CN100553757C - 一种单分散含膦配体中空微胶囊的制备方法 - Google Patents
一种单分散含膦配体中空微胶囊的制备方法 Download PDFInfo
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Abstract
本发明属于功能高分子材料制备技术领域,涉及到一种单分散含膦配体中空微胶囊的制备方法。其特征在于:疏水性含膦配体结构的单体、引发剂与疏水性交联剂及有机溶剂为分散相(O),以含SDS的PVA水溶液为连续相(W),将分散相(O)利用外加压力,通过亲水SPG(Shirasu porous glass)膜分散到连续相(W)中,得到稳定的粒径单分散的O/W型乳状液;引发聚合后,再经离心分离和溶剂蒸发,获得微胶囊。本发明通过SPG膜乳化方法与溶剂蒸发法制备含膦配体中空微胶囊,该方法制备的微胶囊不仅粒径可控、单分散性好、壳层厚度可调,而且一步法向微胶囊内引入膦配体。本发明所制得微胶囊的这种结构特点,将提高负载催化剂的稳定性及催化效果的重现性。
Description
技术领域
本发明属于功能高分子材料化学技术领域,涉及到负载贵重过渡金属催化剂用微胶囊。具体地说是一种单分散含膦配体中空微胶囊的制备方法,通过SPG膜乳化方法与溶剂蒸发法制备含膦配体中空微胶囊,所得微胶囊粒径可控、单分散性好、壳层厚度可调,一步法向微胶囊内引入膦配体。
背景技术
近些年,在医药、食品、涂料、油墨、粘合剂等领域,得到广泛应用的“微胶囊技术”,已被应用于催化化学领域,用作催化剂载体。最初,Kobayashi教授等将传统的微胶囊化技术,应用于制备负载过渡金属催化剂,即利用聚苯乙烯高分子材料的物理性包裹作用及芳环的配位作用,形成了被聚苯乙烯高分子材料包裹的[Pd(PPh3)]催化剂,该催化剂不仅呈多分散性,而且需要向反应体系中不断地添加膦配体,以实现负载催化剂的重复使用,但配体流失现象明显[Akiyama,R.;Kobayashi,S.Angew.Chem.Int.Ed.2001,40,3469.]。Ley等人采用界面聚合的方法制备了聚脲类微胶囊包裹的过渡金属钯催化剂,但很难控制聚合反应过程中生成微胶囊的粒径分布,催化剂在反应体系中的分散性差[Ley,S.V.;Ramarao,C.;Gordon,R.S.;Holmes,A.B.;Morrison,A.J.;McConvey,I.F.;Shirley,I.M.;Smith,S.C.;Smith,M.D.Chem.Commun.2002,1134.]。之后,Kaneda教授等合成了一种具有空腔结构的树枝状高分子材料,这种材料虽然能够很好的负载金属催化剂,提高催化剂在反应体系中的分散度,但是其合成需要通过繁琐的化学反应过程,并且材料本身热稳定性差,很容易热降解[Ooe,M.;Murata,M.;Mizugaki,T.;Ebitani,K.;Kaneda,K.J.Am.Chem.Soc.,2004,126,1604.]。近期,Eiser等采用层层自组装的方法,合成了类似于生物细胞结构的中空聚电解质微胶囊,被负载的金属Pd纳米簇分布在壳层间,其在催化反应过程中,具有明显的凝聚现象,缺乏稳定性[Turkenburg,D.H.;Antipov,A.A.;Thathagar,M.B.;Rothenberg,G.;Sukhorukov,G.B.;Eiser,E.Phys.Chem.Chem.Phys.,2005,7,2237.]。
发明内容
本发明的目的是提供一种对热稳定、粒径可控、单分散性好、壳层厚度可调、内部含膦配体的中空微胶囊载体材料及其制备方法,解决负载催化剂流失和反应体系中分散性差的问题。
本发明采用的技术方案:
一种单分散含膦配体中空微胶囊的制备方法,以疏水性含膦配体结构的单体、引发剂与疏水性交联剂及有机溶剂为分散相(O),以含SDS的PVA水溶液为连续相(W),将分散相(O)利用外加压力,通过亲水SPG膜分散到连续相(W)中,得到稳定的粒径单分散的O/W型乳状液;引发聚合后,再离心分离和溶剂蒸发,从悬浮液中分离;通过选择不同孔径大小的SPG膜,调节分散相(O)中有机溶剂的用量,利用聚合物单体的疏水亲油性,获得对热稳定、粒径可控、单分散性好、壳层厚度可调、内含膦配体的中空微胶囊。
具体操作过程:
1)以疏水性含膦配体结构的单体、引发剂与疏水性交联剂及有机溶剂为分散相(O),其中疏水性含膦配体结构的单体与疏水性交联剂的混合有机溶液浓度是200~800g/L,疏水性含膦配体结构的单体占疏水性含膦配体结构的单体和疏水性交联剂总重量的2~98%,引发剂是偶氮二异丁氰AIBN或过氧化苯甲酰BPO,用量占单体总重量的0.3~10%;
2)配制含十二烷基硫酸钠SDS的聚乙烯醇PVA水溶液为连续相(W),PVA和SDS的浓度分别是5~100g/L以及0.1~2g/L;
3)选择孔径分别是0.9~5.4μm的SPG膜,以压缩氮气为压力源,使分散相通过孔径均一的微孔SPG膜分散到连续相(W)中,制得稳定的粒径单分散的O/W型乳状液,分散相和连续相的体积比是1∶30~1∶10,压力是2.0~50kPa,其中SPG膜是日本SPG Technology公司生产,主成分是B2O3-CaO-Al2O3-SiO2的玻璃经高温相分离,酸洗脱出B2O3-CaO相后形成的无机膜管,膜表面具有亲水性;
4)膜乳化过程结束后,直接加热至聚合反应温度,聚合反应温度50~80℃,待反应完成,再经离心分离和溶剂蒸发法,除去微胶囊内包裹的有机溶剂,获得中空微胶囊,其中离心分离速率是500~3500rpm;
5)采用美国Beckman-Coulter公司LS-100Q型激光粒度仪测定中空微胶囊的粒径大小、分散系数;
6)采用设备型号KYKY-2800的扫描电子显微镜SEM和JSM-6700装载Energy Dispersive Spectroscopy(EDS)分析扫描电子显微镜SEM分别考察微胶囊的外观形态、表面结构及膦配体的存在位置;
7)采用FEI CORPORATION公司的Tecnai G22oS-Twin型透射电子显微镜TEM考察微胶囊的中空结构、壳层厚度。
本发明的效果和益处:
本发明通过选择不同孔径大小的SPG膜,调节分散相(O)中有机溶剂的用量和聚合反应时间,利用聚合物单体的疏水亲油性,形成稳定的单分散O/W型乳状液,一步法向微胶囊内引入膦配体;引发聚合后,再经离心分离和溶剂蒸发法,除去有机溶剂,获得对热稳定、粒径可控、单分散性好、壳层厚度可调、内含膦配体的中空微胶囊;用于负载贵重过渡金属参与催化反应,能提高催化剂的稳定性和催化效果的重现性,并能改善在催化体系中的分散性。
具体实施方式
以下结合技术方案详细叙述本发明的具体实施例。
实施例1:
步骤1以疏水性含膦配体结构的单体对二苯基膦苯乙烯、引发剂偶氮二异丁氰AIBN、交联剂二乙烯基苯DVB及有机溶剂为分散相(O),有机溶剂甲苯,浓度400g/L,其中单体对二苯基膦苯乙烯的含量是25%,AIBN用量占单体总重量的1%。
步骤2配制含十二烷基硫酸钠SDS的聚乙烯醇PVA水溶液为连续相(W),其中PVA和SDS的浓度分别是10g/L以及0.3g/L。
步骤3选择孔径5.4μm的SPG膜,以压缩氮气为压力源,使分散相(O)通过孔径均一的微孔SPG膜分散到连续相(W)中,制得稳定的粒径单分散的O/W型乳状液,分散相和连续相的体积比是1∶20,分散压力2.0~4.0kPa。
步骤4膜乳化过程结束后,氮气气氛下,直接加热至聚合反应温度60℃,待反应结束,再经离心分离和溶剂蒸发法,除去微胶囊内包裹的有机溶剂,获得中空微胶囊,其中离心分离速率是500rpm。
步骤5采用美国Beckman-Coulter公司LS-100Q型激光粒度仪测定中空微胶囊的粒径大小、分散系数(如表1所示)。
步骤6采用设备型号KYKY-2800的扫描电子显微镜SEM和JSM-6700装载Energy Dispersive Spectroscopy(EDS)分析扫描电子显微镜SEM分别考察微胶囊的外观形态、表面结构及膦配体的存在位置,发现微胶囊具有很好的球形度和光滑的球层表面,并且表面几乎没有膦配体的存在。
步骤7采用FEI CORPORATION公司的Tecnai G22oS-Twin型透射电子显微镜TEM考察微胶囊的中空结构、壳层厚度(如表1所示)。
实施例2:
步骤1与实施例1同。
步骤2与实施例1同。
步骤3选择孔径2.8μm的SPG膜,以压缩氮气为压力源,使分散相(O)通过孔径均一的微孔SPG膜分散到连续相(W)中,制得稳定的粒径单分散的O/W型乳状液,分散相和连续相的体积比是1∶20,分散压力6.0~8.0kPa。
步骤4膜乳化过程结束后,氮气气氛下,直接加热至聚合反应温度60℃,待反应结束,再经离心分离和溶剂蒸发法,除去微胶囊内包裹的有机溶剂,获得中空微胶囊,其中离心分离速率是1000rpm。
步骤5与实施例1同,结果见表1。
步骤6与实施例1同。
步骤7与实施例1同,结果见表1。
实施例3:
步骤1以疏水性含膦配体结构的单体对二苯基膦苯乙烯、引发剂偶氮二异丁氰AIBN、交联剂二乙烯基苯DVB及有机溶剂为分散相(O),有机溶剂甲苯,浓度200g/L,其中单体对二苯基膦苯乙烯的含量是25%,AIBN用量占单体总重量的1%。
步骤2与实施例1同。
步骤3与实施例2同。
步骤4与实施例2同。
步骤5与实施例1同,结果见表1。
步骤6与实施例1同。
步骤7与实施例1同,结果见表1。
表1微胶囊粒径、粒径分布*
*Dm:中空微胶囊的平均粒径,SD:标准偏差,CV:单分散系数=(SD/Dm)×100.
Claims (6)
1.一种单分散含膦配体中空微胶囊的制备方法,其特征在于:
疏水性含膦配体结构的单体、引发剂与疏水性交联剂及有机溶剂为分散相(O),以含十二烷基硫酸钠的聚乙烯醇水溶液为连续相(W),将分散相(O)利用外加压力,通过亲水SPG膜分散到连续相(W)中,得到粒径单分散的O/W型乳状液;引发聚合后,再经离心分离和溶剂蒸发,获得微胶囊。
2.按照权利要求1所述的一种单分散含膦配体中空微胶囊的制备方法,其特征在于:具体操作过程为,
1)以疏水性含膦配体结构的单体、引发剂与疏水性交联剂及有机溶剂为分散相(O),其中疏水性含膦配体结构的单体与疏水性交联剂的混合有机溶液浓度是200~800g/L,疏水性含膦配体结构的单体占疏水性含膦配体结构的单体和疏水性交联剂总重量的2~98%,引发剂用量占单体总重量的0.3~10%;
2)配制含十二烷基硫酸钠SDS的聚乙烯醇PVA水溶液为连续相(W),PVA和SDS的浓度分别是10g/L以及0.3g/L;
3)选择孔径分别是0.9~5.4μm的SPG膜,将分散相利用外加压力,通过孔径均一的微孔SPG膜分散到连续相(W)中,制得稳定的粒径单分散的O/W型乳状液,分散相和连续相的体积比是1∶30~1∶10,压力是2.0~4.0或6.0~8.0kPa;
4)膜乳化过程结束后,直接加热至聚合反应温度,待反应完成,再经离心分离和溶剂蒸发法,除去微胶囊内包裹的有机溶剂,获得中空微胶囊。
4.按照权利要求1或2所述的一种单分散含膦配体中空微胶囊的制备方法,其特征在于:所述的疏水性交联剂是二乙烯基苯DVB;所述的引发剂是偶氮二异丁氰AIBN或过氧化苯甲酰BPO,聚合反应温度是50~80℃。
5.按照权利要求2所述的一种单分散含膦配体中空微胶囊的制备方法,其特征在于:所述离心分离和溶剂蒸发法,除去微胶囊内包裹的有机溶剂,离心分离速率是500~3500rpm。
6.按照权利要求2所述的一种单分散含膦配体中空微胶囊的制备方法,其特征在于:所述分散相利用外加压力,通过SPG膜分散到连续相中,采用的压力源是压缩氮气。
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