TWI674294B - 改良包括聚異三聚氰酸酯之反應產物斷裂韌性之方法 - Google Patents
改良包括聚異三聚氰酸酯之反應產物斷裂韌性之方法 Download PDFInfo
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- TWI674294B TWI674294B TW104124978A TW104124978A TWI674294B TW I674294 B TWI674294 B TW I674294B TW 104124978 A TW104124978 A TW 104124978A TW 104124978 A TW104124978 A TW 104124978A TW I674294 B TWI674294 B TW I674294B
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- Prior art keywords
- curable composition
- polyisocyanate
- polyisocyanurate
- isocyanate
- block copolymer
- Prior art date
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Abstract
本發明係關於一種用於製備包括聚異三聚氰酸酯之產物的可固化組合物,其藉由以至少100的異氰酸酯指數組合並混合至少聚異氰酸酯組合物、包括至少50莫耳%二醇之異氰酸酯反應性組合物及包括丙烯酸嵌段共聚物之韌化劑來獲得。
Description
本發明係關於改良包括聚異三聚氰酸酯之材料斷裂韌性的方法。
本發明進一步關於使用特定多元醇組合物以使得包括聚異三聚氰酸酯之材料的聚異三聚氰酸酯基質更具韌性。
本發明進一步關於使用特定嵌段共聚物韌化劑以增加包括聚異三聚氰酸酯之材料的斷裂韌性。
本發明進一步關於具有增加之韌性的包括聚異三聚氰酸酯之材料。
本發明進一步關於具有>100℃玻璃轉移溫度的包括聚異三聚氰酸酯之材料。
特定言之,本發明係關於藉由使用基於反應性可固化組合物之總重量計算>40重量%聚異氰酸酯(較佳超過50%,更佳超過60%)製備的包括聚異三聚氰酸酯之材料。
根據本發明之包括聚異三聚氰酸酯之材料極適合於製備具有>100℃玻璃轉移溫度及顯著改良之斷裂韌性值的包括聚異三聚氰酸酯之材料(PIR)。
結構複合物已知適用於諸多應用,諸如電氣、航空、運輸及戶
外體育設備應用。
異氰酸酯加聚反應產物,諸如包括聚異三聚氰酸酯之材料,常用作結構複合物中之聚合物基質。固化之包括聚異三聚氰酸酯之材料因其良好的熱學、機械及化學性質而為所知,但其缺乏韌性且在固化時往往為脆性的。
此外,包括聚異三聚氰酸酯之材料已知極難以韌化,且一些可能太脆而難以有效地韌化。過去嘗試增加斷裂韌性常常以模數改變(通常降低)及熱學性質(例如,玻璃轉移溫度(Tg))降低為代價,藉此對所得複合物之適用性產生不可接受的限制。
舉例而言,為增加包括聚異三聚氰酸酯之材料的韌性,已添加塑化劑作為添加劑從而給予此等材料以改良之可撓性及耐久性。鄰苯二甲酸酯最常用作塑化劑。塑化劑藉由將自身嵌入於聚合物鏈之間,從而將其隔開(增加「自由體積」)而起作用,然而,此韌性改良通常導致模數及玻璃轉移溫度(Tg)顯著降低。
亦可藉由改變具有高分子量之多元醇之量來實現控制包括聚異三聚氰酸酯之材料的斷裂韌性。然而,此亦導致材料具有較低玻璃轉移溫度及較低模數。
或者,亦可藉由添加核殼粒子來實現包括聚異三聚氰酸酯之材料的斷裂韌性,然而,此包括將固體粒子添加至液體樹脂中,此隱含穩定性問題。
因此,行業中存在開發可固化聚異氰酸酯組合物用於製備具有改良延展性(亦即斷裂韌性)同時仍保持其他關鍵處理(例如,黏度)及效能(例如,玻璃轉移溫度及模數)性質之包括聚異三聚氰酸酯之結構複合物的需求。
本發明之目的為改良具有>100℃玻璃轉移溫度(Tg)之包括聚異三
聚氰酸酯之材料的斷裂韌性。
本發明之另一目標為開發可耐受高外力且可用於(例如)汽車構造中的包括聚異三聚氰酸酯之結構組件。待開發之結構組件(亦稱為複合元件)應當能夠用作已知鋼結構之替換件,且特定言之,在其重量、製造方法及維持強度方面具有優勢。
根據第一態樣,揭示用於製備包括聚異三聚氰酸酯之產物的可固化組合物,該組合物藉由以至少100之異氰酸酯指數組合並混合以下各物獲得:a)聚異氰酸酯組合物,b)異氰酸酯反應性組合物,其包括基於該異氰酸酯反應性組合物中之異氰酸酯反應性化合物之總莫耳數計算至少50莫耳%,較佳至少70莫耳%,更佳至少90莫耳%二醇,c)包括丙烯酸嵌段共聚物之韌化劑,d)三聚催化劑組合物,及e)視情況選用之其他添加劑及/或輔助化合物,其中該可固化組合物中之聚異氰酸酯的量包括基於反應性可固化組合物總重量計算至少40重量%聚異氰酸酯。
根據實施例,該可固化組合物中之聚異氰酸酯的量包括基於反應性可固化組合物總重量計算較佳至少50重量%聚異氰酸酯,更佳至少60重量%聚異氰酸酯。
根據實施例,該異氰酸酯反應性組合物包括芳族多元醇,較佳芳族聚酯多元醇,更佳芳族聚酯二醇。
根據實施例,該等二醇具有小於1000g/mol,較佳小於500g/mol之分子量(MW),且包括對應於式CnH2n(OH)2及CnH2nO(OH)2的伸烷基二醇及/或氧基伸烷基二醇。
根據實施例,該等二醇係選自聚乙二醇及/或聚丙二醇-(1,2)及-(1,3)、聚丁二醇-(1,4)及-(2,3)、聚己二醇-(1,6)、聚辛二醇-(1,8)及其混合物。
根據實施例,該嵌段共聚物韌化劑為自組裝嵌段共聚物,其中至少一個嵌段為具有高於100℃之玻璃轉移溫度(Tg)之聚異氰酸酯/聚異三聚氰酸酯可混溶嵌段,且至少一個嵌段為具有低於0℃(更佳低於-40℃)之Tg之聚異氰酸酯/聚異三聚氰酸酯不可混溶嵌段,且其中該共聚物於可固化組合物中之存在量以可固化組合物總重量計介於0.1重量%至30重量%,較佳0.5重量%至15重量%,更佳1重量%至10重量%之範圍內。
根據實施例,該嵌段共聚物韌化劑為具有至少1000g/mol,較佳在10000至500000g/mol範圍內,更佳在20000至200000g/mol範圍內之數目平均分子量(MW)的自組裝嵌段共聚物。
根據實施例,該嵌段共聚物之聚異氰酸酯/聚異三聚氰酸酯可混溶嵌段係選自聚甲基丙烯酸甲酯(Tg=105℃)及/或聚苯乙烯(Tg=100℃),且該嵌段共聚物之聚異氰酸酯/聚異三聚氰酸酯不可混溶嵌段係選自聚丙烯酸烷酯及/或聚二烯,尤其為聚丁二烯,諸如1,4-聚丁二烯及/或聚異戊二烯及其無規共聚物。
根據實施例,該聚異氰酸酯係選自脂族、環脂族、芳脂族及較佳芳族聚異氰酸酯,諸如其2,4及2,6-異構體形式之二異氰酸甲苯酯及其混合物、二異氰酸二苯基甲烷酯及其變體、及二異氰酸二苯基甲烷酯(MDI)及其具有大於2之異氰酸酯官能度之寡聚物的混合物。
根據實施例,該三聚催化劑組合物係選自較佳具有1至12個碳原子之有機羧酸的鹼金屬及/或鹼土金屬鹽,諸如乙酸鉀或2-乙基己酸鉀,諸如乙酸鉀、己酸鉀、乙基己酸鉀、辛酸鉀、乳酸鉀、乙醇鈉、甲酸鈉、甲酸鉀、乙酸鈉、苯甲酸鉀及其混合物。
根據實施例,該三聚催化劑組合物係選自含有鹵化鋰(較佳LiCl)、環氧樹脂及視情況選用之脲化合物的組合物。
根據實施例,三聚催化劑組合物以基於可固化組合物總重量計算0.001至10重量%,較佳0.1至5重量%,最佳0.5至2.0重量%之量來使用。
根據實施例,該等輔助化合物係選自非異氰酸酯反應性溶劑、界面活性劑、清除劑(如原甲酸烷酯,且尤其為原甲酸三異丙酯)、抗微生物劑、阻燃劑、煙霧抑制劑、UV穩定劑、著色劑、塑化劑、內部脫模劑、流變改質劑、潤濕劑、分散劑及填充劑。
根據實施例,輔助化合物包括選自以下之填充劑材料:木片、木粉、木薄片、木板;紙及卡紙板,均撕碎或層狀;砂、蛭石、黏土、水泥及其他矽酸鹽;橡膠粉、熱塑性塑膠粉、熱固性材料粉;任何材料之蜂窩狀物,如卡紙板、鋁、木材及塑膠;金屬粒子及板材;呈顆粒形式或層狀之軟木;天然纖維,如亞麻、大麻及劍麻纖維;合成纖維,如聚醯胺、聚烯烴、聚芳醯胺、聚酯及碳纖維;礦物纖維,如玻璃纖維及岩絨纖維;礦物填充劑,如BaSO4及CaCO3;奈米粒子,如黏土、無機氧化物及碳;玻璃珠、磨砂玻璃、空心玻璃珠;膨脹或可膨脹珠粒;未處理或經處理廢料,如經碾磨、經短切、經碾碎或經研磨廢料,且尤其為飛灰;編織及非編織紡織物;及兩種或兩種以上此等材料之組合。
根據第二態樣,揭示用於製備該第一態樣之可固化組合物的製程(方法),該製程包括在環境壓力下且在5℃至45℃且更佳在5℃至30℃之溫度下組合並混合成分(a)至(e)。
根據實施例,該方法至少包括使根據第一態樣之可固化組合物以至少100之異氰酸酯指數且在高於50℃(較佳高於80℃)之固化溫度下反應的步驟。
根據實施例,方法為分批、半連續或連續製程;射出、擠出、拉擠成形製程或模製製程,諸如壓縮模製製程、樹脂轉移模製製程、真空輔助模製製程、樹脂灌注模製製程、預浸製程。
根據實施例,異氰酸酯指數在100至15000範圍內,較佳在100至500範圍內,更佳在100至300範圍內。
根據實施例,固化溫度在50℃至350℃之間,且最佳在125℃至250℃之間的範圍內。
根據第三態樣,揭示包括聚異三聚氰酸酯之材料,該材料藉由根據第二態樣之方法獲得,且其玻璃轉移溫度>100℃、斷裂韌性值G1c>1000J/m2,較佳G1c>1500J/m2,及/或韌性值K1c>2MPa.m1/2。
進一步根據第三態樣,揭示包括聚異三聚氰酸酯之材料,該材料藉由根據第二態樣之方法獲得,且其玻璃轉移溫度>150℃、韌性值G1c>500J/m2,更佳G1c>600J/m2,及/或韌性值K1c>1MPa.m1/2。
申請專利範圍獨立項及附屬項陳述本發明的特定及較佳特徵。來自申請專利範圍附屬項之特徵按需要可與申請專利範圍獨立項或其他附屬項之特徵組合。
根據以下詳細描述,結合藉助於實例說明本發明之原理的隨附實例,本發明之以上及其他特性、特徵及優點將變得顯而易見。
在本發明之情形下,以下術語具有以下含義:
1)包括至少一種聚異氰酸酯組合物、三聚催化劑組合物及包括異氰酸酯反應性氫原子之固化劑化合物(諸如,多元醇)或任何其他適合固化劑之組合物在本文中稱為「可固化組合物」。此組合物係指在固化之前(亦即在聚異三聚氰酸酯形成之前)的液體組合物。
2)「異氰酸酯指數」或「NCO指數」或指數為NCO基團比調配物中存在之異氰酸酯反應性氫原子之比率,以百分比給出:
換言之,NCO指數表示實際上用於調配物中的異氰酸酯相對於與調配物中所用異氰酸酯反應性氫之量反應的所需之理論異氰酸酯量的百分比。
應觀察到,如本文所使用之異氰酸酯指數為自製備涉及異氰酸酯成分及異氰酸酯反應性成分之材料的實際聚合方法觀點考慮的。計算異氰酸酯指數考慮在預備步驟中產生經改質之聚異氰酸酯(包括在此項技術中稱為預聚物之該等異氰酸酯衍生物)所消耗的任何異氰酸酯基團或在預備步驟中消耗的任何活性氫(例如與異氰酸酯反應以產生經改質的多元醇或多元胺)。
3)如本文出於計算異氰酸酯指數之目的所用之表述「異氰酸酯反應性氫原子」係指存在於反應性組合物中之羥基及胺基中的全部活性氫原子;此意謂出於在實際聚合方法中計算異氰酸酯指數之目的,一個羥基視為包括一個反應性氫,一個一級胺基視為包括一個反應性氫,且一個水分子視為包括兩個活性氫。
4)術語「平均標稱羥基官能度」(或簡而言之「官能度」)在本文中用於指示多元醇或多元醇組合物之數目平均官能度(每分子羥基之數目),假設此為用於其製備之引發劑的數目平均官能度(每分子活性氫原子之數目),但在實踐中其常常因為一定程度的末端不飽和而略微較小。
5)除非另外規定,否則詞「平均」係指數目平均。
6)「液體」意謂具有根據ASTM D445-11a在20℃下量測的小於10Pa.s之黏度。
7)如本文所使用之「三聚催化劑」係指能夠催化(促進)自聚異氰酸酯形成異三聚氰酸酯基的催化劑。
8)「包括聚異三聚氰酸酯之材料」係指基於材料總重量計算包括超過10重量%聚異三聚氰酸酯,較佳至少50重量%聚異三聚氰酸酯,更佳地75重量%聚異三聚氰酸酯的組合物。
9)「Mc」係指交聯之間的平均分子量,例如在包括聚異三聚氰酸酯之材料中之2個異三聚氰酸酯基團之交聯之間的平均分子量。
10)「密度」係指根據ISO 845量測之整體密度。
11)「玻璃轉移溫度」(Tg)係指發生自硬玻璃狀態至橡膠彈性狀態之可逆轉移的溫度。玻璃轉移溫度(Tg)根據ASTM D 4065-1以雙重懸臂(dual cantilever)中之強制恆定振幅及固定頻率量測。正切δ(tan d)曲線之最大峰值視為Tg。
12)「斷裂韌性」為預先存在裂痕之樣本在其碎裂之前能夠吸收的能量量度。在本發明之情形下,斷裂韌性表示為均根據ISO 13586量測之K1c值及/或G1c值。G1c值(單位J/m2)或臨界能量釋放速率為斷裂能量之量度。K1c值或臨界應力強度因子為針對裂痕生長開始之臨界應力強度抗性之量度。G1c值或K1c值愈高,材料更為阻抗裂痕生長開始。
13)「共聚物」[1]係指具有兩個或兩個以上不同單體單元之聚合物。「嵌段共聚物」[2]包括由共價鍵鍵聯之兩個或兩個以上均聚物嵌段。根據本發明之適合之嵌段共聚物具有至少一個表徵為主要聚異氰酸酯/聚異三聚氰酸酯可混溶嵌段的嵌段,及至少一個表徵為主要聚異氰酸酯/聚異三聚氰酸酯不可混溶嵌段的嵌段。可在本發明中採用的嵌段共聚物可包含(例如)二嵌段共聚物、線性三嵌段、線性四嵌段、較高階多嵌段結構、分枝嵌段結構或星形嵌段結構。
-A-B-A-B-A-B-A-B-A-B- [1]
-B-B-B-B-B-A-A-A-A-A- [2]
14)「丙烯酸酯嵌段共聚物」或「丙烯酸嵌段共聚物」係指包
括丙烯酸酯均聚物嵌段之嵌段共聚物。適合之丙烯酸酯均聚物嵌段之實例為甲基丙烯酸酯、丙烯酸甲酯、丙烯酸乙酯、丙烯酸2-乙基己酯、甲基丙烯酸羥基乙酯、丙烯酸丁酯、甲基丙烯酸丁酯……
圖1A及圖1B說明根據本發明之自組裝丙烯酸嵌段共聚物。圖1A說明由聚丙烯酸丁酯(PBuA)中間嵌段及兩個聚甲基丙烯酸甲酯(PMMA)側嵌段組成之自組裝丙烯酸嵌段共聚物。圖1B說明由一個聚甲基丙烯酸甲酯嵌段(PMMA)及一個聚丙烯酸丁酯嵌段(PBuA)組成之自組裝丙烯酸嵌段共聚物。
圖2說明在固化之後的聚異三聚氰酸酯材料中根據本發明之自組裝嵌段共聚物的存在。
本發明將關於特定實施例加以描述。
應注意到,申請專利範圍中所用之術語「包括」不應解釋為受限於其後所列構件;其並不排除其他元素或步驟。因此,應解釋為指定如提及之所述特徵、步驟或組件的存在,但並不排除一或多個其他特徵、步驟或組件、或其群組的存在或添加。因此,表述「包括構件A及B之裝置」之範疇不應限於僅由組件A及B組成之裝置。就本發明而論,其意謂裝置之僅相關組分為A及B。
貫穿本說明書,提及「一個實施例」或「一實施例」。該等提及指示關於該實施例描述之特定特徵包括於本發明之至少一個實施例中。因此,貫穿本說明書多個地方出現片語「在一個實施例中」或「在一實施例中」不必全部參考同一實施例,但其可以如此。此外,在一或多個實施例中特定性質或特徵可以任何適合之方式組合,此對一般熟習此項技術者而言將為顯而易見。
出人意料地,已經發現藉由使用基於反應性可固化組合物總重
量計算40重量%聚異氰酸酯所製備且具有至少100℃玻璃轉移溫度的包括聚異三聚氰酸酯之材料可顯著改良產物之斷裂韌性及模數。
因此,本發明涉及可固化聚異氰酸酯組合物及用於製備該可固化組合物之方法,該可固化組合物適用於製備斷裂韌性顯著增加的包括聚異三聚氰酸酯之材料。根據本發明之可固化聚異氰酸酯組合物一方面包括特定多元醇組合物作為異氰酸酯反應性化合物(固化劑),且另一方面包括嵌段共聚物作為額外韌化劑。聚異氰酸酯反應性組合物將改質固化之後的包括聚異三聚氰酸酯之基質,同時韌化劑將作為第二相存在於固化之後的包括聚異三聚氰酸酯之基質內。
根據實施例,可固化聚異氰酸酯組合物藉由組合至少以下各物而獲得:a)聚異氰酸酯組合物,b)異氰酸酯反應性組合物,其包括基於該異氰酸酯反應性組合物中之異氰酸酯反應性化合物總莫耳數計算至少50莫耳%,較佳至少70莫耳%,更佳至少90莫耳%二醇,c)包括丙烯酸嵌段共聚物之韌化劑,d)三聚催化劑組合物,及e)視情況選用之其他添加劑及/或輔助化合物,其中,可固化組合物中之聚異氰酸酯量包括基於反應性可固化組合物總重量計算至少40重量%聚異氰酸酯,較佳>50重量%聚異氰酸酯更佳>60重量%聚異氰酸酯。
本發明可包括雙重方法,其中一方面藉由使用特定多元醇組合物作為異氰酸酯反應性組合物且另一方面在聚異三聚氰酸酯基質中引入嵌段共聚物來實現聚異三聚氰酸酯基質之分子重新設計。若想顯著增加斷裂韌性(例如,G1c增加數量級),則該雙重方法至關重要。
根據實施例,藉由組態交聯之間的分子量(Mc,g/mol)達成聚異
三聚氰酸酯基質之分子重新設計。交聯之間的分子量Mc較佳>300g/mol,更佳>500g/mol,最佳700g/mol。目標為增加交聯之間的分子量,藉此減小交聯密度。
根據實施例,可藉由使用低分子量二醇(MW<1000)達成聚異三聚氰酸酯基質之分子重新設計。此等低分子量二醇可充當異三聚氰酸酯交聯之間的『間隔子』。
根據實施例,藉由主要使用二醇作為異氰酸酯反應性組合物達成聚異三聚氰酸酯基質之分子重新設計(多元醇具有給出2個異氰酸酯反應性氫之2個羥基)。
根據實施例,可藉由主要使用具有低旋轉能量障壁之共價鍵的二醇達成聚異三聚氰酸酯基質之分子重新設計。該等『可旋轉』鍵之實例為酯及/或醚鍵。
根據實施例,藉由主要使用二醇作為異氰酸酯反應性組合物達成聚異三聚氰酸酯基質之分子重新設計。異氰酸酯反應性組合物可包括芳族多元醇,該等芳族多元醇較佳為芳族聚酯多元醇,該等芳族多元醇最佳為芳族聚酯二醇。使用此等芳族(聚酯)多元醇將限制聚異三聚氰酸酯基質之芳香性的減少、維持或進一步增加。此為保持樹脂模數之方法。倘若額外芳族多元醇存在於異氰酸酯反應性組合物中,濃度始終使得二醇之量為基於異氰酸酯反應性組合物中之異氰酸酯反應性化合物全部莫耳計算至少50莫耳%,較佳至少70莫耳%,更佳至少90莫耳%二醇。
根據較佳實施例,適合之二醇係選自分子量(MW)低於1000g/mol,較佳低於500g/mol,甚至更佳低於300g/mol的二醇。其宜為通式CnH2n(OH)2的簡單二醇或特徵為在烴鏈中插入醚鍵之由通式CnH2nO(OH)2表示的聚乙二醇。適合之二醇之實例包括聚乙二醇(諸如,二乙二醇、三乙二醇及四乙二醇)、聚丙二醇-(1,2)及-(1,3)(諸
如,二丙二醇、三丙二醇及四丙二醇)、聚丁二醇-(1,4)及-(2,3)、聚己二醇-(1,6)、聚辛二醇-(1,8)……及其混合物。
根據實施例,適合之芳族聚酯多元醇為PET多元醇(二醇),在此情形下,歸因於可旋轉酯鍵之存在,對彎曲及拉伸的高節段性抗性(導致硬度)與節段性可撓性組合。
在芳族聚酯多元醇中,多元醇或聚羧酸(較佳酸)中之至少一者為芳族化合物,且芳香性為基於聚酯多元醇總重量計算至少40重量%。酸組分宜包括至少30重量%鄰苯二甲酸(或其異構體)殘基的聚酯多元醇尤其適用。芳族聚酯多元醇之芳香性較佳在基於聚酯多元醇總重量計算70與90重量%之間。用於本發明之較佳芳族聚酯多元醇包括:STEPA® POL PS2352、PS3152及PS 1752,全部可購自Stepan;Hoopol® F-1390、F-1391、F-3362、F-4361、F-4396及F-7021,全部可購自Syntesia;及Isoexter® 3061、3557、3446及4404,全部可購自Coim。
本發明之嵌段共聚物韌化劑較佳將充當第二相韌化劑,在固化之後,該嵌段共聚物韌化劑自組裝成包括聚異三聚氰酸酯之主體基質中的第二相疇以進一步改良(固化的)包括聚異三聚氰酸酯之材料的韌性。自組裝嵌段共聚物呈現類似界面活性劑的形態,其在極低嵌段共聚物負載(例如,以包括聚異三聚氰酸酯之材料之總重量計約1重量%至約10重量%)下提供增強之斷裂韌性。
「第二相」意謂與包括聚異三聚氰酸酯之基質的另一相相異且不同的實體相。因為改質限於第二相,故僅需要較低含量之嵌段共聚物以獲得所需位準之韌性。一般而言,本發明中作為韌化劑之嵌段共聚物之有效量可在以包括聚異三聚氰酸酯之最終產物之總重量計約0.1重量%至約30重量%,較佳約0.5重量%至約15重量%,且更佳約1重量%至約10重量%範圍內。
在一較佳實施例中,嵌段共聚物可包括(例如)二嵌段共聚物、線性三嵌段、線性四嵌段、較高階多嵌段結構、分枝嵌段結構或星形嵌段結構。
嵌段共聚物具有包括彼此共價鍵聯之化學相異均聚物序列的結構。在本體或選擇性溶劑(例如,聚異氰酸酯或聚異三聚氰酸酯)中,嵌段共聚物自發自組裝以形成奈米結構形態。
根據實施例,兩種或兩種以上不同嵌段共聚物可摻合在一起以組成本發明之嵌段共聚物組分。較佳,在各嵌段共聚物中,至少一個嵌段為聚異氰酸酯/聚異三聚氰酸酯可混溶嵌段,且至少一個嵌段為聚異氰酸酯/聚異三聚氰酸酯不可混溶嵌段。
本發明之嵌段共聚物韌化劑較佳包括至少一或多種嵌段共聚物,其中至少一個嵌段為較佳具有高於100℃之高Tg之聚異氰酸酯/聚異三聚氰酸酯可混溶嵌段,且至少一個嵌段為較佳具有低於0℃,更佳<-40℃之低Tg(橡膠質)之聚異氰酸酯/聚異三聚氰酸酯不可混溶嵌段。
根據實施例,嵌段共聚物不與聚異氰酸酯/聚異三聚氰酸酯基質反應,意謂存在於嵌段共聚物中之單體不具有針對聚異氰酸酯之反應基。此具有使用該等嵌段共聚物可增加韌性而不顯著損失Tg或模數的優勢。
本發明中所使用之嵌段共聚物對於聚異氰酸酯/聚異三聚氰酸酯可混溶嵌段及聚異氰酸酯/聚異三聚氰酸酯不可混溶嵌段兩者之組合可具有至少1000g/mol,較佳在10000g/mol與500000g/mol之間,更佳在20000與200000g/mol之間的數目平均分子量(MW)。
用於合成嵌段共聚物之聚異氰酸酯/聚異三聚氰酸酯不可混溶嵌段的單體之實例可選自由以下選出的二烯:丁二烯、異戊二烯、2,3-二甲基-1,3-丁二烯、1,3-戊二烯或2-苯基-1,3-丁二烯。聚異氰酸酯/聚
異三聚氰酸酯不可混溶嵌段宜選自聚二烯,特定言之,聚丁二烯、聚異戊二烯及其無規共聚物、或部分或完全氫化之聚二烯。宜使用具有最低Tg的聚丁二烯,例如Tg低於1,2-聚丁二烯(Tg大約0℃)的1,4-聚丁二烯(Tg大約-90℃)。
用於合成嵌段共聚物之聚異氰酸酯/聚異三聚氰酸酯不可混溶嵌段的單體之實例可選自丙烯酸烷酯。獲得以下Tg值:丙烯酸乙酯(-24℃)、丙烯酸丁酯(-54℃)、丙烯酸2-乙基己酯(-85℃)、丙烯酸羥基乙酯(-15℃)……宜使用丙烯酸丁酯。丙烯酸酯不同於嵌段共聚物之聚異氰酸酯/聚異三聚氰酸酯可混溶嵌段中之丙烯酸酯,以便觀測聚異氰酸酯/聚異三聚氰酸酯可混溶及不可混溶嵌段不相容的情形。
用於合成嵌段共聚物之聚異氰酸酯/聚異三聚氰酸酯可混溶嵌段的單體之實例可選自甲基丙烯酸甲酯(Tg=105℃)及苯乙烯(Tg=100℃)。
根據實施例,嵌段共聚物具有至少一個聚異氰酸酯/聚異三聚氰酸酯可混溶嵌段,其主要由甲基丙烯酸甲酯單體組成,較佳由至少50質量%甲基丙烯酸甲酯組成,更佳由至少75質量%甲基丙烯酸甲酯組成。
根據較佳實施例,嵌段共聚物為自組裝嵌段共聚物,其可自組織成奈米結構。可自組裝之適合嵌段共聚物較佳由彼此共價鍵聯之線性鏈的兩個或三個嵌段組成,其中一個嵌段為聚異氰酸酯/聚異三聚氰酸酯不可混溶嵌段,且至少一個嵌段為聚異氰酸酯/聚異三聚氰酸酯可混溶嵌段。舉例而言,適合之嵌段共聚物可由聚丙烯酸丁酯(PBuA)中間嵌段及兩個聚甲基丙烯酸甲酯(PMMA)側嵌段組成。由於三個嵌段之間之排斥性相互作用,嵌段共聚物將以奈米級自組織產生自組裝嵌段共聚物。與可與其一個嵌段相容的聚合物摻合,自組裝嵌段共聚物易於分散且施加結構至主體基質。此組織賦予性質之獨特組合,諸如耐衝擊強度、高剛性及透明度。歸因於導致奈米結構化之自
組裝性質,嵌段共聚物可提供相比於反應性橡膠撓化劑的優良韌化。實際上,自組裝嵌段共聚物可在顯著低濃度下使用。自組裝嵌段共聚物之額外優勢包含能夠將此等聚合物溶解於聚異氰酸酯/聚異三聚氰酸酯基質中,且無需費時及不一致的事先分散。
根據實施例,嵌段共聚物為具有兩個聚異氰酸酯/聚異三聚氰酸酯可混溶嵌段及一個聚異氰酸酯/聚異三聚氰酸酯不可混溶嵌段(以下稱作「B」)的三嵌段共聚物,其可表示為「A-B-A」。三嵌段共聚物組合物關於聚異氰酸酯/聚異三聚氰酸酯可混溶A嵌段及聚異氰酸酯/聚異三聚氰酸酯不可混溶B嵌段表示為質量分數之量(總量為100%)為:10%至80%,較佳15%至70% A嵌段90%至20%,較佳85%至30% B嵌段。
根據實施例,嵌段共聚物為自組裝丙烯酸嵌段共聚物,諸如可商購的Nanostrength®嵌段共聚物,例如由聚甲基丙烯酸甲酯嵌段(PMMA)及聚丙烯酸丁酯嵌段(PBuA)組成之嵌段共聚物。PMMA嵌段將給予與聚異三聚氰酸酯基質之相容性,同時PBuA嵌段提供用於韌化之不可混溶的軟橡膠相。可商購的丙烯酸三嵌段共聚物為來自Nanostrength®之M51、M52及M52N,此等所謂的ABA類型嵌段共聚物PMMA-PBuA-PMMA由剛性PMMA及橡膠質PBuA嵌段組成。由於異氰酸酯/異三聚氰酸酯與一側之PMMA之間的親和力,及在異氰酸酯/異三聚氰酸酯與中間PBuA嵌段之間的排斥力,M51、M52及M52N嵌段共聚物易於溶解於聚異氰酸酯/聚異三聚氰酸酯中,且按奈米層級自組織。其他可商購之適合之嵌段共聚物為來自Nanostrength®的M22N、M53及D51N。圖1A說明在聚異三聚氰酸酯基質中之分散相,其說明由球形硬殼層包圍橡膠核製成的球形膠束。
在本發明之另一實施例中,當嵌段共聚物具有多嵌段共聚物結
構時,除聚異三聚氰酸酯可混溶嵌段及聚異三聚氰酸酯不可混溶嵌段之外,其他嵌段可存在於嵌段共聚物中。
用於本發明中之嵌段共聚物韌化劑進一步改良包括聚異三聚氰酸酯之材料的斷裂抗性,從而改良斷裂韌性。當在用於製備異三聚氰酸酯基質的方法中共聚物韌化劑與特定二醇(多元醇)組合使用時,可見包括聚異三聚氰酸酯之材料之韌性改良上的協同效應。
用於製備根據本發明之包括聚異三聚氰酸酯之材料的嵌段共聚物韌化劑之量一般為以包括聚異三聚氰酸酯之材料總重量計約0.1重量%至約30重量%,較佳為以包括聚異三聚氰酸酯之材料總重量計約0.5重量%至約15重量%,且更佳為以包括聚異三聚氰酸酯之材料總重量計約1重量%至約10重量%。
用於製備根據本發明之包括聚異三聚氰酸酯之材料的嵌段共聚物韌化劑之量一般為以可固化組合物之總重量計約0.1重量%至約30重量%,較佳為以可固化組合物之總重量計約0.5重量%至約15重量%,且更佳為以可固化組合物之總重量計約1重量%至約10重量%。
根據實施例,聚異氰酸酯可選自脂族、環脂族、芳脂族及較佳芳族聚異氰酸酯,諸如呈2,4及2,6異構體形式之二異氰酸甲苯酯及其混合物、二異氰酸二苯基甲烷酯及其變體、及二異氰酸二苯基甲烷酯(MDI)及其具有大於2之異氰酸酯官能度之寡聚物(在此項技術中稱為「粗」或聚合MDI(聚亞甲基聚伸苯基聚異氰酸酯))的混合物。亦可使用二異氰酸甲苯酯、二異氰酸二苯基甲烷酯及/或聚亞甲基聚伸苯聚異氰酸酯之混合物。
催化異氰酸酯三聚反應(形成異三聚氰酸酯)之任何化合物可用作本發明中之三聚催化劑。
根據實施例,三聚催化劑組合物包括選自以下之化合物:有機金屬鹽,較佳鹼金屬或鹼土有機金屬鹽,更佳金屬羧酸鹽或烷醇鹽及
其混合物,羧酸鹽/烷醇鹽基較佳具有1至12個碳原子,諸如乙酸鉀、己酸鉀、乙基己酸鉀、辛酸鉀、乳酸鉀、乙醇鈉、甲酸鈉、甲酸鉀、乙酸鈉、苯甲酸鉀及其混合物。
根據實施例,三聚催化劑組合物可選自有機羧酸之鹼金屬鹽,諸如乙酸鉀(可作為Polycat®46商購(購自Air Products及催化劑LB(購自Huntsman)或2-乙基己酸鉀(可作為Dabco®K15商購(購自Air Products)),由於此等物質並不如包括胺之催化劑般促進異氰酸酯/水反應。過度異氰酸酯/水反應將引起初步固化。
根據實施例,三聚催化劑組合物係選自含有鋰鹵化物(較佳LiCl)、環氧樹脂及視情況選用之脲化合物的組合物。此催化劑組合物描述於以引用的方式併入本文中的WO2010/121898中。通常催化劑組合物使得每異氰酸酯當量之鋰鹵化物之莫耳數在0.0001至0.04範圍內。
三聚催化劑組合物一般使得存在於催化劑組合物中之催化劑化合物之量以可固化組合物總重量計在0.001至10重量%範圍內,較佳0.1至5重量%,最佳0.5至2.0重量%。
除三聚促進催化劑之外,亦可添加控制聚胺甲酸酯固化之催化劑。但在較佳實施例中,該催化劑並不存在。
該等適合(形成聚胺甲酸酯)催化劑之實例為本身已知的,且包含三級胺(諸如,三乙胺、三丙胺、三丁胺及三戊胺)、N-甲基嗎啉、N,N-二甲基環己胺、N,N-二甲基苯甲胺、2-甲基咪唑、嘧啶、二甲基苯胺及三伸乙基二胺。含有異氰酸酯反應性氫原子之三級胺之實例為三乙醇胺及N,N-二甲基乙醇胺。其他適合之催化劑為具有碳-矽鍵之矽胺及含氮鹼(諸如,四烷基銨氫氧化物、鹼金屬氫氧化物、鹼金屬酚酸鹽及鹼金屬醇化物)。有機金屬化合物,尤其有機錫化合物,亦可用作催化劑。
根據本發明,用於製備包括聚異三聚氰酸酯之材料的可固化組合物可進一步包括添加劑及/或輔助化合物。
根據實施例,輔助化合物可選自非異氰酸酯反應性溶劑、界面活性劑、清除劑(如原甲酸烷酯及尤其原甲酸三異丙酯)、抗微生物劑、阻燃劑、煙霧抑制劑、UV穩定劑、著色劑、塑化劑、內部脫模劑、流變改質劑、潤濕劑、分散劑及填充劑。
根據實施例,填充劑材料可選自:木片、木粉、木薄片、木板材;紙及卡紙板,均撕碎或層狀;砂、蛭石、黏土、水泥及其他矽酸鹽;橡膠粉、熱塑性塑膠粉、熱固性材料粉;任何材料之蜂窩狀物,如卡紙板、鋁、木材及塑膠;金屬粒子及板材;呈顆粒形式或層狀軟木;天然纖維,如亞麻、大麻及劍麻纖維;合成纖維,如聚醯胺、聚烯烴、聚芳醯胺、聚酯及碳纖維;礦物纖維,如玻璃纖維及岩絨纖維;礦物填充劑,如BaSO4及CaCO3;奈米粒子,如黏土、無機氧化物及碳;玻璃珠、磨砂玻璃、空心玻璃珠;膨脹或可膨脹珠粒;未處理或經處理廢料,如碳碾磨、碳短切、碳碾碎或碳研磨廢料,且尤其為飛灰;編織及非編織紡織物;及兩種或兩種以上此等材料之組合。特定用途為製造含玄武岩纖維、碳纖維、亞麻纖維及/或玻璃纖維的半結構性及結構性複合物。
用以製備根據本發明之可固化組合物的聚異氰酸酯及其他成分之組合及混合較佳在環境壓力且在5℃與45℃之間,且更佳在5℃與30℃之間的溫度下進行,以便儘可能多地避免不當的過早反應。
根據實施例,可首先組合聚異氰酸酯組合物、三聚催化劑組合物及異氰酸酯反應性組合物,接著可添加包括嵌段共聚物之韌化劑及視情況選用之添加劑及/或輔助化合物。
根據實施例,可同時組合製備可固化組合物所需的全部成分。
本發明提供用於製備具有改良斷裂韌性之包括聚異三聚氰酸酯 之材料的方法。該方法至少包括使根據本發明第一態樣之可固化組合物反應的步驟。藉由施加熱,如將可固化組合物加熱至高於50℃且較佳高於80℃之溫度可加速反應開始。隨後可固化組合物快速固化(所謂瞬間固化),同時溫度進一步增加(反應為放熱的)。
根據實施例,用於製備具有改良斷裂韌性之包括聚異三聚氰酸酯之材料的方法包括使至少根據本發明之第一態樣之可固化組合物以至少100之異氰酸酯指數反應,該可固化組合物包括:a)聚異氰酸酯組合物,b)異氰酸酯反應性組合物,其包括基於該異氰酸酯反應性組合物中之異氰酸酯反應性化合物總莫耳數計算至少50莫耳%,較佳至少70莫耳%,更佳至少90莫耳%二醇,c)包括丙烯酸嵌段共聚物之韌化劑,d)三聚催化劑組合物,及e)視情況選用之其他添加劑及/或輔助化合物,其中,可固化組合物中之聚異氰酸酯量包括基於反應性可固化組合物總重量計算至少40重量%聚異氰酸酯,較佳>50重量%聚異氰酸酯,更佳>60重量%聚異氰酸酯。
根據實施例,用於製備具有改良斷裂韌性之包括聚異三聚氰酸酯之材料的方法包括使至少根據本發明第一態樣之可固化組合物(其包括至少組分a)至e))以至少100之異氰酸酯指數反應,特徵在於異氰酸酯反應性化合物b)包括選自二醇之化合物,使得交聯之間的平均分子量(Mc)>300g/mol,較佳>500g/mol,更佳700g/mol。
根據實施例,模製製程可用於製備包括聚異三聚氰酸酯之材料,在彼情況下,其可根據澆築模製製程、壓縮模製製程、樹脂轉移模製製程(且尤其真空輔助製程)、樹脂灌注製程、預浸製程及手工塗佈製程進行。該製程進一步可根據射出製程、擠出製程或拉擠成形製
程進行。亦可施加微波或感應固化。該製程可分批、半連續或連續進行。
根據實施例,包括聚異三聚氰酸酯之材料可為吹製產物,且發泡劑可選自惰性發泡劑及反應性發泡劑。惰性發泡劑之實例為烷烴、氫氟碳、氫氯氟碳化合物、可膨脹微珠及惰性氣體(如空氣、N2、CO2、CO、O2及He),且反應性發泡劑之實例為偶氮二甲醯胺及水。水為最佳發泡劑。所需發泡劑之實際量視用於製備聚異氰酸酯加聚產物的成分、生產製程、所選發泡劑及所需密度而定。一旦已經選定用於製備聚異氰酸酯加聚產物的成分、製程及所需密度,發泡劑量的確定為此項技術中一般熟習者的日常工作。
除以上成分以外,可使用此項技術中用於製造包括複數個胺基甲酸酯、脲及/或異三聚氰酸酯基團之材料之其他成分,如其他催化劑(例如用於促進胺基甲酸酯形成)、界面活性劑、阻燃劑、著色劑、顏料、抗微生物劑、填充劑、內部脫模劑、氣室穩定劑及氣室開放劑。
根據實施例,用於製備本發明之包括聚異三聚氰酸酯之材料的方法包括如下製程,其中使可固化組合物之化合物以在100至15000範圍內之異氰酸酯指數反應。反應較佳以較佳100至500,且最佳100至300之指數進行。
根據實施例,包括聚異三聚氰酸酯(PIR)之材料及用於形成該等包括聚異三聚氰酸酯之材料的方法進一步包括可固化組合物之化合物以在100至15000範圍內之異氰酸酯指數反應之步驟之後,在高溫下固化所獲得之組合物的步驟以便形成固化的包括聚異三聚氰酸酯之材料/產物。固化可在50℃與350℃之間,且最佳在125℃與250℃之間的範圍內的溫度下進行。此反應可耗時5秒至10小時,且較佳耗時15秒至2小時。該製程可在環境壓力或在減壓或高壓下進行。較佳施加熱以便
使(可固化)組合物達到高於50℃,且最佳高於80℃的溫度。隨後,可固化組合物可快速固化(所謂瞬間固化),同時,溫度進一步升高(反應為放熱的)。在固化包括聚異三聚氰酸酯之產物之前,(可固化)組合物可饋入至模具中以便給予其某一形狀,或饋入至目標物空穴中以便為目標物提供聚異三聚氰酸酯內部,或饋入至表面上以便為此種表面提供聚異三聚氰酸酯覆蓋層,或其可用於修復目標物。
根據實施例,包括聚異三聚氰酸酯(PIR)之產物可為以在100至15000範圍內,較佳以在100至300範圍內的異氰酸酯指數製得的吹製產物,且其中水及/或其他發泡劑以例如5pbw之量添加。所需發泡劑之實際量視用於製備包括聚異三聚氰酸酯之產物的成分、生產製程、所選發泡劑及所需密度而定。一旦已經選定用於製備包括聚異三聚氰酸酯之產物的成分、製程及所需密度,發泡劑量的確定為此項技術中一般熟習者的日常工作。
根據實施例,揭示具有增加斷裂韌性的包括聚異三聚氰酸酯之產物,其根據本發明之第二態樣的方法製得。特定言之,包括聚異三聚氰酸酯之產物的玻璃轉移溫度>100℃,較佳>120℃,更佳在120℃至200℃範圍內。
根據實施例,包括聚異三聚氰酸酯之產物之玻璃轉移溫度>100℃且斷裂韌性值G1c>1000J/m2,較佳G1c>1500J/m2。
根據實施例,包括聚異三聚氰酸酯之產物之斷裂韌性值G1c>500J/m2,較佳G1c>600J/m2且玻璃轉移溫度>150℃。
根據實施例,包括聚異三聚氰酸酯之產物之玻璃轉移溫度>100℃且韌性值K1c>2MPa.m1/2。
根據實施例,包括聚異三聚氰酸酯之產物之玻璃轉移溫度>150℃且韌性值K1c>1MPa.m1/2。
根據本發明之包括聚異三聚氰酸酯之產物可用於體育製品、汽
車部件之大量製造、火車部件、航空應用、船舶應用、風力裝置、窗線、結構部件、黏著劑、封裝、囊封劑、絕緣體及(噴霧)塗佈中。
使用以下實例來說明本發明。
所用化學物質:
- 含有4,4'-MDI、2,4'-MDI及聚合MDI之基質聚異氰酸酯,NCO值為32.7%。
- Suprasec® 1306(Huntsman):4,4'-MDI聚異氰酸酯,NCO值為33.5%
- PPG-230:平均分子量為230g/mol、OH值=480至500的聚丙二醇
- PPG-425:平均分子量為425g/mol、OH值=260至270的聚丙二醇
- Hoopol® F1394:平均分子量為450g/mol的PET聚酯
- Nanostrength® M51NP:由2個聚甲基丙烯酸甲酯嵌段(PMMA)及1個聚丙烯酸丁酯嵌段(PBuA)組成之奈米結構丙烯酸嵌段共聚物
- Araldite® GY240:基於雙酚A之環氧樹脂
藉由真空混合異氰酸酯摻合物及多元醇摻合物2分鐘來製備可固化組合物。異氰酸酯摻合物由260.06g基質聚異氰酸酯組成。多元醇摻合物包含0.32g LiCl、60.95g Araldite GY240及80.64g PPG425。在加熱模具(90℃)中固化15分鐘之後,樹脂板在180℃下脫模並後固化25分鐘,包含以3℃/min加熱及冷卻勻變。SEN-3PB斷裂韌性測試(ISO13586)揭示0.714MPa.m1/2之臨界應力強度因子(K1c)及221J/m2之臨界能量釋放速率(G1c)。三點彎曲撓曲測試(ISO178)揭示2.90GPa之
撓曲模數及124MPa之撓曲強度。DMTA揭示214℃之Tg。
藉由真空混合含有三聚催化劑及6.4重量/重量%丙烯酸酯嵌段共聚物的異氰酸酯摻合物及多元醇摻合物2分鐘來製備可固化組合物。異氰酸酯摻合物由226.83g基質聚異氰酸酯及23.83g Nanostrength® M51NP(丙烯酸酯嵌段共聚物)組成。多元醇摻合物含有0.279g LiCl、53.43g Araldite® GY240及70.59g PPG425。在加熱模具(90℃)中固化15分鐘之後,樹脂板在180℃下脫模並後固化25分鐘,包含以3℃/min加熱及冷卻勻變。SEN-3PB斷裂韌性測試(ISO13586)揭示1.27MPa.m1/2之臨界應力強度因子(K1c)及591J/m2之臨界能量釋放速率(G1c)。三點彎曲撓曲測試(ISO178)揭示2.77GPa之撓曲模數及120MPa之撓曲強度。DMTA揭示208℃之Tg。
藉由真空混合含有三聚催化劑及4.9重量/重量%丙烯酸酯嵌段共聚物之異氰酸酯摻合物及多元醇摻合物2分鐘來製備可固化組合物。異氰酸酯摻合物由219.44g Suprasec® 1306及18.36g Nanostrength® M51NP(丙烯酸酯嵌段共聚物)組成。多元醇摻合物含有0.302g LiCl、17.82g Araldite® GY240、29.78g PPG230及89.10g Hoopol® F1390。在加熱模具(90℃)中固化15分鐘之後,樹脂板在140℃下脫模並後固化2小時。SEN-3PB斷裂韌性測試(ISO13586)揭示2.112MPa.m1/2之臨界應力強度因子(K1c)及1702J/m2之臨界能量釋放速率(G1c)。三點彎曲撓曲測試(ISO178)揭示3.05GPa之撓曲模數及134.2MPa之撓曲強度。DMTA揭示170℃之Tg。
藉由在三聚催化劑存在下真空混合以下摻合物兩分鐘來製備具有不同量(重量/重量%)之丙烯酸酯嵌段共聚物的可固化組合物:異氰酸酯摻合物、異氰酸酯-Nanostrength M51NP摻合物及多元醇摻合物。異氰酸酯摻合物由100重量/重量%基質聚異氰酸酯組成。異氰酸酯-Nanostrength M51NP混合物含有85.04重量/重量%基質聚異氰酸酯及14.96重量/重量% Nanostrength® M51NP(丙烯酸酯嵌段共聚物)。藉由在80℃下加熱並攪拌2小時來製備此混合物。多元醇摻合物含有43.0重量/重量% Araldite® GY240及57.0重量/重量% PPG425。可固化組合物之配方示於表1中。
在預加熱模具(90℃)中固化30分鐘之後,具有4mm之厚度的樹脂板在烘箱中在190℃下脫模並後固化25分鐘,包含以3℃/min加熱及冷卻勻變。根據ISO 13586量測斷裂韌性。根據ASTM D 4065-1使用動態機械分析量測玻璃轉移溫度。結果描述於表2中。
Claims (20)
- 一種用於製備包括聚異三聚氰酸酯之產物的可固化組合物,其藉由以至少100之異氰酸酯指數組合並混合以下各者而獲得:a)聚異氰酸酯組合物,b)異氰酸酯反應性組合物,其包括基於該異氰酸酯反應性組合物中之異氰酸酯反應性化合物之總莫耳數計算至少50莫耳%二醇,c)包括丙烯酸嵌段共聚物之韌化劑,及d)三聚催化劑組合物,其中該可固化組合物中之聚異氰酸酯之量包括基於該可固化組合物總重量計算至少50重量%聚異氰酸酯,其中該嵌段共聚物韌化劑為自組裝嵌段共聚物,其中至少一個嵌段為具有高於100℃之玻璃轉移溫度(Tg)之聚異氰酸酯/聚異三聚氰酸酯可混溶嵌段,且至少一個嵌段為具有低於0℃之Tg之聚異氰酸酯/聚異三聚氰酸酯不可混溶嵌段,且其中該共聚物於該可固化組合物中之存在量以該可固化組合物總重量計介於0.1重量%至30重量%之範圍內。
- 如請求項1之可固化組合物,其中該可固化組合物中之聚異氰酸酯之量包括基於該可固化組合物總重量計算至少60重量%聚異氰酸酯。
- 如請求項1至2中任一項之可固化組合物,其中該異氰酸酯反應性組合物包括芳族多元醇。
- 如請求項1至2中任一項之可固化組合物,其中該等二醇具有小於1000g/mol之分子量(MW),且包括伸烷基二醇及/或氧基伸烷基二醇。
- 如請求項1至2中任一項之可固化組合物,其中該等二醇係選自聚乙二醇及/或聚丙二醇-(1,2)及-(1,3)、聚丁二醇-(1,4)及-(2,3)、聚己二醇-(1,6)、聚辛二醇-(1,8)及其混合物。
- 如請求項1至2中任一項之可固化組合物,其中該嵌段共聚物韌化劑為具有至少1000g/mol之數目平均分子量(MW)的自組裝嵌段共聚物。
- 如請求項1至2中任一項之可固化組合物,其中該嵌段共聚物之該聚異氰酸酯/聚異三聚氰酸酯可混溶嵌段係選自聚甲基丙烯酸甲酯(Tg=105℃)及/或聚苯乙烯(Tg=100℃),且該嵌段共聚物之該聚異氰酸酯/聚異三聚氰酸酯不可混溶嵌段係選自聚丙烯酸烷酯及/或聚二烯。
- 如請求項1至2中任一項之可固化組合物,其中該等聚異氰酸酯係選自脂族、環脂族、芳脂族及芳族聚異氰酸酯。
- 如請求項1至2中任一項之可固化組合物,其中該三聚催化劑組合物係選自有機羧酸的鹼金屬及/或鹼土金屬鹽。
- 如請求項1至2中任一項之可固化組合物,其中該三聚催化劑組合物係選自含有鋰鹵化物及環氧樹脂。
- 如請求項1至2中任一項之可固化組合物,其中該三聚催化劑組合物以基於該可固化組合物之總重量計算0.001至10重量%之量使用。
- 如請求項1至2中任一項之可固化組合物,其中該等輔助化合物係選自非異氰酸酯反應性溶劑、界面活性劑、清除劑、抗微生物劑、阻燃劑、煙霧抑制劑、UV穩定劑、著色劑、塑化劑、內部脫模劑、流變改質劑、潤濕劑、分散劑及填充劑。
- 如請求項1至2中任一項之可固化組合物,其中該等輔助化合物包括選自以下之填充劑材料:木片、木粉、木薄片、木板;紙 及卡紙板,均撕碎或層狀;砂、蛭石、黏土、水泥及其他矽酸鹽;橡膠粉、熱塑性塑膠粉、熱固性材料粉;任何材料之蜂窩狀物;金屬粒子及板材;呈顆粒形式或層狀之軟木;天然纖維;合成纖維;礦物纖維;礦物填充劑;奈米粒子;玻璃珠、磨砂玻璃、空心玻璃珠;膨脹或可膨脹珠粒;未處理或經處理廢料;編織及非編織紡織物;及兩種或兩種以上此等材料之組合。
- 一種用於製備如請求項1至13中任一項之可固化組合物的製程,其包括在環境壓力及在5℃至45℃之溫度下組合並混合成分a)至d)。
- 一種用於製備具有改良韌性之包括聚異三聚氰酸酯之材料的方法,該方法至少包括使如請求項1至13中任一項之可固化組合物以至少100之異氰酸酯指數且在高於50℃之固化溫度下反應的步驟。
- 如請求項15之用於製備具有改良韌性之包括聚異三聚氰酸酯之材料的方法,其中該方法為分批、半連續或連續製程、射出製程、擠出製程、拉擠成形製程、模製製程或預浸製程。
- 如請求項15至16中任一項之用於製備具有改良韌性之包括聚異三聚氰酸酯之材料的方法,其中該異氰酸酯指數在100至15000範圍內。
- 如請求項15至16中任一項之用於製備具有改良韌性之包括聚異三聚氰酸酯之材料的方法,其中該固化溫度為50℃至350℃。
- 一種藉由如請求項15至18中任一項之方法獲得之包括聚異三聚氰酸酯之材料,其玻璃轉移溫度>100℃、斷裂韌性值G1c>1000J/m2及/或韌性值K1c>2MPa.m1/2。
- 一種藉由如請求項15至18中任一項之方法獲得之包括聚異三聚 氰酸酯之材料,其玻璃轉移溫度>150℃、韌性值G1c>500J/m2及/或韌性值K1c>1MPa.m1/2。
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EP14183799.7A EP2993195A1 (en) | 2014-09-05 | 2014-09-05 | A method for improving fracture toughness of polyisocyanurate comprising reaction products |
??14183799.7 | 2014-09-05 |
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TWI674294B true TWI674294B (zh) | 2019-10-11 |
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CN (1) | CN106795270B (zh) |
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CA (1) | CA2960308C (zh) |
MX (1) | MX2017002783A (zh) |
PL (1) | PL3189088T3 (zh) |
RU (1) | RU2669384C2 (zh) |
TW (1) | TWI674294B (zh) |
WO (1) | WO2016034313A1 (zh) |
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KR102407460B1 (ko) * | 2015-12-18 | 2022-06-13 | 롬 앤드 하아스 컴패니 | 크롬-무함유 가죽원단 재무두질 |
WO2018087395A1 (de) * | 2016-11-14 | 2018-05-17 | Covestro Deutschland Ag | Kompositwerkstoffe basierend auf isocyanuratpolymeren mit dualer härtung |
CN107973897A (zh) * | 2017-11-30 | 2018-05-01 | 华南理工大学 | 一种水可分散的混合改性tdi三聚体固化剂及其制备方法 |
CN109181280A (zh) * | 2018-09-05 | 2019-01-11 | 安徽省华腾农业科技有限公司 | 一种聚氨酯弹性体及其制备方法 |
US11702499B2 (en) | 2018-12-11 | 2023-07-18 | Trimer Technologies Llc | Polyisocyanurate based polymers and fiber reinforced composites |
KR102481812B1 (ko) | 2018-12-11 | 2022-12-28 | 트라이머 테크놀로지스, 엘엘씨 | 폴리이소시아누레이트 기재 중합체 및 섬유 강화된 복합재 |
CN110790893B (zh) * | 2019-11-20 | 2021-12-28 | 常熟理工学院 | 一种提高聚异氰脲酸酯的韧性与阻燃性能的方法 |
US20220220307A1 (en) | 2021-01-14 | 2022-07-14 | Covestro Llc | Polyisocyanurate thermosets with improved mechanical properties |
CN115679702B (zh) * | 2022-10-18 | 2023-09-12 | 广东裕田霸力科技股份有限公司 | 耐变黄飞织处理剂及其制备方法 |
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- 2015-07-09 EP EP15736822.6A patent/EP3189088B1/en active Active
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US20170283545A1 (en) | 2017-10-05 |
BR112017004158A2 (pt) | 2017-12-05 |
EP3189088A1 (en) | 2017-07-12 |
CN106795270B (zh) | 2020-12-15 |
CA2960308A1 (en) | 2016-03-10 |
US10544253B2 (en) | 2020-01-28 |
RU2017111045A3 (zh) | 2018-10-05 |
TW201612241A (en) | 2016-04-01 |
WO2016034313A1 (en) | 2016-03-10 |
EP3189088B1 (en) | 2020-04-01 |
MX2017002783A (es) | 2017-05-30 |
EP2993195A1 (en) | 2016-03-09 |
BR112017004158B1 (pt) | 2021-12-21 |
RU2017111045A (ru) | 2018-10-05 |
RU2669384C2 (ru) | 2018-10-11 |
CN106795270A (zh) | 2017-05-31 |
PL3189088T3 (pl) | 2020-11-16 |
CA2960308C (en) | 2020-07-21 |
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