TWI739175B - 高官能聚氨酯預聚物、其製法及包含其的固化劑 - Google Patents

高官能聚氨酯預聚物、其製法及包含其的固化劑 Download PDF

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TWI739175B
TWI739175B TW108137725A TW108137725A TWI739175B TW I739175 B TWI739175 B TW I739175B TW 108137725 A TW108137725 A TW 108137725A TW 108137725 A TW108137725 A TW 108137725A TW I739175 B TWI739175 B TW I739175B
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polyurethane prepolymer
functional polyurethane
polyisocyanate
alcohol mixture
polyol
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TW108137725A
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English (en)
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TW202116841A (zh
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王華
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諾華應用材料有限公司
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Priority to TW108137725A priority Critical patent/TWI739175B/zh
Priority to CN201911012062.3A priority patent/CN112679686B/zh
Priority to US16/704,763 priority patent/US11186746B2/en
Publication of TW202116841A publication Critical patent/TW202116841A/zh
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Publication of TWI739175B publication Critical patent/TWI739175B/zh

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Abstract

本創作提供一種高官能聚氨酯預聚物之製法,其包含步驟(A):齊備一醇類混合物,該醇類混合物包含具有2個或3個羥基的第一多元醇和具有4個以上之羥基的第二多元醇;步驟(B):將該醇類混合物與多異氰酸酯進行第一聚合反應,以得到一中間產物;其中,該醇類混合物包含之總羥基與該多異氰酸酯包含之總異氰酸酯基的莫耳比為1:2至1:6;以及步驟(C):加入一催化劑使該中間產物進行第二聚合反應,以得到該高官能聚氨酯預聚物。本創作也提供一種由前述方法所製得的高官能聚氨酯預聚物及包含其的固化劑。

Description

高官能聚氨酯預聚物、其製法及包含其的固化劑
本創作係有關一種聚氨酯預聚物及其製法,尤指一種可作為固化劑之高官能聚氨酯預聚物。
固化劑是一種廣泛應用於塗料、塑膠、油墨、膠黏劑等領域的化工原料,其常與含有可反應基團之單體化合物或低聚物搭配形成樹脂組合物;當樹脂組合物中的固化劑和所述單體化合物或低聚物進行反應而生成高分子後,即能獲得具有一定機械強度和穩定性的產品。由於固化劑所具有的官能基類型和其數目多寡會對所述樹脂組合物的反應速率及反應後所得之產品的特性有著顯著的影響,因此,相關技術領域需不斷開發不同類型的固化劑以滿足不同產品的需求。其中,能在常溫固化的聚氨酯預聚物是常見的固化劑選擇。
於現有技術中,通常使用過量的二異氰酸酯單體與二元醇反應以形成聚氨酯預聚物,因此於製程中或最終產品皆有大量的未反應、游離之二異氰酸酯單體殘留,然而,因多種二異氰酸酯(例如甲苯二異氰酸酯)易引起人體過敏、氣喘、甚至有致癌風險,故在日趨重視工業安全的現今社會中,降低聚氨酯預聚物中的游離二異氰酸酯單體含量成為研究重點之一。
為了解決上述問題,目前已有人提出選用蒸氣壓較低的二異氰酸酯降低產品中游離之二異氰酸酯單體的揮發量,進而降低對人體造成的危害,但這樣會導致固化劑的選擇受限,不利於滿足產品需要的特性。另外,也有人將二異氰酸酯轉變為二聚體或三聚體的形式,但由於其官能度不夠高,最終產品仍有機械強度不足的問題。
有鑑於上述聚氨酯預聚物存在的技術缺陷,本創作之目的在於提供一種高官能聚氨酯預聚物之製法,因利用所述方法製得的聚氨酯預聚物具有大於3之官能度,故能應用於樹脂組成物中形成立體交聯網絡,提升交聯密度,進而獲得良好的機械特性。
本創作之另一目的在於提供一種高官能聚氨酯預聚物之製法,其製程簡單而能符合成本效益,進而更具商業實施的潛力。
本創作之另一目的在於提供一種高官能聚氨酯預聚物之製法,其製得的聚氨酯預聚物應用於樹脂組成物中可使固化所得之層體具有高硬度等良好的機械性質和良好的耐化學性。
本創作之另一目的在於提供一種高官能聚氨酯預聚物之製法,其製得的高官能聚氨酯預聚物中,游離多異氰酸酯單體的含量減少,因而能符合工業安全的訴求。
為達成前述目的,本創作提供一種高官能聚氨酯預聚物之製法,其包含以下步驟:步驟(A):齊備一醇類混合物,該醇類混合物包含第一多元醇和第二多元醇,該第一多元醇具有2個或3個羥基,該第二多元醇具有4個以上之羥基;步驟(B):將該醇類混合物與多異氰酸酯進行第一聚合反應,以得到一中間產物;其中,該醇類混合物包含之總羥基與該多異氰酸酯包含之總異氰酸酯基的莫耳比 (molar ratio)為1:2至1:6;以及步驟(C):加入一催化劑使該中間產物進行第二聚合反應,以得到該高官能聚氨酯預聚物;其中,該高官能聚氨酯預聚物具有4個以上的異氰酸酯基。
根據本創作,藉由搭配具有較少羥基的第一多元醇幫助具有較多羥基的第二多元醇溶解,有助於後續醇類混合物與多異氰酸酯進行反應;此外,因步驟(B)中的該等反應物之總異氰酸酯基超過總羥基的兩倍以上,故多異氰酸酯僅需使用其中一個異氰酸酯基參與第一聚合反應,使得該等反應物進行加成聚合反應後得到的含有胺基甲酸酯基 (urethane group)之中間產物帶有多個異氰酸酯基的末端,且所述中間產物之分子量較小,整體黏度較低;接著,再藉由加入催化劑使該中間產物進行自身聚合的第二聚合反應,最終可獲得具有4個以上的(例如4個、5個、或6個)異氰酸酯基之高官能聚氨酯預聚物,且所述高官能聚氨酯預聚物的分子量分佈較均一。一方面,因為所述聚氨酯預聚物具有多個異氰酸酯基,因此能在後續應用於樹脂組成物時提升整體的交聯密度,進而提升終端產品之機械特性;另一方面,因進行第二次聚合反應將游離的多異氰酸酯單體消耗掉,因此可減少所述聚氨酯預聚物中所含的游離多異氰酸酯單體之含量。
依據本創作,第一多元醇做為第二多元醇的溶媒,可降低第二多元醇的熔融溫度,避免第二多元醇自交聯而膠化。為了使所述醇類混合物能更均勻地混合,較佳的,該第一多元醇和該第二多元醇之莫耳比為1:1至6:1。
另外,還可調控該醇類混合物的混合溫度以提升混合效果。較佳的,於步驟(A)中,可將該醇類混合物加熱至55°C至160°C。在一些實施例中,可將該第一多元醇和該第二多元醇於55°C至80°C混合以形成該醇類混合物後,再提升溫度至100°C至160°C後持續1小時至3小時使該醇類混合物脫水。在另一些實施例中,可將該第一多元醇和該第二多元醇直接於85°C至130°C下混合並使該醇類混合物脫水。
根據本創作,該第一多元醇包括分子量為60至300之脂肪族二醇或分子量為60至300之脂肪族三醇,但不限於此。舉例而言,該脂肪族二醇包括2-甲基-1,3-丙二醇 (2-Methyl-1,3-propanediol)、1,4-環己烷二甲醇 {[4-(Hydroxymethyl)cyclohexyl]methanol}、新戊二醇 (2,2-Dimethyl-1,3-propanediol,NPG)、1,3-丙二醇 (1,3-Dihydroxypropane)、1,4-丁二醇 (1,4-Butanediol)、1,5-戊二醇 (1,5-Pentanediol)、1,6-己二醇 (1,6-Hexanediol)、3-甲基-1,5-戊二醇 (3-Methyl-1,5-pentanediol)、2-乙基-2-丁基-1,3-丙二醇 (2-Butyl-2-ethyl-1,3-propanediol,BEPD)、或2,2,4-三甲基-1,3-戊二醇 (1,3-Dihydroxy-2,2,4-trimethyl pentane,TMPD glycol),但不限於此;該脂肪族三醇包括丙三醇(Propane-1,2,3-triol)、三羥甲基丙烷 (Trimethylolpropane,TMP),但不限於此。當所述製法採用前述脂肪族二醇或脂肪族三醇,所得之高官能聚氨酯預聚物於後續作為固化劑應用時,可使所得之塗層具有不易黃變的優點。
較佳的,該第二多元醇為具有4至6個羥基之多元醇;具體而言,該第二多元醇可包括季戊四醇 (Pentaerythritol)或雙季戊四醇 (Dipentaerythritol,DPE),但不限於此。
為了使第一聚合反應進行地更完全,較佳的,該步驟(B)包括:步驟(B1):將該多異氰酸酯與一酯類溶劑混合,得到一含多異氰酸酯之溶液,其中,該步驟(B1)之溫度為40°C至70°C;以及步驟(B2):將該醇類混合物與該含多異氰酸酯之溶液混合,使該醇類混合物與該多異氰酸酯進行該第一聚合反應,以得到該中間產物;其中,該步驟(B2)之反應溫度為65°C至85°C。
較佳的,該步驟(B1)可於氮氣氣氛下進行。較佳的,於該步驟(B2)中,將經脫水之醇類混合物以滴加的方式添加至該含多異氰酸酯之溶液中進行第一聚合反應。
根據本創作,該多異氰酸酯係碳數為4至20的脂肪族多異氰酸酯或芳香族多異氰酸酯。較佳的,該多異氰酸酯包含二異氰酸酯或三異氰酸酯,但不限於此。舉例而言,該脂肪族多異氰酸酯可為六亞甲基二異氰酸酯 (Hexamethylene diisocyanate,HDI)、三甲基六亞甲基二異氰酸酯 (Trimethylhexamethylene diisocyanate,TMDI)、異佛爾酮二異氰酸酯 (5-Isocyanato-1-(isocyanatomethyl)-1,3,3-trimethylcyclohexane,IPDI)、氫化苯二亞甲基二異氰酸酯 (Hydrogenated m-xylylene diisocyanate,H6XDI)、或4,4’-二環己基甲烷二異氰酸酯 (4,4'-Diisocyanato-methylenedicyclohexane,HMDI),但不限於此;該芳香族多異氰酸酯可為甲苯二異氰酸酯 (Toluene diisocyanate,TDI)、亞甲基二苯基二異氰酸酯 (Methylene diphenyl diisocyanate,MDI)、或間苯二甲基二異氰酸酯 (m-Xylylene diisocyanate),但不限於此。在一些實施例中,該多異氰酸酯可為兩種多異氰酸酯的組合,例如2,4-甲苯二異氰酸酯和2,6-甲苯二異氰酸酯的組合、異佛爾酮二異氰酸酯與六亞甲基二異氰酸酯的組合、或六亞甲基二異氰酸酯與甲苯二異氰酸酯的組合等,但不限於此。較佳的,於2,4-甲苯二異氰酸酯和2,6-甲苯二異氰酸酯的組合中,2,4-甲苯二異氰酸酯佔所述組合之總重的30重量百分比 (wt%)至80 wt%。
較佳的,所述酯類溶劑可為醋酸乙酯 (Ethyl acetate)、醋酸正丙酯 (1-Propyl acetate)、醋酸異丙酯 (Isopropyl ethanoate)、醋酸正丁酯 (1-Butyl acetate)、醋酸異丁酯 (Isobutyl acetate)、乙二醇乙醚醋酸酯 (2-Ethoxyethyl acetate)、或丙二醇甲醚醋酸酯 (1-Methoxy-2-propyl acetate,PMA),但不限於此。
較佳的,該醇類混合物包含之總羥基與該多異氰酸酯包含之總異氰酸酯基的莫耳比為1:3至1:5。
為了更進一步去除未反應的游離之多異氰酸酯單體,較佳的,該步驟(C)包括:步驟(C1):加入該催化劑使該中間產物進行該第二聚合反應,得到一粗產物,其中,該步驟(C1)之溫度為60°C至90°C;以及步驟(C2):該粗產物經純化步驟處理,以得到所述高官能聚氨酯預聚物。於該粗產物中,游離的多異氰酸酯單體之含量為0.5 wt%至2.0 wt%,但不限於此。
根據本創作,所述催化劑可為三丁基膦 (Tributylphosphane)、三丁基氧化錫 (Tributyltin-oxide)、四丁基氧化鈦 (Titanium(IV) butoxide)、三亞乙基二胺 (Triethylenediamine)等之叔胺 (‎Tertiary amine)、環烷酸鉛 (Lead naphthenate)、異辛酸亞錫 (Stannous 2-ethylhexanoate)、2,4,6-三(二甲胺基甲基)苯酚 [2,4,6-tris(dimethylaminomethyl)phenol]、四丁基氫氧化銨 (Tetrabutylammonium hydroxide,TBAH)等之四丁基銨鹽,但不限於此。較佳的,以步驟(B1)中的多異氰酸酯之重量為100重量份,所述催化劑於步驟(C)中的添加量為0.02重量份至0.2重量份。
在一些實施例中,於步驟(C1)中,待所述第二聚合反應進行一段時間後還可加入一終止劑。具體而言,該終止劑可為亞磷酸三苯酯 (Triphenyl phosphite)、硫酸二甲酯 (Dimethyl sulfate,DMS)、對甲苯磺酸甲酯 (4-methylbenzenesulfonic acid,TsOH)、苯甲醯氯 (Benzoyl chloride)或磷酸 (Phosphoric acid),但不限於此。所述第二聚合反應進行一段時間後,可檢測反應後所得之生成物的異氰酸酯基含量(又稱NCO值);較佳的,當NCO值為6 wt%至25 wt%時,再加入所述終止劑。前述NCO值是指所述生成物中的異氰酸酯基之重量佔所述生成物之總重的百分比。較佳的,以步驟(C1)中的催化劑之重量為100重量份,所述終止劑的添加量為30重量份至80重量份。
依據本創作,該步驟(C2)中所進行的純化步驟可採用薄膜蒸發器、蒸餾技術、溶劑萃取及分子篩等方式進行純化分離,但不限於此。較佳的,可選用二級薄膜蒸發器進行純化步驟;其中,一級分離溫度為110°C至130°C、真空度為1000帕(Pa)至3000 Pa,以及二級分離溫度為165°C至180°C、真空度為80 Pa至200 Pa。選用二級薄膜蒸發器的純化方式,可減少分離過程中發生的副反應,且將游離的多異氰酸酯單體去除地更徹底。
此外,本創作另提供一種如前述高官能聚氨酯預聚物之製法所製備而得的高官能聚氨酯預聚物,所述高官能聚氨酯預聚物具有4個以上的異氰酸酯基。較佳的,以所述高官能聚氨酯預聚物之總重為基準,游離的多異氰酸酯之含量為0 wt%至1.0 wt%;更佳的,游離的多異氰酸酯之含量為0 wt%至0.5 wt%。
較佳的,該高官能聚氨酯預聚物的重量平均分子量 (Weight-average molecular weight,Mw)為1000至3000,但不限於此。當該高官能聚氨酯預聚物的重量平均分子量落在前述範圍內時,可使包含其的固化劑具有較適中的黏度,有利於後續應用。
較佳的,該高官能聚氨酯預聚物具有的異氰酸酯基之含量為6 wt%至25 wt%。更佳的,該高官能聚氨酯預聚物具有的異氰酸酯基之總含量為8 wt%至20 wt%。
本創作另提供一種包含前述高官能聚氨酯預聚物的固化劑。
依據本創作,因應後續應用的方便性,可將該高官能聚氨酯預聚物與適當溶劑搭配作為固化劑使用,且依據需求調整所述固化劑的固含量,使所述固化劑之黏度適中。舉例而言,所述溶劑可為醋酸乙酯、醋酸正丙酯、醋酸異丙酯、醋酸正丁酯、醋酸異丁酯、或丙二醇甲醚醋酸酯,但不限於此。較佳的,以所述固化劑之總重為基準,該高官能聚氨酯預聚物之固含量為30 wt%至80 wt%;更佳的,以所述固化劑之總重為基準,該高官能聚氨酯預聚物之固含量為40 wt%至75 wt%。較佳的,該固化劑的黏度為1000厘泊(cps)至5000 cps。
具體而言,前述包含該高官能聚氨酯預聚物之固化劑可與具羥基之樹脂一併包含於一樹脂組成物;所述樹脂組成物因具有前述固化劑而可形成具有高硬度等良好的機械特性、高耐汽油性等良好的耐化學性、以及良好的耐光性和/或高耐高溫高濕性等高可靠性的產品。具體而言,所述具羥基之樹脂可為具羥基之丙烯酸樹脂或具羥基之聚酯樹脂,但不限於此。較佳的,所述樹脂組成物可作為塗料組成物。
以下,將藉由數種實施例示例說明本創作之高官能聚氨酯預聚物之製法、所得之高官能聚氨酯預聚物,以及包含其的固化劑的具體實施方式,熟習此技藝者可經由本說明書之內容輕易地了解本創作所能達成之優點與功效,並且於不悖離本創作之精神下進行各種修飾與變更,以施行或應用本創作之內容。
以下各高官能聚氨酯預聚物的NCO值,以及包含所述高官能聚氨酯預聚物的固化劑之固含量和黏度依照以下方式量測而得: 1. NCO值分析:由ASTM D2369-81的標準方法量測而得; 2. 固含量分析:由ISO 14896-2006的標準方法量測而得; 3. 黏度分析:ASTM D1665-98的標準方法量測而得。
實施例1
將三羥甲基丙烷加熱至70°C使之熔融,再將二季戊四醇加入該熔融的三羥甲基丙烷以形成醇類混合物;接著,將該醇類混合物加熱至120°C且持溫2小時,得到脫水後之醇類混合物;其中,在所述醇類混合物中,三羥甲基丙烷與二季戊四醇的莫耳比為6:1。
在氮氣氣氛下,將醋酸正丁酯和多異氰酸酯混合於一反應釜中,以形成一含多異氰酸酯之溶液;接著將所述含多異氰酸酯之溶液升溫到50°C;其中,所述多異氰酸酯包含2,4-甲苯二異氰酸酯與2,6-甲苯二異氰酸酯,且2,4-甲苯二異氰酸酯佔所述多異氰酸酯總重之69 wt%。接著,將上述脫水後之醇類混合物滴加至所述反應釜中,滴加時間為1小時,且滴加過程中的溫度維持在66°C至78°C之間,使該醇類混合物與該含多異氰酸酯之溶液混合均勻並進行第一聚合反應,以得到一中間產物。其中,該醇類混合物包含之總羥基與該多異氰酸酯包含之總異氰酸酯基的莫耳比為1:4。待該醇類混合物滴加完後,所述反應釜於70°C下持溫1小時,接著,升高溫度至80°C後再持溫1小時後,一次性地加入相對於所述多異氰酸酯之總量為0.05重量份的2,4,6-三(二甲胺基甲基)苯酚作為催化劑,使所述中間產物進行第二聚合反應;待反應2小時後,取樣所述反應釜中的液體進行NCO值測試,測得之NCO值為13 wt%至14 wt%。接著,加入相對於所述催化劑之重量為40重量份的苯甲醯氯繼續反應1小時後停止反應,得到粗產物。
將上述粗產物以2 kg/分鐘的進料速率送入二級薄膜蒸發器進行純化步驟,以除去溶劑和游離的多異氰酸酯單體;其中,二級薄膜蒸發器的設定參數如下:一級分離溫度為120°C、真空度為2000 Pa,以及二級分離溫度為180°C、真空度為200 Pa。待純化處理後,獲得高官能聚氨酯預聚物1,其重量平均分子量為1500±200,其具有的NCO值為13.5 wt%。
最後,將該高官能聚氨酯預聚物1與醋酸正丁酯混合得到固化劑1,且將固化劑1的固含量調整至50±1 wt%,黏度為2000 cps至2400 cps。
實施例2
將三羥甲基丙烷和二季戊四醇混合以形成醇類混合物;接著,將該醇類混合物加熱至120°C且持溫1.5小時,得到脫水後之醇類混合物;在所述醇類混合物中,三羥甲基丙烷與二季戊四醇的莫耳比為4:1。
在氮氣氣氛下,將醋酸正丁酯和多異氰酸酯混合於一反應釜中,以形成一含多異氰酸酯之溶液;接著將所述含多異氰酸酯之溶液升溫到50°C;其中,所述多異氰酸酯包含2,4-甲苯二異氰酸酯與2,6-甲苯二異氰酸酯,且2,4-甲苯二異氰酸酯佔所述多異氰酸酯總重之73 wt%。接著,將上述脫水後之醇類混合物滴加至所述反應釜中,滴加時間為1小時,且滴加過程中的溫度維持在66°C至78°C之間,使該醇類混合物與該含多異氰酸酯之溶液混合均勻並進行第一聚合反應,以得到一中間產物。其中,該醇類混合物包含之總羥基與該多異氰酸酯包含之總異氰酸酯基的莫耳比為1:4。待該醇類混合物滴加完後,所述反應釜於70°C下持溫1小時,接著,升高溫度至80°C後再持溫1小時後,一次性地加入相對於所述多異氰酸酯之總重為0.05重量份的四丁基氫氧化銨作為催化劑,使所述中間產物進行第二聚合反應;待反應3小時後,取樣所述反應釜中的液體進行NCO值測試,測得之NCO值為11.5 wt%至12.5 wt%。接著,加入相對於所述催化劑之重量為60重量份的磷酸繼續反應1小時後停止反應,得到粗產物。
將上述粗產物以2kg/分鐘的進料速率送入二級薄膜蒸發器進行純化步驟,以除去溶劑和游離的多異氰酸酯單體;其中,二級薄膜蒸發器的設定參數如下:一級分離溫度為120°C、真空度為2000 Pa,以及二級分離溫度為180°C、真空度為200 Pa。待純化處理後,獲得高官能聚氨酯預聚物2,其重量平均分子量為1400±200,其具有的NCO值為12.0 wt%。
最後,將該高官能聚氨酯預聚物2與醋酸正丁酯混合得到固化劑2,且將固化劑2的固含量調整至50±1 wt%,黏度為1800 cps至2200 cps。
實施例3
將三羥甲基丙烷和二季戊四醇混合以形成醇類混合物;接著,將該醇類混合物加熱至120°C且持溫2.5小時,得到脫水後之醇類混合物;在所述醇類混合物中,三羥甲基丙烷與二季戊四醇的莫耳比為2:1。
在氮氣氣氛下,將醋酸正丁酯和多異氰酸酯混合於一反應釜中,以形成一含多異氰酸酯之溶液;接著將所述含多異氰酸酯之溶液升溫到65°C;其中,所述多異氰酸酯包含2,4-甲苯二異氰酸酯與2,6-甲苯二異氰酸酯,且2,4-甲苯二異氰酸酯佔所述多異氰酸酯總重之59 wt%。接著,將上述脫水後之醇類混合物滴加至所述反應釜中,滴加時間為1.5小時,且滴加過程中的溫度維持在66°C至78°C之間,使該醇類混合物與該含多異氰酸酯之溶液混合均勻並進行第一聚合反應,以得到一中間產物。其中,該醇類混合物包含之總羥基與該多異氰酸酯包含之總異氰酸酯基的莫耳比為1:4。待該醇類混合物滴加完後,所述反應釜於70°C下持溫1小時,接著,升高溫度至80°C後再持溫1小時後,一次性地加入相對於所述多異氰酸酯之總重為0.02重量份的三亞乙基二胺作為催化劑,使所述中間產物進行第二聚合反應;待反應2.5小時後,取樣所述反應釜中的液體進行NCO值測試,測得之NCO值為9.5 wt%至10.5 wt%。接著,加入相對於所述催化劑之重量為80重量份的亞磷酸三苯酯繼續反應1小時後停止反應,得到粗產物。
將上述粗產物以2 kg/分鐘的進料速率送入二級薄膜蒸發器進行純化步驟,以除去溶劑和游離的多異氰酸酯單體;其中,二級薄膜蒸發器的設定參數如下:一級分離溫度為120°C、真空度為2000 Pa,以及二級分離溫度為180°C、真空度為200 Pa。待純化處理後,獲得高官能聚氨酯預聚物3,其重量平均分子量為1200±200,其具有的NCO值為10.0 wt%。
最後,將該高官能聚氨酯預聚物3與丙二醇甲醚醋酸酯混合得到固化劑3,且將固化劑3的固含量調整至50±1 wt%,黏度為1500 cps至1900 cps。
實施例4
將三羥甲基丙烷和二季戊四醇混合以形成醇類混合物;接著,將該醇類混合物加熱至120°C且持溫2.5小時,得到脫水後之醇類混合物;在所述醇類混合物中,三羥甲基丙烷與二季戊四醇的莫耳比為4:1。
在氮氣氣氛下,將醋酸正丁酯和六亞甲基二異氰酸酯混合於一反應釜中,以形成一含多異氰酸酯之溶液;接著將所述含多異氰酸酯之溶液升溫到60°C。接著,將上述脫水後之醇類混合物滴加至所述反應釜中,滴加時間為1.5小時,且滴加過程中的溫度維持在66°C至78°C之間,使該醇類混合物與所述含多異氰酸酯之溶液混合均勻並進行第一聚合反應,以得到一中間產物。其中,該醇類混合物包含之總羥基與該多異氰酸酯(即六亞甲基二異氰酸酯)包含之總異氰酸酯基的莫耳比為1:4。待該醇類混合物滴加完後,所述反應釜於60°C下持溫4小時後,一次性地加入相對於六亞甲基二異氰酸酯之總重為0.05重量份的叔胺(商品名為DABCO TMR)和相對於六亞甲基二異氰酸酯之總重為0.025重量份的2,4,6-三(二甲胺基甲基)苯酚(商品名為DABCOTMR-30)作為複合催化劑,升溫至70°C使所述中間產物進行第二聚合反應;待反應4小時後,取樣所述反應釜中的液體進行NCO值測試,測得之NCO值為16 wt%至17 wt%。接著,加入相對於所述複合催化劑之總重為40重量份的磷酸繼續反應1小時後停止反應,得到粗產物。
將上述粗產物以2 kg/分鐘的進料速率送入二級薄膜蒸發器進行純化步驟,以除去溶劑和游離的多異氰酸酯單體;其中,二級薄膜蒸發器的設定參數如下:一級分離溫度為120°C、真空度為2000 Pa,以及二級分離溫度為180°C、真空度為200 Pa。待純化處理後,獲得高官能聚氨酯預聚物4,其重量平均分子量為1200±200,其具有的NCO值為16.5 wt%。
最後,將該高官能聚氨酯預聚物4與醋酸正丁酯混合得到固化劑4,且將固化劑4的固含量調整至75±1 wt%,黏度為1000 cps至1200 cps。
實施例5
將三羥甲基丙烷和二季戊四醇混合以形成醇類混合物;接著,將該醇類混合物加熱至120°C且持溫2.5小時,得到脫水後之醇類混合物;在所述醇類混合物中,三羥甲基丙烷與二季戊四醇的莫耳比為4:1。
在氮氣氣氛下,將醋酸正丁酯和異佛爾酮二異氰酸酯混合於一反應釜中,以形成一含多異氰酸酯之溶液;接著將所述含多異氰酸酯之溶液升溫到60°C。接著,將上述脫水後之醇類混合物滴加至所述反應釜中,滴加時間為1.5小時,且滴加過程中的溫度維持在66°C至78°C之間,使該醇類混合物與所述含多異氰酸酯之溶液混合均勻並進行第一聚合反應,以得到一中間產物。其中,該醇類混合物包含之總羥基與該多異氰酸酯(即異佛爾酮二異氰酸酯)包含之總異氰酸酯基的莫耳比為1:4。待該醇類混合物滴加完後,所述反應釜於60°C下持溫4小時後,一次性地加入相對於異佛爾酮二異氰酸酯之總重為0.05重量份的叔胺(商品名為DABCO TMR)和相對於異佛爾酮二異氰酸酯之總重為0.05重量份的2,4,6-三(二甲胺基甲基)苯酚(商品名為DABCOTMR-30)作為複合催化劑,升溫至70°C使所述中間產物進行第二聚合反應;待反應4小時後,取樣所述反應釜中的液體進行NCO值測試,測得之NCO值為12 wt%至13 wt%。接著,加入相對於所述複合催化劑之總重為30重量份的磷酸繼續反應1小時後停止反應,得到粗產物。
將上述粗產物以2 kg/分鐘的進料速率送入二級薄膜蒸發器進行純化步驟,以除去溶劑和游離的多異氰酸酯單體;其中,二級薄膜蒸發器的設定參數如下:一級分離溫度為120°C、真空度為2000 Pa,以及二級分離溫度為180°C、真空度為200 Pa。待純化處理後,獲得高官能聚氨酯預聚物5,其重量平均分子量為1600±100,其具有的NCO值為12.0 wt%。
最後,將該高官能聚氨酯預聚物5與醋酸正丁酯混合得到固化劑5,且將固化劑5的固含量調整至60±1 wt%,黏度為1600 cps至1800 cps。
比較例1
單獨使用二季戊四醇做為與多異氰酸酯反應之多元醇。然而,當二季戊四醇加熱至200°C時,二季戊四醇不僅無法熔融,甚至已發生膠化現象,故二季戊四醇無法單獨與多異氰酸酯進行反應,因而無法得到高官能聚氨酯預聚物。
包含固化劑之塗料組成物的製備
將上述實施例1至5所得之固化劑1至固化劑5和市售之固化劑1(商品型號:拜耳L75,其為TDI-TMP之加成物)、市售之固化劑2(商品型號:拜耳N3300,其為HDI之三聚體)分別與一清漆配方混合,以得到塗料組成物A至G;所述清漆配方的組成如下:以清漆配方的總重為基準,60 wt%的羥基丙烯酸樹脂、15 wt%的醋酸正丁酯、15 wt%的醋酸乙酯、7.6 wt%的丙二醇甲醚醋酸酯、1.8 wt%的二月桂酸二丁基錫試劑 [含有10%二月桂酸二丁基錫 (DBTDL)]、0.1 wt%的平滑助劑(商品名為TEGO GLIDE 450)、以及0.5 wt%的流平劑(商品名為TEGO FLOW 300);其中,羥基丙烯酸樹脂所含的總羥基重為羥基丙烯酸樹脂總重之3 wt%。
根據下表1所示之配比分別混合上述清漆配方和固化劑,經攪拌均勻後分別得到塗料組成物A至G,並將各固化劑中包含的高官能聚氨酯預聚物之NCO值列於表1中。接著,使用常溫(25°C)閃乾5分鐘後再以60°C烘乾4小時,使塗料組成物A至G固化形成塗層,所述塗層的平均厚度約為20微米至25微米。
表1:塗料組成物A至G之配比以及其固化劑包含的高官能聚氨酯預聚物之NCO值
塗料組成物 編號 固化劑編號 / 商品名 固化劑的高官能聚氨酯預聚物之NCO值 固化劑於塗料組成物中的含量 (wt%)
A 1 13.5 wt% 36.60
B 2 12.0 wt% 41.18
C 3 10.0 wt% 49.41
D 4 16.5 wt% 29.95
E 5 12.0 wt% 39.53
F 拜耳L75 13.3 wt% 37.15
G 拜耳N3300 21.6 wt% 22.88
試驗例:塗料組成物A至G之特性分析
為確保特性分析的實驗意義,各塗料組成物係以相同的固化方法形成各塗層,且各塗層亦係由相同的試驗方法進行分析。是以,各塗層的特性差異主要係源自於各塗料組成物中所含的固化劑差異所致。本試驗例係由下述試驗方法分析分別由包含固化劑1至5和市售之芳香族多異氰酸酯類固化劑(拜耳L75)、市售之脂肪族多異氰酸酯類固化劑(拜耳N3300)的塗料組成物A至G所固化而成之塗層的特性,所述特性為附著性、硬度、耐汽油性、耐高溫高濕性、以及耐光性,並將分析結果列於下表2。
試驗方法: 1. 附著性:以ASTM D3359「以膠帶量測附著性的標準試驗方法」評估塗層對基材附著性;將各塗層以百格刀劃深及塗層底部並將之分割為100個1平方毫米(mm2 )的小網格,接著以3M#610號標準膠帶緊黏上述百格,最後以與水平夾角45°的方式抓住膠帶拉扯,評估其附著性:若刻線的邊緣極為平滑且正方形格子的塗層沒有任何脫離,則評為5B;若刻線交錯處有小片塗層脫離,但受到影響的面積小於5%,則評為4B;當級別的數值愈小則表示附著性愈差; 2. 硬度:使用鉛筆硬度計(廠牌:三菱鉛筆)在500公克(g)載重下,在各塗層上不同的地方取三次,直到劃傷塗層表面或在塗層表面留下刮痕,並以未觀察到刮痕時的最大硬度記為表面硬度; 3. 耐汽油性:在荷重500 g下,以3公分的長度為測試範圍,將浸含95汽油之紗布以每分鐘來回60次的頻率摩擦500回,觀察塗層是否顯露底材; 4. 耐高溫高濕性:第一階段係將塗層置於濕度95%、溫度65°C的恆濕恆溫箱內120小時後,觀察塗層的外觀是否異常;第二階段係將經高溫高濕後的塗層放置於室溫下6小時,再以上述百格附著性測試評估其附著性; 5. 耐光性:以UVB-313奈米之紫外線老化燈管照射放置於溫度60°C環境下的塗層,其紫外光的強度為0.71瓦/平方公尺(W/m2 )、連續照射所述塗層100小時後,觀察塗層是否發生龜裂,並記錄其色差值(ΔE*)。
表2:由含有固化劑1至5的塗料組成物A至G所製得之塗層的特性分析結果
塗料組成物 編號 附著性 硬度 耐汽油性 耐高溫高濕性 耐光性/ΔE*
A 5B 3H 未見底材 外觀無異常/ 5B 無龜裂/ 4.2
B 5B 3H 未見底材 外觀無異常/ 5B 無龜裂/ 4.0
C 5B 3H 未見底材 外觀無異常/ 5B 無龜裂/ 4.1
F 5B 2H 顯露底材 -- 無龜裂/ 4.5
D 5B 2H 未見底材 外觀無異常/ 5B 無龜裂/ 1.12
E 5B 3H 未見底材 外觀無異常/ 5B 無龜裂/ 0.96
G 5B H 顯露底材 -- 無龜裂/ 1.54
實驗結果討論
如表2所示,在同樣都是芳香族多異氰酸酯類固化劑的比較中,相較於由塗料組成物F所製得之塗層,當選用分別包含高官能聚氨酯預聚物1至高官能聚氨酯預聚物3的固化劑1至固化劑3的塗料組成物A至C時,其製得之塗層皆具有更高的硬度;同樣地,在同樣都是脂肪族多異氰酸酯類固化劑的比較中,相較於由塗料組成物G所製得之塗層,當選用分別包含高官能聚氨酯預聚物4和高官能聚氨酯預聚物5的固化劑4和固化劑5的塗料組成物D至E時,其製得之塗層亦具有更高的硬度。據此可證,使用本創作之固化劑確實可使所製得之塗層獲得較佳的機械性質。
此外,由表2亦可知,在同樣都是芳香族多異氰酸酯類固化劑的比較中,相較於由塗料組成物F所製得之塗層,當選用分別包含高官能聚氨酯預聚物1至高官能聚氨酯預聚物3的固化劑1至固化劑3的塗料組成物A至C時,其製得之塗層皆具有更佳的耐汽油性;同樣地,在同樣都是脂肪族多異氰酸酯類固化劑的比較中,相較於由塗料組成物G所製得之塗層,當選用分別包含高官能聚氨酯預聚物4和高官能聚氨酯預聚物5的固化劑4和固化劑5的塗料組成物D至E時,其製得之塗層亦具有更佳的耐汽油性。據此可證,使用本創作之固化劑確實可使塗層獲得較佳的如耐汽油性的耐化學性。
由上表2還可知,在同樣都是芳香族多異氰酸酯類固化劑的比較中,相較於由塗料組成物F所製得之塗層,當選用分別包含高官能聚氨酯預聚物1至高官能聚氨酯預聚物3的固化劑1至固化劑3的塗料組成物A至C時,其製得之塗層的色差值更小,即代表由塗料組成物A至C所製得的塗層能具有更優異的耐光性;同樣地,在同樣都是脂肪族多異氰酸酯類固化劑的比較中,相較於由塗料組成物G所製得之塗層,當選用分別包含高官能聚氨酯預聚物4和高官能聚氨酯預聚物5的固化劑4和固化劑5的塗料組成物D至E時,其製得之塗層亦具有更優異的耐光性。此外,塗料組成物A至E所製得的塗層皆具有良好的耐高溫高濕性。據此可證,使用本創作之固化劑確實可使塗層獲得較高的可靠性。
綜合上述分析結果可知,藉由在塗料組合物中加入包含本創作之高官能聚氨酯預聚物的固化劑,能有利於提升所得塗層的機械特性、耐化學性、和/或耐光性等可靠性,進而提升其應用價值。
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Claims (13)

  1. 一種高官能聚氨酯預聚物之製法,其包含以下步驟:步驟(A):齊備一醇類混合物,該醇類混合物包含第一多元醇和第二多元醇,該第一多元醇具有2個或3個羥基,該第二多元醇具有4個以上之羥基,且該第二多元醇包括二季戊四醇;步驟(B):將該醇類混合物與多異氰酸酯進行第一聚合反應,以得到一中間產物;其中,該醇類混合物包含之總羥基與該多異氰酸酯包含之總異氰酸酯基的莫耳比為1:2至1:6;以及步驟(C):加入一催化劑使該中間產物進行第二聚合反應,以得到該高官能聚氨酯預聚物;其中,該高官能聚氨酯預聚物具有6個以上的異氰酸酯基。
  2. 如請求項1所述之高官能聚氨酯預聚物之製法,其中,該第一多元醇和該第二多元醇之莫耳比為1:1至6:1。
  3. 如請求項2所述之高官能聚氨酯預聚物之製法,其中,於步驟(A)中,將該醇類混合物加熱至55℃至160℃。
  4. 如請求項1所述之高官能聚氨酯預聚物之製法,其中,該步驟(B)包括:步驟(B1):將該多異氰酸酯與一酯類溶劑混合,得到一含多異氰酸酯之溶液,其中,該步驟(B1)之溫度為40℃至70℃;以及步驟(B2):將該醇類混合物與該含多異氰酸酯之溶液混合,使該醇類混合物與該多異氰酸酯進行該第一聚合反應,以得到該中間產物;其中,該步驟(B2)之反應溫度為65℃至85℃。
  5. 如請求項1所述之高官能聚氨酯預聚物之製法,其中,該步驟(C)包括: 步驟(C1):加入該催化劑使該中間產物進行該第二聚合反應,得到一粗產物,其中,該步驟(C1)之溫度為60℃至90℃;以及步驟(C2):該粗產物經純化步驟處理,以得到該高官能聚氨酯預聚物。
  6. 如請求項1至5中任一項所述之高官能聚氨酯預聚物之製法,其中,該多異氰酸酯之碳數為4至20。
  7. 如請求項1至5中任一項所述之高官能聚氨酯預聚物之製法,其中,該多異氰酸酯包括六亞甲基二異氰酸酯、三甲基六亞甲基二異氰酸酯、異佛爾酮二異氰酸酯、氫化苯二亞甲基二異氰酸酯、4,4’-二環己基甲烷二異氰酸酯、甲苯二異氰酸酯、亞甲基二苯基二異氰酸酯、或間苯二甲基二異氰酸酯。
  8. 如請求項1至5中任一項所述之高官能聚氨酯預聚物之製法,其中,該第一多元醇包括分子量為60至300之脂肪族二醇或分子量為60至300之脂肪族三醇。
  9. 如請求項1至5中任一項所述之高官能聚氨酯預聚物之製法,其中,該第一多元醇包括2-甲基-1,3-丙二醇、1,4-環己烷二甲醇、新戊二醇、1,3-丙二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、3-甲基-1,5-戊二醇、2-乙基-2-丁基-1,3-丙二醇、2,2,4-三甲基-1,3-戊二醇、丙三醇、或三羥甲基丙烷。
  10. 一種高官能聚氨酯預聚物,其係由請求項1至9中任一項所述之製法製備而得,該高官能聚氨酯預聚物具有6個以上的異氰酸酯基。
  11. 如請求項10所述之高官能聚氨酯預聚物,其中,該高官能聚氨酯預聚物具有的異氰酸酯基之含量為6重量百分比至25重量百分比。
  12. 如請求項11所述之高官能聚氨酯預聚物,其中,該高官能聚氨酯預聚物的重量平均分子量為1000至3000。
  13. 一種固化劑,其包含如請求項10至12中任一項所述之高官能聚氨酯預聚物。
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US4079028A (en) * 1975-10-03 1978-03-14 Rohm And Haas Company Polyurethane thickeners in latex compositions
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CN101955575B (zh) * 2010-03-04 2012-12-26 嘉宝莉化工集团股份有限公司 二苯甲烷二异氰酸酯与含羟基化合物合成聚氨酯固化剂
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