒可以重量計介於10 ppm至1,000 ppm範圍內之量存在於聚醯胺中。在另一態樣中，觸媒可以重量計介於10 ppm至100 ppm範圍內之量存在。觸媒可包括(但不限於)磷酸、亞磷酸、連二磷酸、芳基膦酸、芳基次膦酸、其鹽及其混合物。在一個實施例中，觸媒可為次磷酸鈉、次磷酸錳、苯基亞膦酸鈉、苯基膦酸鈉、苯基亞膦酸鉀、苯基膦酸鉀、六亞甲基二銨雙苯基亞膦酸鹽、甲苯基亞膦酸鉀或其混合物。在一態樣中，觸媒可為次磷酸鈉。 所揭示聚醯胺及聚醯胺組合物可包括「光學增亮劑」。該光學增亮劑可根據分配至INVISTA North America S.à r.l之美國專利申請案第20080090945 A1號來提供。 根據本文所揭示實施例之聚醯胺及聚醯胺組合物之白度外觀可經由添加光學增亮劑來改良。該等聚醯胺可展現永久白度改良且可經由諸如加熱定型等操作保持此白度改良。在一個實施例中，光學增亮劑可以介於0.01 wt.%至1 wt.%範圍內之量存在於聚醯胺中。 在另一實施例中，白度外觀之改良可藉由添加去光澤劑來達成。去光澤劑可為二氧化鈦。 此外，該等聚醯胺組合物可含有抗氧化穩定劑或抗微生物添加劑。此外，聚醯胺組合物可含有消泡添加劑。在一個實施例中，消泡添加劑可以重量計介於1 ppm至500 ppm範圍內之量存在於聚醯胺中。 所揭示之聚醯胺包括固有地為可酸(陰離子)染色、但亦可藉由用在聚合物中共聚之陽離子染料感受性單體使該等聚合物或共聚物改質而表現為鹼性(陽離子)染色形式的彼等。此改質使組合物尤其可感受鹼(陽離子)染料著色。5-硫代間苯二甲酸鈉係該陽離子染料感受性單體之實例。 在又一態樣中，揭示用於產生聚醯胺之製程，該製程包含使二胺、聚(醚二醇)二羧酸與尼龍鹽接觸；形成混合物；在閉合容器中將混合物加熱至足以使混合物聚合之溫度及自生壓力；及形成聚醯胺。 在又一態樣中，揭示用於產生聚醯胺之製程，該製程包含使二胺與尼龍鹽接觸；形成混合物；在閉合容器中將混合物加熱至足以使混合物聚合之溫度及自生壓力；隨後添加聚(醚二醇)二羧酸，繼續該製程及形成期望聚醯胺。 用於產生聚醯胺之製程可進一步包含將觸媒(包括彼等本文所論述者)提供至混合物。該等製程可進一步包含將消泡添加劑提供至混合物。該等製程可進一步包含將光學增亮劑提供至混合物。 聚醯胺之尼龍單體可以鹽、胺基酸或內醯胺形式來添加。尼龍單體可為尼龍6,6鹽且可佔聚醯胺之幾乎全部(例如，99 wt.%、99.5 wt.%、99.9 wt.%或更大)或可以介於約50 wt.%至95 wt.%、96 wt.%、97 wt.%或98 wt.%範圍內之量存於聚醯胺中。 多種處理參數可用於本發明聚醯胺之聚合中，包括溫度及壓力。溫度可介於約190℃至約290℃範圍內且自生壓力可介於約250磅/平方英吋絕對壓力(psia)至約300磅/平方英吋絕對壓力(psia)範圍內。此外，加熱可在部分真空下實施。所獲得之部分真空受高壓釜設計及該製程之經濟考慮之約束。 本發明聚合可涉及多個連續加熱循環。該等循環可個別包含加熱溫度曲線及壓力曲線。目的係經由足夠熔融之溫度與足夠溶解之水含量之組合來保持系統流動。連續加熱循環可包含：第一加熱循環(C1)，其經20分鐘至40分鐘之時段，起始溫度介於170℃至215℃之間且終止溫度介於190℃至230℃之間，壓力介於130 psia至300 psia之間；第二加熱循環(C2)，其經20分鐘至45分鐘之時段，起始溫度介於190℃至230℃之間且終止溫度介於240℃至260℃之間，壓力介於130 psia至300 psia之間；第三加熱循環(C3)，其經15分鐘至45分鐘之時段，起始溫度介於240℃至260℃之間且終止溫度介於250℃至320℃之間，壓力介於300 psia至大氣壓之間；及第四加熱循環(C4)，其經15分鐘至80分鐘之時段，起始溫度介於250℃至320℃之間且終止溫度介於250℃至320℃之間，壓力介於大氣壓與約200毫巴絕對真空之間。最後，使用業內熟知之方法擠出聚合物。所揭示聚醯胺組合物固有地可酸染色且可視情況包含可陽離子染色聚合物。 所揭示聚醯胺組合物可藉由高壓釜製程製得。該製程可起始於自尼龍鹽、胺基酸或內醯胺或例如尼龍6,6鹽之混合物之水溶液製備之濃漿液(術語漿液亦納入溶液之概念)，將該濃漿液提供至高壓釜容器。視情況，漿液可為稀漿液且藉助蒸發步驟變得更濃。漿液可自單體(例如六亞甲基二胺及己二酸)之水溶液以業內已知之方式製得。隨後可將高壓釜容器加熱至約230℃ (或一些其他功能溫度)，從而使得內部(自生)壓力升高。可視情況將去光澤劑二氧化鈦(TiO2
)注入高壓釜及作為水性分散液之單體混合物中。 在一個實施例中，可將聚(醚二醇)二羧酸及視情況聚醚胺之水性漿液與一定量之二胺(例如六亞甲基二胺)一起注入高壓釜容器中之混合物，以產生實質上等莫耳比例之酸基團對胺基團。隨後可將混合物在高壓釜中加熱至約245℃ (或一些其他功能溫度)。保持在此溫度或其他期望溫度狀況的同時，可將高壓釜壓力降低至大氣壓且藉由以已知方式施加真空來進一步降低壓力，以形成聚醯胺組合物。將含有聚醯胺組合物之高壓釜在此溫度下維持約30分鐘。此步驟之後可為(例如)進一步將聚醯胺聚合物組合物在高壓釜中加熱至約285℃。可藉由打開高壓釜容器中之埠並施加4巴至約5巴乾燥氮氣從而容許熔融聚醯胺組合物以帶形式自容器流出而自高壓釜釋放聚合物組合物。該等帶可在水流中冷卻並驟冷。接下來，可藉由已知方式粒化聚醯胺聚合物之帶並進一步用水冷卻。 在一些實施例中，聚合物組合物可在循環階段結束時自高壓釜容器釋放並容許熔融組合物以帶形式自容器流出。在其他實施例中，可將聚合物組合物直接供應至經設計及操作以處理聚合物熔融物之聚合物擠出設備。舉例而言，可在螺桿擠出機(例如雙螺桿擠出機)中處理所揭示聚合物組合物。 在一個實施例中，可添加一定量之二胺(例如六亞甲基二胺)，以使所存在之酸總數與胺基團總數大約相等。隨後可將混合物在高壓釜中加熱至約245℃ (或一些其他功能溫度)，同時維持在期望壓力下。保持在此溫度或其他期望溫度狀況的同時，可將高壓釜壓力降低至大氣壓且藉由以已知方式施加真空來進一步降低壓力，以形成聚醯胺組合物。在該等加熱時段及/或壓力降低期間，可將聚(醚二醇)二羧酸及視情況聚醚胺注入混合物。可將含有聚醯胺組合物之高壓釜在此溫度下維持約30分鐘。此步驟之後可為(例如)進一步將聚醯胺聚合物組合物在高壓釜中加熱至約285℃。可藉由打開高壓釜容器中之埠並施加4-5巴乾燥氮氣並容許熔融聚醯胺組合物以帶形式自容器流出而自高壓釜釋放聚合物組合物。該等帶可在水流中冷卻並驟冷。接下來，可藉由已知方式粒化聚醯胺聚合物之帶並進一步用水冷卻。 上文所闡述之高壓釜製程可提供甲酸方法RV為約20至約80之聚醯胺組合物。在另一實施例中，上文所闡述之高壓釜製程可提供甲酸方法RV為約38至約45之聚醯胺組合物。 視情況，該製程可經改質以製造具有約25至約130莫耳胺端/1000公斤聚合物之聚醯胺組合物，其係藉由將過量六亞甲基二胺水溶液添加至尼龍鹽水溶液中提供。 聚合反應可在連續聚合器中實施。連續聚合器之實例為彼等熟習此項技術者已知，且一個實例揭示於頒予Micka及Poinsatte之WO2014179048中，其內容以引用方式併入本文中，如同本文中詳盡地闡述。 組合物可視情況在高壓釜或連續聚合器中部分聚合且隨後在固相聚合器中完成。固相聚合器之實例為熟習此項技術者已知，且由Yao及McAuley,Simulation of continuous solid-phase polymerization of nylon 6,6 (II): processes with moving bed level and changing particle properties
Chemical Engineering Science 56 (2001) 5327-5342教示。 組合物可視情況在擠出機中製備。該製程可包括將包括二酸及二胺之反應物分開或一起進料至擠出機之進料喉。或者，該方法可包括在跨越擠出機長度定位之一或多個點將反應物進料至一或多個輔助進料喉，其中擠出機包括各個區，其可包括熔融區、混合區及運輸區。頒予Langrick及Hunt之PCT/US16/61604 (Attorney Docket PI4212)揭示具有多個進料喉之螺桿擠出機中之聚合，且以引用方式併入本文中，如同本文中詳盡地闡述。 本文所述之尼龍聚合物及共聚醯胺可固有地可酸染色。在一個實施例中，該等聚合物中游離胺端基(AEG)之數目係至少25莫耳/1000公斤尼龍聚合物。為使聚合物更深度地進行酸染色，可使用增加之游離胺端基含量。更深度酸染色尼龍聚合物具有增加之AEG含量，例如可使用至少60至130莫耳/1000公斤尼龍聚合物之AEG含量。 此外，應注意，可製造包含與適宜二酸(例如己二酸)等量之胺端之聚(醚二醇)二羧酸及視情況聚醚胺的母料。然後可將此母料提供至高壓釜製程。在替代性實施例中，可藉由母料製程來製造本文之聚醯胺組合物，其中使用包含分散於尼龍(尼龍6,6或尼龍6)中之聚(醚二醇)二羧酸及視情況聚醚胺之薄片或熔融物形式。然後隨後添加薄片或熔融物形式作為包含尼龍之母料。在實施例中，以薄片形式含有聚(醚二醇)二羧酸及視情況聚醚胺及尼龍之母料尼龍薄片皆熔融。在實施例中，含有聚(醚二醇)二羧酸及視情況聚醚胺之尼龍薄片熔融並添加至尼龍熔融物。在任一情形下，迫使熔融物自擠出機進入幫浦，該幫浦將聚醯胺組合物泵送至例如用於製造紗線之包(pack)及噴絲嘴中。 亦可使本文所述之尼龍聚合物及共聚醯胺呈鹼性染色形式，即可感受鹼染料(亦稱為陽離子染料)著色。該等鹼染色組合物係自在聚合物中共聚有陽離子染料改質劑之聚醯胺聚合物製造。頒予Windley之美國專利第5,164,261號闡述該等經陽離子染料改質之聚醯胺之製備。在一個實施例中，聚合物可在與0.5 wt.%至4 wt.%之陽離子染料改質劑(例如，5-硫代間苯二甲酸)聚合期間改質。通常，可使用業內已知之標準聚合程序將一定稱重量之5-硫代間苯二甲酸之鈉鹽與已知量之聚醯胺前體鹽於高壓釜中組合。在一個實施例中，存在於聚合物中之陽離子染料改質劑之量可係約0.75 wt.%至約3 wt.%，如藉由聚合物之總硫分析所測定。陽離子染料改質劑之此量報告為等效磺酸根基團。磺酸根基團濃度可係至少25莫耳/1000公斤聚合物至約150莫耳/1000公斤聚合物。聚醯胺紗線
本發明之聚醯胺組合物在紡成紗線時尤其可用。在一個實施例中，可將聚(醚二醇)二羧酸及視情況聚醚胺提供至聚醯胺組合物，且因此在形成織物時為紗線自身所固有而非施加至織物上。在一個實施例中，該紗線展現如藉由多個水蕊吸及回潮率測試所量測之經改良之親水性。 自本文所述之聚醯胺製造之紗線可係呈低順向度紗線(LOY)、部分取向紗線(POY)或全拉伸紗線(FDY)形式之多絲紡織紗線。該紗線可係自部分取向紗線製造之具紋理紗線。此外，該紗線可實質上連續，即由一或多條連續長絲形成。在其他實施例中，可將連續長絲切割成短纖維且後者可藉由紡絲製程轉化成連續絲線，從而產生連續製品或包括較短纖維之物件。該等紗線可用於製造織物，該等織物進而可用於製造衣裝。 在實施例中，所揭示聚合物可以珠粒或薄片形式於50%至65%之相對濕度下儲存一週且隨後熔融紡成服裝纖維而在儲存與熔融紡絲之間無***乾燥步驟。 在一個實施例中，用於紡紗之裝置及方法揭示於美國專利第6,855,425號中，且類似技術可同樣地在本文所製備並闡述之聚醯胺之背景下。 自本文所述之聚醯胺製造之紗線可係尤其可用於服裝紡織品應用之紡織紗線。舉例而言，紗線重量為5 dtex至300 dtex且長絲重量為0.5 dtex至7 dtex之紗線可合意。在某些實施例中，紗線包含1至300條長絲。根據一些實施例，紗線包含3至150條長絲。纖維之線性質量密度係以dtex之單位給出[1 dtex意指1分特且等於1克/10,000米紗線]。且1 「tex」之單位等於1克/1000米紗線之線性質量密度。 根據一些實施例，紗線具有0.5至2.5、例如1至1.5之DPF (dtex/長絲)。 自本文所述之聚醯胺製造之紗線可具有1.5%或更小、更通常1%或更小之長絲均勻度(以烏氏(Uster)% (U%)表示)。該均勻度對於紗線可合意以具有服裝應用所需要之高外觀均勻度，且亦減少紋理化、編織及針織操作中之紗線斷裂。 自本文所述之聚醯胺製造之紗線可具有20%至120%之斷裂伸長率。根據一些實施例，紗線具有20%至90%之斷裂伸長率。通常，紗線具有25 cN/tex至65 cN/tex、例如30 cN/tex至45 cN/tex之韌度。該等拉伸性質對於服裝紡織品應用皆合意。斷裂力係以厘牛頓/tex [cN/tex]表示。 在某些實施例中，聚醯胺之紗線可具有小於0.1 wt.%、且更通常小於0.01 wt.%之二氧化鈦含量，從而使紗線光澤透明或明亮。在其他實施例中，聚醯胺之紗線可具有大於0.3 wt.%及或甚至大於2 wt.%之二氧化鈦含量，從而使紗線無光澤或光澤暗淡。亦可使用介於該等範圍之間之二氧化鈦含量，例如0.1 wt.%至0.3 wt.%。 在一個具體實施例中，聚醯胺之紗線可藉由使用已知熔融物紡絲製程技術來製備。藉助該技術，藉由使用高壓釜製程製造之粒化聚醯胺組合物或由母料製程製造之熔融物皆可具有如上文所闡述之光學增亮劑，且可提供至紡絲機。藉由計量幫浦將熔融聚合物向上傳送至過濾包，並經由含有所選形狀之毛細管口之噴絲板擠出以在紡絲溫度下產生期望長絲橫截面。業內已知之該等橫截面形狀可包括圓形、非圓形、三葉形、中空及空竹形。典型中空長絲可如美國專利第6,855,425號中所揭示來產生。紡絲溫度可介於(例如) 270℃至300℃範圍內。藉由經處理之驟冷空氣冷卻自噴絲板出現之長絲束，用紡絲油劑(spin finish，油/水乳液)處理，視情況使用例如交織噴氣機交織。 在一些實施例中，將由此獲得之連續紗線切割並轉變成短纖維，隨後使用該等短纖維藉由紡絲產生絲線或紗線或藉由水力纏結、針刺、超音波接合、化學鍵結、加熱接合或諸如此類製造非織造物。 在FDY之情形下，紡絲機上之線上處理通常包括繞一組導輥(Godet roll，進料輥)纏繞若干圈，圈數要足以防止在該等輥上滑動，然後將紗線傳送至另一組輥(拉伸輥)上，該另一組輥以足夠速度旋轉以將紗線拉長預定量(拉伸比率)。最後，藉由以下步驟繼續該製程：用蒸汽箱加熱定型並鬆弛紗線，然後以至少3000 m/min、例如至少4000m/min、例如4800 m/min或更高之速度捲繞。視情況，可使用諸如加熱輥等替代性加熱定型(或鬆弛)方法，且可在拉伸輥與捲繞器之間再納入一組導輥以在紗線定型或鬆弛時控制張力。而且，視情況，可在最終捲繞步驟之前再次施加紡絲油劑及/或額外交織。 在POY之情形下，額外線上處理通常僅包括在兩個以相同速度旋轉之導輥上進行S-纏繞，及然後將紗線傳送至高速捲繞器，以至少3000 m/min、例如至少4000 m/min、例如4800 m/min或更高之速度捲繞。使用S-纏繞有益於控制張力，但並非必需。該POY可直接用作用於編織或針織之扁平紗線，或用作用於紋理化之原料。 LOY紡絲製程類似於POY，只是使用1000 m/min或以下之捲繞速度。該等低順向度紗線通常經由例如習用拉伸-撚線機或拉伸-捲繞機上之第二階段進一步處理。 在一個實施例中，本文所揭示之聚醯胺聚合物可高度適於紡成可會聚以形成多絲紗線之連續長絲。將合成聚合物紡成連續長絲並形成多絲紗線之製程為熟習此項技術者已知。通常，長絲之成功紡絲使用具有至少一個單一毛細管口之噴絲板。毛細管口對應於包含紗線之每一個別長絲。端視長絲所尋求之橫截面形狀採用圓形及非圓形橫截面噴絲嘴毛細管口(或擠出管口)。通常，對於每毛細管之某一聚合物通量G (例如，以克/分鐘表示)，應用以下等式：G = ρ ( 熔融物 ) D 2 ( 毛細管 )
(π/4)v ( 擠出 )
等式1. 在此等式中，ρ係聚合物熔融物密度(例如，對於290℃下熔融的尼龍6,6等於1.0克/cm3
)，D係假定為圓形管口之毛細管直徑(等於半徑的兩倍)，且v係長絲之速率。 擠出速率由以下等式給出：v ( 擠出 ) = G
(4/πD 2 ( 毛細管 )
ρ( 熔融物 )
) 等式2. 在一個實施例中，聚合物係以介於20公分/秒至80公分/秒範圍內之擠出速率擠出。在另一實施例中，可使用經空調以已知方式驟冷剛剛擠出之長絲。在此步驟中，在驟冷櫃中使用空調之側向通風冷卻個別長絲，並將其會聚且用如業內已知之初級油劑油浸成紗線。藉由進料輥將紗線向上傳送至拉伸輥對上，其中紗線在該拉伸輥對上經拉長且定向以形成拉伸紗線，該拉伸紗線藉由輥引導至紗線穩定裝置中。該穩定裝置為業內所常見且本文中視情況作為紗線後處理步驟來使用。最後，以介於1000米/分鐘至6500米/分鐘範圍內之紗線速度將紗線捲繞成紗線捲裝。紗線RV (或藉由甲酸方法測定之相對黏度)係約20至約80。 在實施例中，紗線係伸長率為22%至約60%之拉伸紗線，沸水收縮率介於3%至約10%範圍內，紗線韌度介於3克/丹尼(denier)至約7克/丹尼範圍內，且紗線之RV可變化並充分控制在約20至約80、例如約40至約60之範圍內。 表徵此紗線之優異性質之衍生參數稱為紗線品質且參見如等式3中紗線韌度(克/丹尼)與伸長率%之平方根之乘積。 紗線品質 = 韌度 × (伸長率)1/2
等式3. 紗線品質係紗線「韌性」量度之近似值。如彼等熟習此項技術者已知，紗線負載伸長率曲線下之面積與伸長紗線所作之功成正比。若例如韌度係以每單位丹尼之力表示，且伸長率係以每單位長度之變化%表示，則負載伸長率曲線係應力-應變曲線。在此情形下，應力-應變曲線下之面積係延長紗線之功或紗線韌性。紗線品質改良提供在各種應用中更可接受之服裝聚醯胺紗線。該等應用可包括(但不限於)經編針織物、圓編針織物、無縫針織衣裝、針織品、非織造織物及光丹尼技術織物。 在某些實施例中，聚醯胺紗線具有與陰離子染料或陽離子染料不同之染色特徵。該等染色特徵可源於胺端基之不同數目。胺端基(AEG)之濃度影響陰離子染料對聚醯胺染色之程度。另一選擇或此外，聚醯胺可含有使聚醯胺可陽離子染色之陰離子端基，例如磺酸根或羧酸根端基。 在某些實施例中，聚醯胺紗線係經納入乙烯基磺醯基及/或β-硫酸根合乙基磺醯基之纖維反應性染料染色。該等纖維反應性染料自美國專利第5,810,890號得知。 在某些實施例中，聚醯胺紗線係經納入諸如三嗪、嘧啶及喹喔啉等氮雜環基團之鹵素衍生物之纖維反應性染料染色。該等纖維反應性染料闡述於例如美國專利第6,869,453號中。 在其他實施例中，長絲包含六亞甲基二胺之胺組分。 在其他實施例中，長絲包含為含有基於二胺之總重量至少20 wt.%之甲基五亞甲基二胺之六亞甲基二胺之混合物的胺組份。 在又一些其他實施例中，聚醯胺可包括尼龍6。 可使用以下測試論述來表徵如本文所論述之各種參數。紗線韌度及紗線伸長率可使用INSTRON拉伸測試裝置(Instron Corp., Canton, Massachusetts, USA 02021)及恆定夾頭速度根據ASTM方法D 2256-80 (在向美國專利商標局申請本發明時已知)測定。韌度表示為厘牛頓/tex (cN/tex)或克力/丹尼，且伸長率%係在斷裂負載下表示為初始長度之百分比之樣本長度增加。 紗線直鏈密度均勻度(亦稱為紗線烏氏% (U%))可使用熟習此項技術者已知之C型烏氏均勻度測試儀3來測定。 聚合物胺端可藉由用吸收於溶液中之經稱重聚合物樣品之標準化過氯酸溶液之直接滴定來量測。 聚合物之回潮率可藉由以下方法量測。在80℃下在真空下將聚合物之樣品(100 g)乾燥18小時。例如，使用Aquatrac (PET版(4 Digit)；Brabender Messtechnik)在160℃設置下對約1.9 g聚合物量測此乾燥聚合物樣品之初始水分含量。使用此方法量測之小於0.5 wt.%之水分含量被視為指示該聚合物已經充分乾燥。 然後在無任何攪動下在環境溫度(20℃)下將乾燥樣品浸泡於去礦物質水(500 g)中。48小時後，移除樣品(約10 g)且用吸收性薄紙輕拍乾燥。將樣品之一部分(約5 g；濕樣品之重量)精確稱量至箔盤中且在80℃下在真空下於烘箱中放置18小時。移除盤並置於乾燥器中冷卻，且然後再稱重(乾燥後剩餘之重量)。以下列間隔(例如72、144、190及220小時)至220小時重複此程序。藉由以下計算測定水分吸收率：聚合物之回潮率定義為220小時後或直至樣品已達到水分吸收平衡(其定義為在24小時時段中重量變化不大於1%)之前(以較早者為準)之水分吸收率。因此，若220小時後尚未達到水分吸收平衡，則回潮率係220小時時之水分吸收率。當在220小時之前達到水分吸收平衡時，回潮率係在平衡下進行之最初兩次連續量測之水分吸收率之平均數(平均值)。 或者，回潮率可藉由諸如DIN 53814等方法量測，該方法涉及於20℃下用去離子水使紡織品樣品飽和2小時，藉由以4000 m/min離心去除水，及量測於105℃下乾燥後直至不再觀察到重量損失為止之重量變化。 自紗線構造之織物之水蕊吸速率可藉由以下來量測：將1英吋(2.5 cm)寬之條狀經擦洗織物之底部1.8英吋(4.6 cm)垂直浸泡於去離子水中，以視覺方式測定沿織物向上蕊吸之水之高度，並記錄隨時間變化之高度。「初始蕊吸速率」意指蕊吸測試之最初兩分鐘期間之平均蕊吸速率。 可使用織物或衣裝「乾燥時間%」測試來表徵親水性聚醯胺紗線、織物及衣裝。該等亦稱為乾燥時間%測試或「水平蕊吸」測定。乾燥時間%測試係使用天平及電腦來實施；例如，Mettler天平AE163及運行Mettler BalanceLink 3.0程式之電腦。獲得並記錄直徑為2英吋(5.1 cm)之圓形織物樣品之重量。使用自動吸管將0.10 g自來水置於天平上且記錄其重量。立即將圓形織物樣品以該水為中心且然後置於該水上。在此時(時間 = 0分鐘)及在隨後30分鐘內每兩分鐘記錄織物及水之總重量。根據下式計算給定時間內乾燥%結果：乾燥% = 100 - [(W總
- W織物
) /WH2O
] × 100。實例
提出以下實例以為彼等熟習此項技術者提供如何實施本文所揭示及主張之方法及如何使用本文所揭示及主張之組合物及化合物之完整揭示內容及說明。已努力確保數值(例如量、溫度等)之精確性，但應慮及一些誤差及偏差。除非另外指明，否則：份數為重量份數，溫度以℃表示，且壓力以大氣壓表示。標準溫度及壓力定義為25℃及1大氣壓。 實例中所用之材料 數目平均分子量Mn
為2000道爾頓之聚(乙二醇)係自商業來源Alfa Aesar (產品代碼B22181)獲得。 六亞甲基二胺或HMD係自INVISTA Intermediates (在Wichita、Kansas及Wilmington具有辦事處，Delaware，USA)購得。 如本文所用術語「聚(醚二醇)二羧酸」係指具有之一般化學結構之一類聚(乙二醇)雙(羧基甲基)醚，其中n係數值。 數目平均分子量Mn
為600之聚(醚二醇)二羧酸(本文中稱作本揭示內容之實例中之化合物2)係自商業來源VWR International獲得。 如本文所用術語「RE 2000」係指ELASTAMINE®
RE-2000胺；一種可自Huntsman Corp購得之商業產品。ELASTAMINE®
RE-2000胺係源自環氧丙烷封端之聚乙二醇之水溶性脂肪族聚醚二胺。此類型之聚醚胺可用於多種聚合物中。尼龍 66 鹽
如本文所用術語「尼龍66鹽」係指經由至少一種二胺之胺基團與至少一種二羧酸之羧酸基團之酸性質子之間之酸-鹼中和反應形成的鹽。 鹽之二羧酸組分適宜地係至少一種式(I)之二羧酸：HO2
C-R1
-CO2
H，其中R1
代表二價脂肪族、環脂肪族或芳香族基團或共價鍵。R1
適宜地包含2至20個碳原子，例如2至12個碳原子，例如2至10個碳原子。R1
可為包含2至12個碳原子、或2至10個碳原子、例如2、4、6或8個碳原子之直鏈或具支鏈(例如直鏈)伸烷基、未經取代之伸苯基或未經取代之伸環己基。視情況，R1
可含有一或多個醚基團。舉例而言，R1
係伸烷基，例如直鏈伸烷基，其包含2至12個碳原子、或2至10個碳原子、例如2、4、6或8個碳原子。 適宜二羧酸之具體實例包括己烷-1,6-二酸(己二酸)、辛烷-1,8-二酸(辛二酸)、癸烷-1,10-二酸(癸二酸)、十二烷-1,12-二酸、1,2-環己烷二甲酸、1,3-環己烷二甲酸、1,4-環己烷二甲酸、1,2-環己烷二乙酸、1,3-環己烷二乙酸、苯-1,2-二甲酸(苯二甲酸)、苯-1,3-二甲酸(間苯二甲酸)、苯-1,4-二甲酸(對苯二甲酸)、4,4'-氧基雙(苯甲酸)及2,6-萘二甲酸。較佳二羧酸係己烷-1,6-二酸(己二酸)。 鹽之二胺組分適宜地係至少一種式(II)之二胺：H2
N-R2
-NH2
，其中R2
代表二價脂肪族、環脂肪族或芳香族基團。R2
適宜地包含2至20個碳原子、例如4至12個碳原子、例如4至10個碳原子。R2
可為包含4至12個碳原子、例如4至10個碳原子、例如4、6或8個碳原子之直鏈或具支鏈(例如直鏈)伸烷基、未經取代之伸苯基或未經取代之伸環己基。視情況，R2
可含有一或多個醚基團。舉例而言，R2
係伸烷基，例如直鏈伸烷基，其包含4至12個碳原子、或4至10個碳原子、例如2、4、6或8個碳原子。 適宜二胺之具體實例包括四亞甲基二胺、五亞甲基二胺、六亞甲基二胺、八亞甲基二胺、十亞甲基二胺、十二亞甲基二胺、2-甲基五亞甲基二胺、3-甲基五亞甲基二胺、2-甲基六亞甲基二胺、3-甲基六亞甲基二胺、2,5-二甲基六亞甲基二胺、2,2,4-三甲基六亞甲基二胺、2,4,4-三甲基六亞甲基二胺、2,7-二甲基八亞甲基二胺、2,2,7,7-四甲基八亞甲基二胺、1,2-環己烷二胺、1,3-環己烷二胺、1,4-環己烷二胺、4,4'-二胺基二環己基甲烷、苯-1,2-二胺、苯-1,3-二胺及苯-1,4-二胺。較佳二胺係六亞甲基二胺。 舉例而言，鹽之二羧酸組分可為至少一種式(I)之二羧酸，其中R1
係包含2至12個碳原子、或2至10個碳原子、例如2、4、6或8個碳原子之伸烷基，且鹽之二胺組分可為至少一種式(II)之二胺，其中R2
係包含4至12個碳原子、或4至10個碳原子、例如2、4、6或8個碳原子之伸烷基。 例如，至少一種二羧酸可選自己烷-1,6-二酸(己二酸)、辛烷-1,8-二酸(辛二酸)、癸烷-1,10-二酸(癸二酸)及十二烷-1,12-二酸，且至少一種二胺可選自四亞甲基二胺、五亞甲基二胺、六亞甲基二胺、八亞甲基二胺、十亞甲基二胺、十二亞甲基二胺、2-甲基五亞甲基二胺、3-甲基五亞甲基二胺、2-甲基六亞甲基二胺、3-甲基六亞甲基二胺、2,5-二甲基六亞甲基二胺、2,2,4-三甲基六亞甲基二胺、2,4,4-三甲基六亞甲基二胺、2,7-二甲基八亞甲基二胺及2,2,7,7-四甲基八亞甲基二胺。 較佳鹽包括其中二羧酸組分包含己烷-1,6-二酸(己二酸)、辛烷-1,8-二酸(辛二酸)、癸烷-1,10-二酸(癸二酸)及十二烷-1,12-二酸中之一或多者且二胺組分包含四亞甲基二胺、五亞甲基二胺、六亞甲基二胺、八亞甲基二胺、十亞甲基二胺、十二亞甲基二胺中之一或多者之彼等。尤佳鹽係自己烷-1,6-二酸(己二酸)及六亞甲基二胺形成之中和鹽(「尼龍66鹽」)。Applicants have extensively studied the hydrophilicity of nylon yarns used in apparel applications, including inspections of oxyethylene (-OCH)2
CH2
-) The hydrophilicity of the repeating unit incorporated into the polyamine. Desirable properties of softness in nylon yarns for use in apparel applications may be via inclusion of an ether (-OR-) repeat unit (wherein R is (eg, but not limited to) CH2
CH2
Or CH2
CHMe or CH2
CH2
CH2
CH2
) and appear. Substantial research has been conducted in the industry to find an appropriate balance of oxyethylene repeat units in the polyamine polymer backbone. Thus, it has been found that the modified polymer may require varying polymerization conditions and the spinning conditions are not readily predictable or readily adaptable to the conventional textile industry. Disclosed herein are synthetic polyamine compositions suitable for spinning into garment fibers using conventional melt spinning equipment and methods of producing the same. A polyamine product containing a poly(ether diol) [one of the class described as a poly(alkylated oxygen)] component in which the ether (ie, poly(ether diol)) functional group is derived from poly The carboxylic acid component of the condensation reaction is not derived from the amine. In one disclosed polyamine composition, an ether functional group can be present in at least a portion of the diamine and in at least a portion of the dicarboxylic acid. Suitable dicarboxylic acids include dicarboxylic acids of the PEG (poly(ethylene) glycol) source. Polycondensation processes are also disclosed to produce ether-containing polyamines. Fibers and fabrics (including knit, woven, and directly laid non-woven fabrics) having enhanced higher moisture retention/hydrophilicity compared to similar compositions without ether in the dicarboxylic acid component are also disclosed. The disclosed polyamines may comprise nylon and poly(ether diol) dicarboxylic acids, wherein the poly(ether diol) dicarboxylic acid has a number average molecular weight of ≥250 Da, such as ≥600 Da and ≥1500 Da and ≥2500 Da And ≥5000 Da. The moisture regain of the polyamine may range from ≥5 wt% to ≤35 wt%. Unless otherwise stated, the number average molecular weight is given in units of Daltons (Da). The disclosed polyamines are well suited for the preparation of hydrophilic polyamide compositions. Accordingly, the disclosure herein is also directed to improved synthetic polyamide (nylon) polymer compositions. The polyamines disclosed may comprise nylon and poly(ether diol) dicarboxylic acids and optionally polyetheramines. The disclosed compositions are suitable for use in the manufacture of yarns or fibers and textiles or fabrics or garments containing such yarns or fibers. The disclosed polyamines comprise nylon and poly(ether diol) dicarboxylic acid and may have a resurgence ranging from about 5% to about 35%, such as from about 10 to about 25%, such as from about 15% to about 20%. Rate (measured as described herein); all moisture regain values are by weight. This moisture regain can improve the handleability during subsequent processing of the polyamine compositions of the present invention. For example, polyamine can have an elongation at break of from 20% to 90% when spun into a yarn. As discussed herein, the polyamine composition can be an acid (anionic) or base (cationic) dyed polymer. In one embodiment, at least 85% of the polymer backbone (between the guanamine units) may comprise an aliphatic group. The nylons discussed herein may be, for example but not limited to, polyhexamethylene hexamethyleneamine (nylon 6,6), polyhexylamine (nylon 6) or a copolymer of any of these nylons. In one embodiment, the nylon can be nylon 6,6. The nylon may be present in the polyamine in an amount ranging from about 50% to 99% by weight. Poly(ether diol) dicarboxylic acid can be prepared by reacting a poly(ether diol) with an organic base (such as potassium t-butoxide) and an alkylating agent (such as ethyl bromoacetate) (but not limited to this method). Greenwald, R. B. et al.J. Med. Chem.
,1996
,39
, 424-431. This adds an ester functional group to the hydroxyl group of the poly(ether diol). The ester group is then saponified using a suitable aqueous base such as sodium hydroxide. The dicarboxylic acid product can be isolated by acidifying the mixture with a mineral acid such as aqueous hydrochloric acid and catalyzing with an organic solvent such as dichloromethane. The solution is then evaporated to form a concentrated solution and the polymer is precipitated by slowly adding the solution to a stirred antisolvent such as tert-butyl methyl ether. Alternatively, low molecular weight poly(ether diol) dicarboxylic acids (e.g., poly(ethylene glycol)) are commercially available from suppliers such as the Sigma-Aldrich company. Non-limiting examples of suitable poly(ether diol) dicarboxylic acids may include polypropylene glycol dicarboxylic acid, polytetramethylene dicarboxylic acid, polyethylene glycol (PEG), polypropylene glycol (PPG), and polytetramethylene glycol. Block copolymer of (PTMG) block, for example: (PEG)-b-(PPG); or (PEG)-b-(PPG)-b-(PEG); or (PPG)-b-(PEG )-b-(PPG). As discussed herein, poly(ether diol) dicarboxylic acids can be used in the polymerization of nylon monomers to form polyamines that can be spun into nylon yarns that exhibit excellent hydrophilicity. These properties can impart a highly desirable tactile aesthetic and wearing comfort to apparel products made from such yarns. Additionally, the poly(ether diol) dicarboxylic acid can be present in the polyamine and can have a plurality of molecular weights depending on the desired properties of the resulting polymer, including handleability as discussed herein. In one embodiment, the number average molecular weight of the poly(ether diol) dicarboxylic acid (Mn
, measured by Dalton Da) is at least 250 Da. In other aspects, the poly(ether diol) dicarboxylic acid may have a number average molecular weight of at least 600 Da or at least 1500 Da, or at least 2500 Da or even at least 5000 Da. Additionally, the poly(ether diol) dicarboxylic acid may be present in an amount ranging from about 1 wt.% to about 50 wt.% of the polydecylamine. In one aspect, the poly(ether diol) dicarboxylic acid can be present in an amount ranging from about 5 wt.% to about 25 wt.%, such as from about 8 wt.% to about 25 wt.%. In another embodiment, the poly(ether diol) dicarboxylic acid is present in an amount from about 8 wt.% to about 20 wt.%. The polyamines described herein comprise an aliphatic diamine. In one example, the diamine can be an aliphatic diamine containing from 6 to 12 carbon atoms. In one aspect, the diamine can be hexamethylenediamine. The portion of the diamine can be present in the polymer in an amount of substantially equal molar ratio of amine groups to the acid groups of the poly(ether diol) dicarboxylic acid. The polyamines described herein can have a variety of physical properties. In one embodiment, the polyamine can have from 25 to 130 amine end gram equivalents per 1000 kilograms of polymer. Additionally, the polyamine can have a relative viscosity ranging from about 20 to about 80. In another embodiment, the relative viscosity can be calculated based on the formic acid test method according to ASTM D789-86 known at the time of the application of the present invention by the United States Patent and Trademark Office. The disclosed polyamines can have a yellowness index [YI] of from about 25 to about 45. The disclosed polyamines can be characterized by one or more of the following: L* color coordinates from about 75 to about 85; a* color coordinates from about -5 to about 5 and b* color coordinates from about 5 to about 25 . The disclosed polyamines may further comprise one or more poly(ether diol) dicarboxylic acids as described above. In one embodiment, the number average molecular weight of the poly(ether diol) dicarboxylic acid (Mn
) can be ≥ 250 Daltons (Da), such as ≥500 Da, ≥600 Da and ≥1500 Da. In other aspects, the poly(ether diol) dicarboxylic acid Mn
Can be ≥ 2500 Da or even ≥ 5000 Da. The disclosed polyamines may further comprise one or more polyetheramines as described in published PCT application WO 2014/057363. The whiteness of each sample can be determined using a test method consistent with the CIE whiteness rating. The whiteness (W) and yellowness (Y) of the sample can be individually measured using the GRETAG MACBETH "COLOR EYE" reflective spectrophotometer. First, the CIELAB color coordinates L, a*, and b* are determined; and then, W and Y are calculated by means known in the art (see: ASTM Method E313-1996)Standard Practice for Calculating Whiteness and Yellowness Indices from Instrumentally Measured Color Coordinates
). See the details of this measurement.Color Technology in the Textile Industry
Second edition, published by Committee RA 36, AATCC (1997); see this volume: Harold and Hunter,Special Scales for White Colors
, pages 140-146 and references therein, the entire contents of each of which are hereby incorporated by reference. Further, the polyamine of the present invention may further comprise a catalyst. In one embodiment, the catalyst may be present in the polyamine in an amount ranging from 10 ppm to 1,000 ppm by weight. In another aspect, the catalyst can be present in an amount ranging from 10 ppm to 100 ppm by weight. Catalysts can include, but are not limited to, phosphoric acid, phosphorous acid, hypophosphoric acid, arylphosphonic acid, arylphosphinic acid, salts thereof, and mixtures thereof. In one embodiment, the catalyst may be sodium hypophosphite, manganese hypophosphite, sodium phenylphosphinate, sodium phenylphosphonate, potassium phenylphosphinate, potassium phenylphosphonate, hexamethylene diammonium. Diphenylphosphinate, potassium tolylphosphonate or a mixture thereof. In one aspect, the catalyst can be sodium hypophosphite. The disclosed polyamine and polyamine compositions can include "optical brighteners." The optical brightener can be provided in accordance with U.S. Patent Application Serial No. 20080090945 A1 assigned to INVISTA North America S.à. The whiteness appearance of the polyamine and polyamine compositions according to the embodiments disclosed herein can be improved by the addition of optical brighteners. The polyamines can exhibit permanent whiteness improvement and can be maintained via operations such as heat setting. In one embodiment, the optical brightener may be present in the polyamine in an amount ranging from 0.01 wt.% to 1 wt.%. In another embodiment, the improvement in whiteness appearance can be achieved by the addition of a delustering agent. The delustering agent can be titanium dioxide. Additionally, the polyamine compositions may contain antioxidant stabilizers or antimicrobial additives. Further, the polyamide composition may contain an antifoaming additive. In one embodiment, the antifoam additive may be present in the polyamine in an amount ranging from 1 ppm to 500 ppm by weight. The disclosed polyamines include intrinsically acid (anionic) dyeing, but can also be rendered alkaline by modifying the polymers or copolymers with cationic dye-sensing monomers copolymerized in the polymer ( Cation) of the dyed forms. This modification makes the composition particularly susceptible to alkali (cationic) dye coloration. Sodium 5-thioisophthalate is an example of the cationic dye-sensitive monomer. In yet another aspect, a process for producing a polyamine is disclosed, the process comprising contacting a diamine, a poly(ether diol) dicarboxylic acid with a nylon salt; forming a mixture; heating the mixture in a closed vessel to a sufficient extent The temperature at which the mixture is polymerized and the autogenous pressure; and the formation of polyamine. In yet another aspect, a process for producing a polyamine is disclosed, the process comprising contacting a diamine with a nylon salt; forming a mixture; heating the mixture in a closed vessel to a temperature sufficient to polymerize the mixture and autogenous pressure; The poly(ether diol) dicarboxylic acid is added to continue the process and form the desired polyamine. The process for producing the polyamine can further comprise providing the catalyst (including those discussed herein) to the mixture. The processes can further comprise providing an antifoaming additive to the mixture. The processes can further comprise providing an optical brightener to the mixture. The polyamide monomer of polyamine can be added in the form of a salt, an amino acid or an internal guanamine. The nylon monomer can be a nylon 6,6 salt and can comprise almost all of the polyamine (eg, 99 wt.%, 99.5 wt.%, 99.9 wt.% or greater) or can be between about 50 wt.% to An amount in the range of 95 wt.%, 96 wt.%, 97 wt.% or 98 wt.% is present in the polyamine. A variety of processing parameters can be used in the polymerization of the polyamines of the present invention, including temperature and pressure. The temperature can range from about 190 ° C to about 290 ° C and the autogenous pressure can range from about 250 psig to about 300 psig. Furthermore, the heating can be carried out under partial vacuum. Part of the vacuum obtained is governed by the design of the autoclave and the economic considerations of the process. The polymerization of the present invention can involve multiple continuous heating cycles. These cycles may individually include a heating temperature profile and a pressure profile. The objective is to maintain system flow by a combination of a temperature sufficient to melt and a sufficient dissolved water content. The continuous heating cycle may comprise: a first heating cycle (C1) over a period of 20 minutes to 40 minutes, an initial temperature between 170 ° C and 215 ° C and a termination temperature between 190 ° C and 230 ° C, pressure Between 130 psia and 300 psia; a second heating cycle (C2), which lasts between 20 minutes and 45 minutes, with an onset temperature between 190 ° C and 230 ° C and a termination temperature between 240 ° C and 260 ° C The pressure is between 130 psia and 300 psia; the third heating cycle (C3), which takes between 15 minutes and 45 minutes, the starting temperature is between 240 ° C and 260 ° C and the termination temperature is between 250 Between °C and 320 °C, the pressure is between 300 psia and atmospheric pressure; and the fourth heating cycle (C4), between 15 minutes and 80 minutes, the starting temperature is between 250 ° C and 320 ° C and terminates The temperature is between 250 ° C and 320 ° C and the pressure is between atmospheric pressure and about 200 mbar absolute vacuum. Finally, the polymer is extruded using methods well known in the art. The disclosed polyamine compositions are inherently acid soluble and optionally comprise a cationically dyeable polymer. The disclosed polyamine composition can be prepared by an autoclave process. The process can be initiated from a concentrated slurry prepared from an aqueous solution of a nylon salt, an amino acid or an internal amine or a mixture of, for example, a nylon 6,6 salt (the term slurry is also incorporated into the solution), and the concentrated slurry is supplied to the autoclave. container. Optionally, the slurry can be a thin slurry and become more concentrated by means of an evaporation step. The slurry can be prepared from aqueous solutions of monomers such as hexamethylenediamine and adipic acid in a manner known in the art. The autoclave vessel can then be heated to about 230 °C (or some other functional temperature) to increase the internal (autogenous) pressure. Delustering agent titanium dioxide (TiO)2
Injection into an autoclave and a monomer mixture as an aqueous dispersion. In one embodiment, an aqueous slurry of poly(ether diol) dicarboxylic acid and optionally polyetheramine can be injected into the mixture in the autoclave vessel together with an amount of a diamine such as hexamethylenediamine. To produce a substantially equimolar ratio of acid groups to amine groups. The mixture can then be heated in an autoclave to about 245 ° C (or some other functional temperature). While maintaining this or other desired temperature conditions, the autoclave pressure can be lowered to atmospheric pressure and the pressure is further reduced by applying a vacuum in a known manner to form a polyamine composition. The autoclave containing the polyamine composition was maintained at this temperature for about 30 minutes. This step can be followed by, for example, further heating the polyamine polymer composition to about 285 ° C in an autoclave. The polymer composition can be released from the autoclave by opening the crucible in the autoclave vessel and applying 4 bar to about 5 bar of dry nitrogen to allow the molten polyamine composition to flow out of the vessel as a ribbon. The strips can be cooled and quenched in a stream of water. Next, the tape of the polyamide polymer can be granulated by a known method and further cooled with water. In some embodiments, the polymer composition can be released from the autoclave vessel at the end of the recycle stage and allow the molten composition to flow out of the vessel in the form of a strip. In other embodiments, the polymer composition can be supplied directly to a polymer extrusion apparatus that is designed and operated to process the polymer melt. For example, the disclosed polymer compositions can be processed in a screw extruder, such as a twin screw extruder. In one embodiment, a quantity of a diamine (eg, hexamethylenediamine) may be added such that the total number of acids present is approximately equal to the total number of amine groups. The mixture can then be heated in an autoclave to about 245 ° C (or some other functional temperature) while maintaining the desired pressure. While maintaining this or other desired temperature conditions, the autoclave pressure can be lowered to atmospheric pressure and the pressure is further reduced by applying a vacuum in a known manner to form a polyamine composition. Poly(ether diol) dicarboxylic acid and optionally polyetheramine may be injected into the mixture during such heating periods and/or during pressure reduction. The autoclave containing the polyamine composition can be maintained at this temperature for about 30 minutes. This step can be followed by, for example, further heating the polyamine polymer composition to about 285 ° C in an autoclave. The polymer composition can be released from the autoclave by opening the crucible in the autoclave vessel and applying 4-5 bar of dry nitrogen and allowing the molten polyamine composition to flow out of the vessel as a ribbon. The strips can be cooled and quenched in a stream of water. Next, the tape of the polyamide polymer can be granulated by a known method and further cooled with water. The autoclave process described above can provide a polyamidamine composition having a formic acid process RV of from about 20 to about 80. In another embodiment, the autoclave process described above can provide a polyamidamine composition having a formic acid process RV of from about 38 to about 45. Optionally, the process can be modified to produce a polyamine composition having from about 25 to about 130 mole amine ends per 1000 kilograms of polymer by adding an excess of aqueous hexamethylenediamine to the nylon salt. Provided in an aqueous solution. The polymerization can be carried out in a continuous polymerization vessel. Examples of continuous aggregators are known to those skilled in the art, and one example is disclosed in WO 2014179048 to Micka and Poinsatte, the contents of which are hereby incorporated by reference herein. The composition may optionally be partially polymerized in an autoclave or a continuous polymerization vessel and subsequently completed in a solid phase polymerizer. Examples of solid phase aggregators are known to those skilled in the art and are by Yao and McAuley,Simulation of continuous solid-phase polymerization of nylon 6,6 (II): processes with moving bed level and changing particle properties
Chemical Engineering Science 56 (2001) 5327-5342. The composition can be prepared in an extruder as appropriate. The process can include separately or together feeding the reactants comprising the diacid and the diamine to the feed throat of the extruder. Alternatively, the method can include feeding the reactants to one or more auxiliary feed throats at one or more points located across the length of the extruder, wherein the extruder includes various zones, which can include a melt zone, a mixing zone, and Transport area. PCT/US16/61604 (Attorney Docket PI 4212) to Langrick and Hunt discloses polymerization in a screw extruder having multiple feed throats, and is incorporated herein by reference, as set forth in detail herein. The nylon polymers and copolyamides described herein can be inherently acid dyeable. In one embodiment, the number of free amine end groups (AEG) in the polymers is at least 25 moles per 1000 kilograms of nylon polymer. To allow the polymer to be more deeply acid dyed, an increased free amine end group content can be used. More deep acid dyed nylon polymers have an increased AEG content, for example an AEG content of at least 60 to 130 moles per 1000 kilograms of nylon polymer can be used. Furthermore, it should be noted that a masterbatch comprising a poly(ether diol) dicarboxylic acid and optionally a polyetheramine in an equivalent amount to the amine end of a suitable diacid (for example adipic acid) can be produced. This masterbatch can then be supplied to the autoclave process. In an alternative embodiment, the polyamine composition herein can be made by a masterbatch process using a poly(ether diol) dicarboxylic acid comprising dispersed in nylon (nylon 6,6 or nylon 6) Optionally in the form of a sheet or melt of polyetheramine. A flake or melt form is then added as a masterbatch containing nylon. In the examples, the poly(ether diol) dicarboxylic acid in the form of a sheet and optionally the masterbatch nylon sheet of the polyetheramine and nylon are melted. In the examples, a nylon sheet containing a poly(ether diol) dicarboxylic acid and optionally a polyether amine is melted and added to the nylon melt. In either case, the melt is forced from the extruder into a pump that pumps the polyamine composition into, for example, a pack for making the yarn and a spinneret. The nylon polymer and the copolyamine described herein can also be rendered in an alkaline dyed form, i.e., the alkali dye (also known as a cationic dye) can be perceived. The alkali dyeing compositions are produced from a polyamidamide polymer in which a cationic dye modifier is copolymerized in a polymer. The preparation of these cationic dye-modified polyamines is described in U.S. Patent No. 5,164,261, issued to to the entire entire entire entire entire entire entire In one embodiment, the polymer may be modified during polymerization with from 0.5 wt.% to 4 wt.% cationic dye modifier (eg, 5-thioisophthalic acid). Typically, a certain weight of sodium 5-thioisophthalate salt can be combined with a known amount of polyamine precursor salt in an autoclave using standard polymerization procedures known in the art. In one embodiment, the amount of cationic dye modifying agent present in the polymer can range from about 0.75 wt.% to about 3 wt.%, as determined by total sulfur analysis of the polymer. This amount of cationic dye modifier is reported as an equivalent sulfonate group. The sulfonate group concentration can be at least 25 moles per 1000 kilograms of polymer to about 150 moles per 1000 kilograms of polymer.Polyamide yarn
The polyamine compositions of the present invention are especially useful when spun into yarns. In one embodiment, the poly(ether diol) dicarboxylic acid and optionally the polyether amine can be provided to the polyamide composition, and thus are inherent to the yarn itself rather than applied to the fabric when forming the fabric. In one embodiment, the yarn exhibits improved hydrophilicity as measured by a plurality of water cores and moisture regain tests. The yarns produced from the polyamines described herein can be multifilament spun yarns in the form of low aspect yarns (LOY), partially oriented yarns (POY) or fully drawn yarns (FDY). The yarn can be a textured yarn made from a partially oriented yarn. Moreover, the yarn can be substantially continuous, i.e., formed from one or more continuous filaments. In other embodiments, the continuous filaments can be cut into staple fibers and the latter can be converted to continuous filaments by a spinning process to produce a continuous article or article comprising shorter fibers. These yarns can be used to make fabrics which in turn can be used to make garments. In embodiments, the disclosed polymers may be stored in beads or flakes at a relative humidity of 50% to 65% for one week and then melt spun into garment fibers without an intercalation drying step between storage and melt spinning. In one embodiment, the apparatus and method for spinning are disclosed in U.S. Patent No. 6,855,425, and similar techniques are similarly in the context of the polyamines prepared and described herein. Yarns made from the polyamines described herein can be particularly useful as textile yarns for apparel textile applications. For example, yarns having a yarn weight of 5 dtex to 300 dtex and a filament weight of 0.5 dtex to 7 dtex are desirable. In certain embodiments, the yarn comprises from 1 to 300 filaments. According to some embodiments, the yarn comprises from 3 to 150 filaments. The linear mass density of the fiber is given in units of dtex [1 dtex means 1 dtex and equals 1 g / 10,000 m yarn]. And the unit of 1 "tex" is equal to the linear mass density of 1 g / 1000 m yarn. According to some embodiments, the yarn has a DPF (dtex/filament) of from 0.5 to 2.5, such as from 1 to 1.5. Yarns made from the polyamines described herein may have a filament uniformity (expressed in Uster% (U%)) of 1.5% or less, more typically 1% or less. This uniformity is desirable for the yarn to have the high appearance uniformity required for apparel applications, and also to reduce yarn breakage in texturing, weaving, and knitting operations. Yarns made from the polyamines described herein can have an elongation at break of from 20% to 120%. According to some embodiments, the yarn has an elongation at break of from 20% to 90%. Typically, the yarn has a tenacity of from 25 cN/tex to 65 cN/tex, such as from 30 cN/tex to 45 cN/tex. These tensile properties are desirable for apparel textile applications. The breaking force is expressed in centiNewtons/tex [cN/tex]. In certain embodiments, the polyamide yarn may have a titanium dioxide content of less than 0.1 wt.%, and more typically less than 0.01 wt.%, such that the yarn gloss is clear or bright. In other embodiments, the polyamide yarn may have a titanium dioxide content of greater than 0.3 wt.% and or even greater than 2 wt.%, thereby rendering the yarn dull or dull. Titanium dioxide content between these ranges may also be used, for example from 0.1 wt.% to 0.3 wt.%. In a particular embodiment, the polyamide yarn can be prepared by using known melt spinning process techniques. By means of this technique, a granulated polyamide composition produced by using an autoclave process or a melt produced by a masterbatch process can have an optical brightener as set forth above and can be supplied to a spinning machine. The molten polymer is transferred up to the filter pack by a metering pump and extruded through a spinneret containing capillary ports of a selected shape to produce a desired filament cross-section at the spinning temperature. Such cross-sectional shapes are known in the art to include circular, non-circular, trilobal, hollow, and diabolo shapes. A typical hollow filament can be produced as disclosed in U.S. Patent No. 6,855,425. The spinning temperature can range, for example, from 270 ° C to 300 ° C. The filament bundles present from the spinnerette are cooled by treated quench air, treated with a spin finish (oil/water emulsion), optionally using interlaced jets, for example. In some embodiments, the continuous yarn thus obtained is cut and converted into staple fibers, which are then used to produce filaments or yarns by spinning or by hydroentanglement, needling, ultrasonic bonding, chemical bonding Nonwovens are formed by knots, heat bonding or the like. In the case of FDY, on-line processing on a spinning machine typically involves winding a number of turns around a set of goding rolls (feed rolls) sufficient to prevent slipping on the rolls and then transferring the yarn to On the other set of rolls (stretching rolls), the other set of rolls is rotated at a sufficient speed to stretch the yarn by a predetermined amount (stretch ratio). Finally, the process is continued by heating and sizing the yarn with a steam box and then winding at a speed of at least 3000 m/min, for example at least 4000 m/min, for example 4800 m/min or higher. Optionally, an alternative heat setting (or slack) method such as a heated roll can be used, and a set of guide rolls can be incorporated between the draw roll and the winder to control the tension as the yarn is set or relaxed. Moreover, the spinning oil and/or additional interlacing may be applied again prior to the final winding step, as appropriate. In the case of POY, the additional in-line processing typically involves only S-winding on two guide rolls rotating at the same speed, and then transferring the yarn to the high speed winder to at least 3000 m/min, for example at least 4000 Winding at a speed of m/min, for example 4800 m/min or higher. The use of S-wrap is beneficial for controlling tension, but it is not required. The POY can be used directly as a flat yarn for weaving or knitting, or as a raw material for texturing. The LOY spinning process is similar to POY, except that a winding speed of 1000 m/min or less is used. The low directional yarns are typically further processed via a second stage, such as a conventional draw-twist or stretch-winder. In one embodiment, the polyamine polymers disclosed herein are highly suitable for spinning into continuous filaments that can be concentrated to form multifilament yarns. Processes for spinning synthetic filaments into continuous filaments and forming multifilament yarns are known to those skilled in the art. Typically, successful spinning of filaments uses a spinneret having at least one single capillary port. The capillary port corresponds to each individual filament comprising a yarn. The cross-sectional shape sought for the end-of-filament filaments uses round and non-circular cross-section nozzle nozzles (or extruded nozzles). Typically, for a certain polymer flux G per capillary (eg, expressed in grams per minute), the following equation is applied:G = ρ ( Molten ) D 2 ( Capillary )
(π/4)v ( Extrusion )
Equation 1. In this equation, the ρ-based polymer melt density (for example, for molten nylon 6 at 6 °C, 6 is equal to 1.0 g/cm)3
), D is assumed to be the capillary diameter of a circular orifice (equal to twice the radius), and the rate of v is a filament. The extrusion rate is given by the following equation:v ( Extrusion ) = G
(4/πD 2 ( Capillary )
ρ( Molten )
Equation 2. In one embodiment, the polymer is extruded at an extrusion rate ranging from 20 cm/sec to 80 cm/sec. In another embodiment, the filaments that have just been extruded can be quenched by air conditioning in a known manner. In this step, individual filaments are cooled in a quench cabinet using side air venting of the air conditioner and concentrated and immersed into the yarn with primary oil oil as is known in the art. The yarn is conveyed upward by a feed roll onto a pair of draw rolls, wherein the yarn is elongated and oriented on the pair of draw rolls to form a drawn yarn which is guided to the yarn by a roll In the line stabilizer. This stabilizing device is common in the industry and is used herein as a yarn post-processing step as appropriate. Finally, the yarn is wound into a yarn package at a yarn speed ranging from 1000 m/min to 6500 m/min. The yarn RV (or the relative viscosity as determined by the formic acid method) is from about 20 to about 80. In an embodiment, the yarn is a drawn yarn having an elongation of from 22% to about 60%, a boiling water shrinkage of from 3% to about 10%, and a yarn tenacity of between 3 grams/denier (denier) ) to a range of about 7 grams per denier, and the RV of the yarn can vary and be sufficiently controlled to range from about 20 to about 80, such as from about 40 to about 60. Derivative parameters characterizing the superior properties of this yarn are referred to as yarn quality and reference is made to the product of the yarn tenacity (g/danny) and the square root of % elongation as in Equation 3. Yarn quality = toughness × (elongation)1/2
Equation 3. Yarn quality is an approximation of the "toughness" measure of the yarn. As is known to those skilled in the art, the area under the yarn load elongation curve is proportional to the work done by the elongate yarn. If, for example, the toughness is expressed in terms of force per unit of denier and the elongation is expressed as % change per unit length, the load elongation curve is a stress-strain curve. In this case, the area under the stress-strain curve extends the work or yarn toughness of the yarn. Yarn quality improvement provides garment polyamine yarns that are more acceptable in a variety of applications. Such applications may include, but are not limited to, warp knits, circular knits, seamless knitwear, knits, nonwovens, and light denim technical fabrics. In certain embodiments, the polyamide yarn has a different dyeing characteristic than an anionic dye or a cationic dye. These dyeing characteristics can be derived from different numbers of amine end groups. The concentration of the amine end group (AEG) affects the extent to which the anionic dye stains the polyamine. Alternatively or in addition, the polyamine may contain an anionic end group that can cationically dye the polyguanamine, such as a sulfonate or carboxylate end group. In certain embodiments, the polyamide yarn is dyed with a fiber reactive dye incorporating a vinylsulfonyl group and/or a beta-sulfate ethylsulfonyl group. The fiber-reactive dyes are known from U.S. Patent No. 5,810,890. In certain embodiments, the polyamide yarn is dyed by a fiber reactive dye incorporating a halogen derivative of a nitrogen heterocyclic group such as triazine, pyrimidine, and quinoxaline. Such fiber reactive dyes are described, for example, in U.S. Patent No. 6,869,453. In other embodiments, the filaments comprise an amine component of hexamethylenediamine. In other embodiments, the filaments comprise an amine component that is a mixture of hexamethylenediamine containing at least 20 wt.% methylpentamethylenediamine based on the total weight of the diamine. In still other embodiments, the polyamine can include nylon 6. The following test statements can be used to characterize various parameters as discussed herein. Yarn toughness and yarn elongation can be achieved using the INSTRON tensile test device (Instron Corp., Canton, Massachusetts, USA 02021) and constant crosshead speed according to ASTM method D 2256-80 (in the application of the invention to the US Patent and Trademark Office) When known). Toughness is expressed in centiNewtons per tex (cN/tex) or gram force/denier, and elongation % is an increase in sample length expressed as a percentage of the initial length under breaking load. The linear density uniformity of the yarn (also known as the Ubk % (U%) of the yarn) can be determined using a Type C Ubbel uniformity tester 3 known to those skilled in the art. The polymeric amine end can be measured by direct titration with a standardized perchloric acid solution of the weighed polymer sample absorbed in solution. The moisture regain of the polymer can be measured by the following method. A sample of the polymer (100 g) was dried under vacuum at 80 ° C for 18 hours. For example, the initial moisture content of this dried polymer sample was measured on a 1.9 g polymer using an Aquatrac (PET version (4 Digit); Brabender Messtechnik) at a 160 °C setting. A moisture content of less than 0.5 wt.% measured using this method is considered to indicate that the polymer has dried sufficiently. The dried sample was then immersed in demineralized water (500 g) at ambient temperature (20 ° C) without any agitation. After 48 hours, the sample (about 10 g) was removed and patted dry with absorbent tissue. A portion of the sample (about 5 g; the weight of the wet sample) was accurately weighed into a foil pan and placed in an oven at 80 ° C for 18 hours under vacuum. The tray was removed and placed in a desiccator for cooling and then weighed again (the weight remaining after drying). This procedure is repeated at intervals of (e.g., 72, 144, 190, and 220 hours) to 220 hours. The water absorption rate was determined by the following calculation:The moisture regain of the polymer is defined as the moisture uptake rate after 220 hours or until the sample has reached a moisture uptake equilibrium (defined as a weight change of no more than 1% over a 24 hour period), whichever is earlier. Therefore, if the water absorption balance has not been reached after 220 hours, the moisture regain rate is the water absorption rate at 220 hours. When the water absorption equilibrium is reached before 220 hours, the moisture regain is the average (average) of the water absorption rates of the first two consecutive measurements performed under equilibrium. Alternatively, the moisture regain can be measured by methods such as DIN 53814, which involves saturating the textile sample with deionized water for 2 hours at 20 ° C, removing the water by centrifugation at 4000 m/min, and measuring at 105 ° C. The weight change until the weight loss is no longer observed after drying. The water wicking rate of the fabric from the yarn construction can be measured by vertically immersing 1.8 ft (4.6 cm) of the bottom of the 1 mile (2.5 cm) wide strip of scrubbed fabric in deionized water. The height of the water drawn up the fabric is measured visually and the height over time is recorded. "Initial wicking rate" means the average wicking rate during the first two minutes of the wicking test. The "dry time %" test of fabrics or clothing can be used to characterize hydrophilic polyamide yarns, fabrics and clothing. These are also referred to as dry time % tests or "horizontal pull" measurements. Drying time % testing is performed using a balance and a computer; for example, a Mettler balance AE163 and a computer running the Mettler BalanceLink 3.0 program. The weight of a circular fabric sample having a diameter of 2 inches (5.1 cm) was obtained and recorded. 0.10 g of tap water was placed on the balance using an automatic pipette and the weight was recorded. The circular fabric sample was immediately centered on the water and then placed on the water. At this time (time = 0 minutes) and the total weight of the fabric and water was recorded every two minutes for the next 30 minutes. Calculate the % dry result for a given time according to the following formula: Dry % = 100 - [(Wtotal
- WFabric
) /WH2O
] × 100.Instance
The following examples are presented to provide those skilled in the art with a complete disclosure and description of how to implement the methods disclosed and claimed herein and how to use the compositions and compounds disclosed and claimed herein. Efforts have been made to ensure the accuracy of values (eg, amounts, temperatures, etc.), but some errors and deviations should be considered. Unless otherwise indicated: parts are parts by weight, temperature is expressed in ° C, and pressure is expressed in atmospheric pressure. Standard temperature and pressure are defined as 25 ° C and 1 atm. Materials used in the examples Number average molecular weight Mn
A poly(ethylene glycol) system of 2000 Daltons was obtained from commercial source Alfa Aesar (Product Code B22181). Hexamethylenediamine or HMD is commercially available from INVISTA Intermediates (offices in Wichita, Kansas and Wilmington, Delaware, USA). The term "poly(ether diol) dicarboxylic acid" as used herein means havingOne of the general chemical structures is poly(ethylene glycol) bis(carboxymethyl)ether, in which the n coefficient value. Number average molecular weight Mn
A poly(ether diol) dicarboxylic acid of 600 (referred to herein as Compound 2 in the examples of the present disclosure) is available from commercial source VWR International. The term "RE 2000" as used herein refers to ELASTAMINE®
RE-2000 amine; a commercial product available from Huntsman Corp. ELASTAMINE®
The RE-2000 amine is a water-soluble aliphatic polyether diamine derived from propylene oxide-terminated polyethylene glycol. Polyetheramines of this type are useful in a variety of polymers.nylon 66 salt
The term "nylon 66 salt" as used herein refers to a salt formed by an acid-base neutralization reaction between an amine group of at least one diamine and an acidic proton of a carboxylic acid group of at least one dicarboxylic acid. The dicarboxylic acid component of the salt is suitably at least one dicarboxylic acid of the formula (I): HO2
C-R1
-CO2
H, where R1
Represents a divalent aliphatic, cycloaliphatic or aromatic group or covalent bond. R1
Suitably it contains from 2 to 20 carbon atoms, for example from 2 to 12 carbon atoms, for example from 2 to 10 carbon atoms. R1
It may be a linear or branched (e.g., linear) alkyl group containing 2 to 12 carbon atoms, or 2 to 10 carbon atoms, for example 2, 4, 6 or 8 carbon atoms, unsubstituted extension Phenyl or unsubstituted cyclohexyl. Depending on the situation, R1
It may contain one or more ether groups. For example, R1
An alkyl group, for example a linear alkyl group, which contains 2 to 12 carbon atoms, or 2 to 10 carbon atoms, for example 2, 4, 6 or 8 carbon atoms. Specific examples of suitable dicarboxylic acids include hexane-1,6-dioic acid (adipate), octane-1,8-diacid (suberic acid), decane-1,10-diacid (癸二) Acid), dodecane-1,12-diacid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexane Alkane diacetic acid, 1,3-cyclohexane diacetic acid, benzene-1,2-dicarboxylic acid (phthalic acid), benzene-1,3-dicarboxylic acid (isophthalic acid), benzene-1,4-two Formic acid (terephthalic acid), 4,4'-oxybis(benzoic acid) and 2,6-naphthalene dicarboxylic acid. A dicarboxylic acid is preferably hexane-1,6-dioic acid (adipic acid). The diamine component of the salt is suitably at least one diamine of the formula (II): H2
N-R2
-NH2
, where R2
Represents a divalent aliphatic, cycloaliphatic or aromatic group. R2
Suitably it contains from 2 to 20 carbon atoms, for example from 4 to 12 carbon atoms, for example from 4 to 10 carbon atoms. R2
It may be a linear or branched (e.g., linear) alkyl group containing 4 to 12 carbon atoms, for example 4 to 10 carbon atoms, for example 4, 6 or 8 carbon atoms, and an unsubstituted phenyl group. Or unsubstituted Cyclohexyl. Depending on the situation, R2
It may contain one or more ether groups. For example, R2
An alkyl group, for example a linear alkyl group, which contains 4 to 12 carbon atoms, or 4 to 10 carbon atoms, for example 2, 4, 6 or 8 carbon atoms. Specific examples of suitable diamines include tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, octamethylenediamine, decamethylenediamine, dodecamethylenediamine, 2-methylpentamethylenediamine, 3-methylpentamethylenediamine, 2-methylhexamethylenediamine, 3-methylhexamethylenediamine, 2,5-dimethyl Hexamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 2,7-dimethyloctadecylene Diamine, 2,2,7,7-tetramethyloctamethylenediamine, 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexane Amine, 4,4'-diaminodicyclohexylmethane, benzene-1,2-diamine, benzene-1,3-diamine, and benzene-1,4-diamine. Preferred is a diamine hexamethylene diamine. For example, the salt dicarboxylic acid component can be at least one dicarboxylic acid of formula (I), wherein R1
An alkylene group having 2 to 12 carbon atoms, or 2 to 10 carbon atoms, for example 2, 4, 6 or 8 carbon atoms, and the diamine component of the salt may be at least one of the formula (II) Amine, where R2
An alkylene group containing 4 to 12 carbon atoms, or 4 to 10 carbon atoms, for example 2, 4, 6 or 8 carbon atoms. For example, the at least one dicarboxylic acid may be selected from the group consisting of hexane-1,6-dioic acid (adipic acid), octane-1,8-diacid (suberic acid), and decane-1,10-diacid (癸Diacid) and dodecane-1,12-diacid, and at least one diamine may be selected from the group consisting of tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, octamethylene diamine , decamethylene diamine, dodecamethylene diamine, 2-methyl pentamethylene diamine, 3-methyl pentamethylene diamine, 2-methyl hexamethylene diamine, 3 -methylhexamethylenediamine, 2,5-dimethylhexamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexa Methylene diamine, 2,7-dimethyl octamethylene diamine and 2,2,7,7-tetramethyl octamethylene diamine. Preferred salts include those in which the dicarboxylic acid component comprises hexane-1,6-dioic acid (adipic acid), octane-1,8-diacid (suberic acid), decane-1,10-diacid. One or more of (sebacic acid) and dodecane-1,12-diacid and the diamine component comprises tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, eight One or more of methylene diamine, decamethylene diamine, and dodecamethylene diamine. The eucalyptane salt is a naphthyl-1,6-diacid (adipate) and hexamethylenediamine to form a neutralizing salt ("nylon 66 salt").
實例 1
-聚 ( 乙二醇 ) 雙 ( 羧基甲基 ) 醚 ( 化合物 1) 之合成
所有玻璃器皿皆在使用之前進行烘箱乾燥。 將聚(乙二醇) (PEG，Mn
為2000道爾頓，50 g，25 mmol)與無水甲苯(250 ml)混合，升溫至30℃並攪拌直至固體完全溶解(在約30 min內)。貫穿以下製程將反應混合物保持於30℃下。經30 min添加第三丁醇鉀之溶液(75 ml，1M於第三丁醇中，75 mmol)。在整個添加過程中，觀察到最小溫度升高且無色溶液變為黃色。在添加完成時，將溶液攪拌1小時。經30 min以保持內部溫度低於45℃ (以控制放熱過程)之速率添加溴乙酸乙酯(8.3 ml, 75 mmol)。將所得混合物攪拌過夜。 此時，藉由蒸發樣品並使用氘化DMSO作為溶劑獲得1H NMR譜實施過程中檢查。反應完成定義為在δ 4.6 ppm不存在三重峰，其對應於PEG起始材料之羥基質子。 在減壓下蒸發混合物直至剩餘黏性油狀物。此黏著油狀物若冷卻則往往固化。 將上述黏性油狀物與氫氧化鈉水溶液(250 ml, 1M, 250 mmol)混合並於室溫下攪拌4小時。殘餘物穩定溶解以形成橙色溶液。將溶液用鹽酸水溶液(130 ml, 2M, 260 mmol)緩慢酸化(以控制放熱)直至pH小於4 (此時觀察到顏色變為幾乎無色)為止。將溶液冷卻至室溫，且隨後用二氯甲烷萃取兩次。將萃取物合併，用水洗滌，經無水硫酸鈉乾燥並過濾。在減壓下蒸發有機溶液直至剩餘小於50 ml體積為止。將殘餘物逐滴添加至第三丁基甲醚(300 ml)之燒杯中以形成灰白色沈澱。過濾並乾燥固體，以產生約46.3g產物二酸化合物1。 關於製備聚(醚二醇)二羧酸之另一方法，參見期刊論著Greenwald, R. B.等人，J. Med. Chem.
,1996
,39
, 424-431，430。 注意，若所獲得之產物產率較低，則水相可能尚未足夠酸化。若是此種情形，則可如上文所述藉由向水相中進一步添加稀鹽酸直至pH小於4及用二氯甲烷萃取來獲得額外產物。 表徵 產物可藉由NMR、FTIR及/或酸值來表徵。 在本揭示內容之後續實例中，化合物1 (源自Mn
2000道爾頓PEG且根據實例1)用於實例2中，而化合物2 (源自Mn
600道爾頓PEG)用於實例3至5及實例7中。該等聚(醚二醇)二羧酸可自相應PEG合成或自商業來源獲得。實例 2
-具有 8 wt.% 聚 ( 醚二醇 ) 二羧酸 ( 化合物 1) 之聚醯胺 鹽製備
向填充有氮並經氮吹掃之20升經攪拌及夾套溫度控制玻璃容器中添加4000 g水並將容器升溫至35℃。添加尼龍66鹽(3661 g, 13.96 mol)、實例1之化合物1 (280.8 g, 0.14 mol)及80 % (以重量計)六亞甲基二胺水溶液(16.3 g, 0.14 mol) (經計算以使化合物1之羧酸端平衡)並攪拌混合物直至溶解以產生粗略50 wt.%強度鹽溶液為止。在聚合時，此產生約3500 g聚合物。聚合
將上述鹽製備溶液添加至15升高壓釜中。靶向聚合物以相對於最終聚合物重量含有約8 wt.%化合物1。 對於聚合而言，不使用蒸發器，而是進行連續加熱循環0 (C0)以提供類似於蒸發器批料之鹽濃度之位置。基本上在「C0」中，將混合物加熱至約185℃並於137 psia下通風87分鐘之時段，同時將溫度升至約202℃，之後進入連續加熱循環(C1)。 用於連續加熱循環之製程係如下：C1 - T始於約202℃下，終於約220℃下，壓力達到265 psia定義C1結束，且耗用約18 min；C2 - 265 psia達22 min，T升至242℃溫度定義C2結束；連續加熱循環3 (C3) - 經35 min將壓力下降至14.5 psia (atm)，溫度升至275℃之最終溫度；連續加熱循環4 (C4) - 於大氣壓下6 min，施加400毫巴真空達30 min，隨後利用氮反向釋放至大氣並保持5 min。隨後在水浴中澆注聚合物。聚合物之特徵在於表1中所提供之結果。 表1 實例 3
-具有 12 wt.% 聚 ( 醚二醇 ) 二羧酸之聚醯胺 鹽製備
向填充有氮並經氮吹掃之20升經攪拌及夾套溫度控制玻璃容器中添加4000 g水並將容器升溫至35℃。添加尼龍66鹽(3423 g, 13.05 mol)、PEG (Mn
600)二羧酸(化合物2；439 g，0.73 mol)及80% (以重量計)六亞甲基二胺水溶液(85.0 g, 0.73 mol) (經計算以使PEG二酸之羧酸端平衡)並攪拌混合物直至溶解以產生粗略50 wt.%強度鹽溶液為止。在聚合時，此產生約3500 g聚合物。聚合
將上述鹽製備溶液添加至15升高壓釜中。靶向聚合物以相對於最終聚合物重量含有約12 wt.%化合物2。 對於聚合而言，不使用蒸發器，而是進行連續加熱循環0 (C0)以提供類似於蒸發器批料之鹽濃度之位置。基本上在「C0」中，將混合物加熱至約185℃並於137 psia下通風90分鐘之時段，同時將溫度升至約202℃，之後進入連續加熱循環1 (C1)。 用於連續加熱循環之製程係如下：C1 - T始於約202℃下且終於約220℃下，壓力達到265 psia定義C1結束；C2 - 265 psia保持24 min，T升至243℃溫度定義C2結束；連續加熱循環3 (C3) - 經25 min將壓力下降至14.5 psia (1 atm)，溫度升至274℃之最終溫度；及連續加熱循環4 (C4) - 於大氣壓下11 min，施加350毫巴真空達24 min，隨後利用氮反向釋放至大氣並保持6 min。隨後在水浴中澆注聚合物。聚合物之特徵在於表2中所提供之結果。 表2 實例 4
-具有 20 wt.% 聚 ( 醚二醇 ) 二羧酸之聚醯胺 鹽製備
向填充有氮並經氮吹掃之20升經攪拌及夾套溫度控制玻璃容器中添加4000 g水並將容器升溫至35℃。添加尼龍66鹽(3038 g, 11.58 mol)、PEG (Mn
600)二羧酸(化合物2；731.6 g，1.22 mol)及80% (以重量計)六亞甲基二胺水溶液(141.7g, 1.22 mol) (經計算以使PEG二酸之羧酸端平衡)並攪拌混合物直至溶解以產生粗略50 wt.%強度鹽溶液為止。在聚合時，此產生約3500 g聚合物。聚合
將上述鹽製備溶液添加至15升高壓釜中。靶向聚合物以相對於最終聚合物重量含有約20 wt.%化合物2。 對於聚合而言，不使用蒸發器。而是進行連續加熱循環0 (C0)以提供類似於蒸發器批料之鹽濃度之位置 基本上在「C0」中，將混合物加熱至約185℃並於137 psia下通風87分鐘之時段，同時將溫度升至約202℃，之後進入連續加熱循環1 (C1)。 用於連續加熱循環之製程係如下：C1 - T始於約202℃下且終於約220℃下，壓力達到265 psia定義C1結束，耗用約17 min；C2 - 保持265 psia達25 min，T升至243℃溫度定義C2結束；連續加熱循環3 (C3) - 經36 min將壓力下降至14.5 psia (1 atm)，溫度升至275℃之最終溫度；及連續加熱循環4 (C4) - 於大氣壓下5 min，350毫巴真空達30 min，隨後利用氮反向釋放至大氣並保持10 min。隨後在水浴中澆注聚合物。聚合物之特徵在於表3中所提供之結果。 表3 實例 5
–具有 8 wt.% 之利用聚 ( 醚二醇 ) 二羧酸之後期添加製得之聚 ( 醚二醇 ) 二羧酸的聚醯胺 鹽製備
向填充有氮且經氮吹掃之20升經攪拌及夾套溫度控制之玻璃容器中添加4000 g水並將容器升溫至35℃。尼龍66鹽(3615 g, 13.78 mol)，並攪拌混合物直至溶解以產生粗略50 wt.%強度鹽溶液為止。聚合
將上述鹽製備溶液添加至15升高壓釜中。 對於聚合而言，不使用蒸發器，而是進行連續加熱循環0 (C0)以提供類似於蒸發器批料之鹽濃度之位置。基本上在「C0」中，將混合物加熱至約185℃並於137 psia下通風90分鐘之時段，同時將溫度升至約202℃，之後進入連續加熱循環1 (C1)。 用於連續加熱循環之製程係如下：C1 – T始於約202℃且終於約220℃，壓力達到265 psia定義C1結束；C2 – 保持265 psia達24 min，T升至244℃溫度定義C2結束；連續加熱循環3 (C3) – 經25 min將壓力下降至14.5 psia (1 atm)，隨後注入PEG (Mn
600)二羧酸(化合物2；292.6 g, 0.49 mol)與80% (以重量計)六亞甲基二胺水溶液(71 g, 0.49 mol)之混合物並將溫度升至285℃之最終溫度；及連續加熱循環4 (C4) – 於大氣壓下11，施加350毫巴之真空達24 min，隨後利用氮反向釋放至大氣並保持6 min，靶向化合物2之後續添加以關於最終聚合物重量產生約8 wt.%化合物2。隨後在水浴中澆注聚合物。聚合物之特徵在於表4中所提供之結果。 表4 實例 6(a-g)
–熔融紡絲及纖維測試
使用與實例2至5中所述之程序及方法類似之程序及方法，製備七個聚醯胺測試樣品，熔融紡成纖維並經測試以測定其熔融紡絲行為及拉伸性質。下表5代表在組成及紡絲之前之量測水含量方面之該七個測試聚醯胺樣品。在表5中，化合物1係指使用2000道爾頓Mn
聚(乙二醇)且根據實例1製備之聚(醚二醇)二羧酸，而化合物2係指數目平均分子量為600道爾頓之聚(醚二醇)二羧酸。在實例6(f)中，N66聚醯胺中不存在添加劑，且此用作對照樣品。在實例6(g)中，N66聚醯胺中僅存在約10 wt.%之RE 2000組分。RE 2000係指ELASTAMINE®
RE-2000胺；一種可自Huntsman Corp購得之商業產品。 表5
使用單一螺桿擠出機(例如：Haake擠出機或等效物)及捲繞器(例如：Barmag SW 46或等效物)實施部分取向紗線(POY)紡絲。使用兩級Zinser拉伸-扭轉設定將POY紗線拉伸至全拉伸紗線(FDY)。使用Textechno Statimat M拉伸測試器測定紗線之機械性質。根據水保持能力方法第DIN 53814號測定水吸收率。 為改良紡絲穩定性，藉由使用噴絲嘴中之13個300-μm直徑孔獲得單一長絲細度。單一長絲纖度自2.75 dtex增加至5.07 dtex。使用下表6中所示之條件成功紡絲實例6(c)至6(g)樣品。將成功紡絲之POY紗線拉伸至25%之伸長率。對於每一樣品而言，將四條紗線組合並針織。 表6
在所有測試情形下，將幫浦旋轉速度維持於24 RPM且幫浦輸出量係1.2 cm3
。將捲繞器條件維持於4000 m/min捲繞速度、3980-3990 m/min Godet速度及1007 Traverse DH。 測定上述POY及FDY之機械性質且表示於下表7中。6(a)及6(b)紗線樣品不可用於測試，此乃因該等樣品之捲曲遇到一些技術困難。 表7
術語「tex」係纖維、紗線及絲線之線性質量密度之量度的單位且定義為以克表示之質量/1000米。分特(縮寫為「dtex」)係纖維、紗線及絲線之線性質量密度之量度的單位且定義為以克表示之質量/10,000米。用於韌度量測之單位「cN/tex」意指厘牛頓/tex。 藉由將紗線樣品填充至乾燥稱重容器中測定水吸收率，於20℃下向容器中填充去離子水。2小時後，藉由以4000 RPM離心去除水。於105℃下乾燥樣品直至不可再觀察到重量減少為止。水吸收率數據表示於下表8中。 表8 實例 7
–具有 8 wt.% 聚 ( 醚二醇 ) 二羧酸之聚醯胺之 24 升高壓釜批料製備 鹽製備
遵循實例2之程序，使用填充有氮且經氮吹掃之24升經攪拌及夾套溫度控制之玻璃容器實施多批次製備。每一批次之初始裝料量係約15,000 g，其包括約6,800 g尼龍66鹽、約7,500 g水、約549 g化合物2 [即，
自Mn
600道爾頓PEG製得之二羧酸]及約133 g 80% (以重量計)六亞甲基二胺水溶液。攪拌混合物直至溶解以產生粗略50 wt.%強度鹽溶液。在聚合時，每一批次產生約6,500 g聚合物。聚合
靶向聚合物以相對於最終聚合物重量含有約8 wt.%化合物2。對於聚合而言，採用如實例2至5中所述之溫度-壓力循環且不使用蒸發器。在完成聚合後，在水浴中澆注來自每一批次之聚合物。 使用實例7程序，依序運行總共16個24升高壓釜批次以產生足夠量之相對於最終聚合物重量含有約8 wt.%化合物2之所揭示聚合物。此多批次生產亦展現所揭示方法產生了在批間產生中品質一致之產品。所量測RV值介於37 – 43之間之範圍且平均值為約39 RV，且AEG值介於37 – 50之間之範圍且平均值為約44 AEG。 下表9給出根據本發明製備且表徵之聚合物產物之概述。 表9
代表性聚合物樣品係使用實例7之多批次製得之產品構成，且其顏色參數[如表9之最後列所列舉]經量測為L* = 78.83，a* =-0.69，b* = 10.42，且黃度指數[YI]為26.07。 如實例7之多批次中所產生之組合之聚合物材料可用於纖維紡絲及/或其他下游應用，如領域中通常已知。 儘管已具體闡述了本揭示內容之闡釋性實施例，但應理解，在不脫離本揭示內容之精神及範疇之情況下，各種其他修改對於熟習此項技術者將顯而易見並可以容易地做出。因此，本發明之申請專利範圍之範疇並不意欲限於本文所闡述之實例及說明，而是將申請專利範圍解釋為涵蓋本發明中存在之所有可專利的新穎性之所有特徵，包括可由熟習本揭示內容所屬之技術人員視為其等效物之所有特徵。 實施例 1. 一種聚醯胺，其包含以下物質之反應產物： a. 脂肪族二胺；及 b. 二酸，其中該二酸之至少一部分係聚(醚二醇)二羧酸。 2. 如實施例1之聚醯胺，其中該聚(醚二醇)二羧酸之數目平均分子量(Mn)為≥ 250道爾頓且≤ 2000道爾頓。 3. 如實施例2之聚醯胺，其中該聚(醚二醇)二羧酸係脂肪族二羧酸。 4. 如實施例1之聚醯胺，其特徵在於回潮率為≥ 5%至≤ 35%。 5. 如實施例1之聚醯胺，其中該脂肪族二胺係六亞甲基二胺。 6. 如實施例1之聚醯胺，其中含有芳香族部分之重複單元之數目選自由以下組成之群： a. ≤ 10 wt.%之重複單元；及 b. ≤ 5 wt.%之重複單元。 7. 如實施例1之聚醯胺，其係藉由在水存在下在≥ 1巴之壓力下之縮合反應來形成。 8. 如實施例1之聚醯胺，其特徵在於在紡成紗線時斷裂伸長率為20%至90%。 9. 如實施例1之聚醯胺，其中該聚(醚二醇)二羧酸係以基於該聚醯胺中二羧酸之總重量介於≥1重量%至≤50重量%範圍內之量存在。 10. 如實施例9之聚醯胺，其中該聚(醚二醇)二羧酸係以基於該聚醯胺中該二羧酸之總重量介於以重量計≥5 wt.%至≤25 wt.%範圍內之量存在。 11. 如實施例10之聚醯胺，其中該聚(醚二醇)二羧酸係以基於該聚醯胺中該二羧酸之總重量介於以重量計≥8 wt.%至≤20 wt.%範圍內之量存在。 12. 如實施例1之聚醯胺，其中共聚己二醯胺具有根據ASTM D789-86之甲酸測試≥20至≤80之相對黏度。 13. 如實施例1之聚醯胺，其中該共聚己二醯胺具有≥25莫耳至≤130莫耳胺端/1000公斤聚合物之胺端值。 14. 如實施例1之聚醯胺，其特徵在於選自以下中之至少一者： a. L*色坐標為≥75至≤85； b. a*色坐標為≥-5至≤5； c. b*色坐標為≥5至≤25；且 d. 黃度指數為≥25至≤45。 15. 如實施例1之聚醯胺，其進一步包含選自以下中之至少一者： a. 以重量計≥0.01 wt.%至≤2 wt.%之二氧化鈦；及 b. 以重量計0.01 wt.%至1 wt.%之光學增亮劑，其中該光學增亮劑並非二氧化鈦。 16. 一種共聚己二醯胺，其包含： a. 二酸，其中所有C-H鍵皆係飽和的； b. 脂肪族聚(醚二醇)二羧酸；及 c. 至少一種不含醚部分或芳香族部分之二胺； 其中該共聚己二醯胺之特徵在於基於該共聚己二醯胺之重量，50%至65%之相對濕度之空氣中之回潮率為≥5重量%且≤35重量%。 17. 一種產生共聚己二醯胺之方法，其包含： a. 使脂肪族二酸、聚(醚二醇)二羧酸、至少一種不含醚部分之二胺及視情況不含醚部分之尼龍鹽接觸，以形成混合物；及 b. 將該混合物加熱至足以聚合該混合物並形成共聚己二醯胺之溫度。 18. 一種自如實施例1至17中任一實施例之共聚己二醯胺製得之物件，該物件選自由以下組成之群： a. 纖維；及 b. 織物，其中該織物具有選自織造、針織及直接鋪列非織造中之至少一者之結構。 19. 如實施例18之物件，其包含織物，其中該織物於100℃下於1巴壓力下在水中浸沒10分鐘時損失其初始重量之小於10%。 20. 如實施例19之物件，其中該織物損失其初始重量之一部分，在50%至65%相對濕度之空氣中量測，其中所損失重量之部分選自由以下組成之值之群：≤9%、≤8%、≤7%、≤6%、≤5%、≤4%、≤3%、≤2%及≤1%。 Example 1 - Synthesis of Poly ( ethylene glycol ) bis ( carboxymethyl ) ether ( Compound 1) All glassware was oven dried prior to use. Poly (ethylene glycol) (PEG, M n 2000 daltons, 50 g, 25 mmol) and anhydrous toluene (250 ml) were mixed and warmed to 30 deg.] C with stirring until the solid was completely dissolved (in about 30 min) . The reaction mixture was maintained at 30 ° C throughout the following process. A solution of potassium butoxide (75 ml, 1 M in tert-butanol, 75 mmol) was added over 30 min. During the entire addition, a minimum temperature increase was observed and the colorless solution turned yellow. When the addition was completed, the solution was stirred for 1 hour. Ethyl bromoacetate (8.3 ml, 75 mmol) was added over 30 min maintaining the internal temperature below 45 °C (to control the exotherm). The resulting mixture was stirred overnight. At this time, the inspection during the implementation of 1H NMR spectrum was obtained by evaporating the sample and using deuterated DMSO as a solvent. The completion of the reaction was defined as the absence of a triplet at δ 4.6 ppm, which corresponds to the hydroxyl proton of the PEG starting material. The mixture was evaporated under reduced pressure until a viscous oil remained. This adhesive oil tends to solidify if it cools. The above viscous oil was mixed with aqueous sodium hydroxide (250 ml, 1 M, 250 mmol) and stirred at room temperature for 4 hours. The residue was dissolved stably to form an orange solution. The solution was slowly acidified with aqueous hydrochloric acid (130 ml, 2M, 260 mmol) (to control exotherm) until pH was less than 4 (where color was observed to be almost colorless). The solution was cooled to room temperature and then extracted twice with dichloromethane. The extracts were combined, washed with water, dried over anhydrous sodium sulfate and filtered. The organic solution was evaporated under reduced pressure until less than 50 ml of volume remained. The residue was added dropwise to a beaker of tert-butyl methyl ether (300 ml) to give an off-white precipitate. The solid was filtered and dried to yield about 46.3 g of product diacid compound 1. For another method of preparing poly(ether diol) dicarboxylic acids, see Journal of Greenwald, RB et al, J. Med. Chem. , 1996 , 39 , 424-431, 430. Note that if the yield of the product obtained is low, the aqueous phase may not have been sufficiently acidified. If this is the case, additional product can be obtained by further adding dilute hydrochloric acid to the aqueous phase until the pH is less than 4 and extracting with dichloromethane as described above. Characterization products can be characterized by NMR, FTIR and/or acid number. In subsequent instances of the present disclosure, the compound 1 (M n 2000 daltons derived from PEG and according to Example 1) used in Example 2, and compound 2 (from M n 600 dalton PEG) used in Example 3 To 5 and Example 7. The poly(ether diol) dicarboxylic acids can be synthesized from the corresponding PEG or obtained from commercial sources. Example 2 - Polyamine salt preparation with 8 wt.% poly ( ether diol ) dicarboxylic acid ( Compound 1) was added to a 20 liter stirred and jacketed temperature controlled glass vessel filled with nitrogen and purged with nitrogen. 4000 g of water and the vessel was warmed to 35 °C. Nylon 66 salt (3661 g, 13.96 mol), compound 1 of Example 1 (280.8 g, 0.14 mol) and 80% by weight aqueous solution of hexamethylenediamine (16.3 g, 0.14 mol) were added (calculated The carboxylic acid end of Compound 1 was equilibrated) and the mixture was stirred until dissolved to yield a crude 50 wt.% strength salt solution. This produces about 3500 g of polymer upon polymerization. Polymerization The above salt preparation solution was added to a 15-liter autoclave. The targeting polymer contained about 8 wt.% Compound 1 relative to the final polymer weight. For the polymerization, instead of using an evaporator, a continuous heating cycle of 0 (C0) is performed to provide a location similar to the salt concentration of the evaporator batch. Basically in "C0", the mixture was heated to about 185 ° C and ventilated at 137 psia for a period of 87 minutes while raising the temperature to about 202 ° C before entering a continuous heating cycle (C1). The process for continuous heating cycle is as follows: C1 - T starts at about 202 ° C, finally at about 220 ° C, the pressure reaches 265 psia, the end of C1 is defined, and it takes about 18 min; C2 - 265 psia reaches 22 min, T Rise to 242 ° C temperature definition C2 end; continuous heating cycle 3 (C3) - reduce the pressure to 14.5 psia (atm) after 35 min, the temperature rises to the final temperature of 275 ° C; continuous heating cycle 4 (C4) - at atmospheric pressure At 6 min, a vacuum of 400 mbar was applied for 30 min, followed by reverse release to the atmosphere with nitrogen for 5 min. The polymer is then poured in a water bath. The polymer is characterized by the results provided in Table 1. Table 1 Example 3 - Polyamine salt preparation with 12 wt.% poly ( ether diol ) dicarboxylic acid Add 4000 g of water to a 20 liter stirred and jacketed temperature controlled glass vessel filled with nitrogen and purged with nitrogen and The vessel was warmed to 35 °C. Nylon 66 salt (3423 g, 13.05 mol), PEG (M n 600) dicarboxylic acid (compound 2; 439 g, 0.73 mol) and 80% by weight aqueous solution of hexamethylenediamine (85.0 g, 0.73 mol) (calculated to balance the carboxylic acid end of the PEG diacid) and the mixture was stirred until dissolved to yield a crude 50 wt.% strength salt solution. This produces about 3500 g of polymer upon polymerization. Polymerization The above salt preparation solution was added to a 15-liter autoclave. The targeting polymer contained about 12 wt.% Compound 2 relative to the final polymer weight. For the polymerization, instead of using an evaporator, a continuous heating cycle of 0 (C0) is performed to provide a location similar to the salt concentration of the evaporator batch. Basically in "C0", the mixture was heated to about 185 ° C and ventilated at 137 psia for a period of 90 minutes while raising the temperature to about 202 ° C before entering continuous heating cycle 1 (C1). The process for the continuous heating cycle is as follows: C1 - T starts at about 202 ° C and finally at about 220 ° C, the pressure reaches 265 psia defines the end of C1; C2 - 265 psia remains for 24 min, T rises to 243 ° C temperature defines C2 End; continuous heating cycle 3 (C3) - the pressure is lowered to 14.5 psia (1 atm) in 25 min, the temperature is raised to the final temperature of 274 ° C; and the continuous heating cycle 4 (C4) - at atmospheric pressure for 11 min, 350 is applied The mbar vacuum was applied for 24 min and then released back to the atmosphere with nitrogen for 6 min. The polymer is then poured in a water bath. The polymer is characterized by the results provided in Table 2. Table 2 Example 4 - Polyamine salt preparation with 20 wt.% poly ( ether diol ) dicarboxylic acid Add 4000 g of water to a 20 liter stirred and jacketed temperature controlled glass vessel filled with nitrogen and purged with nitrogen and The vessel was warmed to 35 °C. Nylon 66 salt (3038 g, 11.58 mol), PEG (M n 600) dicarboxylic acid (compound 2; 731.6 g, 1.22 mol) and 80% by weight aqueous solution of hexamethylenediamine (141.7 g, 1.22 mol) (calculated to balance the carboxylic acid end of the PEG diacid) and the mixture was stirred until dissolved to yield a crude 50 wt.% strength salt solution. This produces about 3500 g of polymer upon polymerization. Polymerization The above salt preparation solution was added to a 15-liter autoclave. The targeting polymer contained about 20 wt.% Compound 2 relative to the weight of the final polymer. For polymerization, no evaporator is used. Instead, a continuous heating cycle of 0 (C0) is performed to provide a salt concentration similar to that of the evaporator batch substantially at "C0", the mixture is heated to about 185 ° C and ventilated at 137 psia for a period of 87 minutes while The temperature was raised to about 202 ° C and then entered into continuous heating cycle 1 (C1). The process for the continuous heating cycle is as follows: C1 - T starts at about 202 ° C and finally at about 220 ° C, the pressure reaches 265 psia defines the end of C1, which takes about 17 min; C2 - keeps 265 psia for 25 min, T Rise to 243 ° C temperature definition C2 end; continuous heating cycle 3 (C3) - reduce the pressure to 14.5 psia (1 atm) after 36 min, the temperature rises to the final temperature of 275 ° C; and continuous heating cycle 4 (C4) - At atmospheric pressure for 5 min, 350 mbar vacuum for 30 min, then reversed to the atmosphere with nitrogen for 10 min. The polymer is then poured in a water bath. The polymer is characterized by the results provided in Table 3. table 3 Example 5 - Polyamine salt with 8 wt.% of poly ( ether diol ) dicarboxylic acid prepared by subsequent addition of poly ( ether diol ) dicarboxylic acid to nitrogen-filled and nitrogen purged Add 20 g of water to a 20 liter stirred and jacketed temperature controlled glass vessel and raise the vessel to 35 °C. Nylon 66 salt (3615 g, 13.78 mol) and the mixture was stirred until dissolved to give a crude 50 wt.% strength salt solution. Polymerization The above salt preparation solution was added to a 15-liter autoclave. For the polymerization, instead of using an evaporator, a continuous heating cycle of 0 (C0) is performed to provide a location similar to the salt concentration of the evaporator batch. Basically in "C0", the mixture was heated to about 185 ° C and ventilated at 137 psia for a period of 90 minutes while raising the temperature to about 202 ° C before entering continuous heating cycle 1 (C1). The process for the continuous heating cycle is as follows: C1 - T starts at about 202 ° C and finally about 220 ° C, the pressure reaches 265 psia defines the end of C1; C2 - keeps 265 psia for 24 min, T rises to 244 ° C temperature defines C2 ends Continuous heating cycle 3 (C3) – pressure drop to 14.5 psia (1 atm) over 25 min followed by injection of PEG (M n 600) dicarboxylic acid (compound 2; 292.6 g, 0.49 mol) and 80% (by weight a mixture of hexamethylenediamine aqueous solution (71 g, 0.49 mol) and raising the temperature to a final temperature of 285 ° C; and continuous heating cycle 4 (C4) - at atmospheric pressure 11, applying a vacuum of 350 mbar After 24 min, then reverse release to the atmosphere with nitrogen for 6 min, subsequent addition of targeting compound 2 yielded about 8 wt.% of compound 2 with respect to the final polymer weight. The polymer is then poured in a water bath. The polymer is characterized by the results provided in Table 4. Table 4 Example 6 (ag) - Melt Spinning and Fiber Testing Seven polyamine test samples were prepared using procedures and methods similar to those described in Examples 2 through 5, melt spun into fibers and tested to determine their Melt spinning behavior and tensile properties. Table 5 below represents the seven test polyamine samples in terms of composition and water content before spinning. In Table 5, Compound 1 refers to a 2000 Dalton M n poly (ethylene glycol) and poly prepared according to Example 1 of (glycol ether) dicarboxylic acid, the compound 2 means the number average molecular weight of 600 Doyle Poly (ether diol) dicarboxylic acid. In Example 6(f), no additive was present in the N66 polydecylamine and this was used as a control sample. In Example 6(g), only about 10 wt.% of the RE 2000 component was present in the N66 polydecylamine. RE 2000 refers to ELASTAMINE ® RE-2000 amine; a commercial product available from Huntsman Corp. table 5 Partially oriented yarn (POY) spinning is carried out using a single screw extruder (eg, a Haake extruder or equivalent) and a winder (eg, Barmag SW 46 or equivalent). The POY yarn was drawn to a fully drawn yarn (FDY) using a two-stage Zinser stretch-twist setting. The mechanical properties of the yarn were determined using a Textechno Statimat M tensile tester. The water absorption rate was measured according to the water retention capacity method No. DIN 53814. To improve spinning stability, a single filament fineness was obtained by using 13 300-μm diameter holes in the spinneret. Single filament denier increased from 2.75 dtex to 5.07 dtex. The samples of Examples 6(c) to 6(g) were successfully spun using the conditions shown in Table 6 below. The successfully spun POY yarn was stretched to an elongation of 25%. For each sample, four yarns were combined and knitted. Table 6 In all test cases, the pump rotation speed was maintained at 24 RPM and the pump output was 1.2 cm 3 . The winder conditions were maintained at a winding speed of 4000 m/min, a Godet speed of 3980-3990 m/min and a 1007 Traverse DH. The mechanical properties of the above POY and FDY were measured and are shown in Table 7 below. 6(a) and 6(b) yarn samples are not available for testing because of the technical difficulties encountered in the curling of such samples. Table 7 The term "tex" is a unit of measure of the linear mass density of fibers, yarns and threads and is defined as mass in grams per 1000 meters. Ditute (abbreviated as "dtex") is a unit of measure of the linear mass density of fibers, yarns, and threads and is defined as mass in grams per 10,000 meters. The unit "cN/tex" used for toughness measurement means centiNewton/tex. The water absorption rate was measured by filling the yarn sample into a dry weighing container, and the container was filled with deionized water at 20 °C. After 2 hours, the water was removed by centrifugation at 4000 RPM. The sample was dried at 105 ° C until no further weight loss was observed. The water absorption rate data is shown in Table 8 below. Table 8 Example 7 - 24 liter autoclave batch preparation with 8 wt.% poly ( ether diol ) dicarboxylic acid. Preparation of salt Following the procedure of Example 2, using a nitrogen-filled nitrogen purged 24 liters Mixing and jacket temperature controlled glass containers were subjected to multiple batch preparations. Each batch of initial charging amount based about 15,000 g, including from about 6,800 g of nylon 66 salt, about 7,500 g of water, about 549 g of Compound 2 [i.e., obtained from the M n 600 manufactured by Dalton PEG dicarboxylic acid And about 133 g of 80% by weight aqueous solution of hexamethylenediamine. The mixture was stirred until dissolved to yield a crude 50 wt.% strength salt solution. At the time of polymerization, each batch produced approximately 6,500 g of polymer. The polymeric targeting polymer contained about 8 wt.% Compound 2 relative to the weight of the final polymer. For the polymerization, the temperature-pressure cycles as described in Examples 2 to 5 were employed and no evaporator was used. After the polymerization was completed, the polymer from each batch was poured in a water bath. A total of 16 24 liter autoclave batches were run sequentially using the procedure of Example 7 to produce a sufficient amount of the disclosed polymer containing about 8 wt.% Compound 2 relative to the final polymer weight. This multi-batch production also demonstrates that the disclosed method produces a consistent quality product in batch production. The measured RV values ranged from 37 to 43 with an average of about 39 RV and an AEG value in the range between 37 and 50 with an average of about 44 AEG. Table 9 below gives an overview of the polymer products prepared and characterized in accordance with the present invention. Table 9 Representative polymer samples were constructed using the products prepared in multiple batches of Example 7, and their color parameters [as listed in the last column of Table 9] were measured as L* = 78.83, a* = -0.69, b* = 10.42 and the yellowness index [YI] is 26.07. The combined polymeric materials produced in the multiple batches of Example 7 can be used in fiber spinning and/or other downstream applications, as is generally known in the art. Although the illustrative embodiments of the present disclosure have been specifically described, it is understood that various other modifications will be apparent to those skilled in the art without departing from the scope of the disclosure. Therefore, the scope of the invention is not intended to be limited to the examples and descriptions set forth herein, but the scope of the claims is intended to cover all features of all patentable novelity present in the invention, including All features of the equivalents are considered by those skilled in the art. Example 1. A polydecylamine comprising the reaction product of: a. an aliphatic diamine; and b. a diacid wherein at least a portion of the diacid is a poly(ether diol) dicarboxylic acid. 2. The polyamine of embodiment 1, wherein the poly(ether diol) dicarboxylic acid has a number average molecular weight (Mn) of > 250 Daltons and < 2000 Daltons. 3. The polyamine of Example 2, wherein the poly(ether diol) dicarboxylic acid is an aliphatic dicarboxylic acid. 4. Polyamine as in Example 1, characterized in that the moisture regain is from ≥5% to ≤35%. 5. The polyamine of embodiment 1, wherein the aliphatic diamine is hexamethylenediamine. 6. The polyamine of embodiment 1, wherein the number of repeating units containing an aromatic moiety is selected from the group consisting of: a. ≤ 10 wt.% of repeating units; and b. ≤ 5 wt.% of repeating units . 7. The polyamine of Example 1, which is formed by a condensation reaction in the presence of water at a pressure of ≥ 1 bar. 8. Polyamine according to embodiment 1, characterized in that the elongation at break is from 20% to 90% when spun into a yarn. 9. The polyamine of Embodiment 1, wherein the poly(ether diol) dicarboxylic acid is in a range of from ≥1% by weight to ≤50% by weight based on the total weight of the dicarboxylic acid in the polyamidamine The quantity exists. 10. The polyamine of embodiment 9, wherein the poly(ether diol) dicarboxylic acid is between ≥5 wt.% and ≤25 by weight based on the total weight of the dicarboxylic acid in the polyamine. The amount in the range of wt.% exists. 11. The polyamine of embodiment 10, wherein the poly(ether diol) dicarboxylic acid is between ≥8 wt.% and ≤20 by weight based on the total weight of the dicarboxylic acid in the polyamine. The amount in the range of wt.% exists. 12. The polyamine of Example 1, wherein the copolymerized hexamethyleneamine has a relative viscosity of from ≥20 to ≤80 according to the formic acid test of ASTM D789-86. 13. The polyamine of embodiment 1, wherein the copolymerized hexamethyleneamine has an amine end value of from ≥25 moles to ≤130 mole amine ends per 1000 kilograms of polymer. 14. Polyamine according to embodiment 1, characterized in that it is selected from at least one of the following: a. L* color coordinates are ≥75 to ≤85; b. a* color coordinates are ≥-5 to ≤5; c. b* color coordinates are ≥5 to ≤25; and d. yellowness index is ≥25 to ≤45. 15. The polyamine of embodiment 1, further comprising at least one selected from the group consisting of: a. TiO2 ≥ 0.01 wt.% to ≤ 2 wt.% by weight; and b. 0.01 wt% by weight .% to 1 wt.% optical brightener, wherein the optical brightener is not titanium dioxide. 16. A copolymerized hexamethyleneamine comprising: a. a diacid wherein all CH bonds are saturated; b. an aliphatic poly(ether diol) dicarboxylic acid; and c. at least one ether free moiety or a diamine of an aromatic moiety; wherein the copolymerized hexamethylenediamine is characterized in that the moisture regain in air of 50% to 65% relative humidity is ≥5% by weight and ≤35 weight based on the weight of the copolymerized hexamethylenediamine %. 17. A process for the production of copolymerized hexamethylenediamine comprising: a. an aliphatic diacid, a poly(ether diol) dicarboxylic acid, at least one diamine having no ether moiety, and optionally an ether moiety The nylon salt is contacted to form a mixture; and b. the mixture is heated to a temperature sufficient to polymerize the mixture and form a copolymerized hexamethyleneamine. An article obtained by copolymerizing hexamethylenediamine according to any one of embodiments 1 to 17, which is selected from the group consisting of: a. a fiber; and b. a fabric, wherein the fabric has a woven fabric selected from the group consisting of: , knitting, and directly arranging the structure of at least one of the nonwovens. 19. The article of embodiment 18, comprising a fabric, wherein the fabric loses less than 10% of its original weight when immersed in water at 100 bar at a pressure of 1 bar for 10 minutes. 20. The article of embodiment 19, wherein the fabric loses a portion of its original weight, measured in air at 50% to 65% relative humidity, wherein the portion of the lost weight is selected from the group consisting of: ≤9 %, ≤ 8%, ≤ 7%, ≤ 6%, ≤ 5%, ≤ 4%, ≤ 3%, ≤ 2%, and ≤ 1%.