CN106674394B - 甲基丙烯酸酯类单体活性自由基光聚合的引发体系 - Google Patents
甲基丙烯酸酯类单体活性自由基光聚合的引发体系 Download PDFInfo
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- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
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Abstract
本发明公开了甲基丙烯酸酯类单体活性自由基光聚合的引发体系,由有机卤化物引发剂,芳香叔胺类还原剂和带有取代基的苯甲醛类光催化剂组成。上述引发体系可以用可见光(如家用23W节能灯)为光源,在室温下引发甲基丙烯酸酯类单体的活性自由基聚合。在优选的配比条件下,分别实现了甲基丙烯酸甲酯(MMA)、聚乙二醇甲基丙烯酸酯(PEGMA)以及甲基丙烯酸苄基酯(BnMA)等单体的活性自由基聚合。其次,以此引发体系制备的聚合物为大分子引发剂,成功进行了扩链反应,得到了嵌段聚合物。本发明使用催化剂毒性小,聚合反应条件温和。与过渡金属络合物催化的聚合反应相比,有机催化剂的使用大大减低了聚合反应的成本以及后期处理工序。
Description
技术领域
本发明涉及一种用于可见光活性自由基聚合的引发体系,具体是涉及在室温条件下,由含取代基的苯甲醛类有机催化剂,有机卤化物引发剂和芳香叔胺还原剂组成的引发体系。使用该引发体系,可以实现甲基丙烯酸酯类单体的可见光活性自由基聚合。
背景技术
1956年,美国化学家Szwarc首先观察到了一种没有链转移和链终止的苯乙烯阴离子聚合反应,并提出了“活性聚合”的概念。基于活性聚合的发展,Otsu等人在1980年首次提出了利用稳定自由基实现可控自由基聚合的思想。经过近四十年的发展,重要的活性自由基聚合方法主要有引发转移终止剂(Iniferter)聚合法,氮氧自由基调控聚合(NMP)法,可逆加成-断裂链转移(RAFT)聚合法,原子转移自由基(ATRP)聚合法和有机金属调控的自由基聚合法(OMRP)等。活性/可控自由基聚合已取得了巨大的成功,并开发了一些工业应用技术。
目前,大部分活性/可控自由基聚合反应是热聚合。在该类聚合体系中,链引发和链增长反应(包括活化/钝化过程)都要通过热化学反应过程来实现,并最终得到分子量可控以及窄相对分子质量分布的聚合物。作为另外一种重要的活化聚合反应的方式,光辐射由于本身具有一系列的优点而受到人们的广泛关注。与热引发聚合反应相比,它具有聚合反应可在常温下进行、操作简单、反应平稳,以及可以通过“开”/“关”快速启动和停止反应等优点。并且光聚合反应的活化能低,在较大的温度范围内均可反应,特别适用于温敏性单体的聚合。基于以上特点,光聚合具有很大的应用前景,无论在涂料、粘合剂还是在电子行业都获得了重要应用。
一些过渡金属(Cu,Fe,Ru,Ir等)的有机配合物具有光化学反应活性,吸收/释放光子的过程伴随氧化-还原反应。因此,这些过渡金属的配合物被广泛应用在光引发的自由基聚合体系中,尤其是光引发的ATRP以及RAFT聚合。但是过渡金属络合物催化剂的使用存在一定的缺陷。例如,聚合产物的后处理复杂,反应后所使用的大部分催化剂不易从产品中完全除去。另外,制备出的聚合物材料由于金属残留而存在毒性或引发聚合物的降解反应。这一缺陷使得聚合物材料在食品包装,医用材料,电子材料等方面的运用受到限制。此外,过渡金属络合物催化剂的使用大大增加了聚合物材料的制备成本。因此,有机光催化剂调控的自由基聚合反应引起了人们的广泛关注。例如Treat等首先报道了以10-苯基吩噻嗪为有机光催化剂的ATRP聚合(Treat,N.J.;Sprafke,H.;Kramer,J.W.;Clark,P.G.;Barton,B.E.;Read de Alaniz,J.;Fors,B.P.;Hawker,C.J.J.Am.Chem.Soc.2014,136,16096-16101)。此后,包括10-(4-甲氧基苯基)-吩噻嗪、10-(1-萘)-吩噻嗪、二萘嵌苯等有机催化剂也成功地应用到于光诱导的可控活性自由基聚合体系中。但这些有机光氧化还原催化剂结构复杂,成本与贵金属催化剂相比没有多少优势。因此,开发低成本的有机催化剂,对发展可见光活性自由基聚合仍然具有重要意义。
本发明开发了一类结构简单、成本低的芳香醛衍生物(包括但不限于对甲氧基苯甲醛、对氰基苯甲醛和2,4-二甲氧基苯甲醛)可见光氧化还原催化剂,结合有机卤化物引发剂和芳香叔胺类还原剂,实现了甲基丙烯酸酯类单体的可见光活性自由基聚合。
发明内容
本发明的目的是提供一种甲基丙烯酸酯类单体活性自由基光聚合的引发剂以及高效率,低成本和易操作的新型活性自由基聚合方法和绿色反应工艺。本发明所采用的具体技术方案为:首先室温条件下,以家用节能灯(如23W的紧凑型节能灯)为光源,有机卤化物为引发剂,芳香叔胺类物质为还原剂,醛基催化剂(对甲氧基苯甲醛,对氰基苯甲醛以及2,4-二甲氧基苯甲醛)为光氧化还原催化剂,分别实现了甲基丙烯酸甲酯(MMA),聚乙二醇甲基丙烯酸酯(PEGMA),以及甲基丙烯酸苄基酯(BnMA)等甲基丙烯酸酯类单体的活性自由基聚合。在优选的配比条件下,制得的均聚物分子量随转化率的增长而线性增加,并且聚合物的分子量分布较窄。其次,以制得的聚合物为大分子引发剂,进行扩链反应,得到了嵌段聚合物。实验结果表明制得的聚合物末端官能团具有较高的反应活性。1、一种用于甲基丙烯酸酯类单体可见光活性自由基聚合的引发体系,其特征在于:该引
发体系包括单体、催化剂、引发剂和还原剂;单体与催化剂的摩尔比为1.2:1-20:1,催
化剂与还原剂的摩尔比为1:1-17:1,反应温度为室温,反应时间为2-115h;所述催化剂为苯甲醛的衍生物,引发剂为有机卤化物,还原剂为芳香族叔胺化合物。
2、进一步,催化剂为对甲氧基苯甲醛、对氰基苯甲醛或2,4-二甲氧基苯甲醛。
3、进一步,引发剂包括2-溴异丁酸乙酯、α-溴代苯基乙酸乙酯或全氟碘代烷。全氟碘代烷为1-碘全氟己烷、1-碘全氟丁烷或1-碘全氟辛烷
4、进一步,还原剂为N,N-二甲基苯胺。
5、进一步,引发光源为节能灯。
聚合的实施方法与其它的活性自由基聚合相似,需要排除反应物和反应器中的氧。脱氧方法是聚合反应中常用的,例如,聚合前,将单体、引发剂、醛基催化剂、还原剂、溶剂混合后,置于单支口圆底烧瓶中,密封。冷冻抽排三次,最后通入惰性气体(氩气或氮气),使聚合反应在惰性气氛中进行。其中,单体与醛基催化剂的摩尔比为1:1-20:1,醛基催化剂与还原剂的摩尔比为1:1-17:1,反应温度为室温,光源为两个23W紧凑型节能灯。其中光源在420nm波长范围处,光照强度为800μW cm-2。
其中,上述单体为甲基丙烯酸酯类单体,包括但并不限于甲基丙烯酸甲酯、聚乙二醇甲基丙烯酸酯以及甲基丙烯酸苄基酯。醛基催化剂为对甲氧基苯甲醛、对氰基苯甲醛以及2,4-二甲氧基苯甲醛中的任意一种。
扩链反应:聚合前,将单体、大分子引发剂、醛基催化剂、还原剂、溶剂混合后,置于单支口圆底烧瓶中,密封。冷冻抽排三次,最后通入惰性气体(氩气或氮气),使聚合反应在惰性气氛中进行。
其中,上述大分子引发剂为均聚反应制得的大分子聚合物,分别为聚乙二醇甲基丙烯酸甲酯(PPEGMA-I),聚甲基丙烯酸苄基酯(PBnMA-I)。
本发明所用的三类醛基催化剂在光照作用下由基态变为激发态。处于激发态的醛基催化剂可以与休眠种(有机卤化物)发生氧化还原反应,从而生成烷基自由基,进一步引发甲基丙烯酸酯类单体的链增长反应。此外,在还原剂存在条件下,催化剂-卤素的络合物作为增长自由基的封端剂可再次生成基态催化剂以及含卤素的休眠种。这种休眠种与增长链自由基之间的可逆平衡使得聚合体系具有可控性,并最终得到均聚物以及嵌段共聚物。本发明提供的制备方法简便易行,清洁环保,具有较强的实用性。
附图说明
图1是23W节能灯照射条件下光引发聚合反应装置图。
图2为实施例五中(a)大分子引发剂与嵌段共聚物的GPC曲线图;(b)嵌段共聚物的核磁氢谱图。
具体实施方式
以下通过一些实例具体地描述本发明,但本发明不受这些实例的限定。
实施例一,对甲氧基苯甲醛/1-碘全氟己烷引发体系下MMA单体的光聚合
单体MMA在N,N-二甲基甲酰胺(DMF)溶剂(6.0g)中的质量分数为24wt%。按照摩尔比[MMA]/[1-碘全氟己烷]/[对甲氧基苯甲醛]/[DMA]=100/2/5/5,分别将上述原料加入到25mL单支口圆底烧瓶中。密封。冷冻抽排三次,最后通入氩气,使聚合反应在惰性气氛中于两个23W紧致型节能灯照射条件下进行。距离反应装置如图1所示。在不同的时间间隔,用注射器对反应体系少量取样,样品用体积比为7:3的甲醇和水的混合液沉淀三次,真空干燥至恒重,得到白色粉末。样品用于进行转化率及分子量的测试。
在该配比条件下,聚合物分子量随转化率的增长而线性增加。反应46h,单体转化率达77.9%,聚合产物Mn=30400,PDI=1.47。
比较例一
单体MMA在N,N-二甲基甲酰胺(DMF)溶剂(6.0g)中的质量分数为24wt%。按照摩尔比[MMA]/[1-碘全氟己烷]/[对甲氧基苯甲醛]/[DMA]=100/2/5/-以及100/2/-/5,分别将上述原料加入到25mL单支口圆底烧瓶中。其他操作参照实施例一。
当体系中不添加DMA或者对甲氧基苯甲醛时,反应70小时,几乎无聚合物产生,说明还原剂DMA以及有机催化剂的存在对聚合反应的进行十分重要。
实施例二,对甲氧基苯甲醛/1-碘全氟己烷引发体系下PEGMA单体的光聚合
参照实施例一进行对甲氧基苯甲醛/1-碘全氟己烷引发体系下的PEGMA单体的光聚合。摩尔比[PEGMA]/[1-碘全氟己烷]/[对甲氧基苯甲醛]/[DMA]为42/2/5/5。不同时间段所取样品用乙醚沉淀三次,真空干燥至恒重,得到粘稠状物质。20.5h时,单体转化率为88%,GPC测得聚合产物Mn=14200,PDI=1.39。此外,在聚合过程中,聚合物分子量随转化率的增长而线性增加,并且聚合物的分子量分布较窄(小于1.49),符合活性聚合的规律。
实施例三,对甲氧基苯甲醛/其他引发剂引发体系下MMA单体的光聚合
参照实施例一进行对甲氧基苯甲醛/其他引发剂引发体系下的MMA单体的光聚合。不同的是选择的引发剂分别为2-溴异丁酸乙酯、α-溴代苯基乙酸乙酯、1-碘全氟丁烷和1-碘全氟辛烷等。
具体地,单体浓度为33wt%,将摩尔比[MMA]/[2-溴异丁酸乙酯]/[对甲氧基苯甲醛]/[DMA]=100/1/10/50的各物质加入到DMF溶剂中,反应36h,单体转化率为85%,GPC测得聚合产物Mn=26100,PDI=1.72。相同条件下,当摩尔比[MMA]/[α-溴代苯基乙酸乙酯]/[对甲氧基苯甲醛]/[DMA]=100/1/10/50时,反应35h,单体转化率为90%,GPC测得聚合产物Mn=25300,PDI=1.69。当摩尔比[MMA]/[1-碘全氟丁烷]/[对甲氧基苯甲醛]/[DMA]=100/2/10/5时,反应48h,单体转化率为75%,GPC测得聚合产物Mn=31200,PDI=1.49。当摩尔比[MMA]/[1-碘全氟辛烷]/[对甲氧基苯甲醛]/[DMA]=100/2/8/5时,反应39h,单体转化率为73%,GPC测得聚合产物Mn=36800,PDI=1.39。
实施例四,对甲氧基苯甲醛/其他引发剂引发体系下PEGMA单体的光聚合
参照实施例二进行对甲氧基苯甲醛/其他引发剂引发体系下的PEGMA单体的光聚合。不同的是选择的引发剂分别为2-溴异丁酸乙酯、α-溴代苯基乙酸乙酯、1-碘全氟丁烷和1-碘全氟辛烷等。
具体地,单体浓度为30wt%,将摩尔比[PEGMA]/[2-溴异丁酸乙酯]/[对甲氧基苯甲醛]/[DMA]=42/2/5/5的各物质加入到DMF溶剂中,反应24h,单体转化率为80%,GPC测得聚合产物Mn=45000,PDI=1.15。相同条件下,当摩尔比[PEGMA]/[α-溴代苯基乙酸乙酯]/[对甲氧基苯甲醛]/[DMA]=42/2/10/5时,反应30h,单体转化率为90%,GPC测得聚合产物Mn=39500,PDI=1.22。当摩尔比[PEGMA]/[1-碘全氟丁烷]/[对甲氧基苯甲醛]/[DMA]=42/2/10/5时,反应28h,单体转化率为85%,GPC测得聚合产物Mn=30800,PDI=1.25。当摩尔比[PEGMA]/[1-碘全氟辛烷]/[对甲氧基苯甲醛]/[DMA]=42/2/10/5时,反应30h,单体转化率为82%,GPC测得聚合产物Mn=36600,PDI=1.19。
实施例五,对甲氧基苯甲醛/1-碘全氟己烷引发体系下的扩链反应
参照实施例二,将Mn=14200,PDI=1.39的大分子引发剂PPEGMA-I(0.77g),单体MMA(2.6g),对甲氧基苯甲醛(0.14g),DMA(0.13g)以及DMF(6g)依次加入干燥的单支口圆底烧瓶中,其他操作参照实施例一。反应体系在23W紧致型节能灯照射下反应100小时,停止反应,样品用甲醇沉淀三次,真空干燥至恒重,得到白色粉末。称重法测得单体转化率为74.8%,GPC测得聚合物Mn,=64500g mol-1,PDI=1.87。GPC曲线图与嵌段共聚物PPEGMA-b-PMMA的核磁氢谱如图2所示。
实施例六,对氰基苯甲醛/1-碘全氟己烷引发体系下的MMA单体的光聚合
参照实施例一进行对氰基苯甲醛/1-碘全氟己烷引发体系下的MMA单体的光聚合。不同的是单体浓度为24wt%,原料配比为[MMA]/[1-碘全氟己烷]/[对氰基苯甲醛]/[DMA]=100/2/50/5。在该体系中,聚合物的平均分子量均随转化率的增长而线性增加,并且聚合物的分子量分布也较低(1.18-1.91),表现出活性可控的规律。反应100h时,单体转化率为67%,GPC测得聚合产物Mn=11300,PDI=1.69。
比较例二
按照摩尔比[MMA]/[1-碘全氟己烷]/[对氰基苯甲醛]/[DMA]=100/1/50/-以及100/2/50/-,分别将上述原料及DMF溶剂加入到25mL单支口圆底烧瓶中。其他操作参照实施例六。
本发明发现体系中未添加DMA时,聚合反应速率在降低的同时,聚合反应的可控性也大大降低。
实施例七,对氰基苯甲醛/1-碘全氟己烷引发体系下的BnMA单体的光聚合
参照实施例一进行对氰基苯甲醛/1-碘全氟己烷引发体系下的BnMA单体的光聚合。不同的是原料摩尔比为[BnMA]/[1-碘全氟己烷]/[对氰基苯甲醛]/[DMA]为60/1/50/3。112h时,单体转化率为73%,GPC测得聚合物Mn=12500,PDI=1.85。此外,聚合物分子量随转化率的增长而线性增加,符合活性聚合的规律。
实施例八,对氰基苯甲醛/其他引发剂引发体系下MMA单体的光聚合
参照实施例六进行对氰基苯甲醛/其他引发剂引发体系下的MMA单体的光聚合。不同的是选择的引发剂分别为2-溴异丁酸乙酯、α-溴代苯基乙酸乙酯、1-碘全氟丁烷和1-碘全氟辛烷等。当摩尔比[MMA]/[有机卤化物]/[对氰基苯甲醛]/[DMA]=100/2/(25-50)/5时,可得到分子量随转化率的增长而线性增加的聚合物。
具体地,单体浓度为28wt%,将摩尔比[MMA]/[2-溴异丁酸乙酯]/[对氰基苯甲醛]/[DMA]=100/2/25/5的各物质加入到DMF溶剂中,反应100h,单体转化率为70%,GPC测得聚合产物Mn=16100,PDI=1.72。相同条件下,当摩尔比[MMA]/[α-溴代苯基乙酸乙酯]/[对氰苯甲醛]/[DMA]=100/2/50/5时,反应98h,单体转化率为65%,GPC测得聚合产物Mn=15600,PDI=1.69。当摩尔比[MMA]/[1-碘全氟丁烷]/[对氰基苯甲醛]/[DMA]=100/2/50/5时,反应115h,单体转化率为76%,GPC测得聚合产物Mn=11500,PDI=1.72。当摩尔比[MMA]/[1-碘全氟辛烷]/[对氰基苯甲醛]/[DMA]=100/2/50/5时,反应100h,单体转化率为73%,GPC测得聚合产物Mn=15800,PDI=1.73。
实施例九,对氰基苯甲醛/其他催化剂引发体系下的BnMA单体的光聚合
参照实施例七进行对氰基苯甲醛/其他引发剂引发体系下的BnMA单体的光聚合。不同的是选择的引发剂分别为2-溴异丁酸乙酯、α-溴代苯基乙酸乙酯、1-碘全氟丁烷和1-碘全氟辛烷等。当摩尔比[BnMA]/[有机卤化物]/[对氰基苯甲醛]/[DMA]=100/2/(30-50)/5时,可得到分子量随转化率的增长而线性增加的聚合物。
具体地,单体浓度为30wt%,将摩尔比[BnMA]/[2-溴异丁酸乙酯]/[对氰基苯甲醛]/[DMA]=100/2/30/5的各物质加入到DMF溶剂中,反应80h,单体转化率为79%,GPC测得聚合产物Mn=19800,PDI=1.72。相同条件下,当摩尔比[BnMA]/[α-溴代苯基乙酸乙酯]/[对氰苯甲醛]/[DMA]=100/2/50/5时,反应85h,单体转化率为75%,GPC测得聚合产物Mn=16400,PDI=1.79。当摩尔比[BnMA]/[1-碘全氟丁烷]/[对氰基苯甲醛]/[DMA]=100/2/50/5时,反应100h,单体转化率为84%,GPC测得聚合产物Mn=13200,PDI=1.76。当摩尔比[BnMA]/[1-碘全氟辛烷]/[对氰基苯甲醛]/[DMA]=100/2/50/5时,反应100h,单体转化率为82%,GPC测得聚合产物Mn=14900,PDI=1.75。
实施例十,对氰基苯甲醛/1-碘全氟己烷引发体系下的扩链反应
参照实施例七,将Mn=12500,PDI=1.85的大分子引发剂PBnMA-I(0.53g),单体MMA(2.0g),对氰基苯甲醛(1.31g),DMA(0.12g)以及DMF(6g)依次加入干燥的单支口圆底烧瓶中,其他操作参照实施例一。反应体系在23W紧致型节能灯照射下反应65小时,停止反应,样品用甲醇沉淀三次,真空干燥至恒重,得到白色粉末。称重法测得单体转化率为67.8%,GPC测得聚合物Mn,GPC=22300g mol-1,PDI=1.92。
实施例十一,2,4-二甲氧基苯甲醛/1-碘全氟己烷引发体系下的PEGMA单体的光聚合
参照实施例二进行2,4-二甲氧基苯甲醛/1-碘全氟己烷引发体系下的PEGMA单体的光聚合。其中,[PEGMA]/[1-碘全氟己烷]/[2,4-二甲氧基苯甲醛]/[DMA]摩尔比分别为24/1/20/5。反应进行10h,单体转化率达86%,GPC测得Mn=13300,PDI=1.21。此外,聚合物分子量随转化率的增长而线性增加,符合活性聚合的规律。
比较例三
参照实施例二进行2,4-二甲氧基苯甲醛/1-碘全氟己烷引发体系下的PEGMA单体的光聚合。其中,[PEGMA]/[1-碘全氟己烷]/[2,4-二甲氧基苯甲醛]/[DMA]摩尔比为24/1/-/5以及24/1/20/-。
当体系中不添加DMA或者2,4-二甲氧基苯甲醛时,聚合反应速率很慢或者得到的聚合物分子量分布较高,并且聚合反应非活性/可控。
实施例十二,2,4-二甲氧基苯甲醛/1-碘全氟己烷引发体系下的扩链反应
参照实施例十一,将Mn=13000g mol-1,PDI=1.18的大分子引发剂PPEGMA-I(1.98g),单体BnMA(0.516g),2,4-二甲氧基苯甲醛(0.66g),DMA(0.087g)以及DMF(6g)依次加入干燥的单支口圆底烧瓶中,其他操作参照实施例一。反应体系在23W紧致型节能灯照射下反应23小时,停止反应,样品用甲醇沉淀三次,真空干燥至恒重,得到白色粉末。称重法测得单体转化率为33.9%,GPC测得聚合物Mn=54000g mol-1,PDI=2.28。
Claims (6)
1.一种用于甲基丙烯酸酯类单体可见光活性自由基聚合的体系,其特征在于:该体系包括单体、催化剂、引发剂和还原剂;单体与催化剂的摩尔比为1.2:1-20:1,催化剂与还原剂的摩尔比为1:1-17:1,反应温度为室温,反应时间为2-115h;所述催化剂为苯甲醛的衍生物,引发剂为有机卤化物,还原剂为芳香族叔胺化合物。
2.根据权利要求1所述的体系,其特征在于:催化剂为对甲氧基苯甲醛、对氰基苯甲醛或2,4-二甲氧基苯甲醛。
3.根据权利要求1所述的体系,其特征在于:引发剂为2-溴异丁酸乙酯、α-溴代苯基乙酸乙酯或全氟碘代烷。
4.根据权利要求3所述的体系,其特征在于:全氟碘代烷为1-碘全氟己烷、1-碘全氟丁烷或1-碘全氟辛烷。
5.根据权利要求1所述的体系,其特征在于:还原剂为N,N-二甲基苯胺。
6.根据权利要求1所述的体系,其特征在于:引发光源为节能灯。
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