TW201420677A - 芳香族碳二醯亞胺之固化 - Google Patents
芳香族碳二醯亞胺之固化 Download PDFInfo
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- TW201420677A TW201420677A TW102133455A TW102133455A TW201420677A TW 201420677 A TW201420677 A TW 201420677A TW 102133455 A TW102133455 A TW 102133455A TW 102133455 A TW102133455 A TW 102133455A TW 201420677 A TW201420677 A TW 201420677A
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- carbodiimide
- prepolymer
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Classifications
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/4829—Polyethers containing at least three hydroxy groups
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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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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/797—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing carbodiimide and/or uretone-imine groups
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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
- C08G71/00—Macromolecular compounds obtained by reactions forming a ureide or urethane link, otherwise, than from isocyanate radicals in the main chain of the macromolecule
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C—CHEMISTRY; METALLURGY
- 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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- C08G18/72—Polyisocyanates or polyisothiocyanates
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- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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Abstract
一種用於聚合芳香族多官能碳二醯亞胺之方法，該方法係於溫度15℃至90℃，使芳香族多官能碳二醯亞胺與羧酸鹽接觸。
Description
本發明概括而言係有關於低溫固化芳香族碳二醯亞胺之方法。
芳香族碳二醯亞胺之固化方法為普遍悉知。舉例而言，G.C.Robinson,J.Poly.Sci,Part A.,Vol.2,3901-3908(1964)揭示藉由使用濕敏有機金屬催化劑或藉由加熱至高溫之碳二醯亞胺聚合反應。
然而，仍需要更具有商業用途之固化碳二醯亞胺之替代方法。
本發明係有關芳香族多官能碳二醯亞胺之聚合方法；該方法包括於溫度15℃至90℃，使芳香族多官能碳二醯亞胺與羧酸鹽接觸。
本發明進一步係有關包含碳二醯亞胺預聚物與羧酸鹽之可固化之樹脂組成物；其中，碳二醯亞胺預聚物之每一碳二醯亞胺基團鄰接兩個芳香族取代基。
除非另行指示，否則所有百分比為重量百分比(wt%)，而所有溫度單位為℃。除非另行指示，否則聚合物組成之百分比係以固體計，亦即，不包括溶劑。“多官能”意指每一分子或聚合物鏈具有一個以上的異氰酸酯或碳二醯亞胺基團。“芳香族多官能碳二醯亞胺”係任何碳二醯亞胺，其平均碳二醯亞胺官能度至少為1.2且每一碳二醯亞胺基團鄰接兩個芳香族取代基，亦即，其中每一個碳二醯亞胺基團為-Ar-N=C=N-Ar-結構之一部分(其中，Ar為二官能芳香族取代基，例如，-C6H4-CH2-C6H4-)。芳香族取代基為具有至少一個芳香族環及六至二十個碳原子者。較佳之芳香族多官能碳二醯亞胺及碳二醯亞胺預聚物包括衍生自二苯基甲烷二異氰酸酯(MDI)與甲苯二異氰酸酯(TDI)之異氰酸酯封端之預聚物，較佳為衍生自MDI預聚物以及多元醇者。TDI係指以此名稱出售之市售產品，其主要為2,4-異構物、少量2,6-異構物與可能之其他異構物。MDI可為4,4’與2,4’異構物之混合物。
較佳地，該芳香族多官能碳二醯亞胺之平均碳二醯亞胺官能度為1.2至10，較佳為1.3至6，較佳為1.4至5，較佳為1.5至4。較佳地，該芳香族多官能碳二醯亞胺係碳二醯亞胺預聚物。較佳地，該芳香族多官能碳二醯亞胺之碳二醯亞胺含量(亦即，以固體計，化合物或聚合物鏈中之碳二醯亞胺基團(-N=C=N-)之量)為0.5wt%至6wt%，較佳為1wt%至5wt%，較佳為2wt%至5wt%。
較佳地，本發明之碳二醯亞胺預聚物含有：(i)芳香族多官能異氰酸酯與脂族多元醇的聚合殘基、(ii)碳二醯亞胺基團，以及(iii)具有脂族取代基之胺甲酸乙酯基團。該預聚物中可存在游離之芳香族多官能異氰酸酯。較佳地，該碳二醯亞胺預聚物之平均碳二醯亞胺官能度為1.2至10，較佳為1.8至6，較佳為2至5。較佳地，該碳二醯亞胺預聚物之碳二醯亞胺含量為0.5wt%至6wt%，較佳為1wt%至5wt%，較佳為2wt%至5wt%。較佳地，該預聚物係由芳香族多官能異氰酸酯與脂族多元醇形成異氰酸酯封端之預聚物所產生，隨後利用催化劑使25至75%(較佳為30至50%，較佳為35至45%)之異氰酸酯基團轉化為碳二醯亞胺基團，接著使催化劑去活化，最後，實質上使所有殘留之異氰酸酯基團與脂族醇反應形成具有脂族取代基之胺甲酸乙酯基團。此異氰酸酯基團成為碳二醯亞胺基團之部分轉化使預聚物中之wt%異氰酸酯從初始範圍5wt%至17wt%(較佳為6wt%至15.5wt%)異氰酸酯基團降低至最終範圍4wt%至10wt%(較佳為6wt%至9wt%)異氰酸酯。較佳地，所有該等步驟係於25℃至110℃，較佳為40℃至100℃，較佳為50℃至95℃之溫度範圍內進行。較佳地，該催化劑為環狀磷化合物，例如，經取代之磷雜環戊烯(phospholene)-1-氧化物、磷雜環丁烷(phosphetane)4-氧化物或1,3-二氮雜磷啶(phospholidine)氧化物，較佳為1,3-二甲基磷雜環戊烯(phospholine)-1-氧化物、1-乙基-3-甲基磷雜環戊烯-1-氧化物、1-苯基-3-甲基磷
雜環戊烯-1-氧化物、1-苯基磷雜環戊烯-1-氧化物、1,3,2-二氮雜磷啶-2-氧化物或3-甲基-1-苯基-2-磷雜環戊烯-1-氧化物。較佳地，催化劑係3-甲基-苯基-2-磷雜環戊烯-1-氧化物。較佳地，催化劑係利用添加三甲基矽烷基化合物或路易士酸，較佳為參(三甲基矽烷基)磷酸酯或三氟化硼，予以去活化。
較佳地，該碳二醯亞胺預聚物之殘留異氰酸酯含量不大於1wt%，較佳為不大於0.5wt%，較佳為不大於0.3wt%，較佳為不大於0.2wt%。較佳地，產生異氰酸酯封端之預聚物所用之芳香族多官能異氰酸酯具有2至2.5，較佳為2至2.2之平均異氰酸酯官能度。較佳地，芳香族多官能異氰酸酯係MDI或TDI，較佳為MDI。較佳地，該脂族多元醇係羥基封端之聚酯或聚醚多元醇，較佳為聚醚多元醇。較佳地，該脂族多元醇具有2至2.5，較佳為2至2.2，較佳為2至2.1之平均羥基官能度。較佳地，該聚醚多元醇包含環氧乙烷、環氧丙烷或其組合物的聚合殘基。較佳地，該聚醚多元醇包含至少70wt%，較佳為至少80wt%，較佳為至少90wt%，較佳為至少95wt%之環氧丙烷聚合殘基。較佳地，該碳二醯亞胺預聚物含有25wt%至55wt%，較佳為30wt%至50wt%，較佳為31wt%至45wt%之脂族多元醇聚合殘基。較佳地，該脂族多元醇之Mn為500至2500，較佳為800至2200，較佳為1000至2000。可使用一個以上的異氰酸酯及/或一個以上的多元醇產生碳二醯亞胺預聚物。較佳地，該碳二醯亞胺預聚物含有30wt%
至60wt%，較佳為40wt%至55wt%，較佳為42wt%至53wt%之芳香族多官能異氰酸酯聚合殘基。較佳地，該脂族醇係具有一至八個碳原子，較佳為一至四個碳原子之單官能醇。較佳地，該脂族醇係直鏈或支鏈的一級或二級醇；較佳為一級醇。較佳之脂族醇包括甲醇、乙醇、正丙醇、異丙醇、正丁醇、第二丁醇、異丁醇或第三丁醇；較佳為甲醇、乙醇、正丙醇或正丁醇；較佳為正丁醇。較佳地，該碳二醯亞胺預聚物中之殘留脂族醇之量不大於5%，較佳為不大於3%，較佳為不大於2%，較佳為不大於1%，較佳為不大於0.5%。
較佳地，用以催化芳香族多官能碳二醯亞胺或碳二醯亞胺預聚物固化之羧酸鹽為具有二至十八個，較佳為二至八個，較佳為二至四個碳原子之羧酸之鹽；較佳為單羧酸之鹽。較佳地，該等羧酸鹽係未經取代或經鹵素或羥基單取代，較佳為未經取代。特佳之羧酸鹽為乙酸鹽。較佳地，其陽離子為鹼金屬；較佳為鋰、鈉或鉀；較佳為鈉或鉀；較佳為鉀。較佳地，該芳香族多官能碳二醯亞胺係於溫度15℃至90℃，較佳為20℃至85℃，較佳為25℃至60℃與羧酸鹽接觸。較佳之羧酸鹽之量以固體計，且以總可固化之樹脂組成物百分比表示，係0.01wt%至0.5wt%，較佳為0.03wt%至0.3wt%，較佳為0.05wt%至0.2wt%。較佳地，該可固化之樹脂組成物實質上不含烷氧化物、鈦化合物、銅化合物、有機鋰化合物與鋁鹵化物。本文所用之「實質上不含」意指具有小於0.5wt%，較佳為小
於0.3wt%，較佳為小於0.2wt%，較佳為小於0.1wt%，較佳為小於0.05wt%，較佳為小於0.03wt%，較佳為小於0.02wt%，較佳為小於0.01wt%。
於本發明之較佳實施例中，該羧酸鹽係包封(encapsulated)於惰性介質中，該惰性介質容許經包封之羧酸鹽(“催化劑”)被併入碳二醯亞胺預聚物或芳香族多官能碳二醯亞胺中，直到層壓過程中利用機械壓力或加熱去除包封劑之前不會催化固化。經包封之催化劑通常係利用沉積催化劑周圍之殼而產生。該催化劑可包含於膠囊(capsule)內之單一空腔(cavity)或儲槽(reservoir)中，或可位於膠囊內之許多空腔中。該殼的厚度視所用材料、催化劑裝載量、膠囊形成方法以及所欲的最終用途可有很大不同。以經包封之催化劑重量計，催化劑裝載量較佳為5至90%，較佳為10至90%，較佳為30至90%。特定包封方法有助於使其較其他方法具有更高之核心容積裝載。可能需要一個以上的殼以確保過早破裂或滲漏。
經包封之催化劑可利用任何多種微包封技術製造，包括但不限於凝聚、界面添加與縮合、乳化聚合、微流聚合、逆微胞聚合、空氣懸浮、離心擠壓、噴霧乾燥、製粒、BITEM法、缽式包覆法(pan coating)，以及利用M-CAPTM包封法。
凝聚係形成膠囊壁之基本方法。凝聚法之實例列舉於美國專利第2,800,457與2,800,458號中。M-CAPTM法被公認為製造粒徑為30微米且具有高核心裝
載容積(>75%)之經包封之催化劑之較佳方法，且該經包封之催化劑可用壓力使其破裂；此M-CAPTM法詳述於美國專利第5,271,881號。製粒亦被公認為容許使用具有優異阻隔性質以防止過早釋放催化劑之高結晶度蠟之較佳包封方法。製粒，亦稱為噴霧凝結、噴霧冷卻或熔融霧化，係提供大小介於0.5μm與3000μm間且催化劑裝載量典型為5至50%之膠囊。經由製粒方法用於包封之較佳殼材料包括石蠟、合成蠟、微晶蠟、植物蠟、聚乙烯蠟，以及低分子量聚合物。用於製粒之最佳殼材料為石蠟、聚乙烯蠟、熔點為40至120℃之Fischer-Tropsch蠟。BITEM法為用於鹼水性溶液之另一適當包封技術實例，其容許使用具有優異阻隔性質以防止過早釋放催化劑之高結晶度蠟。此方法產生50至500μm之膠囊，其中，含催化劑水溶液之小室係包埋於蠟基質中。經由製粒方法用於包封之較佳殼材料包括石蠟、合成蠟、微晶蠟、植物蠟、聚乙烯蠟，以及低分子量聚合物。用於製粒之最佳殼材料為石蠟、聚乙烯蠟、熔點為40至120℃之Fischer-Tropsch蠟。無關包封技術，用以包封催化劑之材料可包括合成蠟、微晶蠟、植物蠟、聚乙烯蠟、聚醯胺類、聚脲類(例如聚甲基脲或PMU)、Michael加成聚合物(亦即供體(例如乙醯乙酸酯或丙二酸酯)與受體(例如多官能丙烯酸酯)之反應產物)、聚丙烯酸酯類、側鏈可結晶之聚丙烯酸酯類、聚乙烯醇、使用交聯劑(例如硼酸鹽)交聯之聚乙烯醇、聚二甲基矽氧烷類、羧甲基纖維素、聚苯乙烯、聚乙烯乙酸乙烯酯共聚物、聚乙烯丙烯
酸酯共聚物、聚α-烯烴、聚乙烯類、經由非均相催化(例如經茂金屬催化)製備之聚乙烯類、聚丙烯、經由非均相催化(例如經茂金屬催化)製備之聚丙烯類。
高結晶度、熔點明確之材料例如石蠟、合成蠟與聚乙烯蠟，以及高結晶度、低分子量聚合物例如側鏈可結晶之聚丙烯酸酯類，藉由審慎選擇與組成物最終處理條件一致之熔點，可提供熱觸發催化劑釋放之可能性。
可能需要使用數個殼或數個分離塗層以提供足夠之殼強度及完整性，防止含有經包封之催化劑之單組分製劑中之反應物過早開始反應。此類多殼膠囊之實例為石蠟或微晶蠟殼(例如經由製粒完成者)，隨後為聚甲脲(PMU)殼。另一實例係使用蠟殼，隨後為伴隨著利用Michael加成反應製備之殼。
該膠囊之較佳粒徑為0.1至1000μm，更佳為0.1至500μm且最佳為0.1至100μm。可隨該膠囊之應用而調整其粒徑，以確保其於預定條件下破裂。
於塗佈於基材(substrate)之前，先以溶劑稀釋本系統之成分。本文所用之「溶劑」一詞係指於25℃為液體且於常壓之沸點不大於100℃之物質。較佳地，施用至基材之該系統組合成分含有45至75wt%，較佳為46至60wt%，較佳為47至55wt%，較佳為48至53wt%之固體。適當溶劑包括乙酸乙酯、乙酸甲酯與甲基乙基酮；尤其較佳為乙酸乙酯。
本發明之可固化樹脂組成物計畫使用兩種
成分，較佳為於施用至基材以形成黏合劑之前或期間，使用適當混合器(例如，電動、氣動或以其他方式供電之機械混合器，或靜態混合器)使其混合。因此，碳二醯亞胺預聚物成分通常與羧酸鹽成分分別包裝。混合可於層壓過程前之任何適當時間進行。所有該等步驟可於環境常溫或超環境(supra-ambient)條件下進行。舉例而言，二成分可於正要混合之前進行加熱，且於塗佈及層壓過程期間，在升高溫度進行施用。較佳地，溫度不超過50℃。依需要，可針對所得層壓片(laminate)進行加熱或冷卻。較佳地，使用凹版滾筒將混合後之膠黏組成物轉變成膜片，然後將其層壓於第二個膜片。
本發明之黏合劑係用於使二至五個基材黏合在一起。該等基材可為相似或相異材料。於較佳實施例中，該黏合劑之層係施用至第一個基材層，再以第二個基材層覆蓋所得黏合劑層以形成層壓物(laminated article)，其中，該兩個基材係由黏合劑乾燥層黏合在一起。可添加第三與第四層膜片於該層壓片以形成三或四層層壓片。於較佳實施例中，提供之基材層係呈現基材材料捲形式。該等片材(sheets)厚度可為0.5至10mil之量級。其厚度亦可能較大或較小(例如，5或5微米以上之量級)。
本發明組成物可使用習知施用技術施用至所需基材，該等施用技術例如捲筒紙凹版印刷、柔版印刷、傳統或無氣噴塗、輥塗、刷塗、繞線棒塗佈、刮刀塗佈，或塗佈法例如簾狀、滿版(flood)、鐘狀、盤狀與浸塗塗佈
法。以黏合劑塗佈時可於整個表面或僅於部分表面，例如沿著邊緣或於間斷位置進行。該黏合劑對於層壓塑料膜片、金屬膜片或金屬化塑料膜片之包裝與密封之應用尤具吸引力。尤其較佳之膜片包括低密度聚乙烯、高密度聚乙烯、聚丙烯(鑄造、吹製導向、雙軸拉伸)、尼龍、聚苯乙烯、經共擠之膜片、聚酯膜片、經陶瓷(SiOx、AlOx)塗佈之膜片(聚酯、尼龍等)、經聚丙烯酸塗佈之膜片(聚酯、尼龍等)、經聚偏二氯乙烯塗佈之膜片、金屬化膜片(聚酯、聚丙烯等)。
溶液黏度之測量係使用Brookfield黏度計，於溫度大約25℃以及適用於所測量之黏度範圍之裝置進行操作。於Brookfield黏度計上，於所示溫度，使用恆溫之小樣本適配器及具有Spindle #27之樣本室測量純樹脂黏度。如下列程序製備所述之樹脂。
實施例1：碳二醯亞胺預聚物之製備
1.於環境溫度(25至30℃)，於容器中裝填物品1。
2.於氮氣下，攪拌加熱樹脂至65至75℃。
3.於0.50小時期間內，添加物品#2至樹脂混合物中；維持於75至85℃。
4.檢測% NCO；當%NCO6.0%時，進行步驟5。
5.於0.25小時期間內，開始添加物品#3至樹脂混合物中；-維持於75至85℃。
6.添加物品4；維持於75至85℃ 1小時；取樣樹脂供檢測%NCO用。
7.當%NCO<9.0%時，添加物品5與6；維持於75至85℃。
8.添加物品7以降低%NCO至0.10%，監測%NCO。
9.當% NCO0.10%時，於氮氣下進行包裝。
樹脂性質：5.99%碳二醯亞胺，當量重667.78.黏度：45℃
時，323,000cps；45℃時，175,750cps。
實施例2：碳二醯亞胺預聚物之製備
1.於環境溫度(25至30℃)，於容器中裝填物品1。
2.於氮氣下，攪拌加熱樹脂至65至75℃。
3.於0.50小時期間內，添加物品#2至樹脂混合物中；維持於75至85℃。
4.檢測% NCO；當%NCO6.0%時，進行步驟5。
5.於0.25小時期間內，開始添加物品#3至樹脂混合物中；維持於75至85℃。
6.添加物品4；維持於75至85℃ 1小時；取樣樹脂供檢測%NCO用。
7.當%NCO<9.0%時，添加物品5與6；維持於75至85℃。
8.添加物品7以降低%NCO至0.10%，監測%NCO。
9.當% NCO0.10%時，於氮氣下進行包裝。
樹脂性質：3.71%碳二醯亞胺，當量重1078.2。黏度：40℃時，132,000cps；45℃時，71,750cps；50℃時，41,700cps。
實施例3：碳二醯亞胺預聚物之製備
1.於環境溫度(25至30℃)，於容器中裝填物品1。
2.於氮氣下，攪拌加熱樹脂至65至75℃。
3.於1.00小時期間內，添加物品#2至樹脂混合物中；維持於75至85℃。
4.檢測% NCO；當%NCO10.5%時，進行步驟5。
5.開始添加物品#3至樹脂混合物中；維持於75至85℃。
6.維持於80至85℃ 2小時；取樣樹脂供檢測%NCO用。
7.當%NCO<9.0%時，添加物品4與5；維持於75至85℃。
8.添加物品6以降低%NCO至2.00%，監測%NCO。
9.添加物品7以降低%NCO至0.10%。
10.當% NCO0.10%時，於氮氣下進行包裝。
樹脂性質：1.12%碳二醯亞胺，當量重3571.43。黏度：40℃時，42,150cps；45℃時，25,600cps；50℃時，16,100cps。
實施例4：碳二醯亞胺預聚物之製備
1.於周圍溫度(25至30℃)，於容器中裝填物品1。
2.於氮氣下，攪拌加熱樹脂至65至75℃。
3.於1.25小時期間內，添加物品#2至樹脂混合物中；維持於75至85℃。
4.檢測% NCO；當%NCO13.3%時，進行步驟5。
5.開始添加物品#3至樹脂混合物中；維持於75至85℃。
6.維持於80至85℃ 2小時；取樣樹脂供檢測%NCO用。
7.當%NCO<7.7%時，添加物品4與5；維持於75至85℃。
8.添加物品6以降低%NCO至2.00%，監測%NCO。
9.添加物品7以降低%NCO至0.25%。
10.當% NCO0.25%時，於氮氣下進行包裝。
樹脂性質：2.12%碳二醯亞胺，當量重1886.79。黏度：40℃時，91,000cps；45℃時，53,188cps；50℃時，31,900cps。
實施例5：碳二醯亞胺預聚物之製備
1.於環境溫度(25至30℃)，於容器中裝填物品1。
2.於氮氣下，攪拌加熱樹脂至65至75℃。
3.於1.00小時期間內，添加物品#2至樹脂混合物中；維持於75至85℃。
4.檢測% NCO；當%NCO14.5%時，進行步驟5。
5.開始添加物品#3至樹脂混合物中；維持於75至85℃。
6.維持於80至85℃ 2小時；樹脂取樣供檢測%NCO用。
7.當%NCO<6.2%時，添加物品4與5；維持於75至85℃。
8.添加物品6以降低%NCO至2.00%，監測%NCO。
9.添加物品7與8以降低%NCO至0.0.38%。
10.當% NCO0.38%時，於氮氣下進行包裝。
樹脂性質：3.08%碳二醯亞胺，當量重1300.81。黏度：40℃時，135,250cps；45℃時，76,125cps；50℃時，44,750cps。
實施例6：碳二醯亞胺預聚物之製備
1.於環境溫度(25至30℃)，於容器中裝填物品1。
2.於氮氣中，攪拌加熱樹脂至65至75℃。
3.於0.30小時期間內，添加物品#2至樹脂混合物中；維持於75至85℃。
4.檢測% NCO；當%NCO15.5%時，進行步驟5。
5.開始添加物品#3至樹脂混合物中；維持於75至85℃。
6.維持於80至85℃ 2小時；樹脂取樣供檢測%NCO用。
7.當%NCO<10.0%時，添加物品4與5；維持於75至85℃。
8.添加物品6以降低%NCO至2.00%，監測%NCO。
9.添加物品7與8以降低%NCO至0.15%。
10.當% NCO0.15%時，於氮氣下進行包裝。
樹脂性質：2.07%碳二醯亞胺，當量重1932.37。黏度：40℃時，1,860,000cps；45℃時，933,000cps；50℃時，508,600cps。
實施例7：使於10.0g乙酸乙酯溶液中之10.0g實施例1之碳二醯亞胺樹脂與於乙醇中之0.20g之3.37%乙酸鉀混合並塗佈以獲得1.0lbs/rm(1.628g/m2)塗層重。於環境條件固化層壓片。以固化時間為函數，檢測黏合強度並記載於下：
AS：膠黏劑分離Zip：拉鏈式黏合(Zippery bond)
實施例8：使於10.0g乙酸乙酯溶液中之10.0g實施例2之碳二醯亞胺樹脂與於乙醇中之2.0g之0.92%乙酸鉀混合並塗佈以獲得1.0lbs/rm(1.628g/m2)塗層重。於環境條件下固化層壓片。以固化時間為函數，檢測黏合強度並記載於下：
AS：膠黏劑分離Zip：拉鏈式黏合
實施例9：使於10.0g乙酸乙酯溶液中之10.0g實施例3之碳二醯亞胺樹脂與於乙醇中之2.0g0.92%乙酸鉀混合並塗佈以獲得1.0lbs/rm(1.628g/m2)塗層重。於環境條件固化層壓片。以固化時間為函數，檢測黏合強度並記載於下：
AS：膠黏劑分離
實施例10：使於10.0g乙酸乙酯溶液中之10.0g實施例4之碳二醯亞胺樹脂與於乙醇中之2.0g之0.92%乙酸鉀混合並塗佈以獲得1.0lbs/rm(1.628g/m2)塗層重。於環境條件固化層壓片。以固化時間為函數，檢測黏合強度並記載於下：
AS：膠黏劑分離
實施例11：使於10.0g乙酸乙酯溶液中之10.0g實施例5之碳二醯亞胺樹脂與於乙醇中之2.0g 0.92%乙酸鉀混合並塗佈以獲得1.0lbs/rm(1.628g/m2)塗層重。於環境條件固化層壓片。以固化時間為函數，檢測黏合強度並記載於下：
AS：膠黏劑分離
實施例12：使於10.0g乙酸乙酯溶液中之10.0g實施例6之碳二醯亞胺樹脂與於乙醇中之2.0g 0.92%乙酸鉀混合並塗佈以獲得1.0lbs/rm(1.628g/m2)塗層重。於環境條件固化層壓片。以固化時間為函數，檢測黏合強度並記載於下：
AS：膠黏劑分離
Claims (10)
- 一種用於聚合芳香族多官能碳二醯亞胺之方法；該方法包括於溫度15℃至90℃，使該芳香族多官能碳二醯亞胺與羧酸鹽接觸。
- 如申請專利範圍第1項所述之方法，其中，該芳香族多官能碳二醯亞胺為碳二醯亞胺預聚物。
- 如申請專利範圍第2項所述之方法，其中，該碳二醯亞胺預聚物之平均碳二醯亞胺官能度為1.3至6。
- 如申請專利範圍第1項所述之方法，其中，該芳香族多官能碳二醯亞胺之平均碳二醯亞胺官能度為1.3至6。
- 一種可固化之樹脂組成物，其包含碳二醯亞胺預聚物與羧酸鹽；其中，該碳二醯亞胺預聚物之每一碳二醯亞胺基團鄰接兩個芳香族取代基。
- 如申請專利範圍第5項所述之可固化之樹脂組成物，其中，該碳二醯亞胺預聚物含有：(i)芳香族多官能異氰酸酯與脂族多元醇的聚合殘基、(ii)碳二醯亞胺基團，以及(iii)具有脂族取代基之胺甲酸乙酯基團。
- 如申請專利範圍第6項所述之可固化之樹脂組成物，其中，該碳二醯亞胺預聚物之平均碳二醯亞胺官能度為1.3至6。
- 如申請專利範圍第7項所述之可固化之樹脂組成物，其中，該碳二醯亞胺預聚物之殘留異氰酸酯含量不大於1wt%。
- 如申請專利範圍第8項所述之可固化之樹脂組成物，其中，該羧酸鹽之量以固體計且以總可固化之樹脂組成物百分比表示，係0.03wt%至0.3wt%。
- 如申請專利範圍第9項所述之可固化之樹脂組成物，其中，該碳二醯亞胺預聚物包含30wt%至50wt%之聚醚多元醇之聚合殘基，且其中，該羧酸鹽係經包封。
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| US2800457A (en) | 1953-06-30 | 1957-07-23 | Ncr Co | Oil-containing microscopic capsules and method of making them |
| BE530009A (zh) | 1953-06-30 | |||
| JPS56140354A (en) | 1980-04-04 | 1981-11-02 | Hitachi Ltd | Manufacture of composite type electrophotographic plate |
| JPS6140354A (ja) * | 1984-08-01 | 1986-02-26 | Teijin Ltd | 樹脂組成物 |
| JPS61268714A (ja) * | 1985-05-22 | 1986-11-28 | Nisshinbo Ind Inc | 耐熱性の高い熱硬化性樹脂の製造方法 |
| DE3609687A1 (de) * | 1985-03-29 | 1986-10-02 | Nisshinbo Industries, Inc., Tokio/Tokyo | Duroplastisches harz und verfahren zu seiner erzeugung |
| US5271881A (en) | 1987-09-28 | 1993-12-21 | Redding Bruce K | Apparatus and method for making microcapsules |
| IT1230705B (it) * | 1989-01-27 | 1991-10-29 | Boston Spa | Composizione di hot melt reticolabile |
| JPH05320611A (ja) * | 1992-05-18 | 1993-12-03 | Nisshinbo Ind Inc | フィルム状接着剤組成物 |
| US5574083A (en) * | 1993-06-11 | 1996-11-12 | Rohm And Haas Company | Aromatic polycarbodiimide crosslinkers |
| US5357021A (en) | 1993-07-21 | 1994-10-18 | Basf Corporation | Reactive carbodimide compositions |
| JP2002187932A (ja) * | 2000-12-19 | 2002-07-05 | Dainichiseika Color & Chem Mfg Co Ltd | ポリカルボジイミド化合物、その製造方法および物品の処理方法 |
| EP1593728B1 (en) * | 2004-05-03 | 2012-05-09 | Rohm And Haas Company | Michael addition compositions |
| EP1593727B1 (en) * | 2004-05-03 | 2008-08-06 | Rohm And Haas Company | Michael addition compositions |
| EP1640388B1 (en) * | 2004-09-24 | 2015-02-25 | Rohm and Haas Company | Biomass based Michael addition composition |
| ES2335327T3 (es) * | 2007-03-05 | 2010-03-24 | Basf Se | Poliisocianurato compacto con propiedades mejoradas de elaboracion y de produccion asi como procedimiento para su obtencion. |
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| Publication number | Publication date |
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| US9328189B2 (en) | 2016-05-03 |
| CN104704056B (zh) | 2017-03-08 |
| BR112015006952B1 (pt) | 2021-05-25 |
| JP2015531423A (ja) | 2015-11-02 |
| RU2015117392A (ru) | 2016-11-27 |
| CN104704056A (zh) | 2015-06-10 |
| EP2885351A1 (en) | 2015-06-24 |
| RU2642462C2 (ru) | 2018-01-25 |
| EP2885351B1 (en) | 2019-06-26 |
| WO2014058700A1 (en) | 2014-04-17 |
| BR112015006952A2 (pt) | 2017-07-04 |
| MX2015003858A (es) | 2015-07-17 |
| JP6309958B2 (ja) | 2018-04-11 |
| US20150240022A1 (en) | 2015-08-27 |
| TWI500701B (zh) | 2015-09-21 |
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