CN108884181A - 可光固化的含有贫电子烯烃的组合物 - Google Patents
可光固化的含有贫电子烯烃的组合物 Download PDFInfo
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- CN108884181A CN108884181A CN201780021968.4A CN201780021968A CN108884181A CN 108884181 A CN108884181 A CN 108884181A CN 201780021968 A CN201780021968 A CN 201780021968A CN 108884181 A CN108884181 A CN 108884181A
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- Prior art keywords
- cyanoacrylate
- composition
- alkyl
- alkenyl
- group
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- 150000001336 alkenes Chemical class 0.000 title claims abstract description 16
- 230000002950 deficient Effects 0.000 title claims abstract description 12
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- 239000002253 acid Substances 0.000 claims abstract description 13
- XJDDLMJULQGRLU-UHFFFAOYSA-N 1,3-dioxane-4,6-dione Chemical compound O=C1CC(=O)OCO1 XJDDLMJULQGRLU-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000002148 esters Chemical class 0.000 claims abstract description 7
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 claims abstract description 5
- -1 alpha-methyl-2-nitrobenzyl Chemical group 0.000 claims description 29
- MWCLLHOVUTZFKS-UHFFFAOYSA-N Methyl cyanoacrylate Chemical compound COC(=O)C(=C)C#N MWCLLHOVUTZFKS-UHFFFAOYSA-N 0.000 claims description 25
- 229920001651 Cyanoacrylate Polymers 0.000 claims description 24
- 125000000217 alkyl group Chemical group 0.000 claims description 21
- 239000003381 stabilizer Substances 0.000 claims description 18
- 125000003342 alkenyl group Chemical group 0.000 claims description 10
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 9
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- 125000003118 aryl group Chemical group 0.000 claims description 5
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- 125000003710 aryl alkyl group Chemical group 0.000 claims description 3
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
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- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
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- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 125000003504 2-oxazolinyl group Chemical class O1C(=NCC1)* 0.000 claims description 2
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical compound N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 claims description 2
- JSDZSLGMRRSAHD-UHFFFAOYSA-N 3-methylbutan-2-ylcyclopropane Chemical compound CC(C)C(C)C1CC1 JSDZSLGMRRSAHD-UHFFFAOYSA-N 0.000 claims description 2
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- SBGVBOQUFHAXDA-UHFFFAOYSA-N 2-methylidenepent-3-enenitrile Chemical compound CC=CC(=C)C#N SBGVBOQUFHAXDA-UHFFFAOYSA-N 0.000 abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
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- VTJUKNSKBAOEHE-UHFFFAOYSA-N calixarene Chemical class COC(=O)COC1=C(CC=2C(=C(CC=3C(=C(C4)C=C(C=3)C(C)(C)C)OCC(=O)OC)C=C(C=2)C(C)(C)C)OCC(=O)OC)C=C(C(C)(C)C)C=C1CC1=C(OCC(=O)OC)C4=CC(C(C)(C)C)=C1 VTJUKNSKBAOEHE-UHFFFAOYSA-N 0.000 description 3
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- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 3
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- UJHSIDUUJPTLDY-UHFFFAOYSA-N (2-nitrophenyl)-phenylmethanone Chemical compound [O-][N+](=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 UJHSIDUUJPTLDY-UHFFFAOYSA-N 0.000 description 2
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Abstract
本发明涉及可光固化的含有贫电子烯烃的组合物,如含有某些2‑氰基丙烯酸酯、2‑氰基戊二烯酸酯、亚甲基丙二酸酯和偏二氰乙烯以及光潜碱的那些。当暴露于电磁波谱中的辐射时,所述组合物显示出延迟固化性质。
Description
背景技术
领域
本发明涉及可光固化的含有贫电子烯烃的组合物,如含有某些2-氰基丙烯酸酯、2-氰基戊二烯酸酯、亚甲基丙二酸酯和偏二氰乙烯(vinylidine cyanide)以及光潜碱(photolatent bases)的那些。当暴露于电磁波谱中的辐射时,所述组合物显示出延迟固化性质。
有关技术的简介
氰基丙烯酸酯粘合剂因其快速粘合性和粘合各种基材的能力而著称。它们作为"超级胶"型粘合剂销售。它们可用作通用粘合剂,因为它们是单组分粘合剂,因为仅少量粘合剂就可以而非常经济,并且通常不需要任何设备来实现固化。
氰基丙烯酸酯通常是快速固化材料,其可固化成透明的硬质玻璃状树脂,可用作密封剂、涂料,特别是用于将各种基材粘合到一起的粘合剂[参见例如H.V.Coover,D.W.Dreifus and J.T.O'Connor,"Cyanoacrylate Adhesives"in Handbook ofAdhesives,27,463-77,I.Skeist,ed.,Van Nostrand Reinhold,New York,3rd ed.(1990)]。
通常,在与具有表面亲核体的基底材料接触时,含氰基丙烯酸酯的组合物自发聚合形成固化的材料。固化的材料对材料如金属、塑料、弹性体、织物、木材、陶瓷等表现出优异的粘合性质。因此,含氰基丙烯酸酯的组合物被视为通用类的单组分环境温度固化粘合剂。
汉高公司已经获得了一系列美国专利,其重点是可光固化的组合物,所述组合物包含:(a)式H2C-C(CN)-COOR的2-氰基丙烯酸酯单体,其中R选自C1-15烷基、烷氧基烷基、环烷基、烯基、芳烷基、芳基、烯丙基和卤代烷基,(b)茂金属组分,和(c)光引发剂组分。参见美国专利号5,922,783(Wojciak)、6,433,036(Wojciak)、6,726,795(Wojciak)和6,906,112(Wojciak)。还参见美国专利号6,503,959(Mikuni)。
在有些情况下,所述组合物通过电磁波谱的可见光范围内的辐射活化,光引发剂选自dl-樟脑醌、双(η5-2,4-环戊二烯-1-基)-双[2,6-二氟-3-(1H-吡咯-1-基)苯基]钛、双(2,6-二甲氧基苯甲酰基-2,4,4-三甲基戊基)氧化膦、双(2,4,6-三甲基苯甲酰基)苯基氧化膦和它们的任意组合。
在其它情况下,所述组合物通过电磁波谱的UV范围内的辐射活化。有时,所述组合物通过电磁波谱的UV和可见光范围内的辐射活化。
在一个变型中,提供一种可光固化的组合物,包含:(a)2-氰基丙烯酸酯组分、(b)光引发的自由基产生组分、和(c)不同于所述光引发的自由基生成组分的光引发剂组分。在该变型中,光引发剂组分表示为以下结构:
其中Ar、Ar1和Ar2各自为具有或没有取代基的芳基,和X为阴离子。参见美国专利号6,734,221(Misiak)。
在另一变型中,提供一种组合物,其包含:(a)2-氰基丙烯酸酯组分、(b)茂金属组分、(c)光引发剂组分和(d)发光染料。参见美国专利号7,064,155(Wojciak)。
在另一变型中,提供一种贮存稳定的可光固化组合物,其包含:(a)2-氰基丙烯酸酯组分、(b)茂金属组分、和(c)包含夺氢光引发剂和氢供体的组合的光引发剂组分。参见美国专利号6,867,241(Wojciak)。
固化的延迟开始和增加开放时间已赋予氧化还原可固化组合物。实际上,汉高公司在描述光解诱导的氧化还原可固化组合物时引入了这种技术,其包含:(a)选自乙烯基醚、烯基醚、(甲基)丙烯酸酯和它们的任意组合的氧化还原可固化组分;(b)含有茂金属的光引发剂;(c)过氧化物;和(d)酸性活化剂组分。参见美国专利号9,080,084(Konarski)。
虽然已经提出了多种光固化氰基丙烯酸酯的方法,并且来自汉高公司的一些方法在商业上是成功的,但似乎没有一种方法具有固化的延迟开始。
直到现在。
概述
与现有技术状态不同,本发明提供了可光固化的含贫电子烯烃的组合物,如含有某些2-氰基丙烯酸酯、2-氰基戊二烯酸酯、亚甲基丙二酸酯、偏二氰乙烯以及光潜碱的那些。当暴露于电磁波谱中的辐射时,所述组合物显示出延迟固化性质。
本发明还提供了组合物,以及包含自由基稳定剂和阴离子稳定剂中的至少一种的稳定剂包;和任选存在的一种或多种选自固化促进剂、增稠剂、触变剂、增韧剂、赋予耐热性的试剂或增塑剂的添加剂。
本发明的组合物具有优于已知的可光固化的氰基丙烯酸酯组合物的益处,尤其包括:在黑暗中储存时,在环境温度下长时间的贮存期稳定性,几乎没有到没有反应性的损失;组装由受控剂量的不透明(或边缘透光的)材料制成的部件的能力提供了光激活机制,所述机制允许非UV光透明的基材的组装;表面不敏感,因为可以粘合由各种材料构成的基材;良好的延迟固化特性,其允许调整更长或更短的开放时间;和使用本发明的组合物可以实现穿过大的深度(或间隙)的改善固化并且不依赖于基材类型。
传统的可光固化的氰基丙烯酸酯技术难以提供这些特性,因此通常其使用仅限于透明被粘物的组装;小的胶层间隙;和在施加常规氰基丙烯酸酯之前或之后施加两步活化剂(或底漆),因为它们不能在中性(例如聚烯烃构成的基材)或酸性(例如酚醛塑料)表面上固化。
详细说明
如上所述,本发明提供可光固化的含有贫电子烯烃的组合物,如含有某些2-氰基丙烯酸酯、2-氰基戊二烯酸酯、亚甲基丙二酸酯和偏二氰乙烯以及光潜碱的那些。当暴露于电磁波谱中的辐射时,所述组合物显示出延迟固化性质。
所述氰基丙烯酸酯可选自单官能的2-氰基丙烯酸酯、二官能的氰基丙烯酸酯和多官能的2-氰基丙烯酸酯中的一种或多种。
更具体地说,所述氰基丙烯酸酯可以是下述结构内的一种:
其中在这方面,R1选自C1-16烷基、C2-16烷氧基烷基、C3-16环烷基、C2-16烯基(如烯丙基)、C2-16炔基、C5-16芳基、C7-16芳基烷基或C1-16卤代烷基。
具有这种结构的氰基丙烯酸酯选自氰基丙烯酸甲酯、2-氰基丙烯酸乙酯、氰基丙烯酸丙酯、氰基丙烯酸丁酯、氰基丙烯酸辛酯、氰基丙烯酸烯丙酯、氰基丙烯酸β-甲氧基乙酯和它们的任意组合。
所述亚甲基丙二酸酯是下述结构内的一种:
其中在这方面,R2和R3各自独立地选自C1-16烷基、烷氧基烷基、环烷基、烯基、芳烷基、芳基、烯丙基或卤代烷基。
所述光潜碱落入下述结构内:
其中,X是氢、烷基、羟基、巯基或杂烷基中的任一个,Y是亚烷基连接基,Ra是具有1至4个碳原子的烷基或具有2至4个碳原子的烯基,Rb是具有1至4个碳原子的烷基或具有2至4个碳原子的烯基,Rc是具有1至4个碳原子的烷基或具有2至4个碳原子的烯基,或Rb和Rc共同形成3至7个环原子的环状的环结构,所述环结构可以被一个或多个杂原子间断,和n是0或1。
在这种结构中有各种可能的化合物,包括由2-(2-硝基苯基)丙基氯甲酸酯和仲胺的反应制得的氨基甲酸酯或者由2-(2-硝基苯基)丙醇或更通常的是α-甲基-2-硝基苄醇和二烷基氨基甲酰卤的反应制得的氨基甲酸酯。例如,以下化合物的邻-硝基苯基丙氧基羰基或α-甲基-邻硝基苄基氧基羰基化合物:哌啶、吗啉二异丙胺、二环己胺、二乙醇胺或二甲胺。
更具体地说,[(α-甲基-2-硝基苄基)氧基羰基]吗啉("NBM")、[(2-硝基苄基)氧基羰基]二甲胺("NBDMA")和2-(2-硝基苯基)丙氧基羰基哌啶是特别理想的。
适合的稳定剂包括稳定剂包(stabilizer packages),所述稳定剂包可含有自由基稳定剂和酸性稳定剂中的一种或多种。
例如,自由基稳定剂包括氢醌,邻苯二酚,间苯二酚或它们的衍生物,如氢醌单乙醚,或酚类如二叔丁基苯酚或2,6-二叔丁基对甲酚,2,2'-亚甲基-双(4-甲基-6-叔丁基苯酚),双酚A,二羟基二苯基甲烷和苯乙烯化(styrenized)的酚类。
例如,酸性稳定剂包括硫酸、盐酸、磺酸如甲磺酸、乙磺酸或更高级的磺酸、对甲苯磺酸、磷酸或多磷酸、强酸的甲硅烷基酯如三烷基氯硅烷、二烷基二氯硅烷、烷基三氯硅烷、四氯硅烷、三烷基甲硅烷基磺酸、三烷基甲硅烷基-对甲苯磺酸酯、双-三烷基甲硅烷基磺酸酯和三烷基甲硅烷基磷酸酯。
用于稳定通过本发明方法制备的贫电子烯烃的任一种稳定剂的量是本领域普通技术人员所熟知的,并且可以根据由所选择的贫电子烯烃制备的所得组合物的性质而变化。
本发明的组合物可包括选自固化促进剂、增稠剂、触变剂、增韧剂、赋予耐热性的试剂或增塑剂中的一种或多种添加剂。
可与本发明的贫电子烯烃一起被包含以形成本发明组合物的固化促进剂包括杯芳烃和氧杂杯芳烃、硅杂冠醚(silacrowns)、冠醚、环糊精、聚(乙二醇)二(甲基)丙烯酸酯、乙氧基化的含氢化合物(hydric compounds)和它们的任意组合。
杯芳烃和氧杂杯芳烃中的许多是已知的,并已在专利文献中报道。例如,参见美国专利号4,556,700、4,622,414、4,636,539、4,695,615、4,718,966和4,855,461,其中每个的公开内容在此通过引用明确地并入本文。
例如,对于杯芳烃,在下面结构内的那些在此是有用的:
其中在这方面,R1是烷基、烷氧基、取代的烷基或取代的烷氧基;R2是H或烷基;和n是4、6或8。
一种特别理想的杯芳烃是四丁基四[2-乙氧基-2-氧代乙氧基]杯-4-芳烃。
许多冠醚是已知的。例如,可用于本文中的实例包括15-冠-5、18-冠-6、二苯并-18-冠-6、苯并-15-冠-5-二苯并-24-冠-8、二苯并-30-冠-10、三苯并-18-冠-6、不对称(asym)-二苯并-22-冠-6、二苯并-14-冠-4、二环己基-18-冠-6、二环己基-24-冠-8、环己基-12-冠-4、1,2-萘烷基(decalyl)-15-冠-5、1,2-萘并-15-冠-5、3,4,5-萘基-16-冠-5、1,2-甲基-苯并-18-冠-6、1,2-甲基苯并-5,6-甲基苯并-18-冠-6、1,2-叔丁基-18-冠-6、1,2-乙烯基苯并-15-冠-5、1,2-乙烯基苯并-18-冠-6、1,2-叔丁基环己基-18-冠-6、不对称-二苯并-22-冠-6和1,2-苯并-1,4-苯并-5-氧-20-冠-7。参见美国专利号4,837,260(Sato),其公开的内容在此通过引用明确地并入本文。
硅杂冠醚中的许多也是已知的,并已在文献中报道。例如,典型的硅杂冠醚可被表示在下述结构之内:
其中在这方面,R3和R4是本身不引起氰基丙烯酸酯单体聚合的有机基团,R5是H或CH3,n是1和4之间的整数。适合的R3和R4基团的实例是R基团、烷氧基如甲氧基、和芳氧基如苯氧基。R3和R4基团可含有卤素或其他取代基,例如三氟丙基。然而,不适合作为R4和R5基团的基团是碱性基团,如氨基、取代的氨基和烷基氨基。
在本发明的组合物中的有用的硅杂冠醚化合物的具体实例包括:
二甲基硅杂-11-冠-4;
二甲基硅杂-14-冠-5;
和二甲基硅杂-17-冠-6。参见例如美国专利4,906,317(Liu),其公开的内容在此通过引用明确地并入本文。
许多环糊精可以用于本发明中。例如,那些在美国专利号5,312,864(Wens)(其公开的内容通过引用明确地并入本文中)作为在氰基丙烯酸酯中至少部分溶解的α-、β-或γ-环糊精的羟基衍生物描述和保护的那些是用作本文中第一促进剂成分的合适选择。
另外,适合用于本发明的聚(乙二醇)二(甲基)丙烯酸酯包括落入下述结构的那些:
其中,n大于3,如在3至12的范围内,n为9是特别理想的。更具体的实例包括PEG200DMA(其中n约为4)、PEG 400DMA(其中n为约9)、PEG 600DMA(其中n为约14)和PEG 800DMA(其中n为约19),其中所述数字(例如,400)表示分子中除两个甲基丙烯酸酯基团外的乙二醇部分的平均分子量,表示为克/摩尔(即,400克/摩尔)。特别理想的PEG DMA是PEG400DMA。
在乙氧基化的含氢化合物(或可采用的乙氧基化脂肪醇)中,合适的那些可以是选自落入下述结构的那些:
其中,Cm可以是线性或支化的烷基或烯基链,m是1至30之间的整数,例如从5至20,n是2至30之间的整数,例如5至15,并且R在这方面可以是H或烷基,例如C1-6烷基。
当使用时,固化促进剂应以整个组合物的约0.01重量%至约10重量%的范围内包括在所述组合物中,约0.1至约0.5重量%的范围是理想的,和约0.4重量%是特别理想的。
其它添加剂可以与本发明的贫电子烯烃一起被包括以形成本发明的组合物,以赋予另外的物理性能,如改进的抗冲击性、厚度(例如聚甲基丙烯酸甲酯)、触变性(例如气相法硅石)、颜色和增强的抗热降解性[例如,马来酰亚胺化合物如N,N'-间-亚苯基双马来酰亚胺(参见美国专利号3,988,299(Malofsky))、特征在于其芳环上至少三个取代基(其中两个或更多是吸电子基团)的某些单、多或杂芳族化合物(参见美国专利号5,288,794(Attarwala))、某些醌类化合物(参见美国专利号5,306,752(Attarwala))、某些含硫的化合物如亚硫酸酯酐、亚砜、亚硫酸酯/盐、磺酸酯/盐、甲磺酸酯/盐或对甲苯磺酸酯/盐(参见美国专利号5,328,944(Attarwala))、或某些含硫的化合物如亚磺酸酯/盐、被至少一个至少与硝基一样强吸电子的强吸电子基团取代的环状sultinate萘1,8-磺酸内酯化合物(参见美国专利号5,424,343(Attarwala))、和烷基化剂如聚乙烯基苄基氯、4-硝基苄基氯和它们的组合、甲硅烷基化试剂、和它们的组合(参见美国专利号6,093,780(Attarwala)),其中每个的公开内容在此通过引用明确地并入本文]。
这些其它添加剂单独可以约0.05重量%至约20重量%,如约1重量%至15重量%,理想地5重量%至10重量%的量用于本发明的组合物中,当然取决于添加剂的特性。例如,更具体地,柠檬酸可以5ppm至500ppm、理想的10ppm至100ppm的量用于本发明的组合物中。
另外,本发明进一步提供包括共反应物的组合物,所述共反应物例如是选自环氧化物类(如环脂族环氧化物类)、环硫化物类、氧杂环丁烷类、硫代氧杂环丁烷类、二氧戊环类、二噁烷类、异氰酸酯类、聚氨酯类、聚酰胺类、马来酰亚胺类、噁嗪类、噁唑啉类、(甲基)丙烯酸酯类、丙烯酰胺类或乙烯基醚类。
下述实施例是用来说明本发明,但决不限制本发明。
实施例
实施例1-合成[(α-甲基-2-硝基苄基)氧基羰基]吗啉("NBM")
在[(α-甲基-2-硝基苄基)氧基羰基]吗啉("NBM")的该两步合成中,第一步包括中间体α-甲基-2-硝基苄基甲醇("MNBN")的合成。为此,向对空气开放并装备有磁力搅拌棒、冷凝器、加热套和热电偶的三颈1L反应烧瓶中,添加20g(0.12摩尔)的2-硝基苯乙酮(Sigma-Aldrich,95%)和260mL的乙醇(ACS试剂级,>99.5%)。搅拌混合物直到得到透明溶液。然后,分阶段添加4.61g(0.12摩尔)的硼氢化钠(Sigma-Aldrich,粉末,≥98%),保持反应温度低于50℃。在添加所有硼氢化钠之后,然后添加200mL的去离子水,并加热混合物回流。在回流温度下5分钟之后,通过浸渍在冰水浴中快速冷却反应烧瓶。
将粗反应混合物与200mL二氯甲烷(Sigma-Aldrich,试剂级)转移到1-L分液漏斗并摇动。静置时,所述混合物分离成两层,除去下面的二氯甲烷。然后用另外部分的二氯甲烷(3×200mL)萃取剩余水层,并通过硫酸钠干燥混合的二氯甲烷萃取物,直到得到透明溶液(2小时)。过滤所述溶液以除去硫酸钠,并通过在减压下蒸馏除去溶剂,从而得到如琥珀色油一样的粗中间体(19.72g;98%产率)。通过快速色谱法在高性能二氧化硅柱(CombiFlash Rf RediSep 330g Gold)上使用己烷/乙酸乙酯梯度溶剂混合物以200mL/min的流速纯化所述粗产物。合并对应于主要组分的级分,并在减压下除去溶剂,得到MNBN,产率85%。
通过1H NMR光谱分析确认产物的结构。
在第二步中,向装备有磁力搅拌棒、冷凝器和热电偶的三颈250mL烧瓶中,添加19.58g(0.119摩尔)的纯化MNBN、12.02g的三甲胺(Sigma Aldrich,>99%)、30mL的二氯甲烷(Sigma Aldrich,试剂级)和1.45g(0.0119摩尔)的4-(二甲基氨基)吡啶(SigmaAldrich,>99%)。在环境温度下搅拌所述溶液并缓慢添加17.80g(0.119摩尔)的4-吗啉碳酰氯(Sigma Aldrich,98%),在此时间期间将反应温度升至约50℃。使所述混合物冷却至环境温度,并继续搅拌。在24小时之后,所述混合物的红外光谱表明酯化反应是完全的(1690cm-1处的IR吸收峰没有进一步变化)。
通过添加170mL的二氯甲烷稀释所述反应混合物,并用5%的盐酸溶液洗涤(3×200mL)。分离所述有机层,通过硫酸钠干燥并过滤。通过在减压下蒸馏除去溶剂,得到浅色油,将该浅色油根据已描述的方法通过快速色谱法纯化。得到纯化产物,87%产率,并通过1H NMR光谱分析确定为NBM。
实施例2-合成[(2-硝基苄基)氧基羰基]二甲胺("NBDMA")
用二甲胺碳酰氯代替4-吗啉碳酰氯,重复实施例1的步骤。分离所得到的产物[(2-硝基苄基)氧基羰基]二甲胺("NBDMA"),87%的产率。
实施例3
可光活化的氰基丙烯酸酯/NBM组合物
通过在黄光下将表1中列出的组分混合在一起来制备可光活化的氰基丙烯酸酯组合物。
表1
含有百万分之41(ppm)BF3的组合物A是透明、储存稳定的低粘度溶液产品,其在环境温度下在黑暗中储存3个月后没有显示出粘度增加(不稳定性)的迹象。与此相反,发现含有5ppm BF3的组合物B含有少量的凝胶组分,该凝胶组分在光潜碱溶解之前出现。
结果表明,超过5ppm且小于或等于41ppm的BF3稳定剂的浓度提供了在2-氰基丙烯酸乙酯中具有约1重量%NBM的氰基丙烯酸酯组合物的足够的贮存稳定性。包括含有5ppm的BF3且未添加NBM的组合物C用于比较的目的。该组合物在环境温度下长时间稳定。
实施例4
含有NBM的2-氰基丙烯酸乙酯的组合物的UV光引发的固化/活化
通过将5-6滴所述组合物置于清洁的高密度聚乙烯基材(尺寸为:面积25×25mm2,厚度5mm)上制备稳定的未固化组合物A和C(来自实施例3)的涂层。首先,通过用异丙醇清洗表面并使基材在空气流下干燥来清洁所述基材。液滴在表面上扩散,以提供约0.5mm厚的膜。
然后将涂布的基材直接放置在Zeta 7216空气冷却UV固化室的中压汞弧灯下30cm处,并暴露于UV光下持续不同的曝光时间。使用校准的UV辐射计(由EIT提供的UV PowerPuck TM),在涂层表面进行光强度测量,并记录如下:UVA 91mW/cm2;UVB 76mW/cm2;UVC57mW/cm2;和UVV 186mW/cm2。曝光后,通过检查经辐射的涂层的状态定性评价每种涂层的固化程度,并将固化程度分类如下:"没有固化"表示完全液体涂层,溶液粘度没有可观察到的增加;"部分固化"表示初始溶液粘度的显著增加或形成发粘的聚合物;和"完全固化"表示形成干燥、硬的固体聚合物涂层。然后,在环境温度下在黑暗中储存在UV暴露后未完全固化的涂层,并定期重新检查,直到固化或未观察到状态的进一步变化。结果收集在下表2中。
表2
在所描述的条件下,组合物A在暴露于UV光120秒后完全固化。与此相反,组合物C(比较的)在相同的条件下未显示固化的迹象。然后,将在UV暴露期后未完全固化的涂层样品放置于环境温度下的黑暗中,并以相同的方式监测固化,直到完全固化或未观察到固化程度的进一步变化。
观察到在UV暴露后未完全固化的组合物A的所有经辐射的样品在环境温度下在黑暗中进行随后的固化,以最终提供完全固化的膜。发现后固化速率随初始暴露时间或剂量而增加:对于初始60秒暴露,90分钟完全固化时间;和对于初始90秒暴露,10分钟完全固化时间。与此相反,组合物C在任一种研究的条件下没有显示光引发的固化。
这些结果清楚地表明,对于作为组合物的基础的氰基丙烯酸酯的固化,NBM同时用作光引发剂和光活化剂。在没有UV光的情况下,氰基丙烯酸酯和NBM的组合物可以长时间保持为低粘度液体。然而,在用UV光辐射时,溶液经历固化反应,在此期间,低分子量液体单体转化成具有良好粘合性质的高分子量固体聚合物。
NBM可以用作光引发剂或光活化剂,这取决于在暴露期间输送的UV辐射的剂量。在相对高的剂量(长暴露时间)下,在辐射期间实现完全固化,并且在这种条件下,NBM表现为光引发剂。与此相反,在相对低的剂量下,在暴露期间不发生固化,但是粘合剂组合物"被活化"并随后经历在黑暗中更慢进行的固化。
通常,暴露于相对低的UV剂量(例如1J/cm2;100mW/cm2下10秒)活化所述组合物,使得它们在固化开始之前保持液体状态几分钟。这允许对UV光不透明的基材的粘合,并且在永久固定发生之前提供准确对准基材的时间。在较高的UV剂量(例如3J/cm2;100mW/cm2下30秒)下,可在辐射期间完成完全固化。可以通过调节光潜碱/稳定剂比例来控制延迟或开放时间。
实施例5
含有NPC的2-氰基丙烯酸乙酯的组合物的UV光引发的固化/活化
还发现如美国专利号6,965,040中所述制备的2-(2-硝基苯基)丙氧基羰基化合物("NPC")是氰基丙烯酸酯的有用的光固化和光活化剂。
通过在黄光下将表3中列出的组分混合在一起来制备含有NPC的氰基丙烯酸酯组合物。
表3
组分 | 组合物D/量(wt%) |
2-氰基丙烯酸乙酯 | 99.0 |
NPC | 1.0 |
三氟化硼(ppm) | 40 |
如实施例4所述在聚乙烯基材上制备组合物D的涂层,并暴露于来自Zeta 7730 UV光导灯的UV光。将样品放置在光导管的尖端正下方1.5cm处,其中发现如实施例4中所述测量的光强度如下:UVA 96mW/cm2;UVB 62mW/cm2;UVC 0mW/cm2;和UVV 48mW/cm2。曝光后,通过检查经辐射的涂层的状态定性评价每种涂层的固化程度,并如实施例4中所述,将固化程度分类。然后,在环境温度下在黑暗中储存在UV暴露后未完全固化的涂层,并定期重新检查,直到固化或未观察到状态的进一步变化。用于比较的目的,在相同的条件下测试组合物C。
表4
表4中列出的结果清楚地表明,与NBM一样,NPC是氰基丙烯酸酯的有效光引发剂或光活化剂。这些测试还表明,NPC不需要UV辐射的UVC成分也是有效的。组合物D显示出优异的储存稳定性,在室温下在黑暗中储存8周后没有可观察到的粘度增加,并且光化学活性没有损失。
Claims (11)
1.一种可光固化的组合物,其包含:
(a)贫电子烯烃;和
(b)光潜碱。
2.权利要求1所述的组合物,其中所述贫电子烯烃是选自由2-氰基丙烯酸酯、2-氰基戊二烯酸酯、亚甲基丙二酸酯和偏二氰乙烯组成的组的成员。
3.权利要求2所述的组合物,其中所述2-氰基丙烯酸酯是选自由单官能的2-氰基丙烯酸酯、二官能的氰基丙烯酸酯、多官能的2-氰基丙烯酸酯和它们的任意组合组成的组的成员。
4.权利要求2所述的组合物,其中所述2-氰基丙烯酸酯落入下述结构中:
其中在这方面,R1选自C1-16烷基、C2-16烷氧基烷基、C3-16环烷基、C2-16烯基、C2-16炔基、C5-16芳基、C7-16芳基烷基或C1-16卤代烷基。
5.权利要求2所述的组合物,其中所述2-氰基丙烯酸酯选自氰基丙烯酸甲酯、2-氰基丙烯酸乙酯、氰基丙烯酸丙酯、氰基丙烯酸丁酯、氰基丙烯酸辛酯、氰基丙烯酸烯丙酯、氰基丙烯酸β-甲氧基乙酯和它们的任意组合。
6.权利要求2所述的组合物,其中所述亚甲基丙二酸酯落入下述结构中:
其中在这方面,R2和R3各自独立地选自C1-16烷基、烷氧基烷基、环烷基、烯基、芳烷基、芳基、烯丙基或卤代烷基。
7.权利要求1所述的组合物,其中所述光潜碱落入下述结构中:
其中,X是氢、烷基、羟基、巯基或杂烷基中的任一个,Y是亚烷基连接基,Ra是具有1至4个碳原子的烷基或具有2至4个碳原子的烯基,Rb是具有1至4个碳原子的烷基或具有2至4个碳原子的烯基,Rc是具有1至4个碳原子的烷基或具有2至4个碳原子的烯基,或Rb和Rc共同形成3至7个环原子的环状的环结构,所述环结构任选地被一个或多个杂原子间断,和n是0或1。
8.权利要求1所述的组合物,其中所述光潜碱是选自由[(α-甲基-2-硝基苄基)氧基羰基]吗啉、[(2-硝基苄基)氧基羰基]二甲胺和2-(2-硝基苯基)丙氧基羰基哌啶组成的组的成员。
9.权利要求1所述的组合物,其进一步包含稳定剂包,该稳定剂包含有自由基稳定剂和阴离子稳定剂中的至少一种。
10.权利要求1所述的组合物,其进一步包含一种或多种选自由以下组成的组的添加剂:固化促进剂、增稠剂、触变剂、增韧剂、赋予耐热性的试剂和增塑剂。
11.权利要求1所述的组合物,其进一步包含一种或多种选自由以下组成的组的共反应物:环氧化物类、环硫化物类、氧杂环丁烷类、硫代氧杂环丁烷类、二氧戊环类、二噁烷类、异氰酸酯类、聚氨酯类、聚酰胺类、马来酰亚胺类、噁嗪类、噁唑啉类、(甲基)丙烯酸酯类、丙烯酰胺类和乙烯基醚类。
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