温敏性聚(N-异丙基丙烯酰胺)/聚丙烯酰胺互穿网络水凝胶

采用紫外引发法制备了物理交联的聚(N-异丙基丙烯酰胺)和化学交联聚丙烯酰胺为组分的互穿网络水凝胶。利用FFIR对所得的凝胶进行了结构分析;测定了该水凝胶在20℃时的溶胀率和50℃时的水保持率;利用DMA和DSC分别研究了水凝胶的储能模量随温度的变化及相转变行为。结果表明:与聚(N-异丙基丙烯酰胺)水凝胶相比,该水凝胶有较好的溶胀率;且具有超快的响应速率,如10 min内失去90%的水;其储能模量增加;虽然其相转变行为变弱,但临界溶解温度(LCST)有所提高。     

分散聚合法合成聚(N-异丙基丙烯酰胺)温敏性微凝胶

以PVP为稳定剂,在水或醇/水介质中通过分散聚合法合成出聚（N-异丙基丙烯酰胺）（PNIPAM）温敏性微凝胶。研究结果表明,可通过改变稳定剂用量和分散介质极性来控制PNIPAM微凝胶的大小,这两种因素对PNIPAM微凝胶的溶胀比有明显的影响,而对其相转变行为影响不大;交联剂用量对PNIPAM微凝胶的粒径、溶胀比和相转变行为都有比较明显的影响。PNIPAM微凝胶可能主要通过接枝共聚物聚结机理成核,通过初级粒子之间的聚并完成粒子增长过程。     

聚N-异丙基丙烯酰胺微凝胶的合成和应用进展

介绍了聚N-异丙基丙烯酰胺(PNIPAM)微凝胶的合成方法和环境响应性能,重点论述了PNIPAM微凝胶作为先进功能材料的最新进展。作为"智能"材料,PNIPAM微凝胶在不同领域具有广泛的应用,论述了PNIPAM微凝胶在作为微反应器模板合成纳米粒子、光学材料以及药物的定向释放和控制释放载体中的应用。     

pH及温度敏感性N-异丙基丙烯酰胺-丙烯酸共聚微凝胶的制备与表征

通过无皂乳液聚合得到了N-异丙基丙烯酰胺和丙烯酸的无规共聚物微凝胶,用电导仪测定了该微凝胶的表面羧基含量,用分光光度计测定了水凝胶溶液透光率在不同pH值和温度条件下的变化。结果表明,该微凝胶表面羧基含量随着聚合反应中丙烯酸质量分数的增加而增大;微凝胶表面羧基含量直接影响微凝胶的环境敏感性。     

聚(N-异丙基丙烯酰胺-co-丙烯酸)/二氧化钛复合微球的制备及表征

用溶胶凝胶法制备了二氧化钛(TiO2)纳米粒子,并用硅烷偶联剂γ-甲基丙烯酰氧基丙基三甲氧基硅烷(γ-MPS)对其表面进行改性,继而采用光引发自由基聚合制备了聚(N-异丙基丙烯酰胺-co-丙烯酸)/TiO2复合微球。考察了共聚单体丙烯酸(AA)、表面活性剂司盘80(Span80)在反应体系中的加入量对制备微球的影响,并比较了不同干燥方法对微球形态的影响。结果表明:合适的单体加入量、表面活性剂用量以及干燥方法可制备出分散性和球形度较好的复合微球。     

聚N-异丙基丙烯酰胺水凝胶研究进展

简要阐述了聚N-异丙基丙烯酰胺(简称PNIPAM)水凝胶的制备方法、性能特点、应用等方面的研究进展。利用PNIPAM特有的温敏性特点,可以将PNIPAM与其他有机物复合,改善了其机械强度和温度敏感性,大大提高了PNIPAM的响应速度和溶胀率。制备的高分子材料在生物医学、免疫分析、分离提纯、蓄热等领域都有广泛的应用。     

共轴微反应器制备单分散聚N-异丙基丙烯酰胺/蒙脱石纳米复合微凝胶

以蒙脱石(Clay)为交联剂,采用含有N,N,N′N′-四甲基乙二胺(TEMED)的豆油溶液为连续相,含有单体N-异丙基丙烯酰胺(NIPAm)、引发剂过硫酸钾(KPS)和分散有蒙脱石的水溶液为分散相,在共轴毛细管微反应器中制备了单分散聚N-异丙基丙烯酰胺/蒙脱石(PNIPAm/Clay)复合微凝胶。红外光谱分析表明:单体的C C双键的红外特征峰917、965 cm-1和992 cm-1在聚合后的微凝胶红外谱图中消失,而Clay的Si—O键特征峰1 000 cm-1则出现在微凝胶的红外谱图中。研究了不同内径的管头、分散相的流速和表面活性剂的浓度对微凝胶大小的影响。结果表明通过更换微反应器内管管头可以将微凝胶的直径从300μm变为450μm左右;通过调节连续相的流速可以制备粒径分散系数<5%、粒径在315～435μm的微凝胶;连续相中加入表面活性剂聚甘油聚蓖麻醇酯(PGPR)也可以有效降低微凝胶粒径。     

聚N-异丙基丙烯酰胺-丙烯酸共聚微凝胶荧光材料的合成与表征

本文用乳液聚合法合成了聚N-异丙基丙烯酰胺-丙烯酸P（NIPAM-co-AAc）共聚微凝胶,及其与Tb（Ⅲ）离子、α-噻吩甲酰三氟丙酮（HTTA）的二元和三元配合物。用透射电镜、Zeta电位、紫外光谱、红外光谱、荧光光谱进行了表征。结果表明,微凝胶粒径为400nm;Tb（Ⅲ）与微凝胶、HTTA之间以配位作用为主;微凝胶、HTTA和Tb（Ⅲ）之间能进行有效的能量传递。配合物的最佳激发波长为316nm,在此激发波长下Tb（Ⅲ）有荧光特征发射。     

PAA/PNIPAAm互穿网络水凝胶的微波合成与性能研究

以微波为辐射源,对丙烯酸(AA)水溶液进行辐照制得了PAA水凝胶。将脱水后的PAA水凝胶浸泡于含引发剂过硫酸钾(K_2S_2O_8)和交联剂N,N’-亚甲基双丙烯酰胺(BIS)的N-异丙基丙烯酰胺(NIPAAm)水溶液中,待溶胀平衡后取出,进行第二次微波辐照反应,制备了聚丙烯酸/聚N-异丙基丙烯酰胺互穿聚合物网络(PAA/PNIPAAm IPN)水凝胶,并对其溶胀性能进行了研究。研究结果表明,合成的IPN水凝胶兼具pH敏感性和温度敏感性,有望在药物控制释放领域得到应用。     

N-异丙基丙烯酰胺的合成与表征

介绍了一种N-异丙基丙烯酰胺(NIPAM)的改进合成方法,即以丙烯腈(0.15 mol)、异丙醇(0.15 mol)、对羟基苯甲醚(3×10-4 mol)、浓硫酸(0.45 mol)为原料合成NIPAM,收率为54.2%,并结合NIPAM的分子结构,用红外光谱、核磁共振氢谱、碳谱对其结构进行了表征,结果表明,所得的产物为NIPAM。     

Permeability properties of isometrically temperature-responsive poly(acrylic acid)-graft- oligo(N-isopropylacrylamide) gel membranes

A series of temperature-responsive hydrogels were prepared by grafting oligo(N-isopropylacrylamide) (ONIPAAm) chains onto a crosslinked poly(acrylic acid) (PAAc) network, intending an application to drug delivery systems (DDS). Cloud points and swelling ratios of the obtained PAAc-graft-ONIPAAm gels were measured as a function of temperature under various pH conditions. At pH > 4.5, the clear cloud points were observed at 31–33°C, which were almost the same values as that of poly(N-isopropylacrylamide) (PNIPAAm), whereas swelling/shrinkage phenomenon was not observed in the temperature range 25–45°C. It seemed that grafted ONIPAAm chains underwent the coil-to-globule transition, while the crosslinked PAAc network remained unchanged, due to the anionic charges on the main chains. In the presence of NaCl in the buffer solution, the phase transition temperature was slightly lowered. To assess the applicability of these temperature-responsive PAAc-graft-ONIPAAm gels to DDS, permeability of theophylline through the gel membranes was measured as a function of temperature. At a temperature below the cloud point, the permeability of theophylline was low, whereas it was high at an elevated temperature above the cloud point. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 1027–1034, 1998     

Interpolymer complexes of poly(acrylamide) and poly(N-isopropylacrylamide) with poly(acrylic acid): a comparative study

The interpolymer complexation, through successive hydrogen bonding, between poly(acrylamide) (PAAm) and poly(N-isopropylacrylamide) (PNiPAAm) with poly(acrylic acid) (PAA) in aqueous solution has been viscometrically and potentiometrically investigated. The stoichiometry of the complexes formed was determined. By comparing the strength of the two complexes the very important contribution of the hydrophobic interaction in their formation has been indicated.     

Synthesis and characterization of pH-sensitivity semi-IPN hydrogel based on hydrogen bond between poly(N-vinylpyrrolidone) and poly(acrylic acid)

A novel spherically shaped semi-interpenetrating network (semi-IPN) hydrogel, which is based on hydrogen bond between chemical crosslinked poly(N-vinylpyrrolidone) (PVP) and linear poly(acrylic acid) (PAA), was prepared. The semi-IPN hydrogel was synthesized by three steps: (1) linear PAA with different molecular weights were obtained by a reaction of free radical polymerization used 2,2′-azo-bis-iso-butyronitrile (AIBN) as an initiator; (2) crosslinked PVP bead was obtained by a reaction of N-vinylpyrrolidone with AIBN used as an initiator and N,N′-methylene-bis-acrylamide (NNMBA) used as a crosslinker by the way of suspension polymerization; (3) complexation occurred between suitable amount of aqueous solution of PAA and the porous PVP bead and was stabilized by multiple frost-defrost, from this step the semi-IPN hydrogel was obtained. Fourier transform infrared spectroscopy (FTIR) and differential scanning calorimetry (DSC) proved the presence of the hydrogen bond in the hydrogel. The swelling behaviour of the hydrogel was studied in buffer solution with different pH and NaCl aqueous solution. The results showed that the semi-IPN hydrogel had excellent pH-sensitivity in the range of pH from 2.25 to 4.00 and the small molecule salt had little influence on the swelling behaviour of the semi-IPN hydrogel over the range of concentration of NaCl aqueous solution investigated. The results were confirmed further by scanning electron microscope (SEM). The mechanism of swelling and deswelling was discussed.     

Synthesis and properties of a poly(acrylic acid)/montmorillonite superabsorbent nanocomposite

A novel superabsorbent nanocomposite was synthesized through the intercalation polymerization of partially neutralized acrylic acid and a sodium‐type montmorillonite powder with N,N′‐methylenebisacrylamide as a crosslinker and ammonium persulfate and sodium sulfite as a type of mixed redox initiator. The effects of such factors as the amounts of the sodium‐type montmorillonite, crosslinker, and initiator and neutralization degree on the water absorbency of the nanocomposite were investigated. The structure and micrographs of the superabsorbent were characterized with Fourier transform infrared spectroscopy, X‐ray diffraction, and scanning electron microscopy. The results showed that the acrylic acid monomer was successfully intercalated into the montmorillonite layers and banded together with them. The montmorillonite layers were exfoliated and basically dispersed in the composite on a nanoscale after the polymerization. The water absorbency of the nanocomposite was much higher than that of pure poly(acrylic acid). The optimum absorbency of the nanocomposite in distilled water and saline water (NaCl concentration = 0.9%) was 1201 and 83 g/g, respectively. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5725–5730, 2006     

Studies on poly(acrylic acid)/attapulgite superabsorbent composite. I. Synthesis and characterization

A novel poly(acrylic acid)/attapulgite superabsorbent composite was synthesized by graft copolymerization reaction of acrylic acid (AA) on attapulgite micropowder using N,N′‐methylenebisacrylamide (MBA) as a crosslinker and ammonium persulfate (APS) as an initiator in aqueous solution. The effects on water absorbency of such factors as reaction temperature, initial monomer concentration, degree of neutralization of AA, amount of crosslinker, initiator, and attapulgite were investigated. These crosslinked superabsorbent composites were characterized by thermogravimetetric analysis and scanning electron microscopy. The graft copolymerization reaction of AA on attapulgite micropowder was characterized by FTIR. The water absorbencies for these superabsorbent composites in water and saline solutions were investigated and water‐retention tests were carried out. Results obtained from this study show that the water absorbency of the superabsorbent composite synthesized under optimal synthesis conditions with an attapulgite content of 10% exhibited an absorption of 1017 g H₂O/g sample and 77 g H₂O/g sample in distilled water and in 0.9 wt % NaCl solution, respectively. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1596–1603, 2004     

Characteristics of acrylic acid and N-isopropylacrylamide binary monomers–grafted polyethylene film synthesized by photografting

Method for introducing grafted chains consisting of two types of monomer components, acrylic acid (AA) and N-isopropylacrylamide (NIPAAm), into low-density polyethylene (PE) film (thickness = 25 μm) was investigated by two photografting technique using xanthone photoinitiator at 60°C. In the first method (one-step method), AA and NIPAAm binary monomers were graftcopolymerized onto PE film. In the second method (two-step method), AA was first photografted onto PE film and then NIPAAm was further introduced into the AA-grafted PE film by a second-step photografting. Water absorbencies of the grafted films (one- and two-step samples) prepared by the one- and two-step methods, respectively, decreased in the order of AA-grafted film > one-step sample > two-step sample > NIPAAm-grafted film. The water absorbency steeply decreased at 20 to 40°C with increasing temperature when immersed in water at the temperatures (5–60°C) for 24 h. Thermosensitivity, which was defined as the ratio of water absorbencies of the grafted samples at 5 and 60°C, was higher for the one-step sample than the two-step one. The different extent of the water absorbency and the thermosensitivity between both samples is discussed in terms of location of grafted chains in the film substrate, which was determined by electron probe microanalysis and attenuated total reflection–infrared measurements, and monomer sequence distribution of the grafted chains. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:2057–2064, 1998     

Synthesis and characterization of chitosan/poly(acrylic acid) polyelectrolyte complex

Polyelectrolyte complex based on chitosan and acrylic acid monomer by photoinitiated free‐radical polymerization in the absence of crosslinker showed a large transition in swelling in response to changes in pH of surrounding medium. Their ability to swell arises from polyelectrolyte interactions and molecular structure of the complex. The main properties of interest that related to the molecular structure, swelling volumes, glass transition temperature, and elastic modulus of the complex were investigated. The effect of water content, the only variable in the sample component, played an important role in molecular structure of the complex and as a consequence, the extent of intermolecular linkage, especially amide bonds which in turn governed the degree of swelling of the polyelectrolyte complex in this study. The decreased degree of swelling and higher temperature shift of glass transition temperature was found with increased water content, whereas increased modulus of elasticity of dry complex was found in lower water content of synthesis component. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1025–1035, 2002     

A study of blending and complexation of poly(acrylic acid)/poly(vinyl pyrrolidone)

Poly(acrylic acid) (PAA) and poly(vinyl pyrrolidone) (PVP) were chosen to prepare polymer complex and blends. The complex was prepared from ethanol solution and the blends were prepared from 1-methyl-2-pyrrolidone solution. DSC results show that the T_gs of the PAA/PVP blends lie between those of the two constituent polymers, whereas T_g of the PAA/PVP complex is higher than both blends and the two constituent polymers. TGA results show that degradation temperature, T_d, of PAA increases upon adding PVP in the blend, but thermal stability of the complex is higher than that of the blends as reflected by the higher T_d. Both FTIR and high-resolution solid state NMR show strong hydrogen bonding between PAA and PVP by showing significant chemical shift. The T_1ρ(H) measurement shows that the homogeneity scale for the blend is at ∼20 Å and that for the complex is ∼15 Å.     

Synthesis of poly(acrylic acid)/sodium humate superabsorbent composite for agricultural use

A novel poly (acrylic acid)/sodium humate superabsorbent composite was synthesized by graft copolymerization reaction of acrylic acid (AA) on sodium humate micropowder using N,N′‐methylenebisacrylamide (MBA) as a crosslinker and potassium peroxydisulfate (KPS) as an initiator in aqueous solution. The effects on water absorbency of factors such as reaction temperature, initial monomer concentration, and degree of neutralization of AA, amount of crosslinker, initiator, and sodium humate were investigated. The superabsorbent composite was characterized by scanning electron microscopy, and the graft copolymerization reaction of AA on sodium humate micropowder was characterized by IR spectroscopy. Results obtained from this study show that the water absorbency of the superabsorbent composite synthesized under optimal conditions for synthesis with a sodium humate content of 5.3% exhibited absorption of 684 g H₂O/g sample in distilled water. Water‐retention in soil is enhanced by the use of the superabsorbent composite. The effect of superabsorbent composite on the growth of corn is reported. The superabsorbent composite may be of use as water management materials for agriculture purposes in desert and drought‐prone areas. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5137–5143, 2006     

快速响应的温敏性PNIPAAm／粘土复合水凝胶的合成及性能研究

以碳酸钠为制孔剂合成了快速响应的温敏性PNIPAAm／粘土复合水凝胶(NNC水凝胶),DSC分析表明,其体积相转变温度在33℃左右,与传统的PNIPAAm水凝胶没有很大的偏差。动力学研究表明,该水凝胶在温敏膨胀或收缩时,具有快速的响应速率,在5 min内的失水率达90％以上,这与扫描电镜观察到水凝胶具有大而连贯的孔洞结构相一致。