超支化聚合物接枝改性碳纳米管及其分散性能

将碳纳米管用c(K2Cr2O7)=0.25 mol/L,c(H )=1 mol/L混合溶液进行处理,制得表面含有活性羟基的碳纳米管. 在催化剂的存在下,以CNTs为反应中心核,氧化处理后的CNTs表面上的活性羟基与A2B型单体发生一步缩聚反应,将超支化聚合物接到碳纳米管的表面上,实现了碳纳米管的表面修饰. 探讨了反应条件对接枝在CNTs表面上的超支化聚合物(HPAE)量的影响,当反应温度为120 ℃,反应时间为10 h,反应配料比n(CNTs-OH):n(A2B单体)=1:6时,固载量达到0.255. FTIR、XPS、TEM的表征结果证明,CNTs接枝上了超支化聚合物. 透光度的测定和静置实验表明,超支化聚合物接枝改性CNTs在丙酮、乙醇、水等溶剂中具有很好的分散性能.     

表面引发原子转移自由基聚合制备聚电解质修饰的碳纳米管

利用聚电解质对多壁碳纳米管(MWNT)的表面进行修饰,能有效改善碳纳米管在溶剂中的分散性.首先将经硝酸氧化的碳纳米管与二甲亚砜和乙二醇反应,得到羟基修饰的碳纳米管.然后利用羟基与α-溴异丁酰溴(或α-氯丙酰氯)的酯化反应,在碳纳米管的表面引入了原子转移自由基聚合(atom transfer radical polymerization,ATRP)引发基团,引发丙烯酸叔丁酯(tBA)或4-乙烯基吡啶(4VP)聚合,通过投料比的改变,得到接入量不同的聚合物修饰的碳纳米管.利用热重分析(TGA)和红外对聚合物修饰的碳纳米管进行表征.将聚合物修饰的碳纳米管进行水解(或季胺化),制备得到在水溶液中良好分散的聚电解质修饰的碳纳米管.     

用ATRP法构筑核壳型梯度极性的多羟基多臂星状超支化聚合物及聚合物刷——三层聚合物刷的合成与表征

设计并通过原子转移自由基聚合方法 (ATRP)合成了核壳型具有梯度极性的多羟基多臂星状聚合物刷 .端羟基超支化聚 (3 乙基 3 羟甲基氧杂环丁烷 )与 2 溴 异丁基酰溴反应制得大分子引发剂 (HP Br) ,以Cu(I)Br和N ,N ,N′ ,N′ ,N″ 五甲基二乙基三胺 (PMDETA)为催化体系 ,进行甲基丙烯酸甲酯 (MMA)的ATRP反应 ,得到以甲基丙烯酸甲酯为臂的多臂星状超支化聚合物 (HP g PMMA) .又以HP g PMMA为引发剂 ,进行甲基丙烯酸羟乙酯 (HEMA)的ATRP聚合 ,得到核壳型具有梯度极性的多羟基多臂星状超支化聚合物 (HP g PMMA b PHEMA) ,继续将其羟基官能团溴代化 (与 2 溴 异丁基酰溴反应 ) ,引发HEMA的ATRP溶液聚合 ,得到了多臂星状超支化聚合物刷 .产物的结构用1 H NMR、FTIR、GPC等进行了表征和测试 .     

聚苯乙烯修饰碳纳米管表面的研究

利用原子转移自由基聚合方法合成了端基具有一个卤素的聚苯乙烯, 并通过叠氮化反应得到端基为叠氮基团的聚苯乙烯. 利用叠氮基与单壁或复壁碳纳米管的反应， 将聚苯乙烯接到碳纳米管的表面上, 实现了碳纳米管的化学修饰. 通过FTIR, XPS, TEM, UV和Raman光谱等技术证明了聚苯乙烯以共价键形式结合到碳纳米管表面上. 利用TGA估算出连接在碳纳米管上的聚苯乙烯的含量, 并推测出复壁碳纳米管中较多的结构缺陷更有利于聚合物的接枝.     

超支化聚酯修饰多壁碳纳米管

将碳纳米管先用V(H2SO4)∶V(HNO3)=3∶1混合溶液进行处理,再用V(H2SO4)∶V(H2O2=4∶1的混合溶液进一步酸化,制得含有羧基的碳纳米管。将羧基化碳纳米管与二氯亚砜反应使碳纳米管连接酰氯基团,利用酰氯基团与超支化聚酯上的羟基反应,将超支化聚酯接到碳纳米管的表面上,实现了碳纳米管的表面修饰。利用红外光谱、拉曼光谱、透射电镜观察分析测试结果表明,超支化聚酯以共价键形式连接到碳纳米管的表面。热失重分析结果表明,修饰密度为每321个C原子连接1个H20分子,每842个C原子上连接1个H40分子。修饰后的碳纳米管在有机溶剂中的溶解性能明显提高。     

靶向性多肽修饰荧光功能化碳纳米管的制备及靶向肿瘤细胞的初步研究

以羟基化多壁碳纳米管(MWNT-OH)为引发剂,通过原位负离子开环聚合制备了生物相容性多羟基超支化聚缩水甘油接枝的碳纳米管(MWNT-HPG),利用酯化反应将荧光分子罗丹明6B标记于聚合物上,然后聚合物上的羟基和丁二酸酐反应将其转化为羧基.用TGA、FTIR、TEM、SEM等手段对产物进行了表征.用靶向表皮生长因子受体(EGFR)的小分子多肽D4修饰了所得的荧光功能化碳纳米管,并将其做为受体介导靶向肿瘤细胞的纳米载体,通过噻唑蓝(MTT)比色法评价功能化碳纳米管作为载体的安全性.用荧光显微镜观察其与人肺腺癌细胞SPCAI细胞的结合状态.结果证明了其有希望成为受体介导靶向肿瘤系统的纳米载体.     

用多官能团引发剂合成超支化聚苯乙烯及其C60衍生物

通过α-溴丙酰溴与Z5(季戊四醇与2,2-二羟甲基丙酸缩聚的产物)酯化反应制得超支化原子转移自由基聚合(ATRP)引发剂Z5-B(约含19个引发点).在100℃及CuCl/N,N,N,N",N"-五甲基二亚乙基三胺催化下,用Z5-B引发苯乙烯的ATRP聚合(环己酮为溶剂,体积分数为50%),得到超支化的聚苯乙烯,将溴端基叠氮化后与C60反应,获得超支化聚苯乙烯C60衍生物.该超支化C60衍生物可用于光限制材料.     

ATRP与点击化学相结合制备环状聚甲基丙烯酸甲酯

利用原子转移自由基聚合(ATRP)与点击反应相结合制备环状聚合物. 根据ATRP原理, 用含端炔的有机卤化物作为引发剂时, 产物的一端为炔基, 另一端则为卤素原子, 而卤素原子本身可作为叠氮化物的原料, 从而可利用点击反应使聚合物成环.     

不饱和端基超支化聚合物/丙烯酸酯共聚乳液的研究

利用Si—H加成反应制得了以CC为端基的超支化含硅聚合物,并将其与丙烯酸酯类单体进行乳液共聚,对聚合反应机理及所得聚合物的性能进行了测试分析.结果表明,含有大量CC端基的超支化含硅聚合物能与丙烯酸酯类单体稳定聚合,制得了平均粒径小于100nm高度交联的乳胶粒子.共聚物的红外光谱证实,超支化聚合物的不饱和端基已全部反应,形成了以超支化聚合物为多臂交联点的交联型乳胶粒子.随聚合体系中超支化聚合物用量的增加,乳液聚合反应速率增大,乳胶粒粒径减小,共聚物热稳定性显著提高.     

用ATRP法构筑核壳型梯度极性的多羟基多臂星状超支化聚合物及聚合物刷——双层聚合物刷的合成与表征

设计并通过原子转移自由基聚合方法 (ATRP)合成了核壳型多羟基多臂星状超支化聚合物刷 .以 2 溴异丁基酰溴封端的超支化聚 (3 乙基 3 羟甲基氧杂环丁烷 ) (HP Br)作为大分子引发剂 ,采用Cu(I)Br和N ,N ,N′ ,N′ ,N″ 五甲基二乙基三胺 (PMDETA)催化体系 ,在丁酮与丙醇的混和溶液中 ,通过甲基丙烯酸羟乙酯(HEMA)的ATRP溶液聚合 ,得到了一系列含有大量羟基的多臂星状超支化聚合物刷 (HP g PHEMA) ,并考察了其羟基的活性 ,发现羟基还可以与苯甲酰氯发生反应 .产物的结构和热性能用1 H NMR、FTIR、GPC、TGA、DSC等进行了表征和测试 .     

N-苯基马来酰亚胺/对氯甲基苯乙烯活性可控超支化交替共聚合的研究

采用核磁共振氢谱, 研究了N-苯基马来酰亚胺(NPMI)与对氯甲基苯乙烯(PCMS)在氘代氯仿中的络合性能. 以PCMS作为引发剂单体, 通过原子转移自由基聚合(ATRP)引发NPMI-PCMS电子转移络合物(CTC)进行活性可控超支化共聚合. 考察了单体初始摩尔分数对共聚物组成和其玻璃化转变温度的影响, 用Kelen-Tudos法计算得到两种单体的竞聚率分别为 r_NPMI＝0.11和r_PCMS＝0.25. 结果表明, 当单体配比f_NPMI＝0.4～0.7时, 共聚物具有交替结构, 其耐热性随着NPMI含量的增加而提高. 此外还考察了溶剂、聚合温度等对共聚合反应动力学的影响. 并进一步用所得超支化交替共聚物作为大分子引发剂, 引发甲基丙烯酸甲酯(MMA)聚合, 制得了多臂超支化接枝共聚物 poly(NPMI-co-PCMS)/poly(MMA).     

New polynitrogen hyperbranched polymers

A method for the preparation of new representatives of polynitrogen hyperbranched polymers of heterocyclic series was developed involving polymerization of monomeric 2,4-diazido-6-propynyloxy-1,3,5-triazine by 1,3-dipolar cycloaddition. Kinetics of polymerization of diazidoacetylene monomer was compared with the kinetic data of polymerization of its closest analog, 2-azido-4,6-bis(propynyloxy)-1,3,5-triazine monomer. Properties of hyperbranched poly(1,2,3-triazole-1,3,5-triazine)s with terminal azide groups and terminal triple bonds were compared, as well.     

Clickable 2,2-bis(hydroxymethyl)propionic acid-derived AB2 monomers: Hyperbranched polyesters through the CuAAC cycloaddition (click) reaction

We present the synthesis and characterization of two aliphatic AB₂ monomers derived from the readily available 2,2-bis(hydroxymethyl)propionic acid and containing one alkyne group and two azide functionalities. The distance between the polymerizable groups differs in the two monomers by the insertion of an additional carbon atom in the aliphatic structure that addresses the steric demand during polymerization. The synthetic procedure for the monomers is relatively simple and scalable, and the monomers are able to polymerize through the Copper(I)-catalyzed Azide-Alkyne Cycloaddition (CuAAC reaction). The polymerization affords hyperbranched polymers in good yields and molecular weights and moderate degrees of branching. Copyright © 2021 John Wiley & Sons, Ltd.     

Chain‐Growth Click Polymerization of AB2 Monomers for the Formation of Hyperbranched Polymers with Low Polydispersities in a One‐Pot Process

Hyperbranched polymers are important soft nanomaterials but robust synthetic methods with which the polymer structures can be easily controlled have rarely been reported. For the first time, we present a one‐pot one‐batch synthesis of polytriazole‐based hyperbranched polymers with both low polydispersity and a high degree of branching (DB) using a copper‐catalyzed azide–alkyne cycloaddition (CuAAC) polymerization. The use of a trifunctional AB₂ monomer that contains one alkyne and two azide groups ensures that all Cu catalysts are bound to polytriazole polymers at low monomer conversion. Subsequent CuAAC polymerization displayed the features of a “living” chain‐growth mechanism with a linear increase in molecular weight with conversion and clean chain extension for repeated monomer additions. Furthermore, the triazole group in a linear (L) monomer unit complexed Cu^I, which catalyzed a faster reaction of the second azide group to quickly convert the L unit into a dendritic unit, producing hyperbranched polymers with DB=0.83.     

两亲性超支化聚合物的研究进展

两亲性超支化聚合物作为一种新型功能性材料.近年来引起了人们的广泛关注.两亲性超支化聚合物的合成丰要是利用不同亲水性的链段对超支化聚合物端基进行改性,或者首先在超支化聚合物末端产生活性位点,再利用超支化分f作为大分子引发剂引发烯类单体进行斤环聚合、原子转移自由基聚合等得到以超支化聚合物为核的两亲性超支化共聚物;这些分子由...     

Hyperbranched polyurethanes with varying spacer segments between the branching points

Hyperbranched polyurethanes, with varying oligoethyleneoxy spacer segments between the branching points, have been synthesized by a one-pot approach starting from the appropriately designed carbonyl azide that incorporates the different spacer segments. The structures of monomers and polymers were confirmed by IR and ¹H-NMR spectroscopy. The solution viscosity of the polymers suggested that they were of reasonably high molecular weight. Reversal of terminal functional groups was achieved by preparing the appropriate monohydroxy dicarbonyl azide monomer. The large number of terminal isocyanate groups at the chain ends of such hyperbranched macromolecules caused them to crosslink prior to its isolation. However, carrying out the polymerization in the presence of 1 equiv of a capping agent, such as an alcohol, resulted in soluble polymers with carbamate chain ends. Using a biphenyl-containing alcohol as a capping agent, we have also prepared novel hyperbranched polyurethanes with pendant mesogenic segments. These mesogen-containing polyurethanes, however, did not exhibit liquid crystallinity probably due to the wholly aromatic rigid polymer backbone. © 1996 John Wiley & Sons, Inc.     

Plasma polymers from chloromethyltrimethylsilane and their modification with sodium azide

Plasma polymerization of chloromethyltrimethylsilane (CMTMS) was investigated by elemental analysis, infrared spectroscopy, and ESCA, and the modification of Cl substituents in the plasma polymers from CMTMS with sodium azide was discussed. CMTMS was plasma polymerized to yield filmy polymers. The polymer deposition rate was faster than that from tetramethylsilane containing no Cl atom. The plasma polymers from CMTMS were mainly composed of CH₃, CH₂, Si? CH₃, Si? O? Si, and Si? O? C groups with a small amount of C? Cl groups. The Cl substituents incorporated into the plasma polymers were capable of substitution reactions with azide groups to form azide polymers.     

超支化聚碳硅氮烷的合成与表征

聚碳硅氮烷是一种新型含硅有机金属聚合物,其主链由硅氮碳连接而成,侧链为有机基团;与其它含硅聚合物(聚硅氮烷、聚碳硅烷等)类似,聚碳硅氮烷适于用做力学性能极佳且耐高温氧化的氮化硅(Si3N4)和氮化硅/碳化硅(Si3N4/SiC)复相陶瓷的前驱体.[1]超支化聚合物具有溶解性好、粘度低