PS-b-PNVIm(Bu)BF_4离子液体嵌段聚合物的RAFT合成及表征

以S-十二烷基-S’-(α,α’-二甲基-α’’-乙酸)-三硫代碳酸酯为链转移剂,制备了窄分布的聚苯乙烯大分子链转移剂,再用该大分子链转移剂制备聚苯乙烯-b-聚N-乙烯基咪唑(PS-b-PNVIm)两嵌段聚合物。通过与溴代正丁烷发生季铵化反应并与氟硼酸钠进行阴离子交换,得到聚苯乙烯-b-聚1-丁基-3-乙烯基咪唑氟硼化物[PS-bPNVIm(Bu)BF4]。运用1H NMR、IR和凝胶渗透色谱(GPC)等技术对产物的结构和分子量及分子量分布进行表征,结果表明,嵌段聚合物为PS160-b-PNVIm82,分子量分布为1.52,合成过程具有活性/可控聚合特征。PS-bPNVIm具有两亲性,原子力显微镜观察到水溶性球形胶束,胶束以PNVIm链段为壳,PS链段为核。     

P2VP-b-PS-b-PI三嵌段共聚物的RAFT合成及表征

以S-十二烷基-S’-(α,α’-二甲基-α’’-乙酸)-三硫代碳酸酯(DDMAT)为链转移剂,通过可逆加成-断裂链转移自由基聚合(RAFT)方法制备了窄分布的聚2-乙烯基吡啶。再以该聚合物为大分子链转移剂,引发苯乙烯的RAFT聚合,得到聚2-乙烯基吡啶-b-聚苯乙烯(P2VP-b-PS)的两嵌段共聚物。以P2VP-b-PS为RAFT试剂,合成聚2-乙烯基吡啶-b-聚苯乙烯-b-聚异戊二烯(P2VP-b-PS-b-PI)的三嵌段共聚物。运用1H NMR、IR和凝胶渗透色谱(GPC)等技术对产物的结构和分子量及分子量分布进行表征,采用原子力显微镜(AFM)观察三嵌段共聚物薄膜的微相分离结构。结果表明,所得三嵌段共聚物P2VP72-b-PS136-b-PI300分子量分布较窄(PDI=1.69),合成过程具有活性/可控聚合特征,聚合物薄膜经溶剂退火处理后出现了明显的微观相分离结构。     

三嵌段离子液体共聚物P2VP(Bu)TFSI-b-PS-b-P(POEGMA)合成与表征

在链转移剂S-十二烷基-S′-(α,α′-二甲基-α″-乙酸)-三硫代碳酸酯的调控下,偶氮二异丁腈引发单体2-乙烯基吡啶、苯乙烯和聚乙二醇单甲醚甲基丙烯酸酯连续聚合,制备了含有聚2-乙烯基吡啶(P2VP)、聚苯乙烯(PS)和聚(聚乙二醇单甲醚甲基丙烯酸酯)[P(POEGMA)]链段的三嵌段共聚物P2VP105-b-PS...     

PGMA-b-PS二嵌段共聚物的RAFT/细乳液合成及表征

以2-(十二烷基三硫代碳酸酯)-2-甲基丙烯酸为链转移剂,利用RAFT/细乳液联合技术合成了相对分子质量分布较窄(PDI=1.53)的大分子链转移剂聚甲基丙烯酸缩水甘油酯。再以该大分子为可逆加成-断裂链转移(RAFT)试剂,通过连续加料的方式加入苯乙烯后进一步引发聚合,得到PGMA-b-PS二嵌段共聚物。采用GPC、FT-IR、1H-NMR、DSC等方法对聚合产物进行了表征。结果表明:合成的聚合物为线型二嵌段共聚物,相对分子质量分布为1.87,该聚合过程具有活性/可控特征。DSC测得二嵌段共聚物具有2个玻璃化转变温度(Tg),分别为77.33℃和98.30℃。此外,还考察了单体加料顺序对聚合过程的影响。     

三嵌段离子液体共聚物mPEG-b-PS-b-PVBMImTFSI合成及表征

通过可逆加成断裂链转移自由基聚合(RAFT)法,以偶氮二异丁腈为引发剂,合成了含有聚乙二醇单甲醚(mPEG)、聚苯乙烯(PS)和聚对氯甲基苯乙烯(PVBC)链段的三嵌段共聚物mPEG-b-PS-b-PVBC.将合成的共聚物与1-甲基咪唑(NMIm)进行季铵化反应,再与双三氟甲基磺酰亚胺锂(LiTFSI)进行阴离子交换,...     

基于RAFT聚合策略合成功能化聚烯烃嵌段聚合物的研究进展

首先介绍了可逆加成-断裂链转移聚合（RAFT）的聚合机理及其常用的RAFT试剂,并与其它两种活性可控自由基聚合[氮氧化合物媒介的自由基聚合（NMP）和原子转移自由基聚合（ATRP）]进行了简单的优缺点对比。其次,介绍了近些年在基于RAFT聚合制备功能化聚烯烃嵌段聚合物研究中取得的进展,重点综述了制备功能化聚烯烃嵌段聚合物时所采用的6种方法,包括①烯烃配位聚合与RAFT聚合相结合;②阴离子聚合与RAFT聚合相结合;③阳离子聚合与RAFT聚合相结合;④Click反应与RAFT聚合相结合;⑤开环聚合与RAFT聚合相结合;⑥叶立德活性聚合与RAFT聚合相结合。最后,对基于RAFT聚合策略设计合成功能化聚烯烃嵌段聚合物的研究前景与实际应用进行了展望。     

RAFT方法合成两亲性嵌段共聚物的研究进展

可逆加成一断裂链转移(RAFT)聚合是制备嵌段共聚物的重要方法之一,介绍了队RAFT聚合方法的基本原理及其所用的RAFT链转移剂基础上,综述了国内外利用RAFT聚合方法合成两亲性嵌段共聚物的研究现状.     

PCL-b-PNAGA嵌段共聚物的制备及表征

聚己内酯(PCL)是一种性能优良的生物相容性及降解性良好生物材料,在生物医药方面有着巨大的潜能,但其具有很强的疏水性。本文利用N-丙烯酰基甘氨酰胺(NAGA)的亲水性通过可逆加成-断裂链转移聚合(RAFT)制备嵌段共聚物PCL-b-PNAGA,并通过FI-IR和1H-NMR表征证明了各个产物的成功制备。结果表明:成功制备了单体NAGA,大分子链转移剂PCL-CTA和嵌段共聚物PCL-b-PNAGA。     

铕(Ⅲ)诱导聚苯乙烯-聚4-乙烯基吡啶嵌段共聚物的自组装行为及表征

研究了含共轭结构氮杂环的非离子嵌段共聚物参与形成的稀土配合物纳米胶束的形态结构及荧光性能。通过可逆加成-断裂链转移(RAFT)自由基聚合合成了聚苯乙烯-聚4-乙烯基吡啶(PS-b-P4VP)两亲性嵌段共聚物,并以邻菲罗啉(Phen)作为小分子配体协同反应,与Eu(Ⅲ)离子配位诱导自组装成具有核壳结构的荧光聚合物聚集体纳米胶束,分别采用紫外-可见吸收光谱、透射电镜、荧光光谱对胶束的结构形态及其荧光性能进行表征。结果表明,PS-b-P4VP和Phen都通过分子上的氮原子与Eu(Ⅲ)形成螯合键,在N,N-二甲基甲酰胺溶液中共同参与配位络合形成了聚集体;PS-b-P4VP和Phen都对Eu(Ⅲ)离子的荧光强度起到了明显的增强作用;成功制备出尺寸可控的球形纳米胶束,通过调节纳米胶束的大小,使其应用于太阳能电池及其它光电光伏领域。     

两种离子液体嵌段共聚物的合成及其离子传导性表征

采用可逆加成–断裂链转移(RAFT)聚合技术合成了分子量分布窄(1.60)且带有—PhCH2Cl侧基线型三嵌段共聚物——聚甲基丙烯酸甲酯–b–聚对乙烯基苄基氯–b–聚苯乙烯[P(MMA-b-VBC-b-St)],然后经1–甲基咪唑(NMIm)季铵化及锂离子盐(LiTFSI)进行阴离子交换,分别制得两种离子液体嵌段共聚物...     

离子液体聚合物的合成及应用研究进展

离子液体聚合物是一种新型的聚合物材料,近些年来取得了迅速发展。本文主要介绍了离子液体聚合物的合成方法,并综述了离子液体聚合物在聚电解质、吸附及分离材料、催化剂等方面的应用研究进展。     

New synthesis and characterization of ionic polyurethane-urea liquid crystals

A new series of thermotropic ionic polyurethane-urea (PUU) liquid crystals (LCs) were synthesized, each by using the corresponding diisocyanate, 4,4′-bis(6-hydroxyhexoxy)biphenyl, and sodium 2,5-diaminobenzenesulfonate. Morphology, phase transition temperatures, and spectroscopic characteristics of the PUU LCs are reported. Each PUU exhibits a monotropic liquid crystal phase upon slow cooling. The PUU LC phase texture is visible by polarized optical microscopy (POM) and is dependent upon the PUU isocyanate precursor; 1,6-diisocyanatohexane (HDI) and 5-isocyanato-1-(isocyanatomethyl)-1,3,3,-trimethylcyclohexane (IPDI) polymers have schlieren textures, whereas 2,4-diisocyanato-1-methylbenzene (TDI) and methylenebis(4-phenylisocyanate) (MDI) polymers show grain textures.     

苯胺和环氧丙烷共聚物在BMIHSO4中的电化学聚合和表征

在1-丁基-3-甲基咪唑硫酸氢盐(BMIHSO4)离子液体中，采用循环伏安法合成了苯胺和环氧丙烷共聚物（PAN-PPO），并与聚苯胺（PAN）进行了对比。结果表明：在相同条件下，PAN-PPO的电合成速度远大于 PAN。同时采用红外光谱FTIR和扫描电子显微镜SEM对PAN-PPO进行了表征，FTIR表明苯胺和环氧丙烷在BMIHSO4中发生了共聚，SEM表明PAN-PPO由直径小于80 nm的纳米纤维组成。     

酸性离子液催化剂的制备及特性表征

采用两步法合成了4种含—SO3H基团的Brφnsted酸性离子液催化剂,对所合成的离子液体进行了红外光谱表征,运用热重分析仪测定了离子液体的热分解温度,探索采用pH计法和Hammett指数法进行离子液体的酸性测定。实验数据表明,所合成的离子液催化剂具有良好的耐热性和较高的酸强度,其结构特征与目标物吻合,产物中杂质少。     

Poly(4-vinylpyridine)-based hydrogen bonded side-chain liquid crystal polymers

Novel liquid crystalline (LC) poly(4-vinylpyridine) (PVP)-based side-chain polymers were prepared from PVP and cyanobiphenyl (HOCnB) derivatives through intermolecular hydrogen-bonding between hydroxyl groups of the cyanobiphenyl derivatives and the nitrogen of PVP. PVP was used as a hydrogen bond acceptor polymer. A series of HOCnB having a linear alkoxy chain HOCnH_2n + 1O–(n = 2–6) have been used as H-bond donor. The existence of H-bonding was confirmed using FTIR spectroscopy. The polymeric complexes behave as LC polymers and exhibit stable mesophases. DSC and optical microscopy were used to investigate LC behaviour. All PVP–LC-complexes exhibited stable and homogeneous nematic phases. On increasing spacer length or concentration of the hydrogen bonded mesogenic unit in the complex, the clearing temperature and the temperature range of the nematic phase increased. The binary phase diagram of the polymeric complexes PVP–HOCnB showed complete miscibility over the entire range of composition. Molecular interactions of self-assembled SCLCP presented the idea that various LC-complexes could be prepared through mixing a functionalised polymer with various low molar mass mesogens.     

Synthesis and characterization of polymeric ionic liquid poly(imidazolium chloride-1,3-diylbutane-1,4-diyl)

Polymeric ionic liquid poly(imidazolium chloride-1,3-diylbutane-1,4-diyl) with imidazolium cation groups built into the main chain was prepared using two different routes in 92–95% yield, and characterized by FT-IR, ¹H, ¹³C NMR, TGA, and elemental analysis. The first method involved the heating of neat 1-(4-chlorobutyl)-1H-imidazole, whereas the second method involved the heating of an equimolar mixture of 1,1′-(1,4-butanediyl)-bis-imidazole and 1,4-dichlorobutane.     

A redox poly(ionic liquid) hydrogel: Facile method of synthesis and electrochemical sensing

In this article, a redox-responsive poly(ionic liquid) (redox-PIL) hydrogel Poly(1-vinyl-3-propionate imidazole phenothiazine sulfonic acid)-chitosan [Poly(VPI⁺PTZ-(CH₂)₃SO₃⁻)-CS] was produced by using chitosan (CS) crosslinking with redox-PIL Poly(1-vinyl-3-propionate imidazole phenothiazine sulfonic acid [Poly(VPI⁺PTZ-(CH₂)₃SO₃⁻)]. The incorporation of redox-active counter anions 3-(phenothiazine-10-yl) propane 1-sulfonic acid anions (PTZ-(CH₂)₃SO₃⁻) into cationic PIL-polyimidazole rendered Poly(VPI⁺PTZ-(CH₂)₃SO₃⁻) with electron catalytic ability, ionic conductivity, and electron conductivity. Poly(VPI⁺PTZ-(CH₂)₃SO₃⁻)-CS combines the properties of hydrogel and redox-PIL, thus offering intrinsic porous conducting frameworks and promoting the transport of charges, ions, and molecules, leading hydrogel with excellent electrochemical properties. The crosslinking occurrence of Poly(VPI⁺PTZ-(CH₂)₃SO₃⁻) and CS resulting from the synthetic process of hydrogel was verified by differential scanning calorimetry and thermogravimetric analysis. A three-dimensional polymer network hydrogel with good biocompatibility and permeability was formed after crosslinking. In addition, only 64% weight loss within 600 °C was observed in Poly(VPI⁺PTZ-(CH₂)₃SO₃⁻)-CS representing its thermally stable performance. When used as an electrochemical sensor, the hydrogel-modified gold electrode improved the electrocatalytic oxidation of cysteine. Differential pulse voltammetry results indicated that the detection range was from 5 × 10⁻⁸ to 5 × 10⁻³ M and the limit of detection was 6.64 × 10⁻⁸ M. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48051.