CN113950470A - 甲酰胺单体以及由其合成的聚合物 - Google Patents
甲酰胺单体以及由其合成的聚合物 Download PDFInfo
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- CN113950470A CN113950470A CN202080020625.8A CN202080020625A CN113950470A CN 113950470 A CN113950470 A CN 113950470A CN 202080020625 A CN202080020625 A CN 202080020625A CN 113950470 A CN113950470 A CN 113950470A
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- formamide
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C225/00—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones
- C07C225/02—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to acyclic carbon atoms of the carbon skeleton
- C07C225/14—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being unsaturated
- C07C225/16—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being unsaturated and containing six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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Abstract
提供含甲酰胺基团的单体以及通过所述单体聚合制备的聚合物。还提供了使所述单体聚合的方法以及通过聚合前和/或聚合后官能化而合成官能化聚合物的方法。所述单体是无毒的,并且可以在一锅法合成中产生高反应性的异氰酸酯和异腈前体,从而能够将复杂官能团加入由所述单体合成的聚合物的侧链中。
Description
相关申请的交叉引用
本申请要求2019年3月14日提交的美国临时专利申请No.62/818,188的优先权,其全部内容在这里作为参考而引入。
关于政府权利
本发明是在国家科学基金会(National Science Foundation)授予的DMR1121288的政府支持下完成的。政府对本发明拥有一定的权利。
背景技术
受控聚合方法的最新进展使得人们能够前所未有地获得在结构、分子量和分散性方面均得到良好控制的聚合物。活性或受控的自由基聚合(LFRP)和开环易位聚合(ROMP)的进展以及相关引发剂和催化剂的开发迅速扩展了聚合物及其性能的多样性。这些方法产生了新型嵌段共聚物(BCP)、瓶刷状共聚物、刷状聚合物、星形聚合物和其它复杂结构。但它们的进一步应用需要引入多个官能团,这是具有挑战性的。
用于改性聚合物侧链基团的化学转化有很多。虽然这些转化对于小分子来说可能非常有效,但应用相对温和的条件以可放大的模式在聚合物链上高效和高产率地实现这些转化同时获得多种相互正交的官能团,仍具有挑战性。通常应用异氰酸酯和异腈官能团来形成脲、氨基甲酸酯、硫脲、酰氧基羧酰胺、内酰胺和四唑连接键。但这些化学品所带来的安全问题尚未得到普遍解决。这些异氰酸酯和异腈化学品的处理、制造和运输因其毒性而高度危险。因此,尽管在新聚合物官能化路线方面的开发取得了令人难以置信的进展,仍需要更新、更有效的方法。
发明内容
本发明提供含甲酰胺基团的单体和通过使所述单体聚合而制备的聚合物。还提供使所述单体聚合的方法和使由所述单体制备的聚合物官能化的方法。
含甲酰胺基团的单体的一个实施方案包括连接至可聚合基团上的甲酰胺官能团,其中所述可聚合基团包括苯乙烯基团、丙烯酸酯基团、甲基丙烯酸酯基团或环状烯烃基团。通过使一种或多种含甲酰胺基团的单体与任选的一种或多种附加单体聚合可以形成多种聚合物。
在单体聚合之前或之后,可以将所述甲酰胺官能团转化为反应性的异氰酸酯官能团和/或异腈官能团。然后可以将所述异氰酸酯和异腈基团转化为多种有用的化学官能团。这些官能团包括氨基甲酸酯基团、脲基团、羧酰胺基团、β-内酰胺衍生物、四唑衍生物、ATRP引发基团和NMP引发基团。
在将甲酰胺基团转化为异氰酸酯基团的一些实施方案中,甲酰胺基团的转化和异氰酸酯基团的转化在多组分反应中实施。
对本领域熟练技术人员来说,在阅读了如下附图、详细描述和所附权利要求之后,本发明的其它主要特征和优点将变得很明显。
附图说明
下面将参考附图描述本发明的示例性实施方案,其中相同的附图标记代表相同的元件。
图1描述了甲酰胺单体的结构及其聚合,随后应用一锅法多组分反应(MCR)将其转化为异氰酸酯和异氰中间体,并随后官能化为脲、氨基甲酸酯和酰氧基羧酰胺和酰氨基羧酰胺衍生物。
图2描述了应用一锅法MCR将甲酰胺小分子转化为异氰酸酯和异氰中间体,和它们随后官能化为脲、氨基甲酸酯、酰氧基羧酰胺和酰氨基羧酰胺衍生物。这些转化可用于这里描述的甲酰胺官能化的聚合物。
图3描绘了乙烯基苯甲基甲酰胺(VBF)单体的合成方案和纯化单体的质子核磁共振(1H NMR)谱图。
图4描述了VBF单体通过一锅法化学经过异氰酸酯中间体转化为氨基甲酸酯单体,其1H NMR谱图显示了所有预期峰和CHO峰的消失。顶部插图给出了通过可逆加成-片段链转移(RAFT)进行官能化单体的聚合,所得的NMR和气相渗透色谱(GPC)数据显示出受控良好的100%官能化聚合物。
图5A描述了PVBF均聚物的1H NMR谱图和GPC数据。图5B给出了摩尔比为73:27的P(VBF-r-S)共聚物的1H NMR及源自GPC的分散性。
图6描述了苯乙烯、(甲基)丙烯酸酯((M)AF)和环状烯烃甲酰胺单体的结构。
图7A-图7C描述了三种苯乙烯甲酰胺单体的合成方案。图7D描述了(甲基)丙烯酸酯甲酰胺单体的合成方案。图7E-图7G描述了三种环状烯烃单体的合成方案,在这种工况中为降冰片烯甲酰胺(NBF)单体。图7H给出了可在ROMP单体合成中应用的降冰片烯衍生物。
图8描述了形成脲、氨基甲酸酯、酰氧基羧酰胺和β-内酰胺侧链官能化的单体的四个反应。M代表基于VBF、(M)AF或NBF的任何单体。右侧给出了所得到的侧链官能化均聚物(方法1)。
图9描述了在甲酰胺单体上实施3-CR Passerini反应以合成Y形引发单体的方案。利用正交聚合机理(氮氧化物控制的自由基、NMP和原子转移自由基聚合、ATRP)可以聚合Y形引发单体,和所述聚合物用于合成瓶刷共聚物。可以首先应用ROMP引发单体来使聚合物A和B生长,然后再使单体聚合。替代地,在刷子生长之前可使甲酰胺单体聚合。
图10描述了甲酰胺单体的均聚物和共聚物以及它们随后转化为官能化聚合物的示意图。
图11概述了所提出的均聚物和无规共聚物。VBF(左上方案)、(M)AF(左下方案)和VBF(右上和右下方案)分别为与甲基丙烯酸甲酯(MMA)、丙烯酸甲酯(MA)和降冰片烯(NB)共聚。x:y的比分别在7:3、1:1至2:8间变化。
具体实施方式
本发明提供含甲酰胺基团的单体(在这里也称为甲酰胺单体)和通过使所述单体聚合制备的聚合物。还提供使所述单体聚合的方法,以及通过聚合前和/或聚合后官能化合成官能化聚合物的方法。
所述单体是无毒的,且在一锅法合成中可以产生高反应性的异氰酸酯和异腈前体,从而能将复杂官能团加入由所述单体合成的聚合物的侧链中。因此,所述单体和由其形成的聚合物很大程度地扩展了基于异腈/异氰酸酯的反应化学,从而在不需要处理、应用或运输有毒的异氰酸酯或异腈单体的前提下为聚合物赋予复杂的官能团。所得的聚合物可用于生物医学、医药、电子和涂料应用中以及用作反应性聚合物载体。例如,具有反应性官能团的聚合物可用于将工业相关的酶固定在聚合物基质上以实施大规模的酶反应、用作促进有机转化的模板、用作反应性树脂和用作细胞生长和扩张的表面。
甲酰胺单体包括连接到可聚合基团上的一个或多个甲酰胺官能团(-NH-C=O)。可聚合基团的实例包括乙烯基基团、苯乙烯基团、丙烯酸酯基团、甲基丙烯酸酯基团和环状烯烃基团。
可聚合苯乙烯基团通过它们的乙烯基双键聚合,形成含有碳-碳链的聚合物主链。甲酰胺官能团可位于苯乙烯基团的苯环的对位、邻位或间位。苯乙烯基团包括苯乙烯衍生物基团如叔丁基苯乙烯基团,其包括除甲酰胺基团之外的悬垂于其苯环的其它官能团。通过Friedel-Craft反应可以合成各种苯乙烯衍生物基团。
丙烯酸酯和甲基丙烯酸酯基团(统称为(甲基)丙烯酸酯基团)分别通过其乙烯基和R-C=C(CH3)H双链聚合,形成含有碳-碳链的聚合物主链。
环状烯烃经ROMP通过芳族碳-碳双键聚合,形成包含碳-碳双键的聚合物主链。取决于所应用的环状烯烃基团,聚合物主链还可以包含环状环。环状烯烃基团的实例包括降冰片烯基团。降冰片烯基团包括除甲酰胺基团之外还包含悬垂于其降冰片烯环上的其它官能团的降冰片烯衍生物基团。
甲酰胺官能团通过连接剂连接到可聚合基团上。在一些甲酰胺单体中,所述连接剂为单碳原子。但可以选择连接剂的长度以提供想要的特性,如在给定有机溶剂中强化的溶解性。举例来说,连接剂可以包含两个或六个碳原子的碳链,当然也可以使用更长碳链。但连接剂不需要仅由碳原子组成。包括醚键、酯键和/或芳基在内的其它基团也可以是连接剂的一部分。
在图6中给出了甲酰胺单体的实例。它们包括:包含通过含1、2或3个碳原子的碳连接剂连接到苯乙烯基团上的甲酰胺官能团的苯乙烯类甲酰胺单体(左上图);包含通过含2-6个碳原子的碳链连接剂连接至(甲基)丙烯酸酯基团的甲酰胺官能团的(甲基)丙烯酸酯甲酰胺单体(右上图);包含通过含醚键和芳基的连接剂连接至降冰片烯基团的甲酰胺官能团的环状烯烃甲酰胺单体(左下图);包含各自通过含羰基基团和具有2-6个碳原子的碳链的连接剂连接于降冰片烯基团的两个甲酰胺官能团的环状烯烃甲酰胺单体(右下图);和包含通过含酯键和具有2-6个碳原子的碳链的连接剂连接到降冰片烯基团的甲酰胺官能团的环状烯烃甲酰胺单体(右下图)。
在实施例2中提供了合成甲酰胺单体的方法的详细说明。通常,甲酰胺单体可通过甲酰胺前体与包含可聚合基团的单体反应来制备。甲酰胺前体可以是包含甲酰胺基团的化学品,或者是与具有可聚合基团的单体反应形成甲酰胺官能团的化学品。
可以聚合甲酰胺单体以形成均聚物,或与一种或多种附加的单体聚合以形成共聚物。所述附加的单体可以包括其它甲酰胺单体、非甲酰胺单体或它们的组合物。共聚物可以是无规共聚物或嵌段共聚物。可与甲酰胺单体聚合的其它单体的实例包括乙烯单体、苯乙烯单体、苯乙烯衍生物单体如叔-丁基苯乙烯单体、丙烯酸酯单体、甲基丙烯酸酯单体、含环氧基团的单体如甲基丙烯酸缩水甘油酯单体、乙烯吡啶单体、4,4-二甲基-2-乙烯吖内酯单体和环状烯烃单体。可以调节聚合物中各种单体的摩尔比,以提供想要的聚合物性质和溶解度。因此,聚合物中甲酰胺单体的数量取决于聚合物的预期用途。作为说明,在由甲酰胺单体聚合的共聚物的各种实施方案中,甲酰胺单体将占共聚物的至少0.1mol%、至少1mol%、至少5mol%、至少10mol%、至少25mol%、至少50mol%、至少75mol%、至少90mol%、至少95mol%、至少99mol%和至少99.9mol%。正如实施例中所述,对于乙烯、(甲基)丙烯酸酯和环状烯烃单体,可以应用已知的聚合技术进行单体聚合。这些技术包括自由基聚合、RAFT聚合、ATRP和ROMP。
RAFT是一种活性自由基聚合形式,其能够聚合具有复杂结构的聚合物,包括嵌段、接枝、梳状和星形结构。RAFT工艺包括在合适链转移剂的存在下取代单体的常规自由基聚合。
ATRP可用于在高度控制的情况下聚合多种单体。ATRP中的控制来自于通过卤素转移至过渡金属络合物使休眠聚合物链终端(卤化物官能化)可逆地氧化还原活化。
ROMP是一种活性聚合形式,其特点是易于聚合、对官能团耐受以及能够由双环和低聚环状烯烃构建复杂结构。ROMP使用产生金属碳烯物质的催化剂,该催化剂能够引发环状烯烃聚合,形成在主链上具有双键的聚合物。这种特征允许构建复杂的密集替代的结构。
应用已知的甲酰胺反应化学可以将所述单体或由其形成的聚合物的甲酰胺官能团转化为反应性异氰酸酯或反应性异腈中间体,然后这些反应性中间体可以转化为大量有用的官能团。例如,甲酰胺官能团可以通过与氧化剂反应转化为异氰酸酯官能团,或通过利用脱水剂脱水转化为异腈官能团。甲酰胺官能团转化为异氰酸酯或异腈基团可以在甲酰胺单体聚合之前或之后实施。但预聚合转化通常需要在进一步官能化之前对中间体进行分离,这可能是一个缺点,因为中间体是有毒的。与之相对比,聚合后甲酰胺基团转化为异氰酸酯或异腈基团有可能在不需要分离有毒中间体的情况下在多组分反应(MCR;也称为一锅法合成)中实施聚合物的进一步官能化。用于异氰酸酯和异腈的转化反应是公知的,且可以在一锅法合成中应用这些化学反应。基于这些中间体的MCR可以在反应中包括两种、三种、四种或甚至更多种组分,从而开发了利用多种复杂正交官能团使聚合物官能化的能力。
异氰酸酯基团是一类高反应性官能团,已知这类官能团有多种有机转化,包括与二醇反应形成聚氨酯。氨基甲酸酯或氨基甲酸酯链的形成也普遍存在于后官能化反应的聚合物中。异腈也是一类重要的反应性官能团。它们的反应性来自于二价并因此可与亲电试剂和亲核试剂反应的碳中心。它们已被用于多组分反应中,以形成高官能性的分子。它们在Passerini中作为3组分(3-CR)之一或在Ugi反应中作为4-组分(4-CR)之一而加入。
应用图1中氨基甲酸酯转化的简单工况描述了甲酰胺基团通过异氰酸酯中间体向不同官能团的转化。在第一步中,甲酰胺单体聚合为甲酰胺官能化的聚合物。如左图的反应方案所示,在氧化剂的存在下,可以将甲酰胺基团转化为中间体异氰酸酯基团,后者随后在一锅法合成中通过与醇反应转化为氨基甲酸酯官能团。这种转化在实施例1中进行了更详细讨论。替代地,异氰酸酯可以通过与伯胺反应转化为碳酰胺基团。通过使用低聚伯胺,可以将异氰酸酯基团转化为脲基团。
在图1右侧给出了更复杂的转化。在这里,甲酰胺基团首先转化为异腈中间体,其在一锅法合成中应用Passerini-3CR反应通过与醛和酸反应转化为酰氧基羧酰胺官能团。可以应用的其它异腈转化包括应用Ugi-β-内酰胺-3CR反应通过与醛和氨基酸反应转化为β-内酰胺基团、应用Ugi-4-CR反应通过与醛、酸和伯胺反应转化为酰氨基羧酰胺,以及应用Ugi四唑反应通过与醛、伯胺和氨反应转化为四唑衍生物。这些反应在实施例3中进行了更详细讨论。
甲酰胺官能团的转化可能会形成带有复杂分支结构的侧链基团,包括瓶刷结构。例如,甲酰胺基团可转化为异腈基团,而异腈基团又可转化为包含ATRP引发剂和NMP引发剂的支化侧链。NMP是一种受控的自由基聚合,其中在没有外部自由基源或金属催化剂的情况下由热引发聚合。在NMP中,烷氧基胺引发剂可用作单分子试剂,提供反应性引发基团和稳定的调节用氮氧自由基。ATRP引发剂包括烷基卤化物基团,包括仲和叔烷基卤化物。然后两种不同的引发剂可以与两种不同的单体反应,从主刷主链处生长出为两种不同的聚合物链。这种化学在实施例3中进行了更详细讨论。
聚合反应和侧链基团官能化可以在多种有机溶剂中实施。用于给定聚合/官能化反应的特定溶剂取决于所用的单体和反应物。例如,对于通过异氰酸酯中间体官能化来说,可以应用多种溶剂,包括均三甲苯、二甘醇二甲醚、间-二甲苯、二甲基甲酰胺(DMF)、二甲基亚砜(DMSO)、乙腈(MeCN)和氯化溶剂。在转化甲酰胺为氨基甲酸酯的氧化条件下,可以应用氯化溶剂。对于通过异腈中间体的官能化来说,所应用的溶剂取决于脱水剂。对于应用三光气的转化来说,可以使用氯化溶剂。
实施例
如下实施例描述了已聚合或可聚合的甲酰胺基单体的设计和合成。然后可以通过一锅法反应经异腈或异氰酸酯中间体使单体的甲酰胺侧链基团高效官能化为多种官能团。
实施例1:该实施例描述了乙烯基苯甲基甲酰胺(VBF)单体的合成和聚合。
单体设计和合成:在超过75%收率下合成VBF单体。应用在Robertson,J.等的Org.Biomol.Chem.2005,3(23),4246-4251中描述的程序合成对位取代的苯乙烯。由可商购的乙烯苯甲基氯开始,在DMF中应用碘化钠实施向VBF的一步转化。添加二甲酰亚胺钠作为甲酰胺基团的来源。典型的程序如下:将二甲酰亚胺钠(5.91g,62.24mmol)添加至乙烯苯甲基氯(5.0g,32.76mmol)和碘化钠(NaI)(10.80g,72.07mmol)在DMF(40mL)中的搅拌溶液中,并使混合物在100℃下加热48h。将热反应混合物倒入水中。用二氯甲烷(DCM)(200mL)萃取混合物,并在真空中浓缩所合并的有机相。将产品进一步溶解于在DCM(50mL)中,加入KOH(0.1g,1.79mmol)。将混合物在室温下搅拌1h,并在真空中浓缩有机层,以得到淡黄色固体作为产品(3.94g,75.5%)。所述产品通过色谱柱层析(二氧化硅1:2己烷:乙酸乙酯)进一步纯化。1H NMR确认其化学结构(图3)。该单体本身可溶于多种溶剂如DCM、氯仿、四氢呋喃(THF)、DMF、DMSO和甲醇中,和部分可溶于乙腈和己烷中。
通过异氰酸酯中间体甲酰胺转化为氨基甲酸酯链:为了确认VBF单体中甲酰胺的反应性,应用乙醇实施简单的氨基甲酸酯转化。在装有5mL DCM的50mL圆底(RB)烧瓶中放置0.16g VBF和少量MS(分子筛)-4A°。用Ar吹扫反应混合物15min。向该溶液中加入0.430g在1mL DCM中的氧化剂[PhI(COOCF3)2],并继续搅拌10min。通过薄层色谱(TLC)监测甲酰胺全部转化为异氰酸酯,随后向溶液中加入0.43g 2-甲基丁醇。继续反应3h。通过过滤去除分子师,并蒸发掉溶剂。通过闪蒸色谱法纯化粗产品。1H NMR确认甲酰胺质子完全消失,并确认通过异氰酸酯中间体以定量收率形成产品(图4)。苯乙烯双键不受该反应的影响,并可用于聚合。该单体通过RAFT进一步聚合形成了明确定义的聚合物(图4,上图)。
VBF的聚合:应用多种方法测试纯化的VBF单体的可聚合性。首先,应用在75℃下在DMF中的偶氮二异丁腈(AIBN)实施12h的常规自由基聚合,得到聚合物(Mn:14.2K,(Mw/Mn)=1.66)。还探讨了受控自由基聚合的可行性。在可用的方法中,RAFT效果最好。将VBA(1.0g,6.2mmol)、4-氰基-4-[(十二烷基磺酰基硫代羰基)磺酰基]戊酸(24.9mg,0.05mmol)和AIBN(2.5mg,0.0015mmol)与2.5mL DMF一起加入到10mL的Schlenk烧瓶中。用Ar吹扫30min而使反应混合物脱气,随后进行三次冷冻-泵送-解冻循环15min,然后在搅拌的情况下在75℃下加热12h。冷却反应混合物并沉积到大量甲醇中。通过再沉积进一步纯化所得的聚合物。收集淡黄色聚合物粉末。收率:0.66g。由1H NMR和GPC分析确认结构[Mn:5.5K,Mw/Mn=1.14](图5A)。因此,用这些单体可以实现受控的分子量和分散性。这种聚合物在甲醇、DMF和DMSO中是可溶的,并且部分可溶于DCM、THF和氯仿中。VBF还能够通过RAFT与苯乙烯共聚,形成更易溶于DCM的聚合物(图5B)。这种共聚物可进一步用于通过异氰酸酯中间体实施图4中相同的氨基甲酸酯转化,得到超过60%的转化率。
所述单体可通过常规和受控的自由基方法进一步均聚或共聚,同时对分子量和分散性有很好的控制。共聚提高了在有机溶剂如DCM中的溶解度。在单体和聚合物阶段,通过反应性异氰酸酯中间体将这些甲酰胺侧链基团转化为氨基甲酸酯键也是可行的。这些结果表明,使用无毒的可放大单体及其聚合物为目前无法通过一锅法合成的所有后官能化反应构建了一个高度通用的平台。
实施例2(预测):本实施例描述了苯乙烯类甲酰胺单体、(甲基)丙烯酸酯甲酰胺单体和环状烯烃甲酰胺单体的各种合成方案。
可设计单体以及由单体制备的均聚物和共聚物以在有机溶剂中有较宽范围的溶解度。例如,可以合成图6所示的苯乙烯类(VBF)、(甲基)丙烯酸酯和环状烯烃单体。合成路线在图7A–图7G所示的合成方案中描述。对于苯乙烯类单体(图7A–图7C),因为前体(氯、氰或胺)很易获得,连接剂长度(n)可以相当容易地在1-3间变化。但单体也可以利用更长的连接剂形成。对于基于丙烯酸酯(AF)或甲基丙烯酸酯(MF)的单体(图7D),应用可商购的乙醇胺转化为甲酰胺衍生物、随后用可商购的丙烯酰氯或甲基丙烯酰氯进行酯化实施两步合成。
当为环状烯烃单体时,可以合成芳基甲酰胺(图7E)和烷基甲酰胺官能化的降冰片烯单体(图7F、图7G)。这些单体的建议合成如图7A–图7G所示。用ROMP单体,也可以制备双官能的单体,从而为聚合物增加官能团。可用于合成ROMP单体的替代的降冰片烯衍生物如图7H所示。
实施例3(预测):本实施例描述了甲酰胺单体的各种聚合方案
甲酰胺单体是个多用途平台,可以应用两种方法来开发利用它们产生官能化的聚合物。第一种方法是通过异氰酸酯/异腈中间体将所述单体转化为新的官能化单体,然后使官能化单体聚合(图8)以形成聚合物。第二种方法是使甲酰胺单体本身聚合,然后使聚合物官能化。第一种方法基本上是小分子化学,几乎可以定量。官能化单体随后的聚合可以通过RAFT、ATRP或ROMP实施。这种方法也允许以预定进料比混合各种官能化单体,以合成具有选定组成的共聚物。第一种方法是多步方法,可能需要在聚合前合成和纯化官能化单体。第二种方法更便于用户使用,并可以提供可用于在用户端进一步官能化的空白模板。这种空白模板可用于固体载体、微载体等进一步官能化。在下文更详细描述的这些方法强调了这个平台的多功能性,并对聚合物化学家可用的大规模扩展官能工具包提供了指导。
方法1:官能化单体的聚合:这里描述了说明甲酰胺单体的聚合以及聚合前和聚合后官能化的一组转化。这些转化包括甲酰胺单体转化为:(a)用简单醇(2-甲基丁醇)经过异氰酸酯中间体转化为氨基甲酸酯单体、(b)用低聚伯胺[氨基聚乙二醇单甲醚(PEG-NH2),2000g/mol,购自sigma Aldrich]经过异氰酸酯中间体转化为脲单体,(c)应用Passerini-3CR经过异腈中间体通过与醛(2-甲基丁醛)和酸(苯甲酸)反应转化为酰氧基羧酰胺单体,和(d)应用Ugi-β-内酰胺-3CR经过异腈中间体通过与醛(2,5-二甲氧基苯甲醛)和氨基酸(β-丙氨酸)反应转化为β-内酰胺单体。可用于这些转化的反应方案如图2和图8所示。这些转化形成聚合物化学中用于共轭各种低聚物、小分子和肽的重要连接。由上述转化(b)产生的侧链PEG官能化聚合物是用于生物材料、涂层和其它响应性表面的一类重要聚合物。来自Ugi-内酰胺反应的β-内酰胺官能团对于生成尼龙-3聚合物非常相关且很有价值。这些尼龙-3聚合物类似于由α-氨基酸衍生的蛋白质和肽;因此,人们对它们的一系列生物学特性进行了探索,包括对细菌的毒性以及细胞的生长和繁殖。在侧链中具有β-内酰胺官能团可以产生不同的结构,如梳状或瓶刷状共聚物。
合成双头引发单体和瓶刷状共聚物:为验证官能化聚合物的结构提供以下说明,其中应用多组分反应合成双头正交引发剂,它也是一种单体。单体与引发剂的组合被称为“引发单体”。这些引发单体在连接至甲酰胺单体的Y形结构中包含ATRP引发剂和NMP引发剂。当聚合时,所提出的Y形引发单体在每个重复单元上均具有两个这种引发位点。
这种类型的结构对于合成瓶刷状共聚物非常有用。瓶刷状共聚物本身是一类梳状聚合物,其中主链比侧链长。在这种结构中,侧链之间的空间斥力造成主链的延伸链构象。因此可以合成高纵横比的圆柱形瓶刷。使用正交化学法,Y形引发单体可形成由单体“接枝”而来的聚合物A与聚合物B比例为1:1的瓶刷共聚物。接枝到主链上的聚合物A与聚合物B的选择非常广泛,只受聚合方法即NMP或ATRP限制。该方法可应施用于图6中的全部单体。基于VBF单体,在图9中给出了一个这样的实例。即使在空间位阻单体中,由于ROMP方法的高效,NBF单体(图9,下图)也特别有效。可以应用芳族VBF和NBF单体利用聚苯乙烯(PS)和聚甲基丙烯酸甲酯(PMMA)分别作为聚合物A和B形成1:1的瓶刷状共聚物。
方法2:甲酰胺单体的聚合和共聚:所提出的所有苯乙烯类和(甲基)丙烯酸酯单体均首先通过RAFT或ATRP均聚。这两种方法在溶剂、配体、温度和催化剂体系方面均提供足够的选择,以确保聚合条件得到优化(图10)。图11给出了由图6的单体制备的聚合物的结构。对于环状烯烃单体,可以应用标准的Grubbs(G3)钌催化剂实现有效聚合,该催化剂以优异的官能团耐受性、快速引发和传播且基本上为活性聚合而著称。通常,DCM等溶剂在室温下对ROMP非常有效。为了进一步调节所得聚合物的溶解度,可用MMA或NB单体合成一系列含有30、50和80mol%甲酰胺单体的共聚物。初步研究表明,VBF单体与MMA共聚(数据未显示)比与苯乙烯共聚更能提高DCM中的溶解度。因此,可以制备MMA单体和VBF、AF和/或MF单体的共聚物。可以用甲酰胺单体形成嵌段共聚物(BCP)。可以用第二单体合成甲酰胺单体体积比为1:1的BCP,即PVBF-b-PMMA、PNBF-b-PNB和PMAF-b-PMMA。
这里应用的术语"示例性的"用于示例、举例或描述。这里作为“示例性”描述的任何方面或设计均不必理解为对其它方面或设计来说优选或有利的。另外,为了本发明的目的和除非另有规定,“不定冠词”指"一个或多个”。
以上对本发明示例性实施方案的描述是为了说明和描述的目的给出的。它们不用于穷尽本发明或将本发明局限于所公开的精确形式,基于上述教导可以进行调整和改变,也可以通过实施本发明获得调整和改变。选择和描述实施方案是为了解释本发明的原理,和作为本发明的实际应用,使本领域熟练技术人员能够在各种实施方案中利用本发明,并按实际用途的构想进行各种调整。预计本发明的范围由所附权利要求及其等价物进行限定。
Claims (32)
1.一种含连接到可聚合基团的甲酰胺官能团的单体,其中所述可聚合基团包括苯乙烯基团、丙烯酸酯基团、甲基丙烯酸酯基团或环状烯烃基团。
4.权利要求1的单体,其中所述可聚合基团为降冰片烯基团。
5.权利要求4的单体,其中所述降冰片烯基团用烷基甲酰胺基团官能化。
8.权利要求4的单体,其中所述降冰片烯基团用芳基甲酰胺基团官能化。
17.权利要求16的方法,还包括将至少一些甲酰胺侧链基团转化为异氰酸酯基团。
18.权利要求16的方法,还包括将至少一些异氰酸酯基团转化为氨基甲酸酯基团或脲基团。
19.权利要求16的方法,还包括将至少一些甲酰胺侧链基团转化为异腈基团。
20.权利要求19的方法,还包括将至少一些异腈基团转化为羧酰胺基团。
21.权利要求19的方法,还包括将至少一些异腈基团转化为β-内酰胺衍生物。
22.权利要求19的方法,还包括将至少一些异腈基团转化为四唑衍生物。
23.权利要求19的方法,还包括将至少一些异腈基团转化为ATRP引发基团、NMP引发基团或它们的组合。
24.权利要求18的方法,其中在单体聚合后将甲酰胺侧链基团转化为异氰酸酯基团,和其中甲酰胺基团的转化和异氰酸酯基团的转化在多组分反应中实施。
25.权利要求20的方法,其中在单体聚合之后将甲酰胺侧链基团转化为异腈基团,和其中所述甲酰胺基团的转化和异腈基团的转化在多组分反应中实施。
26.一种由甲酰胺单体形成官能化聚合物的方法,其中每种甲酰胺单体具有连接至可聚合基团的甲酰胺官能团,所述方法包括:
使甲酰胺单体的可聚合基团聚合,以形成具有主链和由所述主链延伸的甲酰胺侧链基团的聚合物;
将至少一些甲酰胺侧链基团转化为异氰酸酯基团或异腈基团;和
将至少一些异氰酸酯基团或异腈基团转化为不同的官能团。
27.权利要求26的方法,其中所述可聚合基团包括乙烯基基团、苯乙烯基团、丙烯酸酯基团、甲基丙烯酸酯基团或环状烯烃基团。
28.权利要求26的方法,其中将至少一些甲酰胺侧链基团转化为异氰酸酯基团,和将至少一些异氰酸酯基团转化为氨基甲酸酯基团或脲基团。
29.权利要求26的方法,其中将至少一些甲酰胺侧链基团转化为异腈基团,和将至少一些异腈基团转化为羧酰胺基团。
30.权利要求26的方法,其中将至少一些甲酰胺侧链基团转化为异腈基团,和将至少一些异腈基团转化为β-内酰胺衍生物。
31.权利要求26的方法,其中将至少一些甲酰胺侧链基团转化为异腈基团,和将至少一些异腈基团转化为四唑衍生物。
32.权利要求26的方法,其中至少一些甲酰胺侧链基团为ATRP引发基团、NMP引发基团或它们的组合。
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