CN103012317A - 烷基苯基衍生物和其作为光引发剂的应用 - Google Patents
烷基苯基衍生物和其作为光引发剂的应用 Download PDFInfo
- Publication number
- CN103012317A CN103012317A CN2012105667351A CN201210566735A CN103012317A CN 103012317 A CN103012317 A CN 103012317A CN 2012105667351 A CN2012105667351 A CN 2012105667351A CN 201210566735 A CN201210566735 A CN 201210566735A CN 103012317 A CN103012317 A CN 103012317A
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- China
- Prior art keywords
- compound
- phenyl
- methyl
- tert
- butyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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- 150000002148 esters Chemical class 0.000 claims description 4
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F224/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a heterocyclic ring containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
- C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
- C07D211/08—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms
- C07D211/10—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with radicals containing only carbon and hydrogen atoms attached to ring carbon atoms
- C07D211/14—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with radicals containing only carbon and hydrogen atoms attached to ring carbon atoms with hydrocarbon or substituted hydrocarbon radicals attached to the ring nitrogen atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
- C07D295/10—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by doubly bound oxygen or sulphur atoms
- C07D295/104—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by doubly bound oxygen or sulphur atoms with the ring nitrogen atoms and the doubly bound oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
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Abstract
本发明提供了新的化合物叔丁基苯基-2-甲基-2-(1-哌啶基)-1-丙酮和叔丁基苯基-2-甲基-2-(1-吗啉基)-1-丙酮,其制备方法和其作为光引发剂的用途。本发明还公开了含有所述化合物作为光引发剂的可光聚合的组合物和其应用,以及提供了涂有所述组合物的涂布基材。
Description
技术领域
本发明涉及光引发剂领域。具体的,本发明提供了新的烷基苯基衍生物和其制备方法,以及所述烷基苯基衍生物作为光引发剂的应用。
背景技术
光引发剂又称为光敏剂(photosensitizer)或光固化剂(photocuringagent),是一类能在紫外光区(250~420nm)或可见光区(400~800nm)吸收一定波长的能量,产生自由基、阳离子等,从而引发单体聚合交联固化的化合物。辐射固化技术是一项节能环保新技术,紫外光(UV)和电子束(EB)、红外光、可见光、激光、化学荧光等辐射光照射固化,完全符合“5E”特点:Efficient(高效)、Enabling(实用)、Economical(经济)、Energy Saving(节能)、Environmental Friendly(环境友好),因此被誉为“绿色技术”。光引发剂是光固化胶黏剂的重要组分之一,它对固化速率起着决定性作用。光引发剂受紫外光照射后,吸收光的能量,分裂成2个活性自由基,引发光敏树脂和活性稀释剂发生连锁聚合,使胶黏剂交联固化,其特点是快速、环保、节能。
现在,光引发剂已经在涂料、油墨行业广泛应用。随着人们生活水平的提高,对环境和食品安全问题越来越重视。包装业,尤其是食品包装行业的彩色印刷,对有害挥发性有机物(VOC),如苯、四氯化碳、氯仿等,有明确的限量。过去用于食品领域的光引发剂,如二苯甲酮、二苯乙二酮等,由于在使用过程中受光引发作用,会产生苯,目前已经禁止在食品印刷行业使用。另外,目前市场上光引发剂由于其性能或价格问题,不能够满足生产厂家的要求。
因此,在光聚合技术领域中,仍然需要具有更高活性、容易制备且容易处理等优点的光引发剂。本发明出人意料地发现,本发明提供的创新性的化 合物1-(4-叔丁基苯基)-2-甲基-2-(1-哌啶基)-1-丙酮和1-(4-叔丁基苯基)-2-甲基-2-(1-吗啉基)-1-丙酮是极其有效的光引发剂,而且与现有技术的光引发剂,特别是广泛使用的2-苯基苄-2-二甲基胺-1-(4-吗啉苄苯基)丁酮比较,生产成本明显降低,同时生产工艺简单,后处理简单,满足环境保护要求。
发明内容
本发明提供了具有下式的化合物
在本发明的一个方面,本发明的化合物为:
1-(4-叔丁基苯基)-2-甲基-2-(1-哌啶基)-1-丙酮。
在本发明的一个方面,本发明的化合物为:
1-(4-叔丁基苯基)-2-甲基-2-(1-吗啉基)-1-丙酮。
本发明提供了制备下式化合物的方法,
其中X为C或O,所述方法包括以下步骤:
在本发明其中一个方面,步骤(4)的反应温度为约130℃。
在本发明其中一个方面,制备1-(4-叔丁基苯基)-2-甲基-2-(1-哌啶基)-1-丙酮时,步骤(4)为
在本发明其中一个方面,制备1-(4-叔丁基苯基)-2-甲基-2-(1-吗啉基)-1-丙酮时,步骤(4)为
本发明提供了上述本发明的化合物作为光引发剂的用途。本发明的化合物,例如1-(4-叔丁基苯基)-2-甲基-2-(1-哌啶基)-1-丙酮和1-(4-叔丁基苯基)-2-甲基-2-(1-吗啉基)-1-丙酮,在光聚合反应中具有良好的性能,能够有效地在例如紫外(UV)光的照射时产生聚合引发基。本发明的聚合物光引发剂可用于制备范围广泛的辐射固化材料,包括压敏热熔粘合剂和涂料组合物,例如装饰和耐磨涂料、清漆、纤维增强复合物、微电子封铸材料、塑料主板、光纤涂料、模塑料、UV固化结构树脂等。
在本发明的一个方面,提供了一种可光聚合的组合物,其中包含:
(a)作为光引发剂的下式的化合物
(b)至少一种烯属不饱和可光聚合的化合物。
在本发明的一个方面,所述可光聚合的组合物中的光引发剂为:
1-(4-叔丁基苯基)-2-甲基-2-(1-哌啶基)-1-丙酮。
在本发明的一个方面,所述可光聚合的组合物中的光引发剂为:
1-(4-叔丁基苯基)-2-甲基-2-(1-吗啉基)-1-丙酮。
在本发明的一个方面,本发明提供的可光聚合的组合物中还可含有其它已知的光引发剂。常见的已知的光引发剂例如樟脑醌、二苯甲酮、其它二苯甲酮衍生物、苯乙酮、苯乙酮衍生物,苯偶酰缩酮,苯基乙醛酸及其衍生物、二乙酰基、过酸酯等。
在本发明的一个方面,可光聚合组合物的光引发剂一般包含占组合物的约0.5-20%重量,优选约1-10%重量,最优选约3-6%重量。如果在组合物中使用光引发剂的混合物,该量是指所有添加的光引发剂的总和,即该量是指光引发剂(a)的量,或光引发剂(a)和+其它光引发剂的量。可以根据应用厚度来选择浓度。也可使用两种或多种光引发剂的组合以获得配制组合物可能的最佳固化性。优选使用能在加工生产线上引发固化并且达到最终期望的使用强度的最低必需量的光引发剂。这个用量取决于聚合物组合物以及辐射源、接受的辐射量、生产线速度和在基材上的涂层厚度。
在本发明的一个方面,组分(b)中所述烯属不饱和可光聚合的化合物是 本领域公知的化合物。通常所述烯属不饱和可光聚合的化合物包括一个或多个烯属双键。形成所述烯属不饱和可光聚合的化合物的包含双键的单体的例子为丙烯酸烷基酯、羟烷基酯或氨基酯、或甲基丙烯酸烷基酯等。包含两个或多个双键的单体的例子为乙二醇、丙二醇、新戊二醇、己二醇或双酚A的二丙烯酸酯、以及4,4’-二(2-丙烯酰氧基乙氧基)二苯基丙烷等。
在本发明的一个方面,所述烯属不饱和可光聚合的化合物为烯属不饱和羧酸与多元醇或聚环氧化物的酯。所述不饱和羧酸的例子为丙烯酸、甲基丙烯酸、不饱和脂肪酸如亚麻酸或油酸。优选的,所述不饱和羧酸为丙烯酸和甲基丙烯酸。所述多元醇可为芳族,脂族或环脂族多元醇。芳族多元醇的例子为对苯二酚、4,4’-二羟基联苯、2,2-二(4-羟基苯基)丙烷、以及线型酚醛树脂和酚醛树脂A。
组分(b)中所述烯属不饱和可光聚合的化合物可以是其中的一种,也可以是其中的两种的混合物或是两种以上的混合物。
在本发明的一个方面,所述烯属不饱和可光聚合的化合物为丙烯酸酯化的环氧树脂、丙烯酸烷基酯或其混合物,最优选为环氧丙烯酸酯、三羟甲基丙烷三丙烯酸酯或其混合物。
在本发明的可光聚合的组合物中,组分(b)烯属不饱和可光聚合的化合物一般用量为约10%至约70%,优选约25%至约60%,更优选约29%至约56%。
本发明提供的可光聚合的组合物中还可含有其它添加剂(c)。
在本发明的一个方面,可光聚合组合物中含有的添加剂(c)为反应性胺助引发剂,例如水溶性叔胺类,如三乙醇胺、N-甲基-二乙醇胺、N’N’-二甲基乙醇胺等。本发明的可光聚合组合物中的反应性胺助引发剂通常占该组合物重量的约0.5-10%,最优选为约6-10%。
本发明可光聚合组合物中含有的其它添加剂的例子还包括用于防止过早 聚合反应的热阻聚剂,其例子为对苯二酚、对苯二酚衍生物、对-甲氧基苯酚、β-萘酚或空间位阻苯酚。为了在聚合反应过程中排除大气氧气,可以加入石蜡或类似的蜡状物质。另外,可少量加入的光稳定剂如UV吸收剂,例如羟基苯基三唑、羟基苯基-二苯甲酮、草酰胺或羟基苯基-s-三嗪类。
本领域已知的其它添加剂还包括流动促进剂、粘附促进剂等。添加剂的选择取决于应用领域以及该领域所需的性能。上述添加剂是本领域常用的,因此其加入量为相应场合的常规量。
在本发明的其中一个方面,提供了一种可光聚合组合物,其包含:
本发明的可光聚合组合物的感光性包括190-600纳米(UV-可见光区)。合适的射线可以是日光或来自人造光源的光。因此,可以采用许多明显不同种类的光源。灯与要按照本发明曝光的基材之间的距离可根据预期用途以及灯的种类和输出而变化。也可使用在可见光区的激光。
在本发明的一个方面,提供了至少一个表面上涂有上述可光聚合组合物的涂布基材。本发明的可光聚合组合物适用于其上需涂覆保护层的所有种类的基材,例如木材、纺织品、纸、陶瓷、玻璃、塑料,如聚酯、聚对苯二甲酸乙二醇酯、聚烯烃或乙酸纤维素,尤其是形成膜,以及金属,如Al、Cu、Ni、Fe、Zn、Mg或Co和GaAs、Si或SiO2的涂料,或以成像方式进行曝光以生成图像。
在本发明的一个方面,提供了本发明的上述可光聚合组合物的应用,包括用于生产颜料和非颜料油漆和清漆、粉末涂料、印刷油墨、印刷版、粘合剂、用于电子学的光刻胶,用于包封电气和电子元件的组合物,用于生产磁性记录材料、微机械部件、波导管、光学转换器、电镀蒙罩、刻蚀蒙罩、彩色涂 胶体系、玻璃纤维电缆涂料、丝网印刷模版,用立体平版印刷法生产三维物体,以及作为图像记录材料,尤其是用于全息照相记录、微电子电路、用于图像记录材料的脱色材料、使用微胶囊的图像记录材料。
具体实施方式
通过下述实施例有助于进一步理解本发明,但不用于限制本发明的内容。
实施例1 1-(4-叔丁基苯基)-2-甲基-2-(1-哌啶基)-1-丙酮和1-(4-叔丁基苯基)-2-甲基-2-(1-吗啉基)-1-丙酮的合成
1-(4-叔丁基苯基)-2-甲基-2-(1-哌啶基)-1-丙酮和1-(4-叔丁基苯基)-2-甲基-2-(1-吗啉基)-1-丙酮合成路径包括以下步骤:
(1)1-(4-叔丁基苯基)-2-甲基-1-丙酮的合成:往1000mL的三口烧瓶中加入二氯甲烷500mL,三氯化铝167.9克(1.25mol),于25-30℃,加入异丁酰 氯127.8克(1.2mol)。冰水冷却至0-5℃,滴加叔丁基苯134克(1.0mol)。滴加完毕后,除去冷却设备,升至室温后继续反应2-3小时(HPLC分析含量为98%)。
往2000mL的烧瓶中加入700mL水和50mL浓盐酸,混合均匀后,冷至10-15℃。把上述反应的混合物搅拌滴加入该盐酸水溶液中,保持温度不高于30℃,水解除去三氯化铝。水解结束后静置30分钟,分出水相,有机相再用300mL水洗涤二次。干燥,旋转蒸馏除去溶剂二氯甲烷,得到1-(4-叔丁基苯基)-2-甲基-1-丙酮。1H NMR(300Hz,CDCl3),δ:0.75(d,J=4.2Hz,6H),0.88(s,9H),3.06-3.12(m,1H),6.99-7.03(m,2H),7.42-7.47(m,2H)。
(2)1-(4-叔丁基苯基)-2-甲基-2-氯-1-丙酮的合成:往2000mL的三口烧瓶中加入二氯甲烷200mL,100mL冰乙酸和1.0mol(204.3克)的1-(4-叔丁基苯基)-2-甲基-1-丙酮。温度控制在25-30℃,慢慢通入氯气2.5-4.0小时。用薄层液相色谱法(TLC)跟踪反应情况,直至氯代反应完成。HPLC检测1-(4-叔丁基苯基)-2-甲基-1-丙酮反应完全,1-(4-叔丁基苯基)-2-甲基-2-氯-1-丙酮的含量为95%。
冷却下,搅拌滴加30%的氢氧化钠溶液,中和上述反应混合物值pH为中性。静置、分层。有机层用50mL二氯甲烷萃取二次。合并有机层,干燥、旋转蒸馏除去溶剂二氯甲烷,得到1-(4-叔丁基苯基)-2-甲基-2-氯-1-丙酮。1HNMR(300Hz,CDCl3),δ:1.36(s,9H),2.96(s,6H),7.43-7.46(m,2H),8.10-8.14(m,2H)。
(3)2-(4-叔丁基苯基)-2-甲氧基-3,3-二甲基环氧乙烷的合成:在1000mL的三口烧瓶中加入650mL无水甲醇和27.6克(1.2mol)金属钠,制备出甲醇钠的甲醇溶液。温度控制在25-30℃,1.5-2.0小时内分批加入238.7克(1.0mol)1-(4-叔丁基苯基)-2-甲基-2-氯-1-丙酮。滴加完毕后,继续反应1小时。HPLC检测1-(4-叔丁基苯基)-2-甲基-2-氯-1-丙酮反应完全,2-(4-叔丁基苯基)-2-甲氧基-3,3-二甲基环氧乙烷的合成的含量为90%。
60℃旋转蒸馏除去溶剂甲醇,冷却得到白色固体,为2-(4-叔丁基苯基)-2- 甲氧基-3,3-二甲基环氧乙烷和氯化钠的混合物。
纯化后的2-(4-叔丁基苯基)-2-甲氧基-3,3-二甲基环氧乙烷的氢谱数据为:1H NMR(300Hz,CDCl3),δ:1.12(s,6H),1.55(s,9H),3.42(s,3H),7.35-7.42(m,4H)。
(4)1-(4-叔丁基苯基)-2-甲基-2-(1-哌啶基)-1-丙酮的合成:在1000mL的三口烧瓶中加入117.2克(0.5mol)2-(4-叔丁基苯基)-2-甲氧基-3,3-二甲基环氧乙烷和255克(3.0mol)哌啶,加热回流直至HPLC检测2-(4-叔丁基苯基)-2-甲氧基-3,3-二甲基环氧乙烷反应完全,1-(4-叔丁基苯基)-2-甲基-2-(1-哌啶基)-1-丙酮的含量为96%。
120℃旋转蒸馏除去过量的哌啶,冷却后加入300mL甲苯,搅拌、静置、过滤。固体再用100mL甲苯二次。合并的有机层用200mL水洗涤二次,再加入5克活性炭回流10分钟进行脱色。过滤、110℃旋转蒸馏除去甲苯,得到淡黄色液体1-(4-叔丁基苯基)-2-甲基-2-(1-哌啶基)-1-丙酮。1H NMR(300Hz,CDCl3),δ:1.30(s,6H),1.36(s,9H),1.45-1.50(m,2H),1.54-1.57(m,4H),2.53(t,J=5.1Hz,4H),7.42-7.46(m,2H),8.60(d,J=8.7Hz,2H).MS m/z(C19H30NO=288.2,即M+H)+为288.2。
(5)1-(4-叔丁基苯基)-2-甲基-2-(1-吗啉基)-1-丙酮的合成:在1000mL的三口烧瓶中加入117.2克(0.5mol)2-(4-叔丁基苯基)-2-甲氧基-3,3-二甲基环氧乙烷和261克(3.0mol)吗啉,加热回流直至HPLC检测2-(4-叔丁基苯基)-2-甲氧基-3,3-二甲基环氧乙烷反应完全,1-(4-叔丁基苯基)-2-甲基-2-(1-哌啶基)-1-丙酮的含量为93%。
120℃旋转蒸馏除去过量的吗啉,冷却后加入300mL甲苯,搅拌、静置、过滤。固体再用100mL甲苯二次。合并的有机层用200mL水洗涤二次,再加入5克活性炭回流10分钟进行脱色。过滤、110℃旋转蒸馏除去甲苯,得到淡黄色液体1-(4-叔丁基苯基)-2-甲基-2-(1-吗啉基)-1-丙酮。1HNMR(300Hz,CDCl3),δ:1.32(s,6H),1.38(s,9H),2.58(t,J=6.9Hz,4H),3.70(t,J=6.9Hz,4H),7.43(J=8.7Hz,2H),8.60(d,J=8.7Hz,2H).MS m/z(C18H28NO=290.2, 即M+H)+为290.2。
在制备中发现,在步骤(2)采用溴化反应,即采用Br2代替Cl2作为反应物,不仅成本提高,而且会导致产率大大降低,甚至在某些条件下不能生成需要的产物。
实施例2清漆制剂的制备
根据以下配方配置紫外线固化清漆制剂。
具体配方如下:
根据上述配方,分别以1-(4-叔丁基苯基)-2-甲基-2-(1-哌啶基)-1-丙酮、1-(4-叔丁基苯基)-2-甲基-2-(1-吗啉基)-1-丙酮和2-苯基苄-2-二甲基胺-1-(4-吗啉苄苯基)丁酮作为光引发剂制备得到发明制剂1、发明制剂2和对比制剂。
实施例3固化效果测试
将实施例2中配制所得的清漆制剂用印刷适性仪涂布约15微米厚度于空白纸张上,用一台功率为50W/CM线功率的中压水银弧光灯以100米/分速度进行固化,记录获得良好的表面及彻底固化所需要的灯下通过次数。
结果表明采用本发明的化合物1-(4-叔丁基苯基)-2-甲基-2-(1-哌啶基)-1-丙酮和1-(4-叔丁基苯基)-2-甲基-2-(1-吗啉基)-1-丙酮作为光引发剂而制备得到的清漆制剂的固化速度优于采用2-苯基苄-2-二甲基胺-1-(4-吗啉苄苯基)丁酮为光引发剂而制备得到的清漆制剂。
实施例4苯释放分析
采用如下所述的顶空-气相色谱法测定固化膜中的苯释放量:
1)定量分析工作曲线绘制:
1在250ml容量瓶中加入苯20mg,准确称量(准确至0.1mg),以三醋酸甘油酯定容,定为第1级标准溶液;
2取第1级标准溶液50.00ml,加入250ml容量瓶中,以三醋酸甘油酯定容,定为第2级标准溶液;
3取第2级标准溶液50.00ml,加入250ml容量瓶中,以三醋酸甘油酯定容,定为第3级标准溶液;
4取第3级标准溶液50.00ml,加入250ml容量瓶中,以三醋酸甘油酷酯定容,定为第4级标准溶液;
5取第4级标准溶液50.00ml,加入250ml容量瓶中,以三醋酸甘油酯定容,定为第5级标准溶液;
6分别取第1-5级标准溶液1000uL进行顶空-气相色谱分析,每级标准溶液重复测定两次,取平均值。根据苯的峰面积及其含量(将标液浓度换算为单位面积膜中所含苯的质量数,mg/m2),建立工作曲线,工作曲线原点强制过原点。
2)待测样品制备及测定:
将配制所得的清漆制剂得到的固化样品膜,将膜从玻璃板上剥离,剪取100cm2,放入顶空瓶中,加入1000uL三醋酸甘油酯,进行顶空-气相色谱分析,根据苯的峰面积A及工作曲线斜率K进行释放量的计算,公式:C=A/K。
3)测定结果:
本发明出人意料地发现,创新性的化合物1-(4-叔丁基苯基)-2-甲基-2-(1-哌啶基)-1-丙酮和1-(4-叔丁基苯基)-2-甲基-2-(1-吗啉基)-1-丙酮在光聚合反应中具有良好的性能。能够有效地在例如紫外(UV)光的照射时产生聚合引发基。配方试验证明,同等条件下,与现有技术的光引发剂,特别是广泛使用的2-苯基苄-2-二甲基胺-1-(4-吗啉苄苯基)丁酮比较,采用本发明的化合物作为光引发剂的紫外线固化清漆制剂的性能满足要求。而且本发明的化合物1-(4-叔丁基苯基)-2-甲基-2-(1-哌啶基)-1-丙酮和1-(4-叔丁基苯基)-2-甲基-2-(1-吗啉基)-1-丙酮与现有技术的光引发剂,特别是广泛使用的2-苯基苄-2-二甲基胺-1-(4-吗啉苄苯基)丁酮比较,生产成本明显降低。同时生产工艺简单,后处理简单,满足环境保护要求。
除非另外指出,本发明的实践将使用有机化学、聚合物化学等的常规技术,显然除在上述说明和实施例中所特别描述之外,还可以别的方式实现本发明。其它在本发明范围内的方面与改进将对本发明所属领域的技术人员显而易见。根据本发明的教导,许多改变和变化是可行的,因此其在本发明的范围之内。
如无特别表示,本文中出现的温度的单位“度”是指摄氏度,即℃。
Claims (10)
3.权利要求1或2的化合物作为光引发剂的用途。
4.一种可光聚合的组合物,包含:
(a)权利要求1或2的化合物,其作为光引发剂,优选的,光引发剂(a)占该组合物重量的约0.5-10%,优选3-6%;
(b)至少一种烯属不饱和可光聚合的化合物。
5.根据权利要求4的可光聚合组合物,其中所述烯属不饱和可光聚合的化合物(b)为烯属不饱和羧酸与多元醇的酯或烯属不饱和羧酸与聚环氧化物的酯,优选为丙烯酸酯化的环氧树脂、丙烯酸烷基酯或其混合物。
6.根据权利要求4或5的可光聚合组合物,其还含有反应性胺助引发剂(c),例如水溶性叔胺类,如三乙醇胺、N-甲基-二乙醇胺、N’N’-二甲基乙醇胺、脂肪族叔胺,优选的,所述胺助引发剂(c)占该组合物重量的约0.5-10%,最优选为约6-10%。
8.根据权利要求4-7中任何一项的组合物的应用,用于生产颜料和非颜料的油漆或清漆、粉末涂料、印刷油墨、印刷版、粘合剂、用于电子学的光刻胶,用于包封电气和电子元件的组合物,用于生产磁性记录材料、微机械部件、波导管、光学转换器、电镀蒙罩、刻蚀蒙罩、彩色涂胶体系、玻璃纤维电缆涂料、丝网印刷模版,用立体平版印刷法生产三维物体,以及作为图像记录材料,尤其是用于全息照相记录、微电子电路、用于图像记录材料的脱色材料、使用微胶囊的图像记录材料。
9.至少一个表面上涂有权利要求4-7中任何一项的组合物的涂布基材。
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