树枝状大分子/聚(N-异丙基丙烯酰胺)纳米粒子的制备

使用溴乙酰溴对第四代聚丙烯亚胺树枝状大分子 (DAB-32)进行改性,成功合成了树枝状大分子引发剂DAB-32-Br。以DAB-32-Br/CuBr/Bpy为催化引发体系,分别在水和水/乙醇反应介质中,实现了N－异丙基丙烯酰胺（NIPAAm）的原子转移自由基聚合（ATRP）,得到粒径在60－150 nm范围内的树枝状大分子/聚（N－异丙基丙烯酰胺）纳米粒子。与水介质中ATRP相比,在水/乙醇介质中所得聚合物纳米粒子更加规则,而且粒子间聚集程度较低。     

聚苯乙烯为规整侧链的支化SIS的设计及合成

以苯乙烯和对乙烯基苄氯(VBC)为原料,采用负离子聚合法合成含苯乙烯基末端的聚苯乙烯大分子单体,并以正丁基锂(BuLi)为引发剂,四氢呋喃(THF)为调节剂,环己烷为溶剂进行异戊二烯与大分子单体的负离子共聚合,用一锅法制备出侧链规整的支化结构苯乙烯-异戊二烯-苯乙烯(SIS)嵌段聚合物。通过核磁共振和凝胶渗透色谱等对聚苯乙烯大分子单体和支化SIS结构进行了表征,利用旋转流变仪对支化SIS进行了流变性能表征。结果表明,利用上述聚合方法成功合成了相对分子质量3000～5000的聚苯乙烯大分子单体;使用聚苯乙烯大分子单体制备出相对分子质量为10万～14万,分子量分布为1.1～1.2的支化结构SIS,并且其流体黏度明显低于相同相对分子质量及结合苯乙烯线型结构的SIS。     

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。     

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。     

表面引发原子转移自由基聚合合成聚苯乙烯接枝纳米SiO2复合乳液

采用偶联剂对纳米SiO2粒子表面进行处理,将原子转移自由基聚合(ATRP)引发剂引入到SiO2粒子表面合成大分子引发剂,通过细乳液聚合工艺制备了相对分子质量分布窄的聚合物基纳米SiO2复合乳液,利用红外光谱(FT-IR)、X射线光电子能谱(XPS)和凝胶色谱(GPC)等对复合乳液粒子及表面接枝聚苯乙烯进行了表征分析。结果表明:聚合物的相对分子质量在反应过程中随单体转化率的增大呈线性增长趋势,相对分子质量分布较窄(Mw/Mn=1.34),接枝在纳米SiO2粒子表面聚苯乙烯的分子大小比较均匀;TEM和SEM观察表明:通过合成复合乳液使纳米SiO2粒子在涂膜中达到均匀的单分散状态;所合成的纳米复合粒子在功能涂层材料方面具有良好的应用潜能。     

聚合物接枝纳米碳纤维/聚苯乙烯复合材料的制备与力学性能研究

采用自由基聚合方法,在纳米碳纤维(CNF)表面接枝聚丙烯酸正丁酯(PnBA)和聚苯乙烯(PS),利用接枝的嵌段聚合物作为大分子偶联剂制备CNF/PS复合材料。红外傅里叶变换光谱(FT-IR)研究表明,嵌段聚合物PnBA-b-PS被成功地接枝到CNF表面。扫描电子显微镜(SEM)和力学性能测试结果显示,CNF与PS复合材料界面结合得到改善,力学性能明显提高。     

聚合物/纳米石墨微片复合材料的研究进展

详述了纳米石墨微片（NanoG）的制备工艺、结构特征,重点归纳总结了纳米石墨微片与聚甲基丙烯酸甲酯（PMMA）、聚苯胺(PANI)、聚苯乙烯(PS)以及聚吡咯(PPy)复合材料的复合方法、性能及应用情况。最后对聚合物/纳米石墨微片复合物制备工艺问题,纳米石墨微片在聚合物中的分散性问题以及如何提高聚合物/纳米石墨微片复合物的导电性问题进行了展望,同时提出改性的纳米石墨微片与聚合物复合的应用研究将是一个崭新的研究领域。     

导电聚合物有序超薄膜性质

采用修饰多层LB膜的方法制备导电聚合物聚3,4乙烯二氧噻吩/聚苯乙烯磺酸(PEDOT-PSS)/十八胺(ODA)及硬脂酸(SA)复合层状有序膜.实验表明,PEDOT-PSS纳米粒子对单分子层具有包裹作用,形成了稳定的复合单分子膜;二次离子质谱(SIMS)和小角x射线反射(XRR)分析表明ODA-SA/PEDOT-PSS...     

一种结晶型高顺式共聚弹性体/苯乙烯基聚合物复合材料及其制备方法

正本发明涉及一种结晶型高顺式共聚弹性体/苯乙烯基聚合物复合材料及其制备方法。复合材料中结晶型共聚弹性体是一种由聚苯乙烯与聚共轭二烯烃(如丁二烯、异戊二烯)嵌段共聚物,聚苯乙烯链段具有一定的结晶性,聚共轭二烯烃链段中的顺-1,4结构含量大于95%。苯乙烯基聚合物为聚苯乙烯或苯乙烯与丙烯腈的共聚物。本发明复合材料的制备     

原位还原法制备rGO/PSt复合乳液

采用原位还原法,通过强还原剂水合肼将氧化石墨烯/聚苯乙烯(GO/PSt)复合乳液中氧化石墨烯还原成还原氧化石墨烯片层,制备得到还原氧化石墨烯/聚苯乙烯复合乳液(rGO/PSt)。红外光谱(FT-IR)、X射线衍射仪(XRD)、拉曼光谱(Raman)表征结果表明rGO/PSt复合乳液的成功制备。透射电镜(TEM)、扫描电镜(SEM)表征其微观结构,微观条件下rGO吸附或包裹在PSt表面;通过热重(TG)和差示扫描量热仪(DSC)表征可知rGO/PSt复合物的热性能得到一定程度的改善。     

Synthesis of poly[(decanoic acid)‐block‐styrene] diblock copolymers and their self‐assembly behavior in aqueous medium

Diblock copolymers, poly[(10‐hydroxydecanoic acid)‐block‐styrene] (PHDA‐b‐PSt), were synthesized by combining enzymatic condensation polymerization of HDA and atom transfer radical polymerization (ATRP) as of St PHDA was first obtained via enzymatic condensation polymerization catalyzed by Novozyme‐435. Subsequently, one terminus of the PHDA chains was modified by reaction with α‐bromopropionyl bromide and the other terminus was protected by chlorotrimethylsilane. The resulting monofunctional macroinitiator was used subsequently in ATRP of St using CuCl/2,2′‐bipyridine as the catalyst system to afford diblock copolymers including biodegradable PHDA blocks and well‐defined PSt blocks. Polymeric nanospheres were prepared by self‐assembly of the PHDA‐b‐PSt diblock copolymers in aqueous medium. Copyright © 2008 Society of Chemical Industry     

Synthesis of diblock copolymer poly(10-hydroxydecanoic acid)/polystyrene by combining enzymatic condensation polymerization and ATRP

Summary The diblock copolymers poly(10-hydroxydecanoic acid)-block-polystyrene (PHDA-b-PSt) were synthesized by combining enzymatic condensation polymerization of 10-hydroxydecanoic acid (HDA) and atom transfer radical polymerization (ATRP) of styrene (St). PHDA was firstly obtained via enzymatic condensation polymerization catalyzed by Novozyme-435. Subsequently one end of poly(10-hydroxydecanoic acid) (PHDA) chains was modified by reaction with α-bromopropionyl bromide and the other was protected by chlorotrimethylsilane (TMSCL), respectively, the resulting monofunctional macroinitiator was used in the ATRP of St using CuCl/2,2^′-bipyridine (bpy) as the catalyst system to afford the diblock copolymers including biodegradable PHDA blocks and well-defined PSt blocks.     

Atom transfer radical polymerization of styrene and methyl (meth)acrylates initiated with poly(dimethylsiloxane) macroinitiator: Synthesis and characterization of triblock copolymers

Poly(dimethylsiloxane)(PDMS)‐based triblock copolymers were successfully synthesized via atom transfer radical polymerization (ATRP) initiated with bis(bromoalkyl)‐terminated PDMS macroinitiator (Br‐PDMS‐Br). First, Br‐PDMS‐Br was prepared by reaction between the bis(hydroxyalkyl)‐terminated PDMS and 2‐bromo‐2‐methylpropionyl bromide. PSt‐b‐PDMS‐b‐PSt, PMMA‐b‐PDMS‐b‐PMMA and PMA‐b‐PDMS‐b‐PMA triblock copolymers were then synthesized via ATRP of styrene (St), methyl methacrylate (MMA) and methyl acrylate (MA), respectively, in the presence of Br‐PDMS‐Br as a macroinitiator and CuCl/PMDETA as a catalyst system at 80 ^oC. Triblock copolymers were characterized by FTIR, ¹H‐NMR and GPC techniques. GPC results showed linear dependence of the number‐average molecular weight on the conversion as well as the narrow polydispersity indicies (PDI < 1.57) for the synthesized triblock copolymers which was lower than that of Br‐PDMS‐Br macroinitiator (PDI = 1.90), indicating the living/controlled characteristic of the reaction. Also, there was a very good agreement between the number‐average molecular weight calculated from ¹HNMR spectra and that calculated theoretically. Results showed that resulting copolymers have two glass transition temperatures, indicating that triblock copolymers have microphase separated morphology. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis and characterization of poly(n‐butyl methacrylate)‐b‐polystyrene diblock copolymers by atom transfer radical emulsion polymerization

Poly(n‐butyl methacrylate) (PBMA)‐b‐polystyrene (PSt) diblock copolymers were synthesized by emulsion atom transfer radical polymerization (ATRP). PBMA macroinitiators that contained alkyl bromide end groups were obtained by the emulsion ATRP of n‐butyl methacrylate with BrCH₃CHCOOC₂H₅ as the initiator; these were used to initiate the ATRP of styrene (St). The latter procedure was carried out at 85°C with CuCl/4,4′‐di(5‐nonyl)‐2,2′‐bipyridine as the catalyst and polyoxyethylene(23) lauryl ether as the surfactant. With this technique, PBMA‐b‐PSt diblock copolymers were synthesized. The polymerization was nearly controlled; the ATRP of St from the macroinitiators showed linear increases in number‐average molecular weight with conversion. The block copolymers were characterized with IR spectroscopy, ¹H‐NMR, and differential scanning calorimetry. The effects of the molecular weight of the macroinitiators, macroinitiator concentration, catalyst concentration, surfactant concentration, and temperature on the polymerization were also investigated. Thermodynamic data and activation parameters for the ATRP are also reported. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2123–2129, 2005     

Synthesis and self-assembly of poly(benzyl ether)-b-poly(methyl methacrylate) dendritic-linear polymers

Here, the dendritic chloric poly(benzyl ether) (G₁-Cl, G₂-Cl and G₃-Cl) as the macroinitiator for the controlled atom transfer radical polymerization (ATRP) of methyl methylacrylate was investigated. Polymers obtained were characterizated by GPC, ¹H NMR, FT-IR, TGA and DSC. These dendritic-linear block polymers that consist of linear and dendritic segments have very good solubility in common organic solvents at room temperature. In a selective solvent (THF/H₂O), polymers can self-assembled into the micelles that have a spherical morphology in shape due to the lowest of the surface energies.     

Chemozymatic synthesis and characterization of H-shaped triblock copolymer

The synthesis of well-defined H-shaped block copolymer based on the enzymatic ring-opening polymerization (eROP) and atom transfer radical polymerization (ATRP) is described. The dihydroxyl polycaprolactone (PCL) was synthesized by the eROP of ε-caprolactone (ε-CL) in the presence biocatalyst Novozyme 435 and initiator ethylene glycol. Subsequently, the resulting PCL was converted to tetrafunctional macroinitiator by the esterification with 2,2-dichloro acetyl chloride (DCAC). The H-shaped block copolymer was then synthesized by the ATRP of styrene. The polymers were characterized by NMR and GPC. Linear first-order kinetics, linearly increasing molecular weight with conversion, and low polydispersities observed from the ATRP of St showed that the polymerization was well controlled. (PSt)₂-b-PCL-b-(PSt)₂ block copolymers with varying molecular weight and controllable composition were obtained.     

Chiral-nematic self-ordering of rodlike cellulose nanocrystals grafted with poly(styrene) in both thermotropic and lyotropic states

Graft copolymers of rodlike cellulose nanocrystals (CNC) with poly(styrene) (PSt) were synthesized through atom transfer radical polymerization (ATRP). The hydroxyl groups on CNC were esterified with 2-bromoisobutyrylbromide to yield 2-bromoisobutyryloxy groups, which were used to initiate the polymerization of poly(styrene). The graft copolymers were characterized by thermogravimetric analysis (TGA), fourier transform infrared spectroscopy (FT-IR) and gel permeation chromatography (GPC). The size of the original CNC is 10-40 nm in width and 100-400 nm in length, which was characterized by atomic force microscopy (AFM). The thermal and liquid crystalline properties of the graft copolymers were investigated by differential scanning calorimeter (DSC) and polarizing optical microscope (POM). The graft copolymers exhibit fingerprint texture in both thermotropic and lyotropic states. In thermotropic state, the PSt-grafted CNC orient spontaneously in isotropic melt (PSt side chains acting as a solvent). The thermotropic liquid crystal phase behavior is similar to the lyotropic phase behavior.     

The effects of acrylate monomers and polystyrene addition on the morphology of DOP‐plasticized styrene–acrylate polymer particles prepared by SPG emulsification and suspension polymerization

Fairly uniform copolymer particles of methyl acrylate (MA), butyl acrylate (BA), or butyl methacrylate (BMA) were synthesized via Shirasu porous glass (SPG) membrane and followed by suspension polymerization. After a single‐step SPG emulsification, the emulsion composed mainly of the monomers. Hydrophobic additives of dioctyl phthalate (DOP), polystyrene molecules, and an oil‐soluble initiator, suspended in an aqueous phase containing poly(vinyl alcohol) (PVA) stabilizer and sodium nitrite inhibitor (NaNO₂), were subsequently subjected to suspension polymerization. Two‐phase copolymers with a soft phase and a hard phase were obtained. The composite particles of poly(St‐co‐MA)/PSt were prepared by varying the St/PSt ratios or the DOP amount. The addition of PSt induced a high viscosity at the dispersion phase. The molecular weight slightly increased with increasing St/PSt concentration. The multiple‐phase separation of the St‐rich phase and PMA domains, observed by transmission electron microscopy, was caused by composition drift because the MA reactivity ratio is greater than that of St. The addition of DOP revealed the greater compatibility between the hard‐St and soft‐MA moieties than that without DOP. The phase morphologies of poly(St‐co‐MA), poly(St‐co‐BMA), and their composites with PSt were revealed under the influence of DOP. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1195–1206, 2006     

两亲性聚乙烯醇-b-聚苯乙烯嵌段共聚物的合成及表征

采用原子转移自由基聚合(ATRP)法合成了具有两亲性的聚乙烯醇-b-聚苯乙烯嵌段共聚物P(VA-b-St)。首先利用调聚反应制备了带三氯甲基端基的聚醋酸乙烯大分子引发剂。以联二吡啶作配体、氯化亚铜为催化剂,引发苯乙烯单体聚合,得到结构明确的P(VAc-b-St)嵌段共聚物,而后通过皂化反应将其水解,从而得到两亲性嵌段共聚物P(VA-b- St);产物采用FT-IR、1H NMR、GPC等方法进行结构表征。P(VA-b-St)在不同浓度溶剂中的自组装行为用TEM进行了观察,结果表明:P(VA-b-St)可在DMF溶剂中形成球状囊泡结构,其尺寸达到纳米级。