CN109134737B - 一种负载稀土离子的交联聚合物微球及其制备方法 - Google Patents
一种负载稀土离子的交联聚合物微球及其制备方法 Download PDFInfo
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- CN109134737B CN109134737B CN201810709487.9A CN201810709487A CN109134737B CN 109134737 B CN109134737 B CN 109134737B CN 201810709487 A CN201810709487 A CN 201810709487A CN 109134737 B CN109134737 B CN 109134737B
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
本发明公开了一种负载稀土离子的交联聚合物微球及其制备方法。首先在氮气气氛下及紫外光照下,甲基丙烯酸甲酯聚合单体在溶有小分子链转移剂、稳定分散剂、交联剂、光引发剂及含乙酰丙酮基团的功能共聚单体的反应介质中进行聚合反应,制备得到含有乙酰丙酮基团的交联聚合物微球,然后利用含有乙酰丙酮基团的交联聚合物微球中乙酰丙酮基团对稀土离子的络合作用制得单分散性的负载稀土离子的交联聚合物微球,所述方法工艺简单,操作方便,适合工业化生产,具有较大的应用前景。
Description
技术领域
本发明涉及功能材料技术领域,更具体地,涉及一种负载稀土离子的交联聚合物微球及其制备方法。
背景技术
粒径单分散的稀土/聚合物复合微球,可作为金属编码微球用于质谱流式细胞仪,在生物医学领域如免疫检测等方面有广泛的应用。
负载稀土离子的聚合物微球的制备,一般是先制备含可聚合双键的稀土配合物或稀土纳米粒子,然后利用所得稀土配合物或纳米粒子和有机单体进行分散聚合,形成复合微球(Macromolecules, 2015, 48(11): 3629-3640)。这种方法的一个弱点是可聚合稀土配合物在分散聚合中将会干扰成核过程甚至微球增长过程,导致所得微球的粒径均一性降低,当稀土添加量较高时甚至难以得到微球。这样限制了微球中的稀土元素含量的可调控性,不利于编码微球的制备。此外,该方法还需要预先制备可参与聚合的稀土配合物或稀土纳米粒子,增加了制备过程的复杂性。
发明内容
本发明所要解决的技术问题是克服上述现有稀土/聚合物复合微球制备方法存在的缺陷和不足,提供一种制备工艺简单、稀土离子负载量较高、耐溶剂性好、微球形貌规整、粒径单分散的交联聚合物微球及其制备方法。通过预先制备含有乙酰丙酮基团的交联聚合物微球,利用乙酰丙酮基团对稀土离子的络合作用制得单分散性的稀土交联微球,工艺简单,操作方便,适合工业化生产。
本发明的第一个目的是提供一种含有乙酰丙酮基团的交联聚合物微球。
本发明的第二个目的是提供一种负载稀土离子的交联聚合物微球。
本发明的上述目的是通过以下技术方案给予实现的:
一种含有乙酰丙酮基团的交联聚合物微球的制备方法,在氮气气氛及紫外光照下,将甲基丙烯酸甲酯聚合单体在溶有小分子链转移剂、稳定分散剂、交联剂、光引发剂及含乙酰丙酮基团的功能共聚单体的反应介质中进行聚合反应,得到所述交联聚合物微球。
本发明使用甲基丙烯酸甲酯作为聚合单体,含乙酰丙酮基团的单体作为共聚单体,在可逆加成-断裂链转移剂的存在下进行光引发分散聚合,同时,还加入了作为交联剂的多官能团单体参与聚合反应,制备得到单分散性的交联聚合物微球。其中的乙酰丙酮基可以很好地与稀土离子形成配合物,从而把稀土离子稳定地负载在聚合物微球里面。所得交联微球可以在溶剂中充分溶胀,从而使稀土离子顺利迁移到微球内部并与乙酰丙酮基团相结合。通过改变稀土离子的加入量和微球中乙酰丙酮基团的数量,可以制备不同稀土离子含量的交联聚合物微球。
具体地,是以甲基丙烯酸甲酯(MMA)为聚合单体,加入含乙酰丙酮基团的功能共聚单体,添加稳定分散剂及少量的小分子RAFT试剂,同时,加入交联剂和光引发剂,溶解于乙醇/水混合溶剂中,通氮气后用石英玻璃片做成的盖子密封,在紫外光照下进行分散聚合,得到稳定的白色乳状液,离心分离后,再用乙醇/水混合液清洗,得到交联聚合物微球。
优选地,所述含乙酰丙酮基团的功能单体为甲基丙烯酸乙酰乙酰氧基乙酯、2-(丙烯酰氧基)乙基乙酰乙酸酯、1-甲基-2 - [(1-氧代烯丙基)氧基]乙基乙酰乙酸酯、甲氧基丁二酸二乙酯、乙酰乙酸烯丙酯中的一种或几种。
优选地,所述甲基丙烯酸甲酯聚合单体和含乙酰丙酮基团的功能单体的用量为整个反应体系的5~20wt%。
优选地,所述甲基丙烯酸甲酯和含乙酰丙酮基团的功能单体的摩尔比为3:7~9:1。
优选地,所述稳定分散剂为聚乙烯吡咯烷酮(PVP)、聚乙烯醇(PVA)、聚丙烯酸(PAA)、纤维素衍生物、聚乙二醇型大分子RAFT试剂(mPEGA-TTC)、聚丙烯酸型大分子RAFT试剂(PAA-TTC)、聚丙烯酰胺型大分子RAFT试剂(PDMA-TTC)中的一种,但不局限于此,原理上,用于分散聚合的稳定分散剂都可用于本发明。
更优选地,所述稳定分散剂为聚乙二醇型大分子RAFT试剂(mPEGA-TTC),其结构式如下式(I)所示:
优选地,所述稳定分散剂的用量为单体总量的5%~30%。
优选地,小分子链转移剂为S,S'-双(2-甲基-2 -丙酸基)三硫代碳酸酯(BDMAT)、S-十二烷基-S' -(2-甲基-2丙酸基)三硫代碳酸酯 (DDMAT)、S-乙基-S' -(2-二甲基-2丙酸基)三硫代碳酸酯(EDMAT)、三硫代碳酸二苄酯(DBTTC)中的一种。
更优选地,所述小分子RAFT试剂为S-十二烷基-S' -(2-甲基-2丙酸基)三硫代碳酸酯(DDMAT),其结构式如下式(II)所示:
优选地,所述小分子链转移剂的用量为单体总量的0.05%~5 wt%。
更优选地,所述小分子链转移剂的用量为单体总量的0.1 %~1 wt%。
优选地,所述交联剂为二丙二醇二丙烯酸酯、三丙二醇二丙烯酸酯、1,6-己二醇双丙烯酸酯、1,6-己二醇双甲基丙烯酸酯、二乙二醇双丙烯酸酯、二乙二醇双甲基丙烯酸酯、三乙二醇双丙烯酸酯、三乙二醇双甲基丙烯酸酯、三羟甲基丙烷三丙烯酸酯、三羟甲基丙烷三甲基丙烯酸酯、三(2-羟乙基)异氰酸酯三丙烯酸酯中的一种。
优选地,所述交联剂的用量为单体总量的0.5%~10wt %。
更优选地,所述交联剂的用量为单体总量的1 %~5wt %。
优选地,所述光引发剂为普通的商品化自由基光引发剂,例如:a,a-二甲氧基-a-苯基苯乙酮(又称a,a-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。优选地,所述光引发剂的用量为单体总量的的1%~10 wt %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 wt %,更优选是1~3 wt %。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,所述引发光源为中压汞灯、紫外光无极灯、金属卤素灯或UV-LED光源。
更优选地,所述引发光源为辐射波长为365nm的UV-LED灯源。
优选地,所述引发光源的光强为0.5~30mW/cm2;更优选地,所述引发光源的光强为2~10mW/cm2。
优选地,所述反应时间为0.5~10h;更优选地,所述反应时间为1~5h。
同时,由上述任一制备方法制备得到的含有乙酰丙酮基团的交联聚合物微球也在本发明保护范围内。
本发明制备得到的含有乙酰丙酮基团的交联聚合物微球,其中的乙酰丙酮基可以很好地与稀土离子形成配合物,从而把稀土离子稳定地负载在聚合物微球里面。所得交联微球可以在溶剂中充分溶胀,从而使稀土离子顺利迁移到微球内部并与乙酰丙酮基团相结合。通过改变稀土离子的加入量和微球中乙酰丙酮基团的数量,可以制备不同稀土离子含量的交联聚合物微球。
因此,所述含有乙酰丙酮基团的交联聚合物微球在制备负载稀土离子的交联聚合物微球中的应用也在本发明保护范围内。
一种负载稀土离子的交联聚合物微球的制备方法,是将上述任一所述含有乙酰丙酮基团的交联聚合物微球分散液稀释,并调节PH=7~8,然后向其中缓慢滴加稀土离子溶液,20~90℃(优选30~70℃)反应2~10h(优选3~6h),再经过反复离心洗涤、真空干燥处理后,得到负载稀土离子的交联聚合物微球。
具体地,包括如下步骤:
S1.将含稀土的化合物在去离子水中溶解,配成稀土离子溶液;
S2.将上述含有乙酰丙酮基团的交联聚合物微球分散液在溶剂中按一定比例稀释,并调节溶液的PH=7~8;用恒压滴液漏斗缓慢滴加步骤S1得到的稀土离子溶液,油浴加热条件下磁力搅拌,经过反复离心洗涤、真空干燥处理后,得到负载稀土离子的交联聚合物微球。
优选地,所述含稀土的化合物包括镧、铽、铕、铈、镨、钕、钐、钆、镝、钬、铒、铥、镱、镥的氯化物、氟化物、硝酸盐、醋酸盐及其水合物中的一种或几种。
优选地,所述稀土离子溶液浓度为1~30mol/L。
优选地,所述溶剂为N,N-二甲基甲酰胺、丙酮、丁酮、四氢呋喃、二氯甲烷、氯仿、乙酸乙酯、1’4-二氧六环、二甲基亚砜中的一种或几种。
优选地,所述离心速度为4000~10000转/min,时间1~3min。
本发明还请求保护上述任一所述方法制备得到的负载稀土离子的交联聚合物微球,其平均粒径为0.5~2μm。
与现有技术相比,本发明具有以下有益效果:
(1)本发明提供了一种含有乙酰丙酮基团的交联聚合物微球,其中的乙酰丙酮基可以很好地与稀土离子形成配合物,从而把稀土离子稳定地负载在聚合物微球里面。所得交联微球可以在溶剂中充分溶胀,从而使稀土离子顺利迁移到微球内部并与乙酰丙酮基团相结合,从而利用乙酰丙酮基团对稀土离子的络合作用制得单分散性的稀土交联微球,工艺简单,操作方便,适合工业化生产。
(2)本发明通过改变稀土离子的加入量和微球中乙酰丙酮基团的含量,可以制备不同稀土离子含量的交联微球,可应用于生物检测等领域。
附图说明
图1是本发明实施例1提供的含有乙酰丙酮基团的交联聚合物微球的扫描电镜图(SEM)。
图2是本发明实施例2提供的负载稀土离子的交联聚合物微球的扫描电镜图(SEM)。
图3是本发明实施例3提供的负载稀土离子的交联聚合物微球的扫描电镜图(SEM)。
图4是本发明实施例4提供的负载稀土离子的交联聚合物微球的扫描电镜图(SEM)。
图5是本发明实施例4提供的负载稀土离子的交联聚合物微球的荧光发射光谱。
图6是本发明实施例4提供的交联聚合物微球的热重曲线。
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。
实施例1 制备含有乙酰丙酮基团的交联聚合物微球
1、制备方法
在50mL圆底烧瓶中,加入甲基丙烯酸甲酯单体(MMA,1.2g,6%相对于整个反应体系),甲基丙烯酸乙酰乙酰氧基乙酯单体(AAEM,0.8g,4%相对于整个反应体系),光引发剂D1173(0.06g,3%相对于单体),聚乙二醇型大分子RAFT试剂(mPEGA-TTC,0.3g,15%,相对于单体),DDMAT(0.005g,0.25%,相对于单体),交联剂二丙二醇二丙烯酸酯(DPGDA,0.06g、3%,相对于单体)溶解于乙醇/水(7.2g/10.8g,40/60,w/w)混合溶剂中,通氮气20min后用石英玻璃塞密封。
然后用365nm的UV-LED点光源(光强为0.8mW/cm2)从反应器的顶端光照3h。光照结束后,得到稳定的白色乳液,用12000转/min的离心机离心分离,并用乙醇/水(40/60,w/w)混合溶液清洗三次后得到交联微球,在乙醇/水混合溶液中保存。
2、所得产物扫描电镜图(SEM)如附图1所示。结果表明,该交联聚合物微球形貌规整、粒径单分散。
实施例2 制备负载稀土离子的交联聚合物微球
1、制备方法
将EuCl3•6H2O(0.007g,0.02mmol)溶解在5mL去离子水中,超声震荡溶解,得到无色透明的Eu3+溶液。
在25mL圆底烧瓶中加入实施例1制备得到的交联微球分散液1g(固含量约10%),用N,N-二甲基甲酰胺(DMF)作为溶胀剂稀释10倍,用NaOH水溶液(10%,w)调节PH=7-8,用恒压滴液漏斗缓慢滴加EuCl3•6H2O水溶液,60°C油浴加热5h,磁力搅拌,反应结束后,将混合物离心(5000转/min)1min,然后用去离子水将微球洗涤三次(先超声震荡,再离心,去上清液,再加去离子水重复震荡、离心),然后真空干燥,得到负载稀土离子的交联聚合物微球。
2、所得产物扫描电镜图(SEM)见图2。
实施例3 制备负载稀土离子的交联聚合物微球
本实施例使用EuCl3•6H2O用量为(0.018g,0.05mmol)代替实施例2中的(0.007g,0.02mmol),其余试剂种类和用量以及实施过程与实施例2相同。所得产物的扫描电子显微镜照片(SEM)见图3。
实施例4 制备负载稀土离子的交联聚合物微球
本实施例使用EuCl3•6H2O用量为(0.029g,0.08mmol)代替实施例2中的(0.007g,0.02mmol),其余试剂种类和用量以及实施过程与实施例2相同。所得产物的扫描电子显微镜照片(SEM)见图4。
所述实施例2~实施例4制备得到的负载稀土离子的交联聚合物微球的的荧光发射光谱如图5所示。结果表明,该聚合物微球在612nm附近出现了荧光发射峰(Eu的荧光发射特征峰),不同稀土离子用量的聚合物微球,荧光发射峰强度各不相同。
所述实施例1~实施例4制备得到的交联聚合物微球的热重曲线如图6所示。结果表明,随着稀土离子含量的增加,残余质量分数逐渐增大。通过改变稀土离子的加入量可以得到不同稀土离子含量的聚合物微球。
Claims (6)
1.一种负载稀土离子的交联聚合物微球的制备方法,其特征在于,包括如下步骤:
S1.在氮气气氛及紫外光照下,将甲基丙烯酸甲酯聚合单体在溶有小分子链转移剂、稳定分散剂、交联剂、光引发剂及含乙酰丙酮基团的功能单体的反应介质中进行聚合反应,得到所述交联聚合物微球;
S2.将所述含有乙酰丙酮基团的交联聚合物微球的分散液稀释,并调节pH=7~8,然后向其中缓慢滴加稀土离子溶液,20~90℃反应2~10h,再经过反复离心洗涤、真空干燥处理后,得到所述负载稀土离子的交联聚合物微球;
所述含乙酰丙酮基团的功能单体为甲基丙烯酸乙酰乙酰氧基乙酯、2-(丙烯酰氧基)乙基乙酰乙酸酯、乙酰乙酸烯丙酯中的一种或几种。
2.根据权利要求1所述的制备方法,其特征在于,所述甲基丙烯酸甲酯聚合单体和含乙酰丙酮基团的功能单体的用量为整个反应体系的5~20wt%;所述甲基丙烯酸甲酯和含乙酰丙酮基团的功能单体的摩尔比为3:7~9:1。
3.根据权利要求1所述的制备方法,其特征在于,所述稳定分散剂的用量为单体总量的5%~30wt%;所述小分子链转移剂的用量为单体总量的0.05%~5wt%;所述光引发剂的用量为单体总量的1%~10wt%;所述交联剂的用量为单体总量的0.5%~10wt%。
4.根据权利要求1所述的制备方法,其特征在于,所述稀土离子溶液中的含稀土的化合物为镧、铽、铕、铈、镨、钕、钐、钆、镝、钬、铒、铥、镱、镥的氯化物、氟化物、硝酸盐、醋酸盐及其水合物中的一种或几种。
5.根据权利要求1所述的制备方法,其特征在于,所述稀土离子溶液浓度为1~30mol/L。
6.权利要求1~5任一所述方法制备得到的负载稀土离子的交联聚合物微球。
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