丙烯酸单体接枝纳米纤维素晶须的研究

以K2S2O8为引发剂,在纳米纤维素晶须(NCW)上接枝丙烯酸单体(AA),制备出丙烯酸接枝改性的纳米纤维素晶须.通过傅立叶变换红外光谱(FTIR)、透射电镜(TEM)、热重分析(TGA)等测试方法对接枝产物的性能进行了分析,并采用电导滴定的方法计算了接枝率以及表面取代基团含量.研究了反应条件对接枝率和接枝效率的影响.结果表明,在引发剂浓度为4 mmol/L,引发时间为5 min,纳米纤维素晶须与丙烯酸单体摩尔比为1: 1.5,反应时间为6 h的条件下,得到了接枝率为14.09%的丙烯酸接枝纳米纤维素晶须.实验证明,在NCW上可以接枝上丙烯酸,接枝率为14.09%的产物与NCW具有相似的表面形貌和热性能;TEM分析可知,接枝产物的分散性得到了提高;表面取代基团含量测试表明,接枝产物表面上的亲水性分散基团含量比NCW增加了5倍以上.     

纳米纤维素晶须表面接枝及其液晶性能研究进展

作为一种新兴的纳米生物材料,纳米纤维素日益受到各界的广泛关注,对其进行表面接枝改性并开发新的功能是十分必要的。本文综述了纳米纤维素晶须表面接枝的技术及研究进展,主要介绍了传统自由基聚合、离子和开环聚合及活性自由基聚合技术,包括氮氧自由基调控活性聚合、原子转移自由基聚合、可逆加成-断裂链转移聚合、单电子转移活性自由基聚合,讨论了各种接枝聚合方法的适用范围和优缺点。简述了点击化学在纳米纤维素晶须表面接枝的应用。通过各种聚合方法改性得到的纳米纤维素晶须接枝共聚物往往具有一些特殊的功能,某些接枝共聚物在适当的溶剂中可以形成液晶态,本文重点介绍了接枝改性的纳米纤维素晶须的液晶性能及其形成机理和影响因素等。     

聚丙烯酸甲酯接枝改性纳米纤维素

利用羰基二咪唑(CDI)的高活性活化纳米纤维素(NCC),使NCC表面带有高反应活性的碳碳双键。再以2-溴异丁酸乙酯为引发剂,铜丝为催化剂,制备出低分子量的聚丙烯酸甲酯(PMA)。然后采用活性自由基聚合将PMA接枝到活化的NCC表面,制备出PMA接枝改性的NCC。采用凝胶渗透色谱测定合成的PMA的分子量及分子量分布;通过傅立叶变换红外光谱及X射线衍射分析等测试方法对改性前后的NCC的结构和性能进行了分析。实验结果表明,通过单电子转移活性自由基聚合法合成的PMA分子量为2 000,分子量分布窄(分布指数为1.14),并且其成功接枝到NCC表面。     

竹纳米纤维素晶须的制备

利用硫酸水解竹浆纤维制备纳米纤维素晶须。通过原子力显微镜(AFM)和X射线衍射对纳米纤维素晶须的形貌、结构进行分析和表征,研究不同酸水解时间对纳米纤维素晶须结构的影响。结果表明,用竹浆制备的纳米纤维素晶须为长棒状结构。随着酸水解时间的延长,其长度和直径逐渐减小;在酸水解时间为20 min时无定形区逐渐被降解,其长径比最大,结晶度最高。     

聚合物表面紫外光接枝改性的研究

介绍聚合物表面紫外光接枝改性的研究方法,其中包括液相和气相接枝、接枝反应的引发方式及其机理,溶剂的影响和选择,针对不同改性要求对接枝单体的使用以及连续化操作的发展。此外,还简要介绍了聚合物表面接枝效果的测试方法和接枝后表面形态的观测方法     

纳米纤维素晶须及其在纳米复合材料中的应用进展

在对纤维素的结构及性质进行介绍的基础上,阐述了纤维素晶须悬浊液的制备及其性质及纳米纤维素晶须在复合材料中的应用,指出研究重点应放在制备过程中尺寸可控性、晶须的有机化改性以及有机改性后在非水溶性聚合物中的应用等问题上.     

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。     

硫酸铜助催化制备纳米纤维素晶须

以w(H2SO4)=64%的硫酸为催化剂,加入m(CuSO4)/m(纤维素)=0～3%的硫酸铜作助催化剂,水解脱脂棉,考察了制备纳米纤维素晶须(NCW)反应中反应温度、反应时间及硫酸铜加入量对纳米纤维素晶须产率、颗粒横截面直径、颗粒长度、颗粒长度与横截面直径之比和扫描电镜形貌的影响。结果表明,反应温度50℃、反应时间120min、催化剂投入量以m(CuSO4)∶m(纤维素)=1∶100为最佳工艺条件,纳米纤维素晶须对于脱脂棉的产率达58%左右,粒子的长径比为20～50,在原子力显微镜下观测到产品所成膜最高峰为27.95nm。加入了硫酸铜之后,缩短了反应时间,提高了反应效率和产率,减小了产物的颗粒直径,改善了纳米纤维素晶须的形状,因此,硫酸铜可以作为助催化剂有效地改善制备出的纳米纤维素晶须的形貌和尺寸分布。     

表面接枝PDEGMA纤维素纳米晶的制备及其温敏性

通过电子转移再生催化剂原子转移自由基聚合法(ARGET ATRP)制备了表面接枝聚二(乙二醇)甲基醚甲基丙烯酸甲酯(PDEGMA)的温敏性纤维素纳米晶(CNC-PDEGMA)。红外光谱和热重分析曲线表明纤维素纳米晶表面上成功地接枝了PDEGMA聚合物刷。CNC-PDEGMA室温条件下能在水溶液中稳定分散,温度升高至50℃时絮聚析出,在水溶液中表现出温敏性。CNC-PDEGMA固态薄膜在室温下亲水,高温下疏水且接触角稳定在120o以上,同样表现出明显的温敏性。     

纳米二氧化硅表面接枝聚合改性研究进展

综述了纳米二氧化硅(Nano-SiO2)微粒表面接枝聚合改性的基本方法,分析了各种表面接枝聚合改性方法的特点,以及接枝聚合改性的研究进展。     

Surface modification of ultra‐flat polydimethylsiloxane by UV‐grafted poly(acrylic acid) brushes

The graft density and surface topography of ultra‐flat polydimethylsiloxan films grafted with poly(acrylic acid) brushes by UV irradiation are investigated. The graft density keeps increase with the irradiation time and with the monomer concentration to a maximum, after which it remains unchanged in the former case or drops in the latter. Atomic force microscopy results show that a longer irradiation time, a higher monomer concentration and the addition of ethanol in the grafting solution are favorable to obtain the grafted polydimethylsiloxan films with flat surface. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Grafting of poly(acrylic acid) on polyamide yarn

Graft copolymerization of acrylic acid onto PA6 yarn was examined in this study. Prior to the grafting process, the fibers were activated with a benzene solution of benzoyl peroxide. Next, the fibers were put into a bath containing acrylic acid, a dispersing agent, and the activator of reaction. The effects of the main process parameters and auxiliary additives on the degree of grafting, quantity of the homopolymer formed during grafting, effectiveness of grafting, extent of conversion, and grafting ratio were determined. Using calculation factors such as the reaction efficiency, the extent of reaction, and the ratio of grafting, the conditions of grafting were found that made possible the reduction or elimination of the by‐product. Also determined were the influence of the degree of grafting on the moisture sorption and the swelling of modified fibers. In addition, the value of apparent activation energy was calculated (49.123 kJ/mol). © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1914–1919, 2001     

Poly(acrylic acid)-grafted magnetic nanoparticle for conjugation with folic acid

Poly(acrylic acid) (poly(AA))-grafted magnetite nanoparticles (MNPs) prepared via surface-initiated atom transfer radical polymerization (ATRP) of t-butyl acrylate, followed by acid-catalyzed deprotection of t-butyl groups, is herein presented. In addition to serve as both steric and electrostatic stabilizers, poly(AA) grafted on MNP surface also served as a platform for conjugating folic acid, a cancer cell targeting agent. Fourier transform infrared spectroscopy (FTIR) was used to monitor the reaction progress in each step of the syntheses. The particle size was 8 nm in diameter without significant aggregation during the preparation process. Photocorrelation spectroscopy (PCS) indicated that, as increasing pH of the dispersions, their hydrodynamic diameter was decreased and negatively charge surface was obtained. According to thermogravimetric analysis (TGA), up to 14 wt% of folic acid (about 400 molecules of folic acid per particle) was bound to the surface-modified MNPs. This novel nanocomplex is hypothetically viable to efficiently graft other affinity molecules on their surfaces and thus might be suitable for use as an efficient drug delivery vehicle particularly for cancer treatment.     

改性聚天冬氨酸/聚丙烯酸/羧甲基纤维素复合高吸水性树脂的制备和性能研究

以改性聚天冬氨酸（KPAsp）、丙烯酸(AA)和羧甲基纤维素(CMC)为原料,采用水溶液聚合法合成改性聚天冬氨酸/聚丙烯酸/羧甲基纤维素(KPAsp/PAA/CMC)复合高吸水性树脂。通过红外光谱（FTIR）、热重分析(TGA)和扫描电镜（SEM）对产物组成结构、热稳定性和表面形态进行表征。探讨了CMC和AA用量对复合高吸水性树脂吸液性能的影响,结果表明当m(CMC)/m(AA)/m(KPSI)=0.15:3:1时,树脂的吸液性能最佳,在去离子水和0.9% NaCl溶液中的吸水倍率分别达到830 g/g和130 g/g。研究了不同组成KPAsp/PAA/CMC吸水性树脂的盐敏感性、温度敏感性和pH敏感性,以及树脂在人工血、人工尿和不同浓度乙醇水溶液的吸液性能,结果表明复合树脂盐敏感性提高,在盐溶液中的吸液倍率为NaCl>FeCl3>CaCl2;低临界溶解温度(LCST)比KPAsp提高了15℃;在溶液pH=5和pH=9出现了两吸液高峰;在人工血和人工尿中的吸液倍率最大为211 g/g和142 g/g,在50%的乙醇水溶液中吸液倍率最大为295 g/g。     

Grafting of poly(acrylic acid) onto poly(amidoamine)-functionalized graphene oxide via surface-mediated reversible addition-fragmentation chain transfer polymerization

Graphene oxide was modified with third-generation poly(amidoamine) (PAMAM) to obtain dendrimer-grafted GO (DGO) with high content of functional groups. DGO's amine groups were conjugated with S-(thiobenzoyl)thioglycolic acid as proved by XPS and poly(acrylic acid) was grafted onto surface via RAFT polymerization (DGO@PAA). FT-IR results approved the synthesis of samples whereas TGA revealed 40.3% grafting of PAA. XRD patterns showed that with further modification, d-spacing increased. According to Raman spectra, modification resulted in more disordered structure whereas DGO@PAA showed a high value of I_D/I_G. Morphological studies were performed by SEM and TEM that showed a polymeric layer covered the surface of nanosheets.     

XPS studies of poly(acrylic acid) grafted onto UV photo-oxidized polystyrene surfaces

UV photo-oxidation of polystyrene was achieved with 253.7 and 253.7/184.9?nm radiation in the presence of an atmospheric pressure of oxygen and analyzed by X-ray photoelectron spectroscopy as a function of treatment time. A methodical increase in the atomic percentage (at.%) of oxygen occurred during 253.7?nm activation up to 2?h of treatment time. Photo-oxidation with the 253.7/184.9?nm lamps resulted in a saturation level of ca. 35 at.% O. Initially, C–O and C=O groups were formed and then O–C=O type moieties. Poly(acrylic acid) was partially and/or thinly grafted onto the oxidized polystyrene surfaces.     

Cross-Linked Poly(acrylic acid) Microgels from Precipitation Polymerization

Cross-linked poly(acrylic acid) microgels were prepared via thermally initiated free-radical precipitation polymerization in a binary organic solvent. N,N′-Methylenebisacrylamide (MBA) and 2,2′-azobisisobutyronitrile were used as cross-linker and initiator, respectively. The effect of (MAB) concentration on different features of sample (i.e., spectral characteristics, glass transition temperature, equilibrium swelling, gel content and rheological properties) was investigated. The Flory-Rehner equation and rubber elasticity theory were used to discuss the network structure of polymer. Apparent and rotational viscosities were used to determine the optimal cross-linker concentration. The sample maximum with value of viscosity was obtained using 1.6 mmol/L of the cross-linker. In addition the m and n parameter of Ostwald equation were investigated as well.     

Poly(acrylic acid)–poly(vinyl alcohol) copolymers with superabsorbent properties

Biodegradable polyacrylates were produced by a series of novel copolymerization and/or crosslinking techniques using poly(vinyl alcohol) (PVA) moieties modified by the incorporation of olefinic structures. PVA was modified by a tosylation and/or detosylation reaction. The functionalized PVA was copolymerized and/or crosslinked with acrylic acid or its partially neutralized form to give crosslinked polyacrylates that could swell in water. Their swelling behavior was determined under load. Degradation studies were performed in α-chymotrypsin, trypsin, and papain solutions. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 817–829, 1998     

Grafting of poly(acrylic acid) onto cellulosic microfibers and continuous cellulose filaments and characterization

Results from the grafting of poly(acrylic acid) (PAA) onto cellulosic microfibers and continuous cellulose filaments are presented. The grafting of PAA onto cellulosic fibers offers the possibility of developing enhanced ion exchange and fluid absorbency on the fibers. The grafting of PAA was carried out with a two‐step procedure. First, vinyl‐terminated ethoxy silane was deposited on the surface of the fiber. This was followed by a grafting polymerization reaction in aqueous media of acrylic acid with different concentrations of potassium persulfate (KPS), which acted as the initiator. The percentage of grafting increased with increasing KPS concentration and reached a maximum value at a concentration of about 0.4 wt % with respect to the weight of the fiber. The grafted copolymer was characterized by Fourier transform infrared spectroscopy. Strong evidence that the grafting reaction was successful was given by the presence of a band, with a maximum at 1732 cm^?1, that was characteristic of carbonyl group absorption and was not initially present in the cellulosic fibers. The water absorption of the cellulosic microfibers grafted with PAA was three times greater than the water absorption of the nongrafted microfibers. The mechanical properties of continuous cellulose filaments did not change drastically with PAA grafting. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 386–393, 2002