TWI405783B - 二縮脲化合物,其等之製備與用途,及其等製備過程之中間產物 - Google Patents
二縮脲化合物,其等之製備與用途,及其等製備過程之中間產物 Download PDFInfo
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Description
本發明係關於二縮脲化合物,其等之製備過程與用途。其亦關於氨基甲酸乙酯及/或含尿素之縮脲二酮,其為本發明中用於製備二縮脲化合物之有用的中間產物。
本發明之二縮脲化合物為適用於塗層系統如溶劑性、無溶劑、及水性塗料、PVC塑性溶膠、以環氧為基底之塗層及基於不飽和聚酯樹酯之塗層之搖變劑。
為了控制液態塗層系統之流變學,其通常使用矽、氫化的蓖麻油或有機修飾的皂土,如前述如在美國專利第4,208,218、4,410,364及4,412,018中所述。此外,聚醯胺蠟廣泛地被使用。特別地在聚醯胺及聚醯胺酯的範圍中,其存在數個專利,如DE 69523221、EP 0528363、EP 0239419、US 5,510,452及US 5,349,011。然而,其亦以如EP 0509202及DE 69704691中所述以修飾的皂土與聚醯胺合併使用。
這些物質的缺點為其通常為乾燥固體或糊狀物,其必須利用溶劑及剪力置入半完成產物中,並以所需之溫度控制導入液態塗層系統中。若沒有維持此溫度,所完成的塗層系統中會產生結晶並造成此塗層之缺陷。這些系統之一般缺點為其造成在清澈及透明塗層中之混濁及模糊。此外,操作乾性物質在處理過程易產生不必要的灰塵。聚醯胺酯通常為液態的其相較於固態物質效果較差。
其他用於控制流變學之溶液已出現於專利申請案EP 0198519中。其中,異氰酸酯在結合劑存在下與胺反應形成尿素,其細緻地散佈狀形成針狀的結晶。這些結合劑因此修飾成流變控制及防止凹陷結合劑,稱為”凹陷控制結合劑”。
這些產物的缺點為其總是與已製備之結合劑黏結,並對已完成之塗層材料無法進行接下來之一般校正。
專利申請案EP 0 006 252描述用於製備搖變劑之過程,其去除上述之一些缺點,其描述尿素氨基甲酸乙酯在LiCL存在下在非質子性溶劑中以異氰酸酯加合物與聚醯胺反應製備。該製備產物的缺點為尿素氨基甲酸乙酯呈現未定義之結構,其為此製程之結果。在此製程中,1 mol之二異氰酸酯首先與1 mol之單醇反應。此產生所需的NCO功能性單加合物及非NCO功能性雙加合物。此外,單體二異氰酸酯之特定部分維持未反應的。這些不同化合物之部分為可變的,視可得的NCO基及反應情況而定,如溫度及時間。不過,所有以此方式製備之加合物含有大量未反應之二異氰酸酯,其接下來與聚醯胺反應造成該分子不可控制之鏈延展。這些產物傾向於沉澱或不必要的膠化,因此埋藏於結合劑中。在專利申請案DE 19919482中這些缺點以去除過多的異氰酸酯而克服。然而,這些產物具有僅在高極性溶劑如N-甲基吡咯烷酮及鹼性金屬鹽存在時才能產生穩定溶液之缺點。
發現產生確定結構的搖變劑及接著確定搖變之改良效用及再現性為本發明之目的。
驚訝地此目的可由二縮脲化合物達到,其可由縮脲二酮(成分A)及二元胺(成分B)製備,並具有A-B-A之一般結構。
本發明因此提供具下述通式之二縮脲化合物
其中R1
為C2
-C1 8
烯烴基、環烯烴基、亞芳基或芳基烯烴基,Y為-O-及/或-NH-,R2
為C4
-C2 2
烷基、C3
-C1 8
烯基、環烷基、芳烷基,Cm
H2 m + 1
(O-Cn
H2 n
)x
-(O-CH(C6
H5
)-CH2
)u -
、Cm
H2 m + 1
(OOC-Cv
H2 v
)x
-、X-C6
H4
-(O-Cn
H2 n
)x
-(O-CH(C6
H5
)-CH2
)u -
,其中m=1-22,n=2-4,X=0-15,u=0-15,v=4-5,X為C1
-C1 2
烷基、-(C6
H5
)1 - 4
及R3
、R4
及R5
為C2
-C1 8
烯烴基、環烯烴基、亞芳基或芳基烯烴基,R3
、R4
及R5
為相同或不同都有可能,Z為-COO-、NHCO-、NHCOO-、NHCONH-及/或其混合物,及a為1-20。
較佳地R2
基為含有氧化乙烯及/或氧化丙烯及/或氧化丁烯基之聚烷氧單醇基。
本發明亦提供一用於製備二縮脲化合物之製程,其縮脲二酮通式(A)
其中R1
為C2
-C1 8
烯烴基、環烯烴基、亞芳基或芳基烯烴基,Y為-O-及/或-NH-,R2
為C4
-C2 2
烷基、C3
-C1 8
烯基、環烷基、芳烷基、Cm
H2 m + 1
(O-Cn
H2 n
)x
-(O-CH(C6
H5
)-CH2
)u -
、Cm
H2 m + 1
(OOC-Cv
H2 v
)x
-、X-C6
H4
-(O-Cn
H2 n
)x
-(O-CH(C6
H5
)-CH2
)u
-,其中m=1-22,n=2-4,X=0-15,u=0-15,v=4-5,及X為C1
-C1 2
烷基、或-(C6
H5
)1 - 4
與通式(B)之二元胺反應(B)H2
N-R3
-[Z-R4
-Z-R5
]a
-NH2
其中R3
、R4
及R5
為C2
-C1 8
烯烴基、環烯烴基、亞芳基或芳基烯烴基,R3
、R4
及R5
為相同或不同都有可能,Z為-COO-、NHCO-、NHCOO-、NHCONH-及/或其混合物,及a為1-20。
在製備本發明之二縮脲化合物時,含縮脲二酮之聚異氰酸酯首先與縮脲二酮之保留部份、單醇及/或單胺反應以形成含氨基甲酸乙酯及/或尿素之聚合物,且在第二個步驟本發明之二縮脲化合物由與聚醯胺反應,伴隨著打開縮脲二酮環而製備。
縮脲二酮如熟悉此技藝者所習知,是利用特殊催化劑由單體二異氰酸酯之加成反應所製備(H.J.Laas;R.Halpaap;J.Pedain;J.prakt.Chemie 336(1994),185-200)。
其優先使用HDI縮脲二酮,其為市場可得的,如來自Bayer之Desmodur N 3400,其除了縮脲二酮部份外亦含有HDI三體及脲基甲酸鹽。
在第一步驟中所使用之單醇為脂肪族、環脂肪族及芳基脂肪族醇。關於脂肪族醇,具有C2
-C2 2
鏈長度之直鏈狀、分枝的或環狀醇皆被使用,如乙醇、丙醇、n-丁醇、辛醇、癸醇、十二醇、油醇及硬脂醇。環脂肪族醇包括例如環戊醇及環己醇。芳基脂肪族醇如苯基醇同樣地可使用。聚合體醇如聚烯單醇、聚丙烯酸酯單醇、聚碳酸酯單醇、聚己內酯單醇或聚矽氧烷單醇可同樣的在本發明中使用,及具有不同程度烷氧基化之烷氧基化脂肪醇,來自BASF之商標名Lutensol被熟悉此技藝之人士所熟知。聚烷氧單醇含有氧化乙烯及/或氧化丙烯及/或氧化丁烯基,其被修飾成氧化苯乙烯為較佳地。聚烷氧單醇基如MPEG 350、MPEG 500、及MPEG 750,其為從甲醇製備之聚乙二醇,且含有一終端OH基為較佳的。單醇亦可以混合物形式使用。
單胺為脂肪族、環脂肪族及芳基脂肪族胺。關於脂肪族胺,具有C2
-C2 2
鏈長度之直鏈狀、分枝的或環狀胺皆被使用,如乙胺、丙胺、異丙胺、丁胺、仲-及叔-丁胺、3-甲基-1-丁胺、己胺、2-乙基己胺、辛胺、環戊胺、環己胺、三癸胺、油胺、十八胺及C2
-C2 2
胺之混合物,其為已知的商標名為來自Akzo Nobel之Armeen。基於本發明之胺不只是聚烯胺,如聚異丁烯胺、亦包括較佳地例如聚氧烯烴單胺,其包含氧化乙烯及/或氧化丙烯基,其為已知的來自Huntsman之商標名為Jeffamine M600、M1000、M2005及M2070。芳基脂肪族胺為例如苯胺及糠醛胺之產物。其亦可能用醯胼,如苯醯胼。單胺亦可以混合物形式使用,亦可能與單醇以任何比例形成混合物使用。
單醇中的含縮脲二酮之聚異氰酸酯與縮脲二酮環之存留部分間的反應於溫度15及60℃間執行,較佳地為20及50℃間,其適當地由催化劑幫助,如二丁錫二月桂酸酯(DBTL)。含縮脲二酮之聚異氰酸酯與具有縮脲二酮環之存留部分之單胺間的反應於溫度15及45℃間執行,較佳地為20及30℃之間,共反應物加入的順序通常為隨意的,含縮脲二酮之聚異氰酸酯首先置入一惰性溶劑中,單醇或單胺再逐滴加入。亦可先加入單醇或單胺,含縮脲二酮之聚異氰酸酯再逐滴加入。若使用單醇及單胺之混合物,含縮脲二酮之聚異氰酸酯先與醇反應再與胺反應。較適當地,反應亦可在一惰性溶劑中執行,如甲氧基乙酸丙酯、環己烷、甲苯、二甲苯或較高沸點之芳香族如Shellsol A。N-甲基吡咯烷酮或N-乙基吡咯烷酮同樣地適合當成溶劑。
通式(B)之雙胺由反應聚羧酸,較佳地為二羧酸及/或無水二羧酸與胺而製備,雙胺:聚羧酸比例為2:1及20:9之間,較佳地為3:2及12:11之間,及更加地為4:3及8:7之間。
雙胺較佳地為脂肪族及芳基脂肪族初級雙胺,如乙烯雙胺、新戊烷雙胺、1,2-及1,3-丙烷雙胺、1,6-六亞甲基雙胺、1,8-八亞甲基雙胺、1,12-十二亞甲基雙胺、環己雙胺、4,4-二胺二環己甲烷、3,3-二甲基-4,4-二胺二環己甲烷、異佛酮、4,7-二草酸癸烷-1,10-雙胺、4,7,10-三草酸癸烷-1,13-雙胺、聚氧烯烴雙胺包含氧化乙烯及/或氧化丙烯基以隨機或順時針方向排列,已知為來自Huntsman公司而來之商標名為Jeffamine D及Jeffamine ED,具有平均分子量148及4000 g/mol之間、及對及間苯二甲基雙胺。1,6-六亞甲基雙胺為較佳地。其亦可能用醯胼如草酸二醯胼、丁二酸二醯胼、或已二酸二醯胼。這些雙胺混合物亦是可能的。
聚羧酸較佳地為脂肪族、環脂肪族或芳香族,直鏈狀或分枝狀、飽和或非飽和的二羧酸具有至少2,較佳地介於3及40個碳原子。此類聚羧酸的例子為已二酸、草酸、丙二酸、丁二酸、戊二酸、庚二酸、辛二酸、癸二酸、壬二酸、十一二酸、1,11-十一二羧酸、二癸二酸、六癸二酸、二十二二酸、順丁烯二酸、反丁烯二酸、對苯二甲酸或異苯二甲酸,單獨使用或混合使用。酸酐如順丁烯二酐、戊二酸酐、苯二甲酐及丁二酸酐,其可被烷基或烯烴基修飾,如十二丁二酸酐亦是合適的。聚合體聚羧酸如聚丁二烯之二羧酸亦可被使用,氫氧功能性的聚羧酸如酒石酸、檸檬酸及氫氧苯二甲酸。氧二羧酸如3,6,9-三氧十一二酸及二羧基聚乙二醇亦包括在內。二聚合體脂肪如熟悉此技藝者所習知為二聚酸,具有36個碳原子之碳長度為較佳地。這些二聚酸可具有低單體含量(通常以重量計<8%),或三聚酸之以重量計不超過20%。
聚羧酸可全部或部分被二異氰酸酯取代,及雙胺全部或部分被二元醇取代,在這些案例中酯、氨基甲酸乙酯、及/或尿素基可存在於此聚合體中之較佳地胺部分的旁邊。
二元醇較佳地為聚烯烴基多元醇、聚烯基多元醇、以C1-C4烷基及/或烷氧基適當修飾的、或為聚乙醚多元醇、聚酯多元醇、混合的聚酯聚乙醚多元醇、聚碳酸酯多元醇、聚烯烴多元醇、聚丙烯酸酯多元醇、聚己內酯多元醇及具有較佳地2個終端氫氧基之聚矽氧烷多元醇。
二異氰酸酯可為脂肪族、環脂肪族或芳香族二異氰酸酯,單獨或混合使用。此種二異氰酸酯之例子為1,4-四亞甲基二異氰酸酯、1,6-六亞甲基二異氰酸酯、2,2,4-三甲基-1,6-六亞甲基二異氰酸酯、1,10-十亞甲基二異氰酸酯、1,4-環己烯二異氰酸酯、p-伸苯二異氰酸酯、m-伸苯二異氰酸酯、2,6-甲苯二異氰酸酯、2,4-甲苯二異氰酸酯及其混合物。P-及m-苯二甲基二異氰酸酯、4,4-二異氰酸酯二環己甲烷、3,3-二甲基-4,4-雙伸苯基二異氰酸酯、3,3-二甲基-二異氰酸酯二苯甲烷及C3 6
二體二異氰酸酯。
通式(B)之雙胺以熟知此技藝人士之情況下製備。二羧酸與雙胺/二元醇之濃縮反應之反應溫度為較佳地介於100及250℃之間。更佳地介於140及200℃之間。雙胺及聚羧酸之比例較佳地為選擇使用聚羧酸為n當量,雙胺為(n+1)當量,因此在反應結束後濃縮產物具有一胺數目。雙胺:聚羧酸比例為介於2:1及20:19之間,較佳地為介於3:2及12:11之間,更佳地為介於4:3及8:7之間。二異氰酸酯與雙胺/二元醇之加成反應中,反應溫度較佳地介於40及120℃之間。更加地介於60及100℃之間。
製備本發明之二縮脲化合物時,通式(A)中之縮脲二酮及通式(B)中之雙胺反應溫度介於60及120℃之間,更佳地介於75及90℃之間。在此案例中成分A及B之比例選擇1 mol之A與使用介於0.3 mol及0.7 mol間之B,更佳地為介於0.4 mol及0.6 mol之間,更佳地為0.5 mol。此反應可在有或無溶劑下進行。適當的溶劑為所有的脂肪族、芳香族、質子性溶劑、及非質子性溶劑如甲氧基乙酸丙酯、環己烷、甲苯、二甲苯或較高沸點之芳香族如Shellsol A。N-甲基吡咯烷酮或N-乙基吡咯烷酮、及醇類如乙醇、丙醇、異丁醇或乙二醇丁酯亦同樣適合。混合的溶劑亦可使用。
本發明亦提供上述加成化合物當成流變控制劑之使用,特別地當成抗凹陷劑及抗沉澱劑,特別地有關具有傾向嚴重沉澱之重色素之使用,如鋁色素及雲母色素。
然而,在用於工業地板材料之聚合體塗層案例中為基於環氧或聚氨基甲酸乙酯,或在稱之為膠質塗層案例中為基於不飽和的聚酯樹脂,流變控制劑及本發明中的加成化合物在此使用亦具有優點。
本發明亦提供氨基甲酸乙酯及/或通式(A)之含尿素之縮脲二酮,及其製程,其中具有縮脲二酮部分之殘留部分之含縮脲二酮之聚異氰酸酯與脂肪族、環脂肪族及/或芳基脂肪族單醇及/或其混合物,及/或脂肪族、環脂肪族及/或芳基脂肪族單胺及/或其混合物反應。這些縮脲二酮為本發明之二縮脲化合物製備時新的及有用的中間產物。這些中間產物已詳述於其上。
本發明以參考資料及實施例更進一步說明如下。
一具有攪拌器、回流冷卻器及溫度計之1升3頸的錐形瓶,設置在室溫下連續以79.6g(0.2 mol)之六亞甲基二異氰酸酯縮脲二酮(來自Bayer之Desmodur N3400)及300g(0.4 mol)之甲氧基聚乙二醇750進行操作,並將此起始操作加熱至80℃。此反應進行至異氰酸酯不再偵測到為止。此反應混合物接著冷卻至50℃。
一具有攪拌器、水分離器及溫度計之1升3頸的錐形瓶,設置在室溫下連續以168g(0.3 mol)之二元酸、46.4g(0.4 mol)之六亞甲基雙胺及92g之Shellsol A(高度芳香族碳氫化合物溶劑,Shell)進行操作,並將此起始操作緩慢加熱至160℃。在反應過程中釋出之水分經由水分離器從共沸物分離出來。當酸數目<3時反應達到終點。此反應混合物接著冷卻至50℃。
一具有攪拌器、回流冷卻器及溫度計之1升3頸的錐形瓶,設置在室溫下連續以103.6g(0.1 mol)之來自實施例1之反應產物及153.1g(0.05 mol)之來自實施例2之反應產物加熱至80℃。該反應混合物攪拌3小時至胺數目<3。此產物接著以異丙醇稀釋至50%之固體。
成分A:
成分B:
二縮脲加合物:
操作結果:此發明的產物於2-成分環氧系統測試其形成膠質之能力。此外,確定在黏結劑中得到的薄膜厚度。2-成分(2K)黏結劑系統實行如下:1. Epikote 1001/Epikote 834、基於雙酚A之聚環氧化物,Ancamide 700-x-75,高分子量雙胺2. Epikote 828,基於雙酚A之聚環氧化物,Ancamide 700-x-75,高分子量雙胺
測試配方:Epikote 1001(75%)於二甲苯中 34.5g Epikote 834(80%)於二甲苯中 7.6g Byk 052(消泡劑) 0.3g Bayferrox 130M(氧化鐵色素) 5.0g微滑石粉AT-1(CaCO3
) 12.0g磷酸鋅 12.0g EWO(BaSO4
) 5.6g
溶劑混合物:甲基異丁酮 19.2g異丁醇 3.8g
硬化劑:Ancamide 700X75
將1%之發明的產物以劇烈的攪拌(分散攪拌機,30分鐘/8500s- 1
)成所測試的配方。此配方接著冷卻至20℃並以溶劑混合物稀釋。
接著評估所產生的膠質。
24小時後以攪拌方式加入硬化劑並以有刻度的刮刀片操作。當硬化發生後確定其薄膜厚度。
商標名之說明:Epikote 1001:基於雙酚A之聚環氧化物(Shell)Epikote 834:基於雙酚A之聚環氧化物(Shell)Byk 410:尿素聚醯胺酯,稀釋於N-甲基吡咯烷酮Jeffamine m 600:烷基聚酯胺,MW 600(Huntsman)Jeffamine m 2070:烷基聚酯胺,MW 2000(Huntsman)Jeffamine ED 900:烷基聚酯雙胺,MW900(Huntsman)Jeffamine ED 2003:烷基聚酯胺,MW2000(Huntsman)Ancamide 700-x-75:聚醯胺/環氧化物加合物(Air Products)
Claims (7)
- 一種具下述通式之二縮脲化合物,
- 根據申請專利範圍第1項之二縮脲化合物,其中R2 基為含有氧化乙烯及/或氧化丙烯及/或氧化丁烯基之聚烷氧單醇基。
- 一種製備申請專利範圍第1項之二縮脲化合物之方法, 其特徵為通式(A)之縮脲二酮
- 根據申請專利範圍第3項之方法,其中通式(A)之縮脲二酮比通式(B)之二元胺之比例為介於1:0.3及1:0.7。
- 如申請專利範圍第3或4項之製備二縮脲化合物的方法,其特徵為式(A)及(B)之化合物在介於60℃及120℃間反應。
- 一種下述通式之二縮脲化合物之用途,其係作為流變控制劑
- 一種申請專利範圍第6項之二縮脲化合物的用途,其係 用於搖變塗層系統作為抗凹陷劑及/或抗沉澱劑。
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- 2006-04-03 CA CA2541881A patent/CA2541881C/en active Active
- 2006-04-03 AT AT06007037T patent/ATE512131T1/de active
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- 2006-04-06 JP JP2006105620A patent/JP5259056B2/ja active Active
- 2006-04-07 CN CN2006100725694A patent/CN1847220B/zh active Active
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Patent Citations (1)
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TW200404830A (en) * | 2002-09-09 | 2004-04-01 | Byk Chemie Gmbh | Polymeric urea-urethane rheology control agent and preparation process |
Non-Patent Citations (2)
Title |
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Hans R. Kricheldorf, William E. Hull ," 15N NMR spectroscopy, 27.Part 26: H. R. Kricheldorf, Polym. Bull. 2, 177 (1980). Spectroscopic characterization of polyurethanes and related compounds", Makromolekulare Chemie,1981,Vol.182,p1177~1196 * |
Pritam Singh, Jean L. Boivin ,"Studies On The Stability Of The Dimer Of 2,4-Tolylene Diisocyanate", Canadian Journal of Chemistry,1962,Vol.40,p935~940 * |
Also Published As
Publication number | Publication date |
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DE102005015966A1 (de) | 2006-10-19 |
EP1710228A3 (de) | 2007-12-12 |
EP1710228A2 (de) | 2006-10-11 |
KR20060107417A (ko) | 2006-10-13 |
JP5259056B2 (ja) | 2013-08-07 |
KR101275836B1 (ko) | 2013-06-18 |
US7652166B2 (en) | 2010-01-26 |
CN1847220B (zh) | 2012-01-11 |
DK1710228T3 (da) | 2011-09-19 |
ATE512131T1 (de) | 2011-06-15 |
TW200640973A (en) | 2006-12-01 |
JP2006306869A (ja) | 2006-11-09 |
CN1847220A (zh) | 2006-10-18 |
US20060276675A1 (en) | 2006-12-07 |
EP1710228B1 (de) | 2011-06-08 |
CA2541881C (en) | 2013-07-09 |
CA2541881A1 (en) | 2006-10-07 |
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