Effect of polymer nature on the structure and properties of gel composites with incorporated bentonite particles

Composite gels based on polyacrylamide and poly(N-isopropyl acrylamide) with incorporated sodium bentonite particles are synthesized. It is shown that the presence of hydrophobic isopropyl groups in a polymer molecule promotes the subsequent formation of highly ordered aggregates of clay and cetylpyridinium chloride in a gel composite. An increase in temperature results in the collapse of composite gels based on poly(N-isopropyl acrylamide); however, no marked changes in the structure of lamellar aggregates of clay and surfactant are observed. It is revealed that the gel can stabilize lamellar structures formed in organoclay suspension prior to the incorporation into swollen polymer network.     

Control of particle cluster dispersion using responsive polymeric additives

The dispersion behavior of clusters of hydrophilic and hydrophobic silica treated with a thermoresponsive polymer has been investigated. The influence of the thermoresponsive interfacial chemistry was assessed by performing dispersion studies in poly(dimethylsiloxane) (PDMS) at 25 and 68 degrees C for agglomerates of powders incorporating poly(N-isopropyl acrylamide) (PNIPAM), a thermoresponsive polymer, and water. While the dispersion of clusters of hydrophilic silica was found to be temperature independent, dispersion of hydrophobic silica exhibited a temperature dependency. The response of the polymer upon temperature variation brings about modifications in the interparticle interactions of the PNIPAM-treated powders thus leading to changes in the cluster cohesivity. The dependence of the cluster cohesivity on temperature was evidenced through changes in the dispersion mechanism and kinetics of the treated silica clusters at both tested temperatures. In addition, optical microscopy of silica suspensions with and without PNIPAM at 25 and 60 degrees C, illustrated the effect of the polymer presence and configuration on the particle-particle interaction forces. While micrographs of the particles at 25 degrees C show less evidence of particle aggregation, the micrographs at 60 degrees C illustrate an increase in aggregation suggesting an enhancement in the attractive forces between particles.     

Synthesis of hydrogels based on poly(NIPAM) inserted into collagen sponge

The study presents the preparation of a semi-synthetic hydrogel based on poly(N-isopropyl acrylamide-co-diethylene glycol diacrylate) inserted onto the collagen porous membrane. The synthesis of the hydrogels was performed through radical copolymerization of N-isopropyl acrylamide (NIPAM) with diethylene glycol diacrylate (DEGDA) also as crosslinking agent, using ammonium persulfate as initiator and N,N,N',N'-tetramethylethylene diamine as activator, and it was achieved in the presence of the collagen matrix. The prepared hydrogels were characterized by Attenuated Total Reflectance-Fourier Transform Infrared Spectroscopy and Scanning Electron Microscopy. The swelling behaviour of the semi-interpenetrated polymer network related on the hydrogel composition, it was also evaluated. The pore sizes of the synthesized hydrogels, much larger than the typical mesh size of a conventional hydrogel, allow to consider the hybrid hydrogel based on the inserted poly(NIPAM-co-DEGDA) onto collagen fibrils as a super-porous hydrogel.     

Self-assembly of catecholic macroinitiator on various substrates and surface-initiated polymerization

A catechol-containing macroinitiator has been designed for the surface-initiated atom transfer radical polymerization (SI-ATRP) from various substrates at ambient temperature. Temperature-sensitive poly(N-isopropyl acrylamide) (PNIPAM) brushes were successfully grafted from a range of substrates surfaces, including metals and polyimides, via SI-ATRP using the resulting macroinitiator, which were characterized by X-ray photoelectron spectroscopy (XPS), water contact angle measurements, and atomic force microscopy (AFM). Effects of the temperature response behavior of PNIPAM brushes on the water contact angles and the impedance of the modified surfaces were also exhibited. The self-assembled film of macroinitiator and the resulting polymer brushes were both stable to soaking of basic solvents, and the brushes did not show any exfoliation or delamination even after 2 h of ultrasonic test. The advantages of the macroinitiator in strong interactions with surfaces and high stability and convenience make it possible to modify the native materials with polymer brushes in a convenient and nondestructive way. Importantly, the macroinitiator is compatible with microcontact printing, and patterned polymer brushes on Ti plate were demonstrated by microcontact printing of BrDOPAMA and the following SI-ATRP.     

The sol-gel approach towards thermo-responsive poly(N-isopropyl acrylamide) hydrogels with improved mechanical properties

A new type of thermo-responsive hydrogels based on the polymer poly(N-isopropyl acrylamide) (PNIPAA) has been synthesized with the sol-gel technology. For the preparation of this type of nano-structured hydrogels, the inorganic silica phase was synthesized by the sol-gel process in the presence of an aqueous solution of high molecular weight PNIPAA. This combination of the organic and inorganic phases forms hybrid hydrogels with a semi-IPN morphology. The unique structure of these hydrogels improves the mechanical stability to a great extent as compared to conventional PNIPAA-hydrogels. This was shown by stress-strain experiments and the capability to absorb and desorb large amounts of water. The silica only slightly influences the transition temperature of the hydrogels but allows us to vary the thermo-responsive properties of the materials to a great extent.     

双亲性光敏感遥爪聚合物C-PNIPAAm的合成与性能

以7-羟基-4-甲基香豆素为原料,依次与环氧氯丙烷、二硫化钠反应得一含香豆素基元的二硫化物(C-S-S-C),并以其与三丁基膦复合体系为链转移剂,偶氮二异丁腈(AIBN)为引发剂,N-异丙基丙烯酰胺(NIPAAm)为单体制备了末端为香豆素光响应基元的双亲性遥爪聚合物(C-PNIPAAm).用傅里叶变换红外(FT-IR)光谱、凝胶渗透色谱(GPC)、氢核磁共振(1H-NMR)等对该聚合物进行了结构表征.研究显示该双亲性遥爪聚合物可在水中直接形成胶束,并以荧光素为疏水性客体考察了聚合物胶束的光控释放行为.在波长大于310 nm的紫外光照射下,聚合物链末端的香豆素单元可进行光二聚,胶束结构随之改变,因而所负载的荧光素可得到逐步有效释放.动态激光光散射(DLS)检测显示,光二聚反应使聚合物胶束平均粒径从56.6 nm增大至101.0 nm.     

Synthesis and characterization of core-shell microspheres with double thermosensitivity

We have synthesized doubly thermosensitive core-shell microspheres composed of chemically cross-linked poly(N-n-propyl acrylamide-co-styrene) (P(nPA-co-S)) with different styrene contents as the core and linear poly(N,N-diethyl acrylamide) (PDEA), poly(N-isopropyl acrylamide) (PiPA), or poly(N-isopropyl methacrylamide) (PiPMA) as the shells. The morphologies and swelling properties of the core and the core-shell microspheres have been studied. The P(nPA-co-S) copolymers have a similar volume phase transition temperature regardless of the styrene content, indicating a two-layer structure in the microspheres with a PS-rich inner core and a PnPA-rich outer layer resulting from soap-free emulsion polymerization in water. Upon the addition of the second shell composed of linear thermosensitive polymers, the core-shell microspheres display a two-step shrinking behavior when heated. The P(nPA-co-S) core exhibits a volume phase transition temperature at 13-15 degrees C, while the shells of PDEA, PiPA, and PiPMA have volume phase transition temperatures at 28, 32, and 42 degrees C, respectively. The core-shell microspheres are composed of three layers and possess two volume phase transition temperatures.     

基于互穿网络结构的pH/温度双重刺激响应性微凝胶的研究

室温下采用氧化-还原引发体系,以低交联密度的聚(N-异丙基丙烯酰胺)(PNIPAM)微凝胶为种子,通过种子乳液聚合法合成由PNIPAM和聚丙烯酸(PAA)形成的具有互穿聚合物网络结构的微凝胶.傅立叶变换红外光谱分析结果表明微凝胶由PNIPAM和PAA两种聚合物组成,透射电镜表征结果证实微凝胶中PNIPAM和PAA两种聚合物形成了互穿网络结构.用动态激光光散射测试不同温度或pH值水介质中微凝胶的粒径,结果发现微凝胶具有良好的pH/温度双重刺激响应性.在水介质pH值大于5.5的情况下,PAA组分对微凝胶的体积相转变温度没有影响;而在水介质pH值为4.0的情况下,由于PAA与PNIPAM之间的氢键作用,微凝胶的体积相转变温度稍微降低.微凝胶中PAA组分含量越高,其pH刺激响应性越显著.     

Thermoresponsive poly(ionic liquid): Controllable RAFT synthesis,thermoresponse, and application in dispersion RAFT polymerization

The thermoresponsive poly(ionic liquid) of poly[1‐(4‐vinylbenzyl)‐3‐methylimidozolium tetrafluoroborate] trithiocarbonate (P[VBMI][BF₄]‐TTC) showing the soluble‐to‐insoluble phase transition in the methanol/water mixture at the upper critical solution temperature (UCST) was synthesized by solution RAFT polymerization and the synthesized P[VBMI][BF₄]‐TTC was employed as macro‐RAFT agent to mediate the RAFT polymerization under dispersion condition to afford the thermoresponsive diblock copolymer nanoparticles of poly[1‐(4‐vinylbenzyl)‐3‐methylimidozolium tetrafluoroborate]‐b‐polystyrene (P[VBMI][BF₄]‐b‐PS). The controllable solution RAFT polymerization was achieved as indicated by the linearly increasing polymer molecular weight with the monomer conversion and the narrow molecular weight distribution. The P[VBMI][BF₄]‐TTC macro‐RAFT agent mediated dispersion polymerization afforded the P[VBMI][BF₄]‐b‐PS nanoparticles, the size of which was uncorrelated with the polymerization degree of the P[VBMI][BF₄] block. Several parameters including the polymerization degree, the polymer concentration and the water content in the solvent of the methanol/water mixture were found to be correlated with the UCST of the poly(ionic liquid). The synthesized poly(ionic liquid) is believed to be a new thermos‐responsive polymer and will be useful in material science. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 945–954     

Electron-beam graft-modified membranes with externally controlled flux

Pre-irradiation grafting as a means to modify commerical poly(vinylidene fluoride) (PVDF) membranes has been studied. The membranes prepared were weak cation-exchange membranes (acrylic acid functionality), anion-exchange membranes (trimethyl ammonium functionality) and temperature-sensitive membranes (N-isopropyl amide functionality). Different graft loads were obtained by varying reaction time, radiation dose and in the case of acrylic acid the graft solution composition. The trimethyl ammonium chloride functionality was obtained by grafting vinyl benzyl chloride onto a PVDF membrane and aminating the benzyl chloride groups in a 45% trimethyl amine–water solution. For a membrane grafted with 9 wt% acrylic acid the flux increased approximately 70 times when the pH was decreased from 6 to 2. For a membrane with 5 wt% trimethyl ammonium functionality the flux increased both when pH was decreased below 3 and increased above 11. For a membrane grafted with 18 wt% N-isopropyl acrylamide a sharp increase of flux was observed when the temperature was raised above 32°C.     

Switchable photoluminescence of CdTe nanocrystals by temperature-responsive microgels

In the present study, we report a method for preparing a fluorescent thermosensitive hybrid material based on monodisperse, thermosensitive poly( N-isopropyl acrylamide) (PNIPAM) microgels covered with CdTe nanocrystals of 3.2 nm diameter. The CdTe nanocrystals were covalently immobilized on the surface of PNIPAM microgels. The chemical environment around the CdTe nanocrystals was modified by changing the temperature and inducing the microgel volume-phase transition. This change provoked a steep variation in the nanocrystal photoluminescence (PL) intensity in such a way that when the temperature was under the low critical solution temperature (LCST) of the polymer (36 degrees C) the PL of the nanocrystals was strongly quenched, whereas above the LCST the PL intensity was restored.     

Structure and Surface Properties of High-density Polyelectrolyte Brushes at the Interface of Aqueous Solution

Zwitterionic and cationic polyelectrolyte brushes were prepared by surface-initiated atom transfer radical polymerization of 2-methacryloyloxy- ethyl phosphorylcholine (MPC) and 2-(N,N-dimethylamino)ethyl methacrylate (DMAEMA), respectively. The poly(DMAEMA) brush was treated with methyl iodide to form poly[2-(methacryloyloxy) ethyltrimethylammonium iodide] [poly(METAI)]. The effects of ionic strength on brush structure and surface properties of densely grafted polyelectrolyte brushes were analyzed by contact angle measurements, neutron reflectivity (NR) and macroscopic friction tests. Both polyelectrolyte brushes exhibited hydrophilic properties. The contact angle of the poly(MPC) brush surface against water was ca. 0° in air and the contact angle of the air bubble in water was ca. 170°. The air bubble in water hardly attached to the poly(MPC) brush surface, indicating super hydrophilic characteristics. NR measurements of poly(MPC) and poly(METAI) brushes showed that the grafted polymer chains were extended from the substrate surface in a good solvent such as water. Interestingly, NR study did not reveal the shrinkage of the brush chain in salt solution. The polyelectrolyte brushes immersed in both water and NaCl solution at various concentrations showed a low friction coefficient and low adhesion force.     

刚性聚芳醚腈合成与性能研究

用２，６ 二氟苯甲腈和间苯二酚为原料，在碱性条件下，于非质子极性溶剂中，通过溶液高温缩聚法制备聚芳醚腈［Ｐｏｌｙ（ｃｙａｎｏａｒｙｌｅｔｈｅｒ）ＰＣＥ］．并用ＩＲ、ＤＳＣ、ＴＧ、ＷＡＸＤ等手段对其结构及热性能、结晶行为进行了研究．结果表明，ＰＣＥ高聚物不仅具备较好的耐高温和耐热老化性能，而且具有较好的结晶性能．同时，用对比的方法，对ＰＣＥ的晶体结构进行了初步的探讨．     

Determination of residual levels of unsaturation in partially hydrogenated poly(2,3-diphenyl-1,3-butadiene) using TG

The thermal degradation characteristics of head-to-head poly(styrene) [HHPS] should provide insight with respect to the impact of head-to-head placement on the thermal stability of traditional atactic head-to-tail polymer [HTPS]. The synthesis of head-to-head poly(styrene) must be accomplished indirectly. The head-to-head polymer is most satisfactorily obtained by dissolving metal reduction of poly(2,3-diphenyl-1,3-butadiene) [PDBD] generated by radical polymerization of the corresponding diene monomer. Full saturation of the polymer mainchain requires several iterations of the reduction procedure. Since the decomposition of poly(2,3-diphenyl-1,3-butadiene) is prominent at 374°C and that for head-to-head poly(styrene) is similarly facile at 406°C, it seemed feasible that TG of partially hydrogenated PDBD might be utilized as a convenient means of monitoring the extent of hydrogenation. This has been demonstrated for various levels of unsaturation remaining - from approximately 90 to less than 10%. Within this range the peak areas from the DTG plots of the partially hydrogenated polymer provide a good reflection of the ratio of unsaturated to saturated units in the polymer. Even low levels of unsaturation in the polymer may be detected by the asymmetry of the decomposition peak for the polymer. This revised version was published online in August 2006 with corrections to the Cover Date.     

Thermoactuated diffusion control in soft matter nanofluidic devices

The diffusive transport rate in a soft matter nanofluidic device is controlled with a thermoactuated hydrogel valve. The device consists of three giant unilamellar vesicles linearly conjugated by lipid nanotubes, with a solution of the stimuli-responsive polymer poly(N-isopropyl acrylamide) (PNIPAAm) in the central vesicle. The valve states "high (transport) rate" and "low (transport) rate" are obtained by heat-activated switching between PNIPAAm's dissolved and compact aggregated states. We show that three parameters influence the diffusion rate within the device: the increase of the transport rate caused by a decrease in PNIPAAm concentration upon compaction, the temperature dependence of the buffer viscosity, and the volume excluded by the PNIPAAm hydrogel compartment.     

Block copolymer mediated synthesis of amphiphilic gold nanoparticles in water and an aqueous tetrahydrofuran medium: An approach for the preparation of polymer–gold nanocomposites

The synthesis of polymer‐matrix‐compatible amphiphilic gold (Au) nanoparticles with well‐defined triblock polymer poly[2‐(N,N‐dimethylamino)ethyl methacrylate]‐b‐poly(methyl methacrylate)‐b‐poly[2‐(N,N‐dimethylamino)ethyl methacrylate] and diblock polymers poly(methyl methacrylate)‐b‐poly[2‐(N,N‐dimethylamino)ethyl methacrylate], polystyrene‐b‐poly[2‐(N,N‐dimethylamino)ethyl methacrylate], and poly(t‐butyl methacrylate)‐b‐poly[2‐(N,N‐dimethylamino)ethyl methacrylate] in water and in aqueous tetrahydrofuran (tetrahydrofuran/H₂O = 20:1 v/v) at room temperature is reported. All these amphiphilic block copolymers were synthesized with atom transfer radical polymerization. The variations of the position of the plasmon resonance band and the core diameter of such block copolymer functionalized Au particles with the variation of the surface functionality, solvent, and molecular weight of the hydrophobic and hydrophilic parts of the block copolymers were systematically studied. Different types of polymer–Au nanocomposite films [poly(methyl methacrylate)–Au, poly(t‐butyl methacrylate)–Au, polystyrene–Au, poly(vinyl alcohol)–Au, and poly(vinyl pyrrolidone)–Au] were prepared through the blending of appropriate functionalized Au nanoparticles with the respective polymer matrices {e.g., blending poly[2‐(N,N‐dimethylamino)ethyl methacrylate]‐b‐poly(methyl methacrylate)‐b‐poly[2‐(N,N‐dimethylamino)ethyl methacrylate‐stabilized Au with the poly(methyl methacrylate)matrix only}. The compatibility of specific block copolymer modified Au nanoparticles with a specific homopolymer matrix was determined by a combination of ultraviolet–visible spectroscopy, transmission electron microscopy, and differential scanning calorimetry analyses. The facile formation of polymer–Au nanocomposites with a specific block copolymer stabilized Au particle was attributed to the good compatibility of block copolymer coated Au particles with a specific polymer matrix. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1841–1854, 2006     

Microscopic inhomogeneities in weakly-charged temperature sensitive polymer gels and solutions

A comparison of small-angle neutron scattering (SANS) intensity functions, I(q), was made between gels and solutions of poly(N-isopropyl acrylamide-co-acrylic acid) (NIPA/AAc), where q is the magnitude of the scattering vector. I(q)'s were strongly dependent on polymer concentration as well as temperature. At low temperatures, I(q)'s for both gels and solutions were similar to each other and were monotonous decreasing functions. However, at high temperatures above θ, the so-called theta temperature of poly-NIPA in aqueous solution, both had a distinct peak and a significant difference appeared in I(q) due to the presence or absence of crosslinks. Origins of the peak and the differences in I(q) are discussed.     

Fabrication of dendritic gold nanoparticles by use of an ionic polymer template

A facile method for the fabrication of dendritic gold nanoparticles (NPs) by use of an ionic polymer template has been developed. In situ generation of an imidazolium-based (cationic) polymer, poly[1-methyl-3-(4-vinylbenzyl)imidazolium], with AuCl4- counteranions is achieved by addition of HAuCl4 into a solution containing poly[1-methyl-3-(4-vinylbenzyl)imidazolium chloride]. Subsequent reduction with NaBH4 in water or in a mixture of ethanol and water affords various NPs depending on the conditions, including large dendritic gold NPs that have been analyzed by transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDS), and selected area electron diffraction (SAED). The structures of the dendritic gold NPs were found to depend on the ethanol concentration. Scanning electron microscopy (SEM) images of the ionic polymer reveal that the solvent used to deposit the polymer strongly influences its structure and may be correlated to the structure of the resulting NPs.     

Dynamics of water in partially crystallized polymer/water mixtures studied by dielectric spectroscopy

The dielectric relaxation process of water was investigated for polymer/water mixtures containing poly(vinyl methyl ether), poly(ethyleneimine), poly(vinyl alcohol), and poly(vinylpyrrolidone) with a polymer concentration of up to 40 wt % at frequencies between 10 MHz and 10 GHz in subzero temperatures down to -55 degrees C. These polymer/water mixtures have a crystallization temperature TC of water at -10 to -2 degrees C. Below TC, part of the water crystallized and another part of the water, uncrystallized water (UCW), remained in a liquid state with the polymer in an uncrystallized phase. The dielectric relaxation process of UCW was observed, and reliable dielectric relaxation parameters of UCW were obtained at temperatures of -26 to -2 degrees C. At TC, the relaxation strength, relaxation time, and relaxation time distribution change abruptly, and their subsequent changes with decreasing temperature are larger than those above TC. The relaxation strength of UCW decreases, and the relaxation time and dynamic heterogeneity (distribution of relaxation time) increase with decreasing temperature. These large temperature dependences below TC can be explained by the increase in polymer concentration in the uncrystallized phase C(p,UCP) with decreasing temperature. C(p,UCP) is independent of the initial polymer concentration. In contrast to the relaxation times above TC, which vary with the chemical structure of the polymer and its concentration, the relaxation times of UCW are independent of both of them. This indicates that the factor determining whether the water forms ice crystals or stays as UCW is the mobility of the water molecules.     

SYNTHESIS AND ELECTRO-OPTICAL PROPERTIES OF POLY(2-ETHYNYLPYRIDINIUMTOSYLATE) HAVING PROPAGYL SIDE CHAIN

Novel conjugated ionic polymer was prepared by the polymerization of 2-ethynylpyridine with propargyl tosylate in refluxing methyl alcohol. The polymerization proceeded well in homogeneous manner to give a relatively high yield of polymer. The resulting poly(2-ethynylpyridinium tosylate) having propargyl side chain [poly(EPT-P)] were hygroscopic and soluble in water, methyl alcohol, DMF, and DMSO. The inherent viscosities of the polymers were in the range of 0.08-0.29dL/g. Instrumental analyses using NMR, IR, and UV-visible spectroscopies and elemental analyses indicated that the resulting poly(EPT-P) have a conjugated ionic polymer backbone carrying N-propargyl-2-pyridinium tosylate. Thermal and electro-optical properties of the polymers were also studied.