TW201704272A - 改質聚合物之方法 - Google Patents
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Abstract
本發明係關於一種用於改質聚合物之方法,其包含以下步驟:(a)在介於80℃-250℃範圍內之溫度下將該聚合物與順丁烯二醯亞胺官能化之單疊氮化物及/或甲基順丁烯二醯亞胺官能化之單疊氮化物混合以形成經官能化之聚合物,及(b)使該經官能化之聚合物與含有一或多個可與順丁烯二醯亞胺或甲基順丁烯二醯亞胺官能基反應之官能基的物質反應。
Description
本發明係關於一種使用(環)加成化學改質聚合物之方法。
彈性體習知地藉由使用元素硫與若干硫硫化促進劑組合來交聯。然而,近幾年來,用過氧化物交聯之領域逐漸增加。與經硫交聯之系統相比較,過氧化物交聯之優點為較好抗返原性(reversion resistance)、較好耐熱及耐化學性以及較好壓縮永久變形。
因為不存在不飽和度,聚烯烴一般不採用基於硫之固化系統。另外,由於添加劑之褪色及硫組分之氣味在聚烯烴應用中為高度不合需要的。
聚乙烯通常用過氧化物來固化。然而,已知聚丙烯在過氧化物處理時降解。過氧化物用於藉由產生長鏈分支而增強聚丙烯之熔體強度。
基於硫及過氧化物之交聯兩者均導致有機揮發物釋放;在交聯方法期間且亦自最終經交聯之物品釋放。可想像,在建築及建造材料(例如窗戶及門型材)中,揮發物自經交聯之彈性體釋放為不合需要的。另外,固化系統之組分(亦即硫、促進劑、過氧化物及/或其分解產物)常常傾向於遷移至經處理之聚合物物品的表面(此稱為輝散(blooming)或染色),其可能對皮膚或其他表面造成不合需要之接觸污染。
因此,將需要提供可在不釋放有機揮發物及輝散/染色的情況下
進行的用於聚合物交聯之方法。
此目標藉由本發明之方法來達成,其利用加成化學且可以使得氮氣為所形成之唯一揮發物的方式進行。
該方法涉及在聚合物主鏈上引入順丁烯二醯亞胺及/或甲基順丁烯二醯亞胺基團。在此官能化期間,釋放氮氣。該方法之第二步驟涉及在該等順丁烯二醯亞胺及/或甲基順丁烯二醯亞胺基團與含有一或多個可與順丁烯二醯亞胺或甲基順丁烯二醯亞胺基團反應之官能基的物質之間的反應。
此第二步驟較佳涉及麥克爾加成(Michael addition)或狄爾斯-阿爾德環加成反應(Diels-Alder cycloaddition reaction)。若該物質僅含有一個可與順丁烯二醯亞胺或甲基順丁烯二醯亞胺官能基反應之官能基,則聚合物由其他官能基改質;若該物質含有兩個或兩個以上可與順丁烯二醯亞胺或甲基順丁烯二醯亞胺官能基反應之官能基,則將發生交聯。所得交聯潛在地為可逆的(逆狄爾斯-阿爾德及逆麥克爾加成),其使如此交聯之可再循環利用。
本發明之方法涉及一種用於改質聚合物之方法,其包含以下步驟:a.在介於80℃-250℃範圍內之溫度下將該聚合物與順丁烯二醯亞胺官能化之單疊氮化物及/或甲基順丁烯二醯亞胺官能化之單疊氮化物混合以形成經官能化之聚合物,及b.使該經官能化之聚合物與含有一或多個可與順丁烯二醯亞胺或甲基順丁烯二醯亞胺官能基反應之官能基的物質反應。
在一個較佳實施例中,在步驟b)中所用之物質含有至少兩個可與順丁烯二醯亞胺或甲基順丁烯二醯亞胺官能基反應之官能基,其導致聚合物交聯。
因此,本發明亦係關於一種交聯聚合物之方法,其包含以下步
驟:a.在介於80℃-250℃範圍內之溫度下將該聚合物與順丁烯二醯亞胺官能化之單疊氮化物及/或甲基順丁烯二醯亞胺官能化之單疊氮化物混合以形成經官能化之聚合物,及b.使該經官能化之聚合物與含有至少兩個可與順丁烯二醯亞胺或甲基順丁烯二醯亞胺官能基反應之官能基的物質反應。
本申請案中之術語『聚合物』包括聚合物及寡聚物。亦即,其包括由至少2個、較佳至少5個且最佳至少10個單體單元製造之材料。
可藉由此方法適合地改質之及/或交聯之聚合物包括彈性體、鏈飽和聚合物、聚酯及此等聚合物中之一或多者的摻合物。
彈性體之實例為天然橡膠(NR)、苯乙烯丁二烯橡膠(SBR)、丁二烯橡膠(BR)、丁基橡膠(IIR)、乙烯丙烯共聚物彈性體(EPM)、乙烯丙烯二烯三元共聚物彈性體(EPDM)及乙烯乙酸乙烯酯共聚物(EVA)。
鏈飽和聚合物包括聚烯烴。適合之聚烯烴為聚乙烯(LDPE、LLDPE、HDPE)及聚丙烯(PP),其均聚物及共聚物兩者。此類共聚物之實例為聚烯烴彈性體(POE),其係基於聚乙烯-辛烯或聚乙烯-丁烷共聚物。
聚酯之實例為聚乳酸(亦即聚乳酸交酯,PLA)及聚(羥基烷酸酯),如聚(羥基丁酸酯)、聚(丁二酸伸丁酯)、聚乙交酯及聚(ε-己內酯)。
聚合物摻合物之實例為熱塑性聚烯烴(TPO)摻合物、熱塑性彈性體(TPE)摻合物及TPV(EPDM/聚丙烯)摻合物。
可用於本發明之方法中的順丁烯二醯亞胺官能化之單疊氮化物較佳具有下式:
其中Y為
m為0或1,n為0或1,n+m=1或2,較佳為1;R選自由以下組成之群:氫;視情況經含O、S、P、Si或N之官能基取代的具有1-6個碳原子之直鏈及分支鏈烷基;具有1-6個碳原子之烷氧基;及鹵素,且X為視情況含有雜原子的具有1-12個碳原子之直鏈或分支鏈脂族或芳族烴部分。
可用於本發明之方法中的甲基順丁烯二醯亞胺官能化之單疊氮化物較佳具有下式:
其中Y為
m為0或1,n為0或1,n+m=1或2,較佳為1;R選自由以下組成之群:氫;視情況經含O、S、P、Si或N之官能基取代的具有1-6個碳原子之直鏈及分支鏈烷基;具有1-6個碳原子之烷氧基,及鹵素,且X為視情況含有雜原子的具有1-12個碳原子之直鏈或分支鏈脂族或芳族烴
部分。
在上式中,R較佳為氫。
當上式中之X含有雜原子時,其較佳具有以下結構中之一者:
其中P為介於1至6範圍內之整數,且R選自由以下組成之群:H、烷基、芳基、苯基及經取代之苯基。
然而,更佳地,X為具有1-12個、更佳1-6個且最佳2-4個碳原子之脂族烷二基。
尤其較佳的順丁烯二醯亞胺官能性單疊氮化物為4-(2,5-二側氧基-2,5-二氫-1H-吡咯-1-基)苯磺醯基疊氮化物:
尤其較佳之甲基順丁烯二醯亞胺官能性單疊氮化物為
或
亦即,分別為4-(3-甲基-2,5-二側氧基-2,5-二氫-1H-吡咯-1-基)苯磺醯基疊氮化物(亦稱為甲基順丁烯二醯亞胺苯磺醯基疊氮化物)及疊氮甲酸2-(3-甲基-2,5-二側氧基-2,5-二氫-1H-吡咯-1-基)乙酯(亦稱為甲基順丁烯二醯亞胺-C2-疊氮基甲酸酯)。
官能化步驟a)可在能夠在80℃-250℃範圍內之溫度下混合聚合物的任何適合之設備中進行。此類設備之實例為分批式密閉混合器(常常稱為班伯里混合器(Banbury mixer))、雙輥筒研磨機(其限制條件為輥筒可經加熱)、擠出機及其類似設備。官能化之結果為含有順丁烯二醯亞胺及/或甲基順丁烯二醯亞胺官能基之聚合物。
較佳將經官能化之疊氮化物以0.01-20phr、更佳0.05-10phr且最佳0.1-5phr之量與聚合物混合。術語「phr」意謂:每一百重量份聚合物之重量份。
除聚合物及經官能化之疊氮化物以外,亦可向混合物中添加自由基清除劑及抗氧化劑。自由基清除劑之實例為第三丁基氫醌(TBHQ)、2,2,6,6-四甲基哌啶氧基(TEMPO)及4-羥基-2,2,6,6-四甲基哌啶-1-氧基(OH-TEMPO)。適合之抗氧化劑之實例為位阻多核酚類(例
如Vulkanox® SKF、Vulkanox® DS、Vulkanox BKF、Irganox 1010)、胺類抗氧化劑(例如Flectol TMQ)、基於二苯基二胺之抗氧化劑(例如Santonox 6PPD)及亞磷酸酯(例如Weston TNPP)。
官能化係在介於80℃-250℃、較佳90℃-230℃、更佳100℃-200℃且最佳110℃-180℃範圍內之溫度下進行。所選溫度係視聚合物類型及疊氮化物類型而定。
在此官能化反應期間,形成N2。
磺醯基疊氮化物(疊氮基磺酸酯)通常在約130℃開始分解成反應性氮烯(nitrene)物質,且峰值在約180℃;疊氮基甲酸酯在高於110℃下開始分解,且峰值在160℃。所形成之氮烯部分與聚合物反應,使得氮烯接枝至聚合物上。
疊氮化物可與不飽和聚合物反應之另一種機制係經由所謂的「點擊(click)」機制,其可在低於疊氮化物之分解溫度下發生。在完全飽和之聚合物上,此「點擊」機制將不會發生。
較佳反應時間為1-120分鐘,更佳為1-60分鐘,且最佳為2-30分鐘。
使經官能化之聚合物與含有一或多個可與順丁烯二醯亞胺或甲基順丁烯二醯亞胺官能基反應之官能基的物質反應。
此反應可為麥克爾加成反應或狄爾斯-阿爾德環加成反應。在一個較佳實施例中,在官能化步驟a)之後向經官能化之聚合物中添加該物質。然而,當反應根據狄爾斯-阿爾德環加成機制進行時,亦可在官能化步驟a)之前或在其期間向該聚合物中添加該物質。
官能基較佳選自胺、硫醇、呋喃及山梨酸酯基團。胺及硫醇經由麥克爾加成與順丁烯二醯亞胺及甲基順丁烯二醯亞胺官能基反應;呋喃山梨酸酯酯基團經由狄爾斯-阿爾德環加成反應。
僅含有一個可與順丁烯二醯亞胺或甲基順丁烯二醯亞胺官能基
反應之官能基且可適合地用於改質聚合物之特性(例如改良與極性填充劑之相互作用)的物質之實例為胺基醇、胺基酸、聚醚單胺(Jeffamines)、呋喃、胺基官能性矽烷、巰基酸及巰基醇。
胺基醇之實例為具有一級胺基團之胺基醇,諸如乙醇胺、丙醇胺、丁醇胺等。
呋喃之實例為呋喃甲基醇(furfurylalcohol)、甲基丙烯酸呋喃甲酯、呋喃甲基縮水甘油醚及呋喃甲基異氰酸酯。
胺基官能性矽烷之實例為(3-胺基丙基二異丙基乙氧基矽烷、3-胺基丙基二甲基乙氧基矽烷、N-(2-胺基乙基)-3-胺基丙基三甲氧基-矽烷、N-(2-胺基乙基)-3-胺基丙基三乙氧基矽烷、N-(6-胺基己基)胺基甲基三乙氧基矽烷、N-(6-胺基己基)胺基丙基三甲氧基矽烷、N-(2-胺基乙基)-11-胺基十一烷基三甲氧基矽烷、(胺基乙基胺基甲基)苯乙基三甲氧基矽烷、N-(2-胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、N-(2-胺基乙基)-3-胺基異丁基甲基二甲氧基矽烷、(胺基乙基胺基)-3-異丁基二甲基甲氧基矽烷及(3-三甲氧基矽烷基丙基)二伸乙基三胺)。
硫醇之實例為3-巰基丙酸、1-巰基-2-丙醇、3-巰基-1-丙醇、4-巰基-1-丁醇、6-巰基己酸、6-巰基-1-己醇、8-巰基辛酸、8-巰基-1-辛醇、9-巰基-1-壬醇、11-巰基十一烷酸、11-巰基十一烷醯胺、11-疊氮基-1-十一烷硫醇、11-巰基-1-十一烷醇、11-巰基十一烷基膦酸、12-巰基十二烷酸、11-(1H-吡咯-1-基)十一烷-1-硫醇、12-巰基十二烷酸NHS酯、16-巰基十六烷酸、三乙二醇單-11-巰基十一烷基醚、(11-巰基十一烷基)四(乙二醇)及(11-巰基十一烷基)六(乙二醇)。
較佳硫醇為3-巰基丙酸、1-巰基-2-丙醇、3-巰基-1-丙醇、4-巰基-1-丁醇、6-巰基己酸及6-巰基-1-己醇。
與聚合物之相互作用可由於此方法而改良的填充劑之實例為碳黑、二氧化矽、矽酸鹽、雲母、氧化鋁、氫氧化物(如氫氧化鎂及氫
氧化鋁)、碳酸鹽(如碳酸鈣)、黏土、奈米黏土、硫酸鹽(如硫酸鋇)及具有極性特徵之天然有機填充劑(如木材或木質素纖維、纖維素纖維及大麻)。
若物質含有兩個或兩個以上可與順丁烯二醯亞胺或甲基順丁烯二醯亞胺官能基反應之官能基,則此兩個或兩個以上官能基較佳選自胺、硫醇、呋喃及山梨酸酯基團。至少兩個官能基可相同或不同。
具有至少兩個硫醇基之物質的實例包括具有三個巰基之物質,諸如1,2,6-己三醇三硫代羥乙酸酯、1,3,5-三聚硫氰酸、三羥甲基丙烷參(3-巰基丙酸酯)或三羥甲基丙烷三硫代羥乙酸酯;及具有四個或四個以上巰基之物質,諸如季戊四醇肆(3-巰基丙酸酯)、季戊四醇肆硫代羥乙酸酯、季戊四醇六(3-巰基丙酸酯)或季戊四醇六硫代羥乙酸酯。
具有至少兩個胺基之物質的實例包括雙(六亞甲基)三胺、1,6-二胺基己烷、異佛爾酮二胺(isophorone diamine)、參(2-胺基乙基)胺、4-胺基苯基醚、1,2-二胺基丁烷、1,4-二胺基丁烷、1,5-二胺基戊烷、1,5-二胺基(2甲基)戊烷、1,7-二胺基庚烷、1,8-二胺基辛烷、1,9-二胺基壬烷、1,10-二胺基癸烷、1,12-二胺基十二烷、1,6-二胺基-(2,2,3-三甲基)己烷、三環十二烷二胺、間苯二甲基二胺、(鄰-間-及對-)二胺基苯(苯二胺)、2,2'-二硫基雙(乙胺)、二苯胺甲烷、二苯胺醚、二苯胺碸、2,2',6,6'-四乙基二苯胺甲烷、2,2',6,6'-四甲基二苯胺甲烷、2,2'-二甲基-6,6'-二乙基二苯胺甲烷、2,2',6,6'-四-異丙基二苯胺甲烷、2,2'-二異丙基-6,6'-二甲基二苯胺甲烷、1,8-二胺基-薄荷烷、4-胺基甲基-1,8-辛烷二胺、N-苯基-1,4-苯二胺、4,4'二苯胺基二苯胺、1,8-二胺基-3,6-二氧雜辛烷、1,5-二胺基-3-氧雜戊烷、α,ω-聚四氫呋喃基二胺、α,ω-聚乙二醇二胺(Jeffamine®)、α,ω-聚丙氧基二胺(Jeffamines®)、α,ω-聚乙氧基-丙氧基二胺、3,5-二胺基苯甲酸、3,4-
二胺基二苯甲酮、1,2-二胺基環己烷、二胺基萘及二胺基甲苯。
較佳多官能胺為雙(六亞甲基)三胺、1,6-二胺基己烷、異佛爾酮二胺、參(2-胺基乙基)胺及4-胺基苯基醚。
具有胺及硫醇基之物質的實例包括3-胺基-1-丙硫醇鹽酸鹽、6-胺基-1-己硫醇鹽酸鹽、8-胺基-1-辛硫醇鹽酸鹽、11-胺基-1-十一烷硫醇鹽酸鹽及16-胺基-1-十六烷硫醇鹽酸鹽。
具有兩個或兩個以上經由狄爾斯-阿爾德環加成與順丁烯二醯亞胺及甲基順丁烯二醯亞胺基團反應之官能基的物質之實例包括2,2-二(2-呋喃基)丙烷、硫代二亞甲基二呋喃及乙烷-1,2-二基(2E,2'E,4E,4'E)-雙(己-2,4-二烯酸酯)。
可在分子一側經由狄爾斯-阿爾德環加成反應且在另一側經由麥克爾加成反應的物質之實例為呋喃甲基胺及呋喃甲基硫醇。
含有一或多個可與順丁烯二醯亞胺或甲基順丁烯二醯亞胺官能基反應之官能基的物質較佳以0.1-3.0、更佳0.2-2.0且最佳地0.5-1.5之莫耳當量比添加至經官能化之聚合物中。術語「莫耳當量比」係指可與順丁烯二醯亞胺或甲基順丁烯二醯亞胺官能基反應之官能基的總數相對於順丁烯二醯亞胺及甲基順丁烯二醯亞胺基團之總數的比。
含有一或多個可與順丁烯二醯亞胺或甲基順丁烯二醯亞胺官能基反應之官能基的物質可使用例如雙輥筒研磨機或擠出機混合至經官能化之聚合物中。混合可在室溫下或在允許在不過早交聯之情況下混合的任何其他溫度下進行。較佳溫度範圍為20℃-40℃。
可添加催化劑以便加速加成反應,但此並非必需的。若物質含有硫醇官能基,則較佳添加鹼催化劑。適合之催化劑的實例包括1,4-二氮雜雙環[2.2.2]辛烷(DABCO)、三乙胺、奎寧環醇(quinuclidinol)、三苯基膦及氫氧化物。
若含有一或多個可與順丁烯二醯亞胺或甲基順丁烯二醯亞胺官
能基反應之官能基的物質含有脂族胺官能基,則不需要催化劑;而若該物質含有芳族胺官能基,則可添加酸催化劑,例如乙酸。
狄爾斯-阿爾德環加成不需要任何催化劑。
視情況選用之催化劑可以按經官能化之聚合物的重量計0.01-2.0wt%、更佳0.02-1.0wt%且最佳地0.05-0.50wt%之濃度添加至經官能化之聚合物中。
所得混合物可以所需形式成形。此成形可在鑄模(壓縮、注射或傳遞模塑)、擠出機(其中成形模具可安裝在擠出機頂部)或砑光機(以將聚合物熔體加工成片材或薄膜)中進行。另外,所謂的熱成形方法可用於由聚烯烴箔片或片材形成形狀。
可隨後在介於40℃-250℃、較佳45℃-200℃且最佳地50℃-190℃範圍內之溫度下對經成形之混合物進行熱處理以便使交聯反應發生。
藉由本發明之方法可獲得的經交聯之聚合物可在許多應用中用作在硫固化促進劑或過氧化物存在下交聯之聚合物的替代物,該等應用包括建築及建造材料(窗戶及門型材)、電線及電纜應用、輪胎(側壁、胎面)、(傳送機)皮帶、氣囊、軟管、管、密封件、手套、對接擋板、鞋類、地板及自動扶梯扶手。
用甲基順丁烯二醯亞胺苯磺醯基疊氮化物使無不飽和度之乙烯-丙烯共聚物(EPM,來自Exxon Mobil之VistalonTM 404)官能化。為達成此官能化,將47公克EPM與0.93公克甲基順丁烯二醯亞胺苯磺醯基疊氮化物混合,且在班伯里型密閉混合器中在150℃-180℃下熱處理20分鐘以使疊氮化物接枝至EPM上。
向所得經官能化之EPM中添加季戊四醇肆(3-巰基丙酸酯)及0.1wt%催化劑DABCO(1,4二氮雜雙環[2.2.2]辛烷,亦稱為三伸乙基二
胺),且在雙輥筒研磨機上在介於20℃-40℃之間的溫度下混合該等物質。所添加之季戊四醇肆(3-巰基丙酸酯)之量按總混合物計對應於1.1wt%,且甲基順丁烯二醯亞胺官能基與四硫醇之莫耳比為3:1。
藉由使用Alpha Technologies MDR2000流變儀在170℃下使樣品固化30分鐘來測試固化速度及交聯效能。根據ISO 6502-1991(用無轉子固化儀量測硫化特徵)分析結果。
固化時間(t90;達成最終最大交聯密度之90%所需之時間)為15分鐘。最終交聯密度指標△轉矩(△S)為0.23Nm。
除了以下之外,重複實例1:-使用順丁烯二醯亞胺苯磺醯基疊氮化物代替甲基順丁烯二醯亞胺苯磺醯基疊氮化物,-使用0.2wt% DABCO,-不使用或使用0.8wt%季戊四醇肆(3-巰基丙酸酯)(使得順丁烯二醯亞胺官能基與四硫醇之莫耳比為約4:1),且-聚合物在180℃下進行交聯,代替170℃。
結果列於表1中。
表2列出用所指示之量的交聯劑(四硫醇)改質之EPM的交聯效能。列出的為t90,亦即獲得最終最大交聯密度90%所需之時間,及在流變儀中所量測之△轉矩△S。實驗明確展示,交聯反應發生需要四硫醇。
用順丁烯二醯亞胺苯磺醯基疊氮化物官能化乙烯-丙烯二烯三元
共聚物(EPDM,來自Lanxess Elastomers之Keltan 5470C)。為達成此官能化,將50公克EPDM與1公克順丁烯二醯亞胺苯磺醯基疊氮化物及1公克Vulkanox® SKF(防止凝膠形成之穩定劑,由此改良可加工性)混合,且在班伯里型密閉混合器中在120℃-170℃下熱處理25分鐘以使疊氮化物接枝至EPDM上。
在官能化之後,使用雙輥筒研磨機在20℃-40℃下向經改質之EPDM中添加1當量硫代二亞甲基二呋喃。順丁烯二醯亞胺官能基與雙呋喃交聯劑之莫耳比為2:1。
交聯藉由將所得混合物在150℃下加熱5分鐘且在50℃下再繼續加熱24小時來進行。此允許狄爾斯-阿爾德交聯反應進行。
表2展示用於官能化之配方(第3A項)及使用雙呋喃交聯經官能化之EPDM。
實例3B-3D為比較實例,其展示起始EPDM(3B)及用不同量之過氧化二異丙苯交聯之EPDM(3C及3D)的交聯密度。樣品3C及3D藉由加熱至170℃持續30分鐘以使過氧化物充分分解為有效自由基來進行交聯。
交聯密度()使用甲苯中之平衡溶脹方法及在交聯密度()與以實驗方式測定的經溶脹之樣品中橡膠體積分數(Φ)之間的弗洛里-雷納關係(Flory-Rehner relationship)來量測。EPDM與甲苯之組合使用弗洛里-哈金斯相互作用參數(Flory-Huggins interaction parameter)0.429+0.218Φ。
表2中之結果指示,EPDM自身不展示交聯密度,而利用本發明之狄爾斯-阿爾德交聯系統交聯之EPDM的交聯密度與用0.2-0.4phr過氧化物(過氧化二異丙苯)交聯之EPDM相當。
*未交聯之EPDM完全溶解於甲苯中。
用甲基順丁烯二醯亞胺苯磺醯基疊氮化物官能化丁基橡膠(BR,Rubber Neocis® BR40)。為達成此官能化,將47公克BR與0.94公克甲基順丁烯二醯亞胺苯磺醯基疊氮化物混合,且在班伯里型密閉混合器中在150℃-180℃下熱處理20分鐘以使疊氮化物接枝至BR上。
向所得經官能化之BR中添加0.24公克乙醇胺,且將物質在雙輥筒研磨機上在介於20℃-40℃之間的溫度下混合。甲基順丁烯二醯亞胺官能基與乙醇胺之莫耳比為約1:1
在1H-NMR光譜(使用CDCl3作為溶劑)中,自由乙醇胺在2.8及3.6ppm處給出信號。在以上處理之後,此等信號分別移動至3.1及3.7ppm。1D-DOSY NMR展示,3.1及3.7ppm處之此等信號屬於高分子量級分,其證明乙醇胺連接至丁基橡膠。
Claims (16)
- 一種用於改質聚合物之方法,其包含以下步驟:a.在介於80℃-250℃範圍內之溫度下將該聚合物與順丁烯二醯亞胺官能化之單疊氮化物及/或甲基順丁烯二醯亞胺官能化之單疊氮化物混合以形成經官能化之聚合物,及b.使該經官能化之聚合物與含有一或多個可與順丁烯二醯亞胺或甲基順丁烯二醯亞胺官能基反應之官能基的物質反應。
- 如請求項1之方法,其中該物質含有至少兩個可與順丁烯二醯亞胺或甲基順丁烯二醯亞胺官能基反應之官能基。
- 如請求項1或2之方法,其中該經官能化之聚合物與該含有一或多個可與順丁烯二醯亞胺或甲基順丁烯二醯亞胺官能基反應之官能基的物質之間的反應涉及麥克爾(Michael)加成反應或狄爾斯-阿爾德(Diels-Alder)環加成反應。
- 如請求項1或2之方法,其中該一或多個官能基係選自胺、硫醇、呋喃及山梨酸酯基團。
- 如請求項1之方法,其中該含有一或多個可與順丁烯二醯亞胺或甲基順丁烯二醯亞胺官能基反應之官能基的物質係選自由以下組成之群:胺基醇、胺基酸、聚醚單胺(Jeffamines)、呋喃、胺基官能性矽烷、巰基酸及巰基醇。
- 如請求項2之方法,其中該含有至少兩個可與順丁烯二醯亞胺或甲基順丁烯二醯亞胺官能基反應之官能基的物質係選自由以下組成之群:1,2,6-己三醇三硫代羥乙酸酯、1,3,5-三聚硫氰酸、三羥甲基丙烷參(3-巰基丙酸酯)、三羥甲基丙烷三硫代羥乙酸酯、季戊四醇肆(3-巰基丙酸酯)、季戊四醇肆硫代羥乙酸酯、季戊四醇六(3-巰基丙酸酯)及季戊四醇六硫代羥乙酸酯。
- 如請求項2之方法,其中該含有至少兩個可與順丁烯二醯亞胺或甲基順丁烯二醯亞胺官能基反應之官能基的物質係選自由以下組成之群:雙(六亞甲基)三胺、1,6-二胺基己烷、異佛爾酮二胺、4-胺基苯基醚及參(2-胺基乙基)胺。
- 如請求項2之方法,其中該含有至少兩個可與順丁烯二醯亞胺或甲基順丁烯二醯亞胺官能基反應之官能基的物質係選自由以下組成之群:2,2-二(2-呋喃基)丙烷、二呋喃甲基硫化物、硫代二亞甲基二呋喃及乙烷-1,2-二基(2E,2'E,4E,4'E)-雙(己-2,4-二烯酸酯)。
- 如請求項2之方法,其中該含有至少兩個可與順丁烯二醯亞胺或甲基順丁烯二醯亞胺官能基反應之官能基的物質係選自由以下組成之群:季戊四醇肆(3-巰基丙酸酯)、雙(六亞甲基)三胺、參(2-胺基乙基)胺、2,2-二(2-呋喃基)丙烷及二呋喃甲基硫化物。
- 如請求項1或2之方法,其中該聚合物為彈性體。
- 如請求項10之方法,其中該彈性體係選自由以下組成之群:天然橡膠(NR)、苯乙烯丁二烯橡膠(SBR)、丁二烯橡膠(BR)、丁基橡膠(IIR)、乙烯丙烯共聚物彈性體(EPM)、乙烯丙烯二烯三元共聚物彈性體(EPDM)及乙烯乙酸乙烯酯共聚物(EVA)。
- 如請求項1或2之方法,其中該聚合物為聚烯烴。
- 如請求項12之方法,其中該聚烯烴係選自由以下組成之群:聚乙烯、聚丙烯及聚烯烴彈性體。
- 如請求項1或2之方法,其中該順丁烯二醯亞胺官能化之疊氮化物具有以下結構:
- 如請求項1或2之方法,其中該甲基順丁烯二醯亞胺官能化之疊氮化物具有以下結構:
- 如請求項1或2之方法,其中該單疊氮化物係選自由以下組成之群:4-(2,5-二側氧基-2,5-二氫-1H-吡咯-1-基)苯磺醯基疊氮化物、4-(3-甲基-2,5-二側氧基-2,5-二氫-1H-吡咯-1-基)苯磺醯基疊氮化物(亦稱為甲基順丁烯二醯亞胺苯磺醯基疊氮化物)及疊氮甲酸2-(3-甲基-2,5-二側氧基-2,5-二氫-1H-吡咯-1-基)乙酯(亦稱為甲基順丁烯二醯亞胺-C2-疊氮基甲酸酯)。
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TWI287536B (en) | 2000-04-18 | 2007-10-01 | Ind Tech Res Inst | Method for preparing azide photo-initiators |
MXPA03008498A (es) | 2001-03-20 | 2005-06-30 | Univ Zuerich | Procesamiento en dos fases de polimeros termosensibles para uso como biomateriales. |
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ZA200707867B (en) * | 2005-03-17 | 2008-12-31 | Dow Global Technologies Inc | Fibers made from copolymers of ethylene/alpha-olefins |
WO2007071619A1 (en) | 2005-12-20 | 2007-06-28 | Stichting Dutch Polymer Institute | Process for cross-linking copolymers using a sulfur-containing co-agent |
WO2008130894A1 (en) | 2007-04-16 | 2008-10-30 | Designer Molecules, Inc. | Low temperature curing acrylate and maleimide based formulations and methods for use thereof |
US7906592B2 (en) * | 2008-07-03 | 2011-03-15 | Bridgestone Corporation | Polymers functionalized with imide compounds containing a protected amino group |
US8658707B2 (en) * | 2009-03-24 | 2014-02-25 | W. L. Gore & Associates, Inc. | Expandable functional TFE copolymer fine powder, the expanded functional products obtained therefrom and reaction of the expanded products |
EP2678326B1 (en) | 2011-02-25 | 2017-08-02 | University of Massachusetts Medical School | Monomers and polymers for functional polycarbonates and poly (ester-carbonates) and peg-co-polycarbonate hydrogels |
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