CN110964145A - 一种基于乙酰丙酮基的磁性聚合物微球及其制备方法 - Google Patents
一种基于乙酰丙酮基的磁性聚合物微球及其制备方法 Download PDFInfo
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- CN110964145A CN110964145A CN201911103155.7A CN201911103155A CN110964145A CN 110964145 A CN110964145 A CN 110964145A CN 201911103155 A CN201911103155 A CN 201911103155A CN 110964145 A CN110964145 A CN 110964145A
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- methacrylate
- acrylate
- microspheres
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- microsphere
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Images
Classifications
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Abstract
本发明公开了一种基于乙酰丙酮基的磁性聚合物微球及其制备方法。首先以乙酰乙酸甲基丙烯酸乙二醇酯和丙烯酸酯类单体共聚，加入交联剂、光引发剂、小分子RAFT试剂、交联剂，使用大分子的可逆加成‑断裂链转移剂作为稳定分散剂，通过RAFT光分散聚合，制备得到内部含有双乙酰丙酮基的交联聚合物微球。然后将交联聚合物微球在有机溶剂中溶胀后，利用微球内部的双乙酰丙酮基把金属离子吸附，在加热和催化剂作用条件下，进行原位氧化还原，得到内部载有磁性的聚合物微球。本发明的磁性聚合物微球，所述微球形状规则，粒径均匀，单分散性好，稳定性好，微球经过在溶剂中溶胀和还原后，微球粒径尺寸和粒径分布能够保持不变，具有较大的应用前景。
Description
技术领域
本发明涉及高分子材料技术领域，更具体地，涉及一种基于乙酰丙酮基的磁性聚合物微球及其制备方法。
背景技术
磁性聚合物微球通常由无机磁性材料和有机聚合物材料构成，是一种新型的无机/有机复合材料。无机磁性纳米颗粒给微球带来超顺磁性，使其能够在磁场作用下快速被分离；而有机聚合物使得纳米颗粒更加稳定，同时为后续的功能化应用提供了可能。磁性聚合物微球除了具有普通聚合物微球粒径均匀、比表面积大、稳定性好等特点，还具有磁响应性和表面功能性基团多样性，能够通过各种物理或化学方式高效地与目标化合物结合，在外磁场的作用下简单、快速的实现分离，可省去离心、过滤等繁杂操作，这对于在细胞标记分类、蛋白质提纯分离、医学治疗显像、药物释放和生物工程酶的固定化等领域的应用，具有独特的优势，也非常受国外专家、科研者们的关注。
根据磁性物质加入步骤和聚合物微球的形成的次序，磁性聚合物微球的制备方法大致可以分两种：一是先制备磁性无机粒子，加入到聚合物微球的聚合过程中，然后用适当的方法使之与聚合物结合获得磁性聚合物微球，主要有包埋法、无皂乳液聚合法等。这种方法得到的磁性微球是因为内部包含磁性颗粒二具有磁响应特征，制备过程简易，但是形状不规则，粒径范围广，且表面不含功能基团，限制了其进一步的应用。其次是两步法，典型的代表是溶胀法(原位法)，第一步是通过分散聚合、乳液聚合等传统方法制备交联的单分散微球，此微球中含有可与二价或三价铁离子形成配位键或离子键的基团如：-NH2，-COOH，-SO3H，-NO2等，第二步是使聚合物微球在铁离子的溶液中溶胀，铁离子经过渗透而被吸附、包埋，升高温度后，在合适催化剂下被原位氧化还原即可得到磁性聚合物微球；然而其可用的磁性组分有限，且功能单体的使用会对聚合物成核期有干扰，导致磁性微球形状不规则，粒径不均匀，无法得到单分散功能微球，且微球经过在溶剂中溶胀和还原后，微球粒径尺寸和粒径分布也会产生较大变化，无法满足实际需求。
发明内容
本发明的目的在于克服现有技术中存在的上述缺陷和不足，提供一种基于乙酰丙酮基的磁性聚合物微球的制备方法，通过使用乙酰乙酸甲基丙烯酸乙二醇酯(AAEM)与其他聚合单体一起，通过RAFT光分散聚合的方法一步制得了内部含有乙酰丙酮基的共聚交联微球，然后经过溶胀、吸附、还原等方法获得了磁性聚合物微球，所述微球形状规则，粒径均匀，单分散性好，稳定性好，微球经过在溶剂中溶胀和还原后，微球粒径尺寸和粒径分布能够保持不变。
本发明的第二个目的在于提供通过上述方法制备得到的磁性聚合物微球。
本发明的上述目的是通过以下技术方案给予实现的：
一种基于乙酰丙酮基的磁性聚合物微球的制备方法，包括如下步骤：
S1.在反应容器中，加入乙酰乙酸甲基丙烯酸乙二醇酯与丙烯酸酯类单体、稳定剂、光引发剂、可逆加成-断裂链转移剂(RAFT试剂)、交联剂，溶解于乙醇/水混合溶剂中，通氮气，密封反应容器，光源照射引发聚合反应，反应结束后即得到稳定的白色乳状液，离心，用乙醇/水混合液清洗，得到共聚微球。
S2.所步骤S1的共聚微球除去原有溶剂后置于反应容器在中，加入有机溶剂使微球充分溶胀，通氮气，冰浴；加入金属离子溶液，加热条件下，经过催化剂原位氧化还原后，获得内部载有磁性的功能聚合物微球。
本发明的关键在于使用了一种含有乙酰丙酮基的功能单体-乙酰乙酸甲基丙烯酸乙二醇酯(AAEM)，其含有可聚合的丙烯酸双键，能够进行自由基聚合，而且还含有的乙酰丙酮基还能够与铁、铜、锌、锡、镁、锰多种金属离子生成螯合物；原理上其它同时含有乙酰丙酮基与可自由基聚合双键(丙烯酸酯基、甲基丙烯酸酯基、苯乙烯基等)的单体均应该适用于本发明。本发明选用乙酰乙酸甲基丙烯酸乙二醇酯(AAEM)功能单体，与其他聚合单体一起，加入稳定剂、光引发剂、RAFT试剂、交联剂，在紫外光照射下进行分散聚合，制备得到内部含有双乙酰丙酮基的交联聚合物微球，将所获得微球再溶胀吸附金属离子后，经原位氧化还原，最终获得磁性聚合物微球。具体为在磁力搅拌作用下，金属离子进入到微球的内部，被乙酰丙酮基吸附、螯合，加热条件下，经过催化剂原位氧化还原后，获得内部载有磁性的功能聚合物微球。
优选地，聚合单体浓度为反应体系的5～20wt％，稳定剂浓度为聚合单体的0.1～15wt％，光引发剂浓度为聚合单体的1～10wt％，小分子RAFT试剂浓度为聚合单体的0.2～5wt％，交联剂浓度为聚合单体的的3wt％。
本发明可通过调节AAEM单体与其他单体的比例，改变微球内部乙酰丙酮的含量，从而改变聚合物微球的磁含量。具体优选地，当AAEM单体与其他单体的比例为1:1时，得到的聚合物微球的磁含量为22％。
优选地，所述丙烯酸酯类单体为丙烯酸甲酯、丙烯酸乙酯、丙烯酸异冰片酯、丙烯酸丁酯、丙烯酸月桂酯、丙烯酸-2-羟乙酯、丙烯酸缩水甘油酯、丙烯酸异丁酯、丙烯酸异癸酯、丙烯酸异辛酯或丙烯酸-2-羟丙酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸异冰片酯、甲基丙烯酸丁酯、甲基丙烯酸月桂酯、甲基丙烯酸-2-羟乙酯、甲基丙烯酸缩水甘油酯、甲基丙烯酸异丁酯、甲基丙烯酸异癸酯、甲基丙烯酸异辛酯、甲基丙烯酸二甲基氨基乙酯或甲基丙烯酸-2-羟丙酯中的任意一种。
优选地，所述稳定剂为聚乙烯吡咯烷酮或亲水性的大分子RAFT试剂；例如聚丙烯酸-三硫代碳酸酯(PAA-TTC)，聚丙烯酸羟乙酯-三硫代碳酸酯(PHEA-TTC)，聚N,N-二甲基丙烯酰胺-三硫代碳酸酯(PDMA-TTC)，聚甲氧基乙二醇丙烯酯-三硫代碳酸酯(PmPEGA-TTC)等。
优选地，所示光引发剂为普通的商品化自由基光引发剂，例如α,α-二甲氧基-α-苯基苯乙酮(又称α,α-二甲基苯偶酰缩酮，Ciba公司商品名为Irgacure 651)，2-羟基-2-甲基-1-苯基丙酮-1(Ciba公司商品名为Darocur 1173)，1-羟基-环己基苯酮(Ciba公司商品名为Irgacure 184)，2-甲基-1-[4-甲巯基苯基]-2-吗啉丙酮-1(Ciba公司商品名为Irgacure 907)，2-苯基-2-二甲氨基-1-(4-吗啉苯基)-丁酮-1(Ciba公司商品名为Irgacure 369)，2,4,6-三甲基苯甲酰基-二苯基氧化膦(TPO)，苯基双(2,4,6-三甲基苯甲酰基)氧化膦(BAPO)等。原理上来说，现有的已商品化自由基光引发剂都适用于本发明。光引发剂的用量不受特别限制，可根据实际情况选用合适的用量，例如，对于Darocur 1173，其用量相对于单体的重量百分含量可以是0.5～5％，更优选是1～3％。除此之外，还可以采用适用于(甲基)丙烯酰氧基的交联反应的其他公知的光引发剂。
优选地，所述交联剂为二缩丙二醇双丙烯酸酯(DPGDA)、三羟基甲烷三丙烯酸酯(TMPTA)或其它常规的含两个或两个以上可自由基聚合双键的化合物。
本发明的原理是利用RAFT试剂控制共聚分子链的增长，克服了功能单体的加入对成核期的干扰，从而得到单分散功能微球。原理上，其它具有可控/“活性”特征的聚合方法如原子转移自由基聚合(ATRP)都可用于控制成核期，但RAFT聚合具有更广泛的单体普适性，可用于制备多种聚合物微球。
在本发明制备基于乙酰丙酮基的磁性聚合物微球的过程中，所述的RAFT试剂一般为二硫代甲酸酯或三硫代甲酸酯类化合物，其化学通式为：
其中，R、R1和R2称为离去基团，Z为活化基团。典型的离去基团包括烷基，
典型的活化基团包括芳基、胺基、烷氧基等。
原理上来说，上述二硫代甲酸酯类及三硫代甲酸酯类RAFT试剂都适用于本发明。RAFT试剂相对于单体的用量可以在0.1～5.0％(重量百分含量，下同)之间调节，较理想的用量为0.25～1.0％。RAFT试剂的合成采用通用的合成方法即可，本领域技术人员知道如何合成RAFT试剂，在此不再赘述。
优选地，所述分子RAFT试剂为S-1-十二烷基-S′-(α,α′-二甲基-α″-乙酸)三硫代碳酸酯。
优选地，所述乙醇/水混合溶剂中乙醇与水的重量比为20:80～80:20。
优选地，所述光源为中压汞灯、紫外光无极灯、金属卤素灯或UV-LED光源，光强为0.2～100mW/cm2。
优选地，考虑到由于镍、钴等存在毒性，在生物、医药等领域的应用受到严格限制，而铁的氧化物(Fe3O4)，Fe2O3)因其低毒(LD50约2000mg/kg体重，远远高于目前临床应用剂量)、易得等特点通常被用作磁性聚合物微球的磁性组分，所以所述金属离子为Fe2+和Fe3+；具体地，所述铁离子和亚铁离子为FeCl3.6H2O和FeCl2.4H2O。
优选地，所述的有机溶剂包括N,N-二甲基甲酰胺、乙腈、二甲基亚砜、二氧六环或四氢呋喃等。
优选地，所述催化剂包括氨水、三乙胺、吡啶等
本发明还请求保护上述任一所述制备方法制备得到的磁性聚合物微球。所述磁性聚合物微球粒径均匀，平均粒径为700nm，单分散性好。
与现有技术相比，本发明具有以下有益效果：
本发明提供了一种基于乙酰丙酮基的磁性聚合物微球的制备方法，乙酰丙酮基含有可聚合的丙烯酸双键，能够进行自由基聚合，而且还含有的乙酰丙酮基还能够与铁、铜、锌、锡、镁、锰多种金属离子生成螯合物，金属离子被吸附、包裹在微球内部，通过氧化还原形成的磁性微球非常稳定。本法可以通过调节AAEM单体与其他单体的比例，改变微球内部乙酰丙酮的含量，从而改变聚合物微球的磁含量。本发明获制备到的磁性微球形状规则，粒径均匀，单分散性好，稳定性好，此外由于交联的作用，微球经过在溶剂中溶胀和还原后，微球粒径尺寸和粒径分布能够保持不变。
附图说明
图1为实施例1聚合物微球SEM图。
图2为实施例2聚合物微球SEM图。
图3为实施例3聚合物微球SEM图。
图4为磁性聚合物微球的磁性吸附效果。
图5为磁性聚合物微球SEM图。
图6为磁性聚合物微球TEM图。
图7为磁性聚合物中磁含量的测试图。
具体实施方式
以下结合说明书附图和具体实施例来进一步说明本发明，但实施例并不对本发明做任何形式的限定。除非特别说明，本发明采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。
除非特别说明，以下实施例所用试剂和材料均为市购。
实验例1交联P(AAEM+MMA)共聚微球的制备
乙醇/水混合物的重量比40/60(7.2g+10.8g)被引入25mL的圆底烧瓶中作为溶剂，然后加入1.0g的甲基丙烯酸甲酯(MMA)单体(5wt％相对于体系)，1.0g的乙酰乙酸甲基丙烯酸乙二醇酯(AAEM)单体(5wt％相对于体系)，0.30g的稳定分散剂聚丙烯酸三碳酸酯(PAA-TTC)(15wt％相对于单体)，0.005g的S-1-十二烷基-S′-(α,α′-二甲基-α″-乙酸)三硫代碳酸酯(DDMAT)(0.25wt％相对于单体)、0.06g的Darocur 1173(3wt％相对于单体)和0.06g二丙二醇二丙烯酸(3wt％相对于单体)，磁力搅拌溶解。
反应混合物用氮气除氧30分钟，用带有石英玻璃片的玻璃塞密封，然后在持续搅拌下以365nm波长的LED灯(光强度2.5mW/cm2)从圆底烧瓶顶部照射3小时。产物采用离心法分离，用乙醇/水(50/50，w/w)清洗，反复离心洗涤2～3次，得到交联聚合物微球。所述产物的扫描电子显微镜照片(SEM)如图1所示，所得微球单分散性良好，粒径在500nm左右。
实验例2交联P(AAEM+MMA)共聚微球的制备
本实施例使用的稳定分散剂为(聚N,N-二甲基丙烯酰胺-三硫代碳酸酯)PDMA-TTC代替实施例1中的PAA-TTC，其余试剂种类和用量以及实施过程与实施例1相同。所得产物的扫描电子显微镜照片(SEM)见图2，所得微球单分散性良好，粒径在700nm左右。
实验例3交联P(AAEM+MMA)共聚微球的制备
本实施例使用的稳定分散剂为聚乙烯吡咯烷酮(PVP)代替实施例1中的PAA-TTC，其余试剂种类和用量以及实施过程与实施例1相同。所得产物的扫描电子显微镜照片(SEM)见图3，所得微球单分散性良好，粒径在1.0μm左右。
实验例4交联P(AAEM+MMA)共聚微球的制备
乙醇/水混合物的重量比40/60(6.8g+10.2g)被引入25mL的圆底烧瓶中作为溶剂，然后加入2.0g的甲基丙烯酸甲酯(MMA)单体(10wt％相对于体系)，1.0g的乙酰乙酸甲基丙烯酸乙二醇酯(AAEM)单体(5wt％相对于体系)，0.30g的稳定分散剂聚丙烯酸三碳酸酯(PAA-TTC)(10wt％相对于单体)，0.03g的S-1-十二烷基-S′-(α,α′-二甲基-α″-乙酸)三硫代碳酸酯(DDMAT)(1wt％相对于单体)、0.03g的Darocur 1173(1wt％相对于单体)和0.09g二丙二醇二丙烯酸(3wt％相对于单体)，磁力搅拌溶解。
，磁力搅拌溶解。
反应混合物用氮气除氧30分钟，用带有石英玻璃片的玻璃塞密封，然后在持续搅拌下以365nm波长的LED灯(光强度2.5mW/cm2)从圆底烧瓶顶部照射3小时。产物采用离心法分离，用乙醇/水(50/50，w/w)清洗，反复离心洗涤2～3次，得到交联聚合物微球。
实验例5交联P(AAEM+MMA)共聚微球的制备
乙醇/水混合物的重量比40/60(6.4g+9.6g)被引入25mL的圆底烧瓶中作为溶剂，然后加入3.0g的甲基丙烯酸甲酯(MMA)单体(15wt％相对于体系)，1.0g的乙酰乙酸甲基丙烯酸乙二醇酯(AAEM)单体(5wt％相对于体系)，0.04g的稳定分散剂聚丙烯酸三碳酸酯(PAA-TTC)(1wt％相对于单体)，0.04g的S-1-十二烷基-S′-(α,α′-二甲基-α″-乙酸)三硫代碳酸酯(DDMAT)(1wt％相对于单体)、0.2g的Darocur 1173(5wt％相对于单体)和0.12g二丙二醇二丙烯酸(3wt％相对于单体)，磁力搅拌溶解。
反应混合物用氮气除氧30分钟，用带有石英玻璃片的玻璃塞密封，然后在持续搅拌下以365nm波长的LED灯(光强度2.5mW/cm2)从圆底烧瓶顶部照射3小时。产物采用离心法分离，用乙醇/水(50/50，w/w)清洗，反复离心洗涤2～3次，得到交联聚合物微球。
实验例6磁性聚合物微球的制备
(1)取实施例1所获得的交联共聚微球2mL固含量(5％)离心除去原有溶剂后，加入N,N-二甲基甲酰胺溶剂10mL，分散于25mL的圆底烧瓶，使微球充分溶胀，通氮气15分钟，冰浴。
(2)FeCL3·6H2O(0.04g，0.15mmol)和FeCL2·4H2O(0.026g，0.18mmol)溶于N,N-二甲基甲酰胺溶剂(5mL)后加入至步骤(1)的溶液中，撤掉冰浴，继续搅拌反应1h。然后将反应移至油浴中加热至60℃，加入0.5mL氨水，搅拌1h，冷却至常温，离心，并用0.1M HCl洗2～3次后，将微球再次分散在乙醇/水(40/60，w/w)混合溶剂中。
所得产物在磁场作用下被吸附移动，其部分结果图4，所得产物的扫描电子显微镜(SEM)和透视电镜(TEM)结果分别见图5和图6所示，所得微球大小均匀，粒径大小在500nm左右，单分散性良好。
实施例7磁性微球磁含量的测试
聚合物微球的磁含量通过热重分析测得，AAEM单体与MMA单体含量为1:1时，所得磁性微球中磁性物的质量分数约为22％。调节AAEM单体与MMA单体的比例为1：2或1：3，得到微球内部乙酰丙酮的含量大约为17％，如图7所示。
Claims (11)
1.一种基于乙酰丙酮基的磁性聚合物微球的制备方法，其特征在于，包括如下步骤：
S1.在反应容器中，加入乙酰乙酸甲基丙烯酸乙二醇酯与丙烯酸酯类单体、稳定剂、光引发剂、可逆加成-断裂链转移剂、交联剂，溶解于乙醇/水混合溶剂中，通氮气，密封反应容器，光源照射引发聚合反应，反应结束后即得到稳定的白色乳状液，离心，用乙醇/水混合液清洗，得到共聚微球。
S2.所步骤S1的共聚微球除去原有溶剂后置于反应容器在中，加入有机溶剂使微球充分溶胀，通氮气，冰浴；加入金属离子溶液，加热条件下，经过催化剂原位氧化还原后，获得内部载有磁性的功能聚合物微球。
2.根据权利要求1所述的制备方法，其特征在于，聚合单体浓度为反应体系的5～20wt％，稳定剂浓度为聚合单体的0.1～15wt％，光引发剂浓度为聚合单体的1～10wt％，小分子RAFT试剂浓度为聚合单体的0.2～5wt％，交联剂浓度为聚合单体的的3wt％。
3.根据权利要求1或2所述的制备方法，其特征在于，所述丙烯酸酯类单体为丙烯酸甲酯、丙烯酸乙酯、丙烯酸异冰片酯、丙烯酸丁酯、丙烯酸月桂酯、丙烯酸-2-羟乙酯、丙烯酸缩水甘油酯、丙烯酸异丁酯、丙烯酸异癸酯、丙烯酸异辛酯或丙烯酸-2-羟丙酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸异冰片酯、甲基丙烯酸丁酯、甲基丙烯酸月桂酯、甲基丙烯酸-2-羟乙酯、甲基丙烯酸缩水甘油酯、甲基丙烯酸异丁酯、甲基丙烯酸异癸酯、甲基丙烯酸异辛酯、甲基丙烯酸二甲基氨基乙酯或甲基丙烯酸-2-羟丙酯。
4.根据权利要求1或2所述的制备方法，其特征在于，所述稳定剂为聚乙烯吡咯烷酮或亲水性的大分子RAFT试剂。
5.根据权利要求1或2所述的制备方法，其特征在于，所示光引发剂为α,α-二甲氧基-α-苯基苯乙酮，2-羟基-2-甲基-1-苯基丙酮-1，1-羟基-环己基苯酮，2-甲基-1-[4-甲巯基苯基]-2-吗啉丙酮-1，2-苯基-2-二甲氨基-1-(4-吗啉苯基)-丁酮-1，2,4,6-三甲基苯甲酰基-二苯基氧化膦或苯基双(2,4,6-三甲基苯甲酰基)氧化膦。
6.根据权利要求1或2所述的方法，其特征在于，所述分子RAFT试剂为S-1-十二烷基-S′-(α,α′-二甲基-α″-乙酸)三硫代碳酸酯。
7.根据权利要求1或2所述的方法，其特征在于，所述的交联剂为二丙二醇二丙烯酸或三羟基甲烷三丙烯酸酯。
8.根据权利要求1或2所述的方法，其特征在于，所述乙醇/水混合溶剂中乙醇与水的重量比为20:80～80:20。
9.根据权利要求1或2所述的方法，其特征在于，所述光源为中压汞灯、紫外光无极灯、金属卤素灯或UV-LED光源，光强为0.2～100mW/cm2。
10.根据权利要求1或2所述的方法，其特征在于，所述金属离子为Fe2+和Fe3+。
11.权利要求1～10任一所述方法制备得到的磁性聚合物微球。
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