TWI751100B - 生物衍生之聚胺基甲酸酯纖維 - Google Patents
生物衍生之聚胺基甲酸酯纖維 Download PDFInfo
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- TWI751100B TWI751100B TW104114180A TW104114180A TWI751100B TW I751100 B TWI751100 B TW I751100B TW 104114180 A TW104114180 A TW 104114180A TW 104114180 A TW104114180 A TW 104114180A TW I751100 B TWI751100 B TW I751100B
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Classifications
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- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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- D—TEXTILES; PAPER
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Abstract
本發明係關於一種製備彈性體纖維之方法,其包含:(a)提供聚合二醇組合物;其來自生物衍生之丁二醇;(b)使該聚合二醇組合物與至少一種二異氰酸酯接觸;(c)將封端二醇溶解於溶劑中以提供封端二醇溶液;(d)使該封端二醇溶液與增鏈劑組合物接觸;及(e)使該溶液紡絲以形成該彈性體纖維;其中該聚合二醇組合物包括至少一種使用來自生物衍生之1,4-丁二醇製備之聚合二醇。
Description
包括藉由溶液紡絲法製備之彈性纖維,諸如彈性人造纖維,包括衍生自聚合二醇之聚胺基甲酸酯組合物,其中聚合二醇已至少部分地衍生自生物衍生之1,4-丁二醇。
彈性纖維,諸如彈性人造纖維(spandex)(亦稱為彈力纖維(elastane))現今用於多種產品中。實例尤其包括針織襪、游泳衣、衣服、衛生產品(諸如尿布)。用於製備彈性纖維之聚胺基甲酸酯組合物具有一些侷限性,已導致諸如包括添加劑或改變聚合物組合物以防止降解且提高染色性等之修改。此等彈性纖維目前使用衍生自非可再生資源之聚合二醇或多元醇製備。
目前已知自可再生資源,亦即生物衍生之資源製備1,4-丁二醇之方法。需要將維持纖維之有利特性(諸如彈性)之新的彈性纖維,其為諸如服裝、游泳衣及針織襪之商業產品所需,同時允許包括生物衍生、可再生及/或可持續的來源。
本發明如申請專利範圍中所描述。
包括部分地衍生自可再生/可持續生物來源之彈性體纖維。本文中所描述之任何纖維可為單組分、雙組分或多組分纖維。為清楚起見,下文包括定義。
如本文所用,「溶劑」係指有機溶劑,諸如二甲基乙醯胺(DMAC)、二甲基甲醯胺(DMF)及N-甲基吡咯啶酮。
如本文所用之術語「溶液紡絲」包括自溶液製備纖維,其可為濕式紡絲或乾式紡絲方法,兩者皆為纖維生產之常用技術。
如本文所用之術語「多組分纖維」意謂具有至少兩個具有可辨別邊界的不同組分之獨立且相異的區域,亦即沿纖維長度連續的兩個或兩個以上不同組成之區域之纖維。與此相比而言為聚胺基甲酸酯或聚胺基甲酸酯脲摻合物,其中組合一種以上組合物以形成不含相異的且沿纖維之長度連續之邊界之纖維。術語「多組分纖維(multiple component fiber)」與「多組分纖維(multicomponent fiber)」在本文中同義且可互換使用。
術語「組成上不同」定義為包括不同聚合物、共聚物或摻合物之兩種或兩種以上組合物或具有一或多種不同添加劑之兩種或兩種以上組合物,其中組合物中所包括之聚合物可相同或不同。兩種比較組合物亦為「組成上不同」,其中其包括不同聚合物及不同添加劑。
術語「邊界(boundary/boundaries)」及「邊界區域」用於描述多組分纖維橫截面之不同區域之間的接觸點。此接觸點經「良好界定」,其中兩個區域之組合物之間存在最小重疊或無重疊。當重疊確實存在於兩個區域之間時,邊界區域將包括兩個區域之摻合區域。此摻合區域可為各別的均勻摻合部分,摻合邊界區域與其他兩個區域中之每一者之間具有獨立邊界。替代地,邊界區域可包括鄰近於第一區域之第一區域之較高濃度組合物至鄰近於第二區域之第二區域之較高
濃度組合物之梯度。
在一些實施例中為包括溶液紡絲聚胺基甲酸酯脲組合物之多組分或雙組分纖維,其亦稱為彈性人造纖維或彈力纖維。多組分纖維之不同區域之組合物包括不同聚胺基甲酸酯脲組合物,其中聚合物不同、添加劑不同或聚合物及添加劑皆不同。藉由提供多組分纖維,可實現多種不同益處。舉例而言,由於在纖維之僅一個區域中使用添加劑或較昂貴的聚胺基甲酸酯脲組合物而降低成本,同時維持相當之特性。此外,可藉由引入將與習知單組分彈性人造纖維紗不相容之新添加劑或經由組合兩種組合物之協同效應實現改善的纖維特性。
為了幫助確保彈性人造纖維在含於服裝中時對紗線加工、織物製造及消費者滿意度之適用性,可調整多種額外特性。彈性人造纖維組合物為此項技術中熟知的且可包括諸如Monroe Couper中所揭示者的可能變化。Handbook of Fiber Science and Technology:Volume III,High Technology Fibers Part A.Marcel Dekker,INC:1985,第51頁-第85頁。其一些實例列於本文中。
彈性人造纖維可含有消光劑(諸如TiO2)或另一種其他粒子,其具有不同於基礎纖維聚合物之折射率,含量為0.01-6重量%。當需要明亮或有光澤的外觀時,較低含量亦適用。隨著含量增加,紗線之表面摩擦力可能改變,可影響在加工期間纖維接觸表面之摩擦力。
如以每單位丹尼爾斷裂力之公克數量測之纖維斷裂強度(以公克/丹尼爾計之韌度)可視分子量及/或紡絲條件而定自0.7公克/丹尼爾調整至1.2公克/丹尼爾。
纖維之丹尼爾可基於所需織物構造而經製造為5-2000。5-30丹尼爾之彈性人造纖維紗可具有1與5之間的長絲支數,且30-2000丹尼爾的紗線可具有2至200之長絲支數。該纖維可視織物之所需最終用途而定以0.5%至100%含量用於任何種類之織物(編織物、經紗針織物或緯
紗針織物)中。
彈性人造纖維紗可單獨使用或其可與如由聯邦貿易委員會(Federal Trade Commission;FTC)公認之任何其他紗線(諸如適合於服裝最終用途之彼等紗線)合股、加撚、共插入或混雜。此包括(但不限於)由耐綸、聚酯、多組分聚酯或耐綸、棉、羊毛、黃麻、劍麻、助劑(help)、亞麻、竹子、聚丙烯、聚乙烯、聚氟碳化物、人造絲、任何種類之纖維素製品製成之纖維及丙烯酸系纖維。
彈性人造纖維可在製造過程期間具有施加至其之潤滑劑或整理劑以改進纖維之後續加工。整理劑可以0.5重量%至10重量%之量施用。
彈性人造纖維可含有添加劑來調整彈性人造纖維之初始顏色或防止或遮蔽在暴露於可起始聚合物降解之元素(諸如氯、煙、UV、NOx或燃燒氣體)之後的黃化效果。彈性人造纖維可經製成為具有40至160範圍內之「CIE」白度。
可用於製備纖維或長鏈合成聚合物之聚胺基甲酸酯脲組合物包括至少85重量%之嵌段聚胺基甲酸酯。通常,此等組合物包括聚合二醇或多元醇,該聚合二醇或多元醇與二異氰酸酯反應形成NCO封端預聚物(「封端二醇」),該預聚物接著溶解於適合溶劑(諸如二甲基乙醯胺、二甲基甲醯胺或N-甲基吡咯啶酮)中,且接著與雙官能增鏈劑反應。當增鏈劑為二醇時形成聚胺基甲酸酯(且可在無溶劑情況下製備)。當增鏈劑為二胺時形成聚胺基甲酸酯脲(聚胺基甲酸酯之子類)。在可紡絲成彈性人造纖維之聚胺基甲酸酯脲聚合物之製備中,藉由羥基端基與二異氰酸酯及一或多種二胺之連續反應延伸二醇。在各情況下,二醇必須經歷鏈延伸以提供具有必要特性(包括黏度)之聚合物。若需要,則二月桂酸二丁基錫、辛酸亞錫、無機酸、三級胺(諸如三
乙胺)、N,N'-二甲基哌嗪及其類似物及其他已知催化劑可用於協助封端步驟。
適合多元醇組分(亦稱為聚合二醇)包括數目平均分子量為約600至約3,500之聚醚二醇、聚碳酸酯二醇及聚酯二醇。可包括兩種或兩種以上多元醇之混合物或共聚物。多元醇組分合意地包括至少一種衍生自生物衍生之1,4-丁二醇之聚合物。
可在重組微生物中經由4-羥基丁酸鹽自丁二酸鹽或α-酮戊二酸鹽(亦稱為2-酮戊二酸鹽)合成1,4-丁二醇(BDO),重組微生物包括2-酮戊二酸脫羧酶或丁二醯基-CoA合成酶、丁二酸半醛脫氫酶、4-羥基丁酸脫氫酶、4-羥基丁酸-CoA轉移酶、4-羥基丁酸-CoA還原酶及乙醇脫氫酶。在此類重組微生物中,可使用丁二醯基-CoA合成酶將丁二酸鹽轉化成丁二醯基-CoA,隨後使用CoA依賴性丁二酸半醛脫氫酶將丁二醯基-CoA轉化成丁二醯基半醛。可使用4-羥基丁酸脫氫酶將丁二醯基半醛轉化成4-羥基丁酸鹽,隨後使用4-羥基丁酸-CoA轉移酶將4-羥基丁酸鹽轉化成4-羥基丁基-CoA,接著使用4-羥基丁酸-CoA還原酶轉化成4-羥基丁醛。可使用乙醇脫氫酶將4-羥基丁醛轉化成BDO。在一些實施例中,2-酮戊二酸脫羧酶用於將α-酮戊二酸鹽轉化成丁二醯基半醛,丁二醯基半醛可如上文所描述轉化成BDO。參見例如Yim,等人,Nat.Chem.Biol.,7:445-452(2011);及美國專利第8,067,214號。亦參見EP2690109 A1。應理解,以上步驟中之一或多個(例如,兩個、三個、四個、五個或六個)可使用分離或純化形式之相關酶(例如,自表現其之重組細胞分離或純化之酶)在活體外執行。在使用分離/純化酶執行的彼等步驟之前及/或之後在重組細胞中執行之步驟可藉由向重組細胞提供適當的酶受質來執行。
BDO可在酸催化劑存在下在高溫下脫水形成四氫呋喃(THF),接
著聚合形成聚THF(亦稱為聚(四亞甲基醚)二醇)。替代地,可如下文所描述共聚合THF。
可使用之聚醚多元醇之實例包括具有兩個或兩個以上羥基,來自環氧乙烷、環氧丙烷、氧雜環丁烷、四氫呋喃及3-甲基四氫呋喃之開環聚合及/或共聚合,或來自各分子中具有小於12個碳原子之多元醇(諸如二醇或二醇混合物)之縮聚之彼等二醇,諸如乙二醇、1,3-丙二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、新戊二醇、3-甲基-1,5-戊二醇、1,7-庚二醇、1,8-辛二醇、1,9-壬二醇、1,10-癸二醇及1,12-十二烷二醇。線性雙官能聚醚多元醇為較佳的,且分子量為約1,700至約2,100之聚(四亞甲基醚)二醇,諸如官能度為2之Terathane® 1800(Wichita之INVISTA,KS)為特定適合多元醇之一個實例。共聚物可包括聚(四亞甲基-共-伸乙基醚)二醇。
可使用之聚酯多元醇之實例包括具有兩個或兩個以上羥基,藉由脂族聚羧酸與各分子中具有不超過12個碳原子之低分子量多元醇或其混合物之縮聚產生的彼等酯二醇。適合聚羧酸之實例為丙二酸、丁二酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、十一烷二羧酸及十二烷二羧酸。用於製備聚酯多元醇之適合多元醇之實例為乙二醇、1,3-丙二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、新戊二醇、3-甲基-1,5-戊二醇、1,7-庚二醇、1,8-辛二醇、1,9-壬二醇、1,10-癸二醇及1,12-十二烷二醇。熔融溫度為約5℃至約50℃之線性雙官能聚酯多元醇為特定聚酯多元醇之一實例。
可使用之聚碳酸酯多元醇之實例包括具有兩個或兩個以上羥基,藉由光氣、氯甲酸酯、碳酸二烷基酯或碳酸二烯丙酯與各分子中具有不超過12個碳原子之低分子量脂族多元醇或其混合物之縮聚產生的彼等碳酸酯二醇。用於製備聚碳酸酯多元醇之適合多元醇之實例為二乙二醇、1,3-丙二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、新戊
二醇、3-甲基-1,5-戊二醇、1,7-庚二醇、1,8-辛二醇、1,9-壬二醇、1,10-癸二醇及1,12-十二烷二醇。熔融溫度為約5℃至約50℃之線性雙官能聚碳酸酯多元醇為特定聚碳酸酯多元醇之一實例。
二異氰酸酯組分亦可包括單一二異氰酸酯或不同二異氰酸酯之混合物,該混合物包括含有4,4'-亞甲基雙(異氰酸苯酯)及2,4'-亞甲基雙(異氰酸苯酯)之二苯基甲烷二異氰酸酯(MDI)之異構體混合物。可包括任何適合的芳族或脂族二異氰酸酯。可使用之二異氰酸酯之實例包括(但不限於)1-異氰酸酯基-4-[(4-異氰酸酯基苯基)甲基]苯、1-異氰酸酯基-2-[(4-氰酸酯基苯基)甲基]苯、雙(4-異氰酸酯基環己基)甲烷、5-異氰酸酯基-1-(異氰酸酯基甲基)-1,3,3-三甲基環己烷、1,3-二異氰酸酯基-4-甲基-苯、2,2'-甲苯二異氰酸酯、2,4'-甲苯二異氰酸酯及其混合物。特定聚異氰酸酯組分之實例包括Mondur® ML(Bayer)、Lupranate® MI(BASF)及Isonate® 50 O,P'(Dow Chemical)及其組合。
增鏈劑可為水或用於聚胺基甲酸酯脲之二胺增鏈劑。視聚胺基甲酸酯脲及所得纖維之所需特性而定,可包括不同增鏈劑之組合。適合二胺增鏈劑之實例包括:肼;1,2-乙二胺;1,4-丁二胺;1,2-丁二胺;1,3-丁二胺;1,3-二胺基-2,2-二甲基丁烷;1,6-己二胺;1,12-十二烷二胺;1,2-丙二胺;1,3-丙二胺;2-甲基-1,5-戊二胺;1-胺基-3,3,5-三甲基-5-胺甲基環己烷;2,4-二胺基-1-甲基環己烷;N-甲胺基-雙(3-丙胺);1,2-環己二胺;1,4-環己二胺;4,4'-亞甲基-雙(環己胺);異佛爾酮二胺;2,2-二甲基-1,3-丙二胺;間四甲基二甲苯二胺;1,3-二胺基-4-甲基環己烷;1,3-環己烷-二胺;1,1-亞甲基-雙(4,4'-二胺基己烷);3-胺甲基-3,5,5-三甲基環己烷;1,3-戊二胺(1,3-二胺基戊烷);間二甲苯二胺;及Jeffamine®(Texaco)。
當需要聚胺基甲酸酯時,增鏈劑為二醇。可使用之此類二醇之實例包括(但不限於)乙二醇、1,3-丙二醇、1,2-丙二醇、3-甲基-1,5-戊
二醇、2,2-二甲基-1,3-三亞甲基二醇、2,2,4-三甲基-1,5-戊二醇、2-甲基-2-乙基-1,3-丙二醇、1,4-雙(羥基乙氧基)苯及1,4-丁二醇及其混合物。
可視情況包括單官能醇或單官能二烷基胺阻斷劑以控制聚合物之分子量。亦可包括一或多種單官能醇與一或多種單官能二烷基胺之摻合物。
適用於本發明之單官能醇之實例包括至少一個選自由以下組成之群的成員:具有1至18個碳之脂族及環脂族一級醇及二級醇;酚;經取代之酚;分子量小於約750(包括分子量小於500)之乙氧基化烷基酚及乙氧基化脂肪醇;羥胺;經羥甲基及羥乙基取代之三級胺;經羥甲基及羥乙基取代之雜環化合物及其組合,包括糠醇、四氫糠醇、N-(2-羥乙基)丁二醯亞胺、4-(2-羥乙基)嗎啉、甲醇、乙醇、丁醇、新戊醇、己醇、環己醇、環己烷甲醇、苄醇、辛醇、十八醇、N,N-二乙基羥胺、2-(二乙胺基)乙醇、2-二甲胺基乙醇及4-哌啶乙醇及其組合。
適合單官能二烷基胺阻斷劑之實例包括:N,N-二乙胺、N-乙基-N-丙胺、N,N-二異丙胺、N-第三丁基-N-甲胺、N-第三丁基-N-苄胺、N,N-二環己胺、N-乙基-N-異丙胺、N-第三丁基-N-異丙胺、N-異丙基-N-環己胺、N-乙基-N-環己胺、N,N-二乙醇胺及2,2,6,6-四甲基哌啶。
適用於與本文中所描述之纖維組合之其他聚合物包括可溶性或可以微粒形式包括之其他聚合物。可溶性聚合物可溶解於聚胺基甲酸酯脲溶液中或與溶液紡絲聚胺基甲酸酯脲組合物共擠出。共擠出之結果可為具有並列同心外鞘-纖芯或偏心外鞘-纖芯橫截面之雙組分或多組分纖維,其中一個組分為聚胺基甲酸酯脲溶液且另一組分含有另一種聚合物。其他可溶性聚合物之實例尤其包括聚胺基甲酸酯(如上文所描述)、聚醯胺、丙烯酸聚合物及芳族聚醯胺。
適用於本發明之多組分及/或雙組分纖維之其他聚合物包括以微粒形式包括之其他半結晶不可溶聚合物。有用的聚醯胺包括耐綸6、耐綸6/6、耐綸10、耐綸12、耐綸6/10及耐綸6/12。有用的聚烯烴包括由C2至C20單體製備之聚合物。此包括共聚物及三元共聚物,諸如乙烯-丙烯共聚物。有用的聚烯烴共聚物之實例揭示於Datta等人之美國專利第6,867,260號中,該專利以引用的方式併入本文中。
各種不同橫截面適用於本發明之一些實施例。此等橫截面包括單組分(其可為不同聚合物之摻合物)、雙組分或多組分同心或偏心外鞘-纖芯及並列的雙組分或多組分。
當提供外鞘-纖芯或並列橫截面時,其在至少兩種組成上不同的聚胺基甲酸酯脲組合物之間包括邊界區域。該邊界在此等圖形中之每一者中呈現為定義明確的邊界,但該邊界可包括摻合區域。當邊界包括摻合區域時,邊界自身為獨特區域,其為第一與第二(或第三、第四等)區域之組合物之摻合物。此摻合物可為均質摻合物或可包括第一區域至第二區域之濃度梯度。
以下列舉可視情況包括於聚胺基甲酸酯脲組合物中之添加劑之類別。包括例示性及非限制性清單。然而,額外添加劑為此項技術中熟知的。實例包括:抗氧化劑、UV穩定劑、著色劑、顏料、交聯劑、相變材料(固體石臘)、抗微生物劑、礦物(亦即,銅)、微囊封添加劑(亦即,真蘆薈(aloe vera)、維生素E凝膠、真蘆薈、海帶、菸鹼、咖啡鹼、香料或香精)、奈米粒子(亦即,二氧化矽或碳)、奈米黏土、碳酸鈣、滑石、阻燃劑、抗黏劑、抗氯降解添加劑、維生素、藥物、芳香劑、導電添加劑、染色及/或染料輔助試劑(諸如四級銨鹽)。可添加至聚胺基甲酸酯脲組合物之其他添加劑包括助黏劑、抗靜電
劑、抗蠕變劑、光學增亮劑、聚結劑、導電添加劑、發光添加劑、潤滑劑、有機及無機填充劑、防腐劑、調質劑、熱變色添加劑、驅蟲劑及潤濕劑、穩定劑(受阻酚、氧化鋅、受阻胺)、助滑劑(聚矽氧油)及其組合。
添加劑可提供一或多種有利特性,包括:染色性、疏水性(亦即,聚四氟乙烯(PTFE))、親水性(亦即,纖維素)、摩擦控制、抗氯性、抗降解性(亦即,抗氧化劑)、黏著性及/或可熔性(亦即,黏著劑及助黏劑)、阻燃性、抗微生物特性(銀、銅、銨鹽)、障壁、導電性(碳黑)、拉伸特性、顏色、發光、可循環性、可生物降解性、芳香、黏性控制(亦即,金屬硬脂酸鹽)、觸覺特性、定形能力、熱調節(亦即,相變材料)、營養品、消光劑(諸如二氧化鈦)、穩定劑(諸如水滑石)、碳鈣鎂礦與水菱鎂礦之混合物、UV屏蔽劑及其組合。
雙組分彈性人造纖維亦可藉由分離毛細管以形成獨立長絲,其隨後聚結以形成單一纖維來製備。
藉由來自具有習知胺基甲酸酯聚合物溶劑(例如DMAc)之溶液的聚胺基甲酸酯-脲聚合物之溶液紡絲(濕式紡絲或乾式紡絲)產生一些實施例之纖維。聚胺基甲酸酯脲聚合物溶液可包括上文所描述之組合物或添加劑中之任一者。藉由使有機二異氰酸酯與適當二醇以1.6至2.3、較佳1.8至2.0範圍內之二異氰酸酯與二醇之莫耳比反應以產生「封端二醇」來製備聚合物。接著使封端二醇與二胺增鏈劑之混合物反應。在所得聚合物中,軟鏈段為聚合物鏈之聚醚/胺基甲酸酯部分。此等軟鏈段展現小於60℃之熔融溫度。硬鏈段為聚合物鏈之聚胺基甲酸酯/脲部分;此等硬鏈段具有高於200℃之熔融溫度。硬鏈段相當於聚合物總重量之5.5至9%,較佳6%至7.5%。
在製備纖維之一個實施例中,經由分配板及孔之所需配置來計
量含有30-40%聚合物固體之聚合物溶液以形成長絲。擠出之長絲藉由以下步驟乾燥:在300℃-400℃下引入熱惰性氣體且氣體:聚合物質量比為至少10:1,且以至少400公尺/分鐘(較佳至少600m/min)之速度牽拉且接著以至少500公尺/分鐘(較佳至少750m/min)之速度捲繞。標準方法條件為此項技術中熟知的。
由根據本發明製得之彈性纖維形成之紗線一般具有至少0.6cN/dtex斷裂強度、至少400%斷裂伸長率、至少27mg/dtex之在300%伸長率下的卸載模數。
根據ASTM D 2731-72之通用方法量測彈性人造纖維之強度及彈性特性。就報導之實例而言,使具有5cm標距之彈性人造纖維長絲在50公分/分鐘之恆定伸長率下在0%與300%伸長率之間循環。模數確定為在第一次循環時在100%(M100)及200%(M200)伸長率下之力且以公克報導。在第五次循環時在200%伸長率下測定卸載模數(U200)且以公克報導。在第六次延伸循環時量測斷裂伸長率百分比及斷裂力。
如第五次卸載曲線返回實質上零應力時所處之點指示,將定形百分比確定為在第五次循環與第六次循環之間剩餘之伸長率。在已對樣品進行五次0-300%伸長/鬆弛循環之後30秒時量測定形百分比。接著以定形%=100(Lf-Lo)/Lo計算該定形百分比,其中Lo及Lf為五次伸長/鬆弛循環之前(Lo)及之後(Lf)當不用拉力保持筆直時的長絲(紗線)長度。
藉由以下實例更充分展示本發明之特徵及優點,該等實例係出於說明之目的提供且不解釋為以任何方式限制本發明。
雖然已描述目前咸信為本發明之較佳實施例,但熟習此項技術者應認識到,可在不背離本發明之精神的情況下對其進行改變及修改,且意欲將所有此類改變及修改包括為屬於本發明之真實範疇內。
Claims (12)
- 一種製備彈性體纖維之方法,其包含:(a)提供聚合二醇組合物;(b)使該聚合二醇組合物與至少一種二異氰酸酯接觸以提供封端二醇;(c)將該封端二醇溶解於溶劑中以提供封端二醇溶液;(d)使該封端二醇溶液與增鏈劑組合物接觸;及(e)使該溶液紡絲以形成該彈性體纖維;其中該聚合二醇組合物包括至少一種使用生物衍生之1,4-丁二醇製備之聚合二醇,該生物衍生之1,4-丁二醇係由重組微生物獲得。
- 如請求項1之方法,其中該彈性體纖維為彈性人造纖維(spandex)。
- 如請求項1之方法,其中將該生物衍生之1,4-丁二醇轉化成四氫呋喃,隨後聚合形成聚合二醇。
- 如請求項3之方法,其中該聚合二醇為四氫呋喃與至少一個由以下組成之群的成員之共聚物:環氧乙烷、環氧丙烷、氧雜環丁烷、3-甲基四氫呋喃及其組合。
- 如請求項1之方法,其中該二異氰酸酯包括至少一種選自由以下組成之群的二異氰酸酯:4,4'-亞甲基雙(異氰酸苯酯)、2,4'-亞甲基雙(異氰酸苯酯)1-異氰酸酯基-4-[(4-異氰酸酯基苯基)甲基]苯、1-異氰酸酯基-2-[(4-氰酸酯基苯基)甲基]苯、雙(4-異氰酸酯基環己基)甲烷、5-異氰酸酯基-1-(異氰酸酯基甲基)-1,3,3-三甲基環己烷、1,3-二異氰酸酯基-4-甲基-苯、2,2'-甲苯二異氰酸酯、2,4'-甲苯二異氰酸酯及其混合物。
- 如請求項1之方法,其中該增鏈劑組合物包括至少一種二醇或二胺增鏈劑。
- 如請求項1之方法,其中該增鏈劑組合物包括至少一種選自由以下組成之群的二胺增鏈劑:肼;1,2-乙二胺;1,4-丁二胺;1,2-丁二胺;1,3-丁二胺;1,3-二胺基-2,2-二甲基丁烷;1,6-己二胺;1,12-十二烷二胺;1,2-丙二胺;1,3-丙二胺;2-甲基-1,5-戊二胺;1-胺基-3,3,5-三甲基-5-胺甲基環己烷;2,4-二胺基-1-甲基環己烷;N-甲胺基-雙(3-丙胺);1,2-環己二胺;1,4-環己二胺;4,4'-亞甲基-雙(環己胺);異佛爾酮二胺;2,2-二甲基-1,3-丙二胺;間四甲基二甲苯二胺;1,3-二胺基-4-甲基環己烷;1,3-環己烷-二胺;1,1-亞甲基-雙(4,4'-二胺基己烷);3-胺甲基-3,5,5-三甲基環己烷;1,3-戊二胺(1,3-二胺基戊烷);間二甲苯二胺及其組合。
- 如請求項1之方法,其中該溶液進一步包含阻斷劑。
- 如請求項1之方法,其中該溶液進一步包含至少一種選自由以下組成之群的添加劑:抗氧化劑、UV穩定劑、著色劑、顏料、交聯劑、相變材料、抗微生物劑、礦物、微囊封添加劑、奈米粒子、奈米黏土、碳酸鈣、滑石、阻燃劑、抗黏添加劑、抗氯降解添加劑、維生素、藥物、芳香劑、導電添加劑、染色及/或染料輔助試劑及其組合。
- 如請求項1之方法,其中該溶液進一步包含選自由以下組成之群的添加劑:助黏劑、抗靜電劑、抗蠕變劑、光學增亮劑、聚結劑、導電添加劑、發光添加劑、潤滑劑、有機及無機填充劑、防腐劑、調質劑、熱變色添加劑、驅蟲劑及潤濕劑、穩定劑、助滑劑及其組合。
- 如請求項1之方法,其中該溶液進一步包含提供選自由以下組成 之群的特性之添加劑:染色性、疏水性、親水性、摩擦控制、抗氯性、抗降解性、黏著性及/或可熔性、阻燃性、抗微生物特性、障壁、導電性、拉伸特性、顏色、發光、可循環性、可生物降解性、芳香、黏性控制、觸覺特性、定形能力、熱調節、營養品、諸如二氧化鈦之消光劑、諸如水滑石之穩定劑、碳鈣鎂礦與水菱鎂礦之混合物、UV屏蔽劑及其組合。
- 如請求項1之方法,其中該彈性體纖維具有至少400%之斷裂伸長率。
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- 2015-05-05 US US15/308,480 patent/US10883198B2/en active Active
- 2015-05-05 KR KR1020167032215A patent/KR102381226B1/ko active Active
- 2015-05-05 BR BR112016025833-9A patent/BR112016025833B1/pt active IP Right Grant
- 2015-05-05 CN CN201580036735.2A patent/CN106605014B/zh active Active
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- 2015-05-05 EP EP15789550.9A patent/EP3140439B8/en active Active
- 2015-05-05 JP JP2016567040A patent/JP7211695B2/ja active Active
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Also Published As
| Publication number | Publication date |
|---|---|
| WO2015171631A1 (en) | 2015-11-12 |
| EP3140439A4 (en) | 2017-11-29 |
| BR112016025833A2 (pt) | 2018-01-16 |
| TW201600532A (zh) | 2016-01-01 |
| JP2017519121A (ja) | 2017-07-13 |
| EP3140439B8 (en) | 2025-07-09 |
| CN106605014A (zh) | 2017-04-26 |
| KR20160143845A (ko) | 2016-12-14 |
| CN106605014B (zh) | 2021-03-12 |
| US10883198B2 (en) | 2021-01-05 |
| JP7211695B2 (ja) | 2023-01-24 |
| US20170051436A1 (en) | 2017-02-23 |
| KR102381226B1 (ko) | 2022-04-01 |
| BR112016025833B1 (pt) | 2022-02-01 |
| EP3140439B1 (en) | 2025-04-09 |
| EP4578888A2 (en) | 2025-07-02 |
| EP4578888A3 (en) | 2025-10-15 |
| EP3140439A1 (en) | 2017-03-15 |
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