TWI811576B - 水性聚氨酯樹脂的製備方法 - Google Patents

水性聚氨酯樹脂的製備方法 Download PDF

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TWI811576B
TWI811576B TW109137020A TW109137020A TWI811576B TW I811576 B TWI811576 B TW I811576B TW 109137020 A TW109137020 A TW 109137020A TW 109137020 A TW109137020 A TW 109137020A TW I811576 B TWI811576 B TW I811576B
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add
water
based polyurethane
prepolymer
polyurethane resin
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TW109137020A
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TW202216824A (zh
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廖德超
徐森煌
蔡佳龍
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南亞塑膠工業股份有限公司
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Priority to TW109137020A priority Critical patent/TWI811576B/zh
Priority to CN202110339128.0A priority patent/CN114478973A/zh
Priority to US17/378,904 priority patent/US11639414B2/en
Publication of TW202216824A publication Critical patent/TW202216824A/zh
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Abstract

本發明公開一種水性聚氨酯樹脂及其製備方法，水性聚氨酯樹脂的製備方法包括：預聚物的製備、預聚物的稀釋、水分散及擴鏈以及壓克力合成。製備方法中包括混合聚多元醇以及多元異氰酸酯，得到預聚物，再加入壓克力單體稀釋。本發明的水性聚氨酯樹脂中，聚多元醇、多元異氰酸酯以及壓克力單體之至少一者包括環狀結構的化合物，藉此增強分子間作用力，提高了水性聚氨酯樹脂的熱穩定性，達到改善耐熱黃變的目的。

Description

水性聚氨酯樹脂的製備方法
本發明涉及一種水性聚氨酯樹脂及其製備方法，特別是涉及一種包含環狀結構的水性聚氨酯樹脂及其製備方法。
聚氨酯樹脂的應用領域相當廣泛，例如：合成皮的面料或表面處理劑。在生產聚氨酯的製程中，需要使用大量有機溶劑，導致聚氨酯產品含有揮發性有機化合物(Volatile Organic Compounds；VOCs)的問題。近年來，在環保意識備受關注的情況下，水性聚氨酯已經逐漸地取代溶劑型聚氨脂，並且廣泛應用於紡織品的塗佈加工、皮革加工、接著劑、密封劑和塑膠成型等多元用途。水性聚氨酯的合成方法，是以聚醚或聚酯多元醇與異氰酸酯反應，合成末端為NCO官能基的高粘度預聚物。
水性聚氨酯樹脂應用在合成皮面料，如：車用皮面面料時，於高溫條件下(120℃x7天)，耐熱黃變及耐候等物性較差，現有技術是通過添加光穩定劑、抗氧化劑與熱穩定劑等助劑來達到改善黃變之目的，然而，其改善程度仍不甚理想。
本發明所要解決的技術問題在於，針對現有技術的不足提供一 種包含環狀結構的水性聚氨酯樹脂及其製備方法。
為了解決上述的技術問題，本發明所採用的其中一技術方案是提供一種一種水性聚氨酯樹脂的製備方法，其包括以下步驟：(1)預聚物的製備：將一聚多元醇105.24g真空脫水後，加入一反應槽中，以油浴加熱升溫至溫度70至80℃，再於所述反應槽中加入一多元異氰酸酯51.3g，使其合成反應，以得到一預聚物；(2)預聚物的稀釋：於所述預聚物中加入一壓克力單體179g以稀釋降黏，並維持溫度介於85至90℃，反應2至3小時，直到NCO%達到目標值，然後加入一磺酸鹽親水劑26.4g，持續反應25至40分鐘，得到一聚合物；(3)水分散及擴鏈：將步驟(2)的所述聚合物降溫至室溫，並在轉速500rpm下，加入去離子水472.6g，然後加入一鏈延長劑1.9g進行擴鏈反應約30分鐘，以得到一水性聚氨酯；以及(4)壓克力合成：於步驟(3)的所述水性聚氨酯中加入一乳化劑4.8g混合形成一乳化液，攪拌均勻後升溫至50至70℃，再滴加一起始劑0.4g，於溫度75至85℃進行壓克力聚合1至3小時，降溫至50至70℃後加入一還原劑0.15g，得到一水性聚氨酯樹脂；其中，所述聚多元醇、所述多元異氰酸酯以及所述壓克力單體之至少一者包括環狀結構的化合物。
本發明的其中一有益效果在於，本發明所提供的水性聚氨酯樹脂及其製備方法，其能通過“所述聚多元醇、所述多元異氰酸酯以及所述壓克力單體之至少一者包括環狀結構的化合物”的技術方案，以提高樹脂熱穩定性。
為使能更進一步瞭解本發明的特徵及技術內容，請參閱以下有關本發明的詳細說明與圖式，然而所提供的圖式僅用於提供參考與說明，並非用來對本發明加以限制。
圖1為本發明水性聚氨酯樹脂的製備方法的流程圖。
以下是通過特定的具體實施例來說明本發明所公開有關“水性聚氨酯樹脂及其製備方法”的實施方式，本領域技術人員可由本說明書所公開的內容瞭解本發明的優點與效果。本發明可通過其他不同的具體實施例加以施行或應用，本說明書中的各項細節也可基於不同觀點與應用，在不背離本發明的構思下進行各種修改與變更。另外，本發明的附圖僅為簡單示意說明，並非依實際尺寸的描繪，事先聲明。以下的實施方式將進一步詳細說明本發明的相關技術內容，但所公開的內容並非用以限制本發明的保護範圍。另外，本文中所使用的術語“或”，應視實際情況可能包括相關聯的列出項目中的任一個或者多個的組合。
參閱圖1，本發明提供一種水性聚氨酯樹脂的製備方法，其包括以下步驟：S100預聚物的製備、S200預聚物的稀釋、S300水分散及擴鏈以及S400壓克力合成，其中，水性聚氨酯樹脂製備的反應物中聚多元醇、多元異氰酸酯以及壓克力單體之至少一者包括環狀結構的化合物。更詳細來說，在聚多元醇、多元異氰酸酯以及壓克力單體至少一者的結構中包括環狀結構，環狀結構的化合物是指分子中原子以環狀排列的化合物，舉例來說，脂環族化合物或芳香烴。較佳地，壓克力單體的結構中包括環狀結構。
S100預聚物的製備：將聚多元醇105.24g真空脫水後，加入反應槽中，以油浴加熱升溫至溫度70至80℃，再於所述反應槽中加入多元異氰酸酯51.3g，使其合成反應，以得到預聚物。
聚多元醇是選自聚酯多元醇以及聚醚多元醇所組成的群組。也就是說，可以是單獨使用聚酯多元醇或聚醚多元醇，或是混合多種不同的聚 酯多元醇以及聚醚多元醇。
聚酯多元醇可以是由低分子二醇與二羧酸縮合而得，舉例來說：由乙二醇、1,3-丙二醇、1,4-丁二醇等的低分子多元醇與琥珀酸、戊二酸、己二酸、庚二酸、軟木酸(suberic acid)、壬二酸(azelaic acid)、癸二酸(sebacic acid)、癸烷二羧酸、環己烷二羧酸等的脂肪族二羧酸縮合而得的縮合系聚酯多元醇。
另外，也可使用ε-己內酯等的環狀酯、二醇的一部分反應為六亞甲基二胺或異佛爾酮二胺(isophorone diamine)等胺類的聚酯醯胺多元醇等。
除此之外，聚酯多元醇也可以是由1,4環己烷二甲醇或三環癸烷二甲醇(TCD-alcohol)與二元酸聚合而成，舉例來說，1,4環己烷二甲醇與二元酸聚合成的聚環己烷二甲酯、三環癸烷二甲醇(TCD-alcohol)與二元酸聚合成的聚三環癸烷二甲酯，如下所示：
Figure 109137020-A0305-02-0006-1
聚醚多元醇為選自聚四亞甲基醚二醇(PTMG)、聚丙二醇(PPG)以及主鏈和側鏈的聚乙二醇(PEG)所組成群組。
二異氰酸酯可以是脂肪族二異氰酸酯、脂環族二異氰酸酯或芳香族二異氰酸酯。較佳地，二異氰酸酯具有環狀結構的脂環族二異氰酸酯。
舉例來說，脂肪族二異氰酸酯可以是四亞甲基二異氰酸酯、六亞甲基二異氰酸酯、十亞甲基二異氰酸酯(decamethylene diisocyanate)、賴胺酸二異氰酸酯(lysine diisocyanate)。
舉例來說，二異氰酸酯可以是甲苯二異氰酸酯(TDI)、二苯基甲烷二異氰酸酯(MDI)、異佛爾酮二異氰酸酯(isophorone diisocyanate，IPDI)、二甲苯二異氰酸酯(xylylene Diisocyanate，XDI)、四甲基二甲苯二異氰酸酯(tetramethylxylene diisocyanate)、二環己基甲烷二異氰酸酯(4,4'-Methylene dicyclohexyl diisocyanate，H12MDI)、三甲基六亞甲基二異氰酸酯(trimethylhexamethylene diisocyanate，TMDI)。
舉例來說，芳香族聚異氰酸酯可以是2,4-甲苯二異氰酸酯、2,6-甲苯二異氰酸酯、二甲苯-1,4-二異氰酸酯、二甲苯-1,3-二異氰酸酯、4,4’-二苯甲烷二異氰酸酯、2,4’-二苯甲烷二異氰酸酯、4,4’-二苯醚二異氰酸酯、2-硝基二苯基-4,4’-二異氰酸酯、2,2’-二苯丙烷-4,4’-二異氰酸酯、3,3’-二甲基二苯基甲烷-4,4’-二異氰酸酯、4,4’-二苯丙烷二異氰酸酯、間苯二異氰酸酯、對苯二異氰酸酯、萘-1,4-二異氰酸酯、萘-1,5-二異氰酸酯、3,3’-二甲氧基二苯基-4,4’-二異氰酸酯等的芳香族二異氰酸酯、聚苯聚亞甲基聚異氰酸酯(polyphenylene polymethylene polyisocyanate)、未精製的甲苯二異氰酸酯(crude tolylene diisocyanate)。
較佳地，二異氰酸酯是異佛爾酮二異氰酸酯(IPDI)或二環己基甲烷二異氰酸酯(H12MDI)。
S200預聚物的稀釋：於所述預聚物中加入壓克力單體179g以稀釋降黏，並維持溫度介於85至90℃，反應2至3小時，直到NCO%達到目標值， 然後加入磺酸鹽親水劑26.4g，持續反應25至40分鐘，得到聚合物。
壓克力單體可以是選自下述單體：甲基丙烯酸環己酯、甲基丙烯酸異冰片酯、丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、丙烯酸異辛酯、丙烯酸丁酯、甲基丙烯酸丁酯、丙烯酸乙基己基酯、丙烯酸2羥乙酯、順丁烯二酸單甲酯、衣康酸單甲酯、反丁烯二酸單甲酯、苯乙烯所組成的群組。較佳地，壓克力單體是選自多種單體混用。更佳的，壓克力單體是選用丙烯酸類單體，並結合具有環狀結構的壓克力單體。
較佳地，壓克力單體是選自甲基丙烯酸環己酯(CHMA)、甲基丙烯酸異冰片酯(IBOMA)、丙烯酸2羥乙酯(2-Hydroxyethyl Acrylate，2-HEA)、甲基丙烯酸甲酯(Methyl Methacrylate，MMA)及丙烯酸乙酯(Ethyl Acrylate，EA)所組成的群組。
更詳細來說，丙烯酸2羥乙酯、甲基丙烯酸甲酯及丙烯酸乙酯可以做為溶劑，以省略一般現有技術中使用的丙酮，丙烯酸2羥乙酯含羥基(-OH)可與異氰酸鹽反應，甲基丙烯酸甲酯與丙烯酸乙酯可提高壓克力分子量，可以提升水性聚氨酯的機械強度以及耐水性。
除此之外，甲基丙烯酸環己酯以及甲基丙烯酸異冰片酯皆具有環狀結構，可提高樹脂耐熱黃變，如下結構式所示。
Figure 109137020-A0305-02-0008-2
具體而言，本發明的壓克力單體是以下壓克力單體的配比組合：(a)甲基丙烯酸甲酯的含量為50至90wt%；(b)丙烯酸2羥乙酯的含量為4至9wt%；(c)丙烯酸乙酯的含量為2至6wt%； (d)甲基丙烯酸環己酯的含量為0至15wt%；以及(e)甲基丙烯酸異冰片酯的含量為0至20wt%。
較佳地，若單純選用丙烯酸系壓克力單體，則在水性聚氨酯的其他組分中另須包含其他環狀結構的成分。然而，具有環狀結構的甲基丙烯酸環己酯以及甲基丙烯酸異冰片酯可提供更優異的耐黃變效果。
更佳地，本發明的壓克力單體是以下壓克力單體的配比組合：(a)甲基丙烯酸甲酯的含量為50至90wt%；(b)丙烯酸2羥乙酯的含量為4至9wt%；(c)丙烯酸乙酯的含量為2至6wt%；(d)甲基丙烯酸環己酯的含量為7至14wt%；以及(e)甲基丙烯酸異冰片酯的含量為10至18wt%。
磺酸鹽親水劑是作為聚氨酯親水劑，且可作為高分子乳化劑，較佳地，磺酸鹽親水劑是乙二胺基乙氧基乙磺酸鈉。
NCO%目標值是指聚氨酯(PU)反應中，多元異氰酸酯的異氰酸基(-NCO)與聚多元醇所含的羥基(-OH)完全反應後，剩餘的異氰酸基重量占所有參與的反應物重量的百分比。其NCO%目標值=(多元異氰酸酯的用量/多元異氰酸酯的分子量-聚多元醇的用量/聚多元醇的分子量)×42×2×%，其NCO%目標值為0.5-10%，在實施例中，NCO%反應滴定值是在進行反應時，即在製備方法的步驟中加水並進行乳化前，使用二丁基胺(dibutylamine)滴定法所量測而得的NCO%。
由於該聚氨酯樹脂的NCO%反應滴定值是介於NCO%理論值的50%至85%之間，使得其在水性聚氨酯分散液中是呈現穩定分散的狀態，避免該聚氨酯樹脂產生團聚凝膠。若在合成聚氨酯時過度地反應消耗多元異氰酸酯，使得該NCO%反應滴定值低於NCO%目標值的50%，則因為聚氨酯 反應過量導致聚氨酯網狀結構交聯度太高，進而導致聚氨酯在水相中產生大量團聚凝膠而失敗；若該NCO%反應滴定值高於NCO%目標值的85%，則會因為合成後的聚氨酯的網狀結構比例不足，導致水性聚氨酯加工形成薄膜後，該薄膜表面產生過高的黏滯性，易造成薄膜間沾黏而產生報廢。
S300水分散及擴鏈：將步驟S200的聚合物降溫至室溫，並在轉速500rpm下，加入去離子水472.6g，然後加入鏈延長劑1.9g進行擴鏈反應約30分鐘，以得到水性聚氨酯。
通過調整二異氰酸酯、聚多元醇和離子水的配比，可以改良成品的發泡特性。鏈延長劑可以是乙二胺、六亞甲基二胺、二甲苯二胺、異佛爾酮二胺、二乙烯三胺、N-胺基乙基-N-乙醇胺等的(數平均)分子量未滿500的低分子聚胺等。
S400壓克力合成：於步驟S300的水性聚氨酯中加入乳化劑4.8g混合形成乳化液，攪拌均勻後升溫至50至70℃，再滴加起始劑0.4g，於溫度75至85℃進行壓克力聚合1至3小時，降溫至50至70℃後加入還原劑0.15g，得到水性聚氨酯樹脂。
具體來說，乳化劑可使用陰離子、非離子或反應型乳化劑。舉例來說，如特辛基苯氧乙基多(39)-乙氧基乙醇、十二烷氧多(10)乙氧基乙醇、壬基苯氧乙基-多(40)乙氧基乙醇、聚乙二醇2000單油酸酯、羥乙基化蓖麻油、氟化烷酯與烷氧化物、多氧乙烯(20)花楸糖醇單月桂酸酯、蔗糖單椰酸酯、二(2-丁)苯氧基多(20)乙氧基乙醇、羥乙基纖維素多丙烯酸丁酯接枝共聚物。乳化劑是一種表面活性劑，它可以大幅降低表面張力，使互不相溶的油水兩相藉由攪拌的作用轉變為能夠穩定存在、不易分層的白色乳液。
離子型乳化劑可以是十二烷基硫酸鈉(SLS)、十二烷基苯磺酸鈉、硬脂酸鉀、二辛基磺基琥珀酸鈉、十二烷基二苯化氧基二磺酸鈉、壬基苯氧 乙基多(1)乙氧乙硫酸銨鹽、苯乙烯磺酸鈉、十二烷基烯丙基磺基琥珀酸鈉、亞麻子油脂肪酸、乙氧化壬基酚磷酸酯的鈉或銨鹽、octoxynol-3-磺酸鈉、椰基肌胺酸鈉、1-烷氧基-2-羥丙基磺酸鈉、α-烯烴(C14-C16)磺酸鈉、羥基烷醇之硫酸鹽、N-(1,2-二羧基乙)-N-十八烷基磺基琥珀醯胺酸四鈉、N-十八烷基磺基琥珀醯胺酸二鈉、烷醯胺基多乙氧基磺基琥珀酸二鈉、乙氧化壬酚磺基琥珀酸半酯二鈉、乙氧乙基硫酸鈉鹽。
進一步來說，起始劑可以是過氧化氫、特丁基過氧化物、鹼金屬過硫酸鹽如過硫酸鈉、鉀與鋰及過硫酸銨(APS)。
進一步來說，還原劑可以是亞硫酸鹽如偏亞硫酸鹼金屬鹽、亞硫氫鹽及次亞硫酸鹽、甲醛合次硫酸氫鈉(SFS)、叔丁基過氧化氫(TBHP)及還原糖類如抗壞血酸與異抗壞血酸。在乳液聚合後期，為避免升溫造成乳液凝聚，可用還原劑在50-70℃條件下進行單體的後消除，降低單體殘留率。
本發明進一步通過以下實施例及比較例說明本發明，然而，該等實施例只是其中一可行的實施方案而並非用以限定本發明。
[實施例1]
將三環癸烷二甲醇(TCD-alcohol)與己二酸(AA)合成聚酯多元醇。混合78.8g PTMG2000(聚醚二元醇，分子量2000)、6.44g 1,4-BG(1,4-丁二醇，分子量90)以及20g前述聚酯多元醇於反應槽中，勻速攪拌並升溫至80℃，加入51.3g二環己基甲烷二異氰酸酯(H12MDI)，升溫至85至90℃，並在此溫度下反應2至3小時。接著，批次加入壓克力單體147.2g甲基丙烯酸甲酯(MMA)、8g丙烯酸2羥乙酯(2-HEA)、4.8g丙烯酸乙酯(EA)，預聚物加入26.4g乙二胺基乙氧基乙磺酸鈉，持續反應25至40分鐘後，降溫至室溫，在500rpm轉速下加入472.6g去離子水，再加入1.9g乙二胺進行擴鏈反應約30分鐘，得到水性聚氨酯。
將4.8g十二烷基硫酸鈉(SLS)在快速攪拌下加入上述水性聚氨酯，升溫至50至70℃，之後滴加過硫酸銨水溶液(APS)0.40g，續升溫至75至85℃，於此溫度恆溫1至3小時，降溫至50至70℃後加入還原劑叔丁基過氧化氫水溶液(TBHP)0.15g及甲醛合次硫酸氫鈉(SFS)0.16g，反應30分鐘，得到壓克力接枝改質水性聚氨酯。
[實施例2]
混合98.8g PTMG2000(聚醚二元醇，分子量2000)以及6.44g 1,4-BG(1,4-丁二醇，分子量90)於反應槽中，勻速攪拌並升溫至80℃，加入43.5g異佛爾酮二異氰酸酯(IPDI)，升溫至85至90℃，並在此溫度下反應2至3小時。接著，批次加入壓克力單體127.2g甲基丙烯酸甲酯(MMA)、8g丙烯酸2羥乙酯(2-HEA)、4.8g丙烯酸乙酯(EA)、16.8g甲基丙烯酸環己酯(CHMA)以及22.2g甲基丙烯酸異冰片酯(IBOMA)，預聚物加入26.4g乙二胺基乙氧基乙磺酸鈉，持續反應25至40分鐘後，降溫至室溫，在500rpm轉速下加入472.6g去離子水，再加入1.9g乙二胺進行擴鏈反應約30分鐘，得到水性聚氨酯。
將4.8g十二烷基硫酸鈉(SLS)在快速攪拌下加入上述水性聚氨酯，升溫至50至70℃，之後滴加過硫酸銨水溶液(APS)0.40g，續升溫至75至85℃，於此溫度恆溫1至3小時，降溫至50至70℃後加入還原劑叔丁基過氧化氫水溶液(TBHP)0.15g及甲醛合次硫酸氫鈉(SFS)0.16g，反應30分鐘，得到壓克力接枝改質水性聚氨酯。
[實施例3]
將三環癸烷二甲醇(TCD-alcohol)與己二酸(AA)合成聚酯多元醇。混合78.8g PTMG2000(聚醚二元醇，分子量2000)、6.44g 1,4-BG(1,4-丁二醇，分子量90)以及20g前述聚酯多元醇於反應槽中，勻速攪拌並升溫至80℃，加入51.3g二環己基甲烷二異氰酸酯(H12MDI)，升溫至85至90℃，並在此溫度 下反應2至3小時。接著，批次加入壓克力單體127.2g甲基丙烯酸甲酯(MMA)、8g丙烯酸2羥乙酯(2-HEA)、4.8g丙烯酸乙酯(EA)、16.8g甲基丙烯酸環己酯(CHMA)以及22.2g甲基丙烯酸異冰片酯(IBOMA)，預聚物加入26.4g乙二胺基乙氧基乙磺酸鈉，持續反應25至40分鐘後，降溫至室溫，在500rpm轉速下加入472.6g去離子水，再加入1.9g乙二胺進行擴鏈反應約30分鐘，得到水性聚氨酯。
將4.8g十二烷基硫酸鈉(SLS)在快速攪拌下加入上述水性聚氨酯，升溫至50至70℃，之後滴加過硫酸銨水溶液(APS)0.40g，續升溫至75至85℃，於此溫度恆溫1至3小時，降溫至50至70℃後加入還原劑叔丁基過氧化氫水溶液(TBHP)0.15g及甲醛合次硫酸氫鈉(SFS)0.16g，反應30分鐘，得到壓克力接枝改質水性聚氨酯。
[比較例1]
混合98.8g PTMG2000(聚醚二元醇，分子量2000)以及6.44g 1,4-BG(1,4-丁二醇，分子量90)於反應槽中，勻速攪拌並升溫至80℃，加入43.5g異佛爾酮二異氰酸酯(IPDI)，升溫至85至90℃，並在此溫度下反應2至3小時。接著，批次加入147.2g甲基丙烯酸甲酯(MMA)、8g丙烯酸2羥乙酯(2-HEA)、4.8g丙烯酸乙酯(EA)稀釋降黏，預聚物加入26.4g乙二胺基乙氧基乙磺酸鈉，持續反應25至40分鐘後，降溫至室溫，在500rpm轉速下加入472.6g去離子水，再加入1.9g乙二胺進行擴鏈反應約30分鐘，得到水性聚氨酯。
將4.8g十二烷基硫酸鈉(SLS)在快速攪拌下加入上述水性聚氨酯，升溫至50至70℃，之後滴加過硫酸銨水溶液(APS)0.40g，續升溫至75至85℃，於此溫度恆溫1至3小時，降溫至50至70℃後加入還原劑叔丁基過氧化氫水溶液(TBHP)0.15g及甲醛合次硫酸氫鈉(SFS)0.16g，反應30分鐘，得到壓克力接枝改質水性聚氨酯。
上述實施例1至3與比較例1的組成分別列表於表1，並進一步將該等水性聚氨酯樹脂應用於合成皮上並測試產品物性，結果如表2所示：
Figure 109137020-A0305-02-0014-3
Figure 109137020-A0305-02-0014-4
Figure 109137020-A0305-02-0015-5
[實施例的有益效果]
本發明的其中一有益效果在於，本發明所提供的水性聚氨酯樹脂及其製備方法，其能通過“所述聚多元醇、所述多元異氰酸酯以及所述壓克力單體之至少一者包括環狀結構的化合物”的技術方案，以提高樹脂熱穩定性。
具體來說，現有技術的水性聚氨酯樹脂應用在合成皮面料或表面處理劑時，於高溫條件下(120℃x7天)，耐熱黃變及耐候等物性較差，一般通過添加光穩定劑、抗氧化劑與熱穩定劑等助劑來達到改善黃變的目的，然而，其改善程度仍不甚理想。
進一步來說，本發明的聚多元醇較佳可以是1,4環己烷二甲醇與二元酸聚合成的聚環己烷二甲酯、三環癸烷二甲醇(TCD-alcohol)與二元酸聚合成的聚三環癸烷二甲酯，二異氰酸酯較佳地是異佛爾酮二異氰酸酯(IPDI)以及二環己基甲烷二異氰酸酯(H12MDI)，該等化合物的結構中都包含了環狀結構。
更進一步來說，壓克力單體可以是丙烯酸2羥乙酯(2-Hydroxyethyl Acrylate，2-HEA)、甲基丙烯酸甲酯(Methyl Methacrylate，MMA)及丙烯酸乙酯(Ethyl Acrylate，EA)的組合，再搭配具有環狀結構的甲基丙烯酸環己酯(CHMA)以及甲基丙烯酸異冰片酯(IBOMA)。
本發明分別於聚多元醇、多元異氰酸酯以及壓克力單體引入環 狀結構，改變鏈段結構，使分子間作用力增強來改善，提高了水性聚氨酯樹脂的熱穩定性，應用於PVC膠皮及PU合成皮處理劑，可達到120℃x7天耐熱黃變△E較低的物性。
以上所公開的內容僅為本發明的優選可行實施例，並非因此侷限本發明的申請專利範圍，所以凡是運用本發明說明書及圖式內容所做的等效技術變化，均包含於本發明的申請專利範圍內。

Claims (4)

  1. 一種水性聚氨酯樹脂的製備方法，其包括以下步驟：(1)預聚物的製備：將一聚多元醇105.24g真空脫水後，加入一反應槽中，以油浴加熱升溫至溫度70至80℃，再於所述反應槽中加入一多元異氰酸酯51.3g，使其合成反應，以得到一預聚物；其中，所述聚多元醇包含聚醚二元醇78.8g、1,4-丁二醇6.44g及三環癸烷二甲醇與己二酸合成的聚酯多元醇20g，並且所述多元異氰酸酯為二環己基甲烷二異氰酸酯；(2)預聚物的稀釋：於所述預聚物中加入一壓克力單體179g以稀釋降黏，並維持溫度介於85至90℃，反應2至3小時，直到NCO%達到目標值，然後加入一磺酸鹽親水劑26.4g，持續反應25至40分鐘，得到一聚合物；其中，所述壓克力單體包含甲基丙烯酸環己酯16.8g、甲基丙烯酸異冰片酯22.2g、甲基丙烯酸甲酯127.2g、丙烯酸乙酯4.8g及丙烯酸2羥乙酯8g；以及(3)水分散及擴鏈：將步驟(2)的所述聚合物降溫至室溫，並在轉速500rpm下，加入去離子水472.6g，然後加入一鏈延長劑1.9g進行擴鏈反應30分鐘，以得到一水性聚氨酯；以及(4)壓克力合成：於步驟(3)的所述水性聚氨酯中加入一乳化劑4.8g混合形成一乳化液，攪拌均勻後升溫至50至70℃，再滴加一起始劑0.4g，於溫度75至85℃進行壓克力聚合1至3小時，降溫至50至70℃後加入一還原劑0.15g，得到一水性聚氨酯樹脂；其中，所述聚多元醇、所述多元異氰酸酯以及所述壓克力單體之至少一者包括環狀結構的化合物。
  2. 如請求項1所述的水性聚氨酯樹脂的製備方法，其中，所述聚多元醇、所述多元異氰酸酯以及所述壓克力單體皆包括環狀結構的化合物。
  3. 如請求項1所述的水性聚氨酯樹脂的製備方法，其中，所述聚多元醇與所述多元異氰酸酯是以NCO/OH當量比為1.1至2.3進行反應。
  4. 如請求項1所述的水性聚氨酯樹脂的製備方法，其中，所述起始劑是選自過氧化氫、特丁基過氧化物、過硫酸鈉、過硫酸鉀與過硫酸鋰以及過硫酸銨所組成的群組，且所述起始劑的用量為以丙烯酸系單體總量為基礎0.01至3重量比。
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