ATRP法均相制备纤维素/甲基丙烯酸丁酯接枝聚合物

在纤维素LiCl/DMAc均相溶液中,通过氯乙酰氯(ClC2OCl)与纤维素的均相酰化反应制得纤维素氯乙酸酯(Cellulose-ClAc)后,将其溶解在DMAc中,在FeCl2/4-二甲氨基吡啶(DMAP)的催化作用下,引发甲基丙烯酸丁酯(BMA)的均相ATRP聚合反应,制备了纤维素/BMA接枝共聚物(Cellulose-g-PBMA),考察了反应时间、反应温度、反应物配比等对酰化及接枝聚合反应的影响,并通过测试Cellulose-g-PBMA薄膜的接触角,对最终产物的疏水性能进行了研究;采用FTIR、NMR、SEM、TEM、AFM等分析手段对Cellulose-ClAc及Cellulose-g-PBMA的结构进行了表征;利用GPC分析了接枝聚合反应的活性特征。     

纤维素-甲基丙烯酸丁酯的原子转移自由基聚合

以2-溴异丁酰溴为溴化剂,在离子液体([Amim]Cl)中与纤维素反应制备溴化纤维素大分子引发剂,以溴化纤维素/CuBr/N,N',N',N″,N″-五甲基二乙烯基三胺(PMDETA)为引发体系,N,N-二甲基甲酰胺(DMF)为溶剂,研究了甲基丙烯酸丁酯(BMA)的原子转移自由基聚合反应(ATRP)。合成了结构明晰的以纤维素为主链,聚甲基丙烯酸丁酯为支链的接枝共聚物Cellulose-g-PBMA。通过FTIR、1HNMR和GPC分别对大分子引发剂和接枝聚合物进行了分析。考察了聚合反应的活性特征,反应时间、催化体系、溶剂对聚合物相对分子质量(简称分子量,下同)及分子量分布的影响。结果表明,聚合反应转换率随时间呈线性增加,反应过程是活性可控聚合,催化剂和溶剂分别选用PMDETA/CuBr和DMF使反应更高效。     

铈离子引发纤维素接枝甲基丙烯酸丁酯吸油材料的制备

以棉浆粕为基材,硝酸铈铵/HNO3为引发剂,甲基丙烯酸丁酯(BMA)为接枝单体,N,N′亚甲基双丙烯酰胺为交联剂,采用悬浮接枝聚合反应制备了纤维素基吸油材料。采用红外光谱、X射线衍射、扫描电镜、热重分析、差示量热等手段对产物结构进行了表征,考察了棉浆粕的引发及其后的接枝聚合反应,得到最佳工艺条件为:采用含有铈离子的0.15 mol/L的HNO3水溶液在45℃下将棉浆粕活化处理2.5 h后,在HNO3水溶液及交联剂存在下,与BMA发生接枝聚合反应;反应配比为纤维素/引发剂/单体/交联剂=1/0.03/1.5/0.03,聚合反应温度为50℃,反应时间为24 h。所得纤维素与BMA的接枝共聚物有较高的接枝率及理想的吸油性能。     

铈离子引发纤维素接枝甲基丙烯酸丁酯制备吸油材料的制备

以棉浆粕为基材,硝酸铈铵/HNO3为引发剂,甲基丙烯酸丁酯(BMA)为接枝单体,N ,N'-亚甲基双丙烯酰胺为交联剂,采用悬浮震荡接枝聚合反应制备了纤维素基吸油材料。采用红外光谱、X射线衍射、扫描电镜、热重分析、差示量热等手段对产物结构进行了表征,考察了棉浆粕的引发及其后的接枝聚合反应,得到最佳工艺条件为：采用含有铈离子的0.15 mol/L的HNO3水溶液在45 ℃下将棉浆粕活化处理2.5 h后,在HNO3水溶液及交联剂存在下,与BMA发生接枝聚合反应;反应配比为纤维素/引发剂/单体/交联剂=1/0.03/1.5/0.03,聚合反应温度为50 ℃,反应时间为24 h。所得纤维素与BMA的接枝共聚物有较高的接枝率及理想的吸油性能。     

纤维素在离子液体中均相酰化反应动力学

以离子液体1-烯丙基-3-甲基咪唑氯盐（AmimCl）为反应媒介,以微晶纤维素为原料,研究了离子液体中纤维素与酸酐均相酰化反应的动力学,通过实验考察了纤维素初始羟基浓度（0.21～0.85 mol·L^-1）及反应温度（353～373 K）对酰化反应速率的影响。结果表明,随着离子液体中纤维素羟基浓度的增大和反应温度的升高,纤维素酰化反应的速率都呈增大趋势。通过实验得到了纤维素均相酰化反应的动力学方程,纤维素乙酐酰化及乙酐、丁酐混合酸酐酰化反应的反应级数均为1,表观活化能分别为19.03 kJ·mol^-1和20.04 kJ·相似文献   

均相制备纤维素/丙烯酰胺/甲基丙烯酸丁酯接枝共聚物的研究

以氢氧化钠/硫脲/尿素新型溶液溶解纤维素,在均相条件下以丙烯酰胺(AM)、甲基丙烯酸丁酯(BMA)为接枝单体,过硫酸铵为引发剂,N,N′-亚甲基双丙烯酰胺(MBA)为交联剂,通过自由基聚合法制备出了纤维素/AM/BMA接枝共聚物。考察了聚合温度、时间以及(NH4)2S2O8、AM、BMA、MBA的用量对接枝效果的影响。利用红外光谱(FT-IR)、X射线衍射(XRD)和扫描电镜(SEM)对接枝产物进行了结构表征。实验结果表明,纤维素/AM/BMA接枝共聚物的最佳合成条件为:m(纤维素)∶m(AM)∶m(BMA)∶m[(NH4)2S2O8]∶m(MBA)=1∶4∶2∶0.05∶0.006,反应温度为65℃,反应时间为2h,在此条件下接枝率可达87%,接枝效率为36%。制备的纤维素/AM/BMA接枝共聚物的吸水倍率为583g/g。     

丙烯酸纤维素的合成与表征

以丙烯酰氯为酰化剂与纤维素的(5%-10%)LiCl/DMAc的均相溶液酰化反应,制备丙烯酸纤维素.采用FTIR、元素分析对反应产物进行了结构表征和取代度的测定.探讨反应温度、反应时间、酰化剂用量以及纤维素浓度对反应产物取代度的影响.得到了丙烯酰氯对纤维素较佳酰化反应条件:反应温度为50℃,反应时间为3.5h,丙烯酰氯官能团与纤维素羟基的物质的量之比为3.35,纤维素浓度为1.95%.     

茂金属/有机硼化物催化1-癸烯均相聚合反应动力学

以茂金属体系rac-Et（1-Ind）₂ZrCl₂/C₆H₅NH（CH₃）₂B（C₆H₅）₄/Al（i-Bu）₃催化1-癸烯聚合,对不同反应条件下（如温度,铝锆摩尔比）聚合反应动力学进行了研究。通过中间取样并利用GC测定单体浓度、GPC测定聚合物相对分子质量,获取动态的变化数据;结合聚合反应机理和物料平衡,对烯烃聚合反应做了一些假设,建立了聚合反应的动力学模型,该模型包括链引发、链增长、链转移至单体、链转移至活性中心和链终止几个反应。借助Levenberg-Marquardt算法对模型参数进行优化,通过该模型可以预测聚合反应速率、数均分子量和重均分子量等参数,验证实验结果表明模型预测值与实验数据相接近。模型显示链引发过程在几秒内完成,链增长反应相对于链转移反应具有较低的活化能,温度升高有利于链转移反应的进行。     

阳离子絮凝剂在纤维素/离子液体中的均相合成

纤维素在离子液体中有良好的溶解性能形成均相体系,文中制备了1-烯丙基-3-甲基氯代咪唑[Amim]Cl离子液体,与丙烯酰胺进行接枝共聚合及阳离子化,合成不同聚合度的纤维素阳离子絮凝剂,并与LiCl/DMAc体系进行比较,探讨其絮凝性能.结果显示:纤维素在[Amim]Cl中溶解性能良好、接枝共聚反应活性较好;纤维素聚合度...     

乙醇/水介质体系纳米碱式氯化镁晶须悬浮接枝甲基丙烯酸甲酯的研究

本文采用普通级卤片经“卤片——氨水法”制备纳米级碱式氯化镁晶须（nano-BMC）。并以此nano-BMC为原料,先将硅烷偶联剂γ-MPS引入其表面,再以乙醇/水为分散介质体系,水溶性引发剂K2S2O8(KPS)引发甲基丙烯酸甲酯（MMA）进行nano-BMC表面接枝聚合反应。通过傅立叶变换红外光谱仪（FT-IR）、扫描电镜(SEM)和X射线衍射仪（XRD）表征了nano-BMC/γ-MPS/PMMA纳米复合材料的结构及形态。分别讨论了乙醇/水介质体系、反应时间对晶须形态和悬浮接枝聚合反应的影响,通过设计正交实验分析了反应时间、反应温度、单体浓度、以及引发剂用量对接枝率、接枝效率的影响,得出了最佳接枝聚合反应条件。     

Graft copolymerization of vinyl monomers on modified cottons XV. Initiation by decomposition of aryl diazonium groups

Cellulose bearing aromatic amino groups was prepared by reacting cellulose with 2,4-dichloro-6-(p-nitroaniline)-s-triazine in presence of alkali followed by subsequent reduction of the nitro groups to amino groups. The latter were diazotized and grafting was achieved without homopolymer contamination through decomposition of the cellulose diazonium salt under the effect of metal ions. The dependence of grafting on the nature of the monomers was governed by the pH of the polymerization medium, reaction temperature and concentration of emulsifier. Using a large liquor ratio decreased the graft yield. The cellulose macroradical formed via decomposition of the diazo group was found very effective in inducting methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, butyl methacrylate, isopentyl methacrylate, acrylamide and 2-methyl-5-vinyl pyridine.     

A novel ligand for atom transfer radical polymerization

A ligand is a crucial element for atom transfer radical polymerization (ATRP). A new nitrogen-containing compound, 1,1’-(2,2’-(ethane-1,2-diylbis(butyl azanediyl)) -bis(ethane-2,1-diyl)) dipyrrolidin-2-one (DBBD), was synthesized and utilized as the ligand of copper halide for ATRP of methyl methacrylate (MMA) and methyl acrylate (MA). It was found that the CuBr/DBBD and Ethyl 2-bromoisobutyrate (EBIB) system could mediate the polymerization of MMA and the reaction was first-order kinetics, although the control of molecular weights was not perfect. When CuCl was used to replace CuBr, the molecular weights of obtained polymers were well controlled, which indicated the halide exchange could improve the controllability. In the polymerization of MA using Methyl 2-bromopropronate (MBP) or EBIB as initiator and CuCl/DBBD as catalyst, good control of the polymerization could be achieved and the molecular weights were very close to the predicted value.     

Synthesis and characterization of PBMA‐b‐PSt‐b‐PBMA triblock copolymers by atom transfer radical emulsion polymerization

Poly(n‐butyl methacrylate)‐b‐polystyrene‐b‐poly(n‐butyl methacrylate) (PBMA‐b‐PSt‐b‐PBMA) triblock copolymers were successfully synthesized by emulsion atom transfer radical polymerization (ATRP). Difunctional polystyrene (PSt) macroinitiators that contained alkyl chloride end‐groups were prepared by ATRP of styrene (St) with CCl₄ as initiator and were used to initiate the ATRP of butyl methacrylate (BMA). The latter procedure was carried out at 85°C with CuCl/4,4′‐di (5‐nonyl)‐2,2′‐bipyridine (dNbpy) as catalyst and polyoxyethylene (23) lauryl ether (Brij35) as surfactant. Using this technique, triblock copolymers consisting of a PSt center block and PBMA terminal blocks were synthesized. The polymerization was nearly controlled, ATRP of St from those macroinitiators showed linear increases in the number average molecular weight (Mn) with conversion. The block copolymers were characterized with infrared (IR) spectroscopy, hydrogen‐1 nuclear magnetic resonance (¹HNMR), and differential scanning calorimetry (DSC). The effects of the molecular weight of macroinitiators, concentration of macroinitiator, catalyst, emulsion, and temperature on the polymerization were also investigated. Thermodynamic data and activation parameters for the ATRP were also reported. POLYM. ENG. SCI., 45:1508–1514, 2005. © 2005 Society of Plastics Engineers     

还原剂对AGET ATRP乳液体系制备含氟涂料性能的影响

利用电子活化再生原子转移自由基聚合(AGETATRP)法,在Tween-80乳化体系下合成了甲基丙烯酸甲酯(MMA)-丙烯酸丁酯(BA)-丙烯酸六氟丁酯(HFBA)的三元共聚物。由于AGETATRP反应体系中加入了还原剂来还原Cu2+,所以研究了还原剂的用量对聚合反应可控性的影响以及对共聚物涂料性能的影响。研究发现增加还原剂用量,涂料的防水性、防油性、力学性能略有降低,但仍然表现出优异的防水性和良好的力学性能。     

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     

Studies on atom transfer radical emulsion polymerization of n‐butyl methacrylate

Atom transfer radical polymerization (ATRP) of n‐butyl methacrylate (BMA) in water‐borne media, catalyzed and initiated by CuCl/4,4′‐di (5‐nonyl)‐2,2′‐bipyridine (dNbpy) and Ethyl 2‐bromopropinate (BrCH₃CHCOOC₂H₅₎ was conducted. The influence of several factors, such as the amount of surfactant, catalyst, initiator and the reaction time, temperature on the stability of the latexes and the control of the polymerization was investigated. The nucleation mechanism of the latexes, thermodynamic data and activation parameters for the ATRP emulsion polymerization of BMA were also reported. POLYM. ENG. SCI. 45:297–302, 2005. © 2005 Society of Plastics Engineers.     

Properties of poly(n‐butyl methacrylate) prepared by reverse atom transfer radical polymerization in an aqueous dispersed system

Reverse atom transfer radical polymerization (ATRP) of n‐butyl methacrylate (BMA) in waterborne media using Cu(II) complexes with azo initiators (i.e., reverse ATRP) was conducted. The influence of several factors, such as surfactant, catalyst, and reaction time, on the stability of the emulsion, the particle size, the morphology of the emulsion particles, and the control of the polymerization was investigated. The results showed great differences between ATRP and conventional emulsion polymerization, especially the nucleation mechanism and the kinetics. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1542–1547, 2003     

纤维素自组装材料的研究进展

纤维素自组装材料具有可再生、生物相容性好、可生物降解且力学性能高的优点,是最有潜力的绿色材料之一。纤维素及其衍生物可直接与第二组装单体构筑纤维素自组装材料,也可利用化学修饰研究改性后的纤维素及衍生物的自组装行为,其中改性处理是最主要的构筑方式。本文着重介绍了纤维素及纤维素衍生物的改性与自组装,对比分析了长碳链疏水化、乙烯基类单体原子转移自由基聚合、脂肪族聚酯单体开环聚合、氨基酸单体可逆-加成断裂链转移聚合改性合成组装分子的原理与特点,综述了组装分子在水体系和非水体系中构筑纤维素自组装材料的最新研究状况,指出纤维素及纤维素衍生物改性后构筑的组装材料具有智能响应性,可通过外界环境变化（如温度、pH、CO₂等）调节纤维素自组装形态,在药物控释、生物传感器及生物膜材料方面有潜在的应用价值;最后对纤维素自组装材料的可增长点进行了展望。