Preparation of silica/poloxamer composite by sol-gel process and pore control of silica gel obtained from the composite

Silica gels that controlled the pore size were prepared by calcination of silica/organic polymer (50/50 wt %) composites prepared by the sol-gel process. Poly(ethylene oxide) (PEO)-poly(propyrene oxide) (PPO)-PEO triblock copolymers, which are called poloxamers, were used as an organic polymer. The pore control of the silica gels was carried out by changing the molecular weight of PEO or PPO in the poloxamers. The silica gels obtained by the above procedure had a dual pore size of around 4 nm and below 2 nm in diameter, and the specific surface area was 500–1000 m²/g. The poloxamer molecules were supposed to be dispersed monomolecularly in the composites. Therefore, the pore structure of the silica gels reflected the structure of the poloxamer and, particularly, the radius of gyration of PPO in the composites. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 763–768, 1997     

Synthesis and properties of acrylate‐acrylic acid‐acrylate triblock copolymers with gemini structure by RAFT polymerization

A class of gemini structure block copolymers with a trithiocarbonate ester spacer group had been synthesized with S, S′‐bis (R, R′‐dimethylacetic acid) trithiocarbonate as reversible addition fragmentation chain transfer agents and acrylic acid as the second monomer. These triblock copolymers were characterized by ¹H NMR spectroscopy, gel permeation chromatography in terms of their compositions, molecular weights and behaviour at the air–water interface. The results showed that the weight‐average molecular weight was larger than theoretical molecular as the acrylate side chain increased. The polymer neutralized by sodium hydroxide solution had low critical micelle concentration which was <10^?2 mol L^?1 in water. TEM and DLS showed that it formed a special micelle structure with large pore structure which might lead to low surface tension and critical micelle concentration in water. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43017.     

Star‐shaped amphiphilic block polyurethane with pentaerythritol core for a hydrophobic drug delivery carrier

To obtain polyurethane micelles with excellent stability as a drug delivery carrier, star‐shaped amphiphilic block polyurethane (SAPU) was successfully synthesized by the ‘arm‐first’ method, using methoxypoly(ethylene glycol) and poly(ε‐caprolactone) diol as soft segments, hexamethylene diisocyanate as hard segments and pentaerythritol as the core. The structure of the SAPU was characterized by Fourier transform infrared spectroscopy, ¹H NMR spectroscopy and gel permeation chromatography. The micellization behaviour and micelle properties of SAPU were measured by the pyrene fluorescence probe technique, ¹H NMR, SEM and dynamic light scattering. The results indicated that SAPU could self‐assemble to form nanomicelles in aqueous solution and that the micelles showed excellent stability upon dilution and storage. Indometacin as a model drug could be incorporated into SAPU micelles and be released sustainedly. Meanwhile, the hydrophilic segment content and the molecular weight of SAPU had effects on the micelle properties. In addition, SAPU exhibited good cytocompatibility estimated by methylthiazole‐tetrazolium assay. © 2016 Society of Chemical Industry     

Influence of gel and molecular weight on the properties of natural rubber

The influence of gel and molecular weight on the properties of natural rubber has been described. Crystallization, stress relaxation and orientation properties of different samples have been studied. Samples having different gel contents but similar molecular weights and samples having the same gel content with varying molecular weights have been prepared by extracting whole natural rubber. The gel content was varied from 1.5 to 29% and molecular weight from 1 × 10⁵ to 9.9 × 10⁵ g mol⁻¹. The gels reduce the overall crystallinity measured by differential scanning calorimetric experiments after freezing the samples for different time periods at −15°C. They also have a stiffening effect on the tensile relaxation modulus and decrease the rate of relaxation significantly. Birefringence, which measures the orientation and stress-induced crystallization, increases with time at high elongation for samples containing gels. At lower elongation, however, the birefringence of unvulcanized samples decreases with time. This decrease is less for gel samples. Natural rubbers of high molecular weight behave similarly in the above properties when compared to low molecular weight samples. The effect of gel is more predominant than that of molecular weight.     

Preparation and properties of poly(benzyl glutamate)–poloxamer–poly(benzyl glutamate) and poly(glutamic acid)–poloxamer–poly(glutamic acid) triblock polymers

The novel block copolymer poly(benzyl glutamate) (PBLG)–polomamer–PBLG were synthesized from glutamic acid and poloxamer in six steps with three different molecular weights, and another new block copolymer, poly(glutamic acid) (PGA)–poloxamer–PGA, was obtained by the benzyl deprotection of PBLG–poloxamer–PBLG. The obtained compounds were characterized by IR spectroscopy, gel permeation chromatography, and ¹H‐NMR. The in vitro biological degradation and water absorption of PBLG showed that a greater proportion of PBLG in the copolymer led to a slower degradation and weaker water absorption, so the speed of degradation and water absorption could be adjusted through adjustment of the ratio of poloxamer. Both PBLG–poloxamer–PBLG and PGA–poloxamer–PGA exhibited lower cytotoxicity and good biocompatibility in the methyl thiazolyl tetrazolium (MTT) assay. The results show that both block polymers are promising as drug‐carrier materials. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Effect of zone drawing accompanied with crosslinking on the structure and properties of ultrahigh molecular weight polyethylene gel film

To enhance the thermal properties of ultrahigh molecular weight (UHMW) (viscosity-average molecular weight of 6 × 10⁶) polyethylene (PE) gel film, this was crosslinked by dicumyl peroxide (DCP) during a high-temperature zone drawing, which is effective to orient film. Through a series of experiments, it turned out that crosslinking actualized by an optimum amount of DCP and high-temperature zone drawing technique caused significant changes in the structure and properties of UHMW PE gel film. That is, crosslinking increased storage modulus of UHMW PE gel film at 25°C, resulting in improving thermal properties of the film. On the contrary, the crosslinking effect played a hindering role in raising the draw ratio of UHMW PE gel film. Maximum storage modulus of 165 GPa at 25°C could be obtained at the draw ratio of 324 of uncrosslinked homo-PE gel film. In the case of crosslinked PE gel film, the highest storage modulus at 25°C reached 65 GPa at maximum draw ratio of 150. Crosslinked film exhibited high modulus, even at 190°C, to some extent, while uncrosslinked homo-PE gel film was molten completely at 150°C. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 1583–1590, 1997     

In situ gel forming systems of poloxamer 407 and hydroxypropyl cellulose or hydroxypropyl methyl cellulose mixtures for controlled delivery of vancomycin

Poloxamers are a family of triblock copolymers consisting of two hydrophilic blocks of polyoxyethylene separated by a hydrophobic block of polyoxypropylene, which form micelles at low concentrations and form clear thermally reversible gels at high concentrations. The objective of this study was to develop an in situ gel forming drug delivery system for vancomycin using the minimum possible ratio of poloxamer 407 (P407). Decreasing the concentration of poloxamer could reduce the risk of hypertriglyceridemia induction. Different additives were added to the poloxamer formulations. It was observed that among different additives, hydroxypropyl methyl cellulose (HPMC) and hydroxypropyl cellulose (HPC) can decrease poloxamer concentration required to form in situ gelation from 18 to 10%. The dynamic viscoelastic properties of the samples were determined. Both the storage modulus and the loss modulus of the samples increased abruptly as the temperature passed a certain point. The gelling temperature was in the order of P407 : HPC (10 : 10 w/w) < P407 : HPMC (10 : 10 w/w) < P407 : HPMC (15 : 5 w/w) < P407 : HPC (15 : 5 w/w). Drug release rate could be controlled by changing the type and ratio of additives as well as the amount of drug loaded. It can be concluded that combining P407 and cellulose derivatives could be a promising strategy for preparation of thermally reversible in situ gel forming delivery systems with low poloxamer concentration. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Development of a poloxamer analogs/bioadhesive polymers‐based in situ gelling ophthalmic delivery system for tiopronin

The purpose of this study was to develop a poloxamer analogs/bioadhesive polymers‐based in situ gelling ophthalmic delivery system aiming at enhancing bioavailability and anticataract effect. The effect of poloxamer 407 (P407), poloxamer 188 (P188), carbopol 934P (C934), and sodium hyaluronate (NaHA) concentration on the gelation temperature (GT) was examined. The GT of P407 based in situ gel increased with an increase in the P188 concentration. NaHA and C934 lowered the GT of poloxamer analogs based in situ gel. Correlation analysis demonstrated that in vitro drug release from in situ gel was controlled by gel dissolution and followed zero‐order kinetics. Tiopronin in vitro transcorneal transit accorded with zero‐order kinetics. Twenty‐two percent P407 and 6% P188 containing 0.2% NaHA based formulation can be chosen as in situ gel matrix of tiopronin because of proper GT and sustained releasing ability. In vivo study showed that the area under the aqueous humor–concentration time curve of tiopronin increased by 1.6 folds for in situ gel, compared with tiopronin aqueous solution. High‐dose tiopronin in situ gel and solution delayed the development of selenite cataract 6 d and 4 d, respectively. The results showed that tiopronin in situ gel exhibits higher bioavailability and therapeutical effect. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Molecular weights of poly(butyl 2-cyanoacrylate) produced during nanoparticle formation

The molecular weights and distributions of poly(buty1 2-cyanoacrylate) produced during the formation of nanoparticles under a range of polymerisation conditions have been determined by gel permeation chromatography. The data indicate that the type of steric stabiliser and concentration of the monomer added to the polymerisation medium influences the resulting molecular weight of the polymer. In all systems the bulk of the polymer had a low molecular weight (<10000) but nanoparticles stabilised with dextrans or poloxamer 188 also yielded a high molecular weight component (>20000). The results are interpreted with regard to the possible effects on the degradation of nanoparticles and their drug release characteristics. Tentative proposals are made concerning the mechanisms of nanoparticle formation.     

Improved texture analysis for hydrogel characterization: Gel cohesiveness,adhesiveness, and hardness

The texture properties of formulation are an important parameter in optimization of topical formulations. These properties will affect applicability of the formulation at the administration site and therapy outcome. Our aim was to develop a fast and reliable method to characterize texture properties of hydrogels, namely cohesiveness, adhesiveness, and hardness. During the method development, we realized that the measurements setup needed to be adjusted for each hydrogel type, namely Carbopol, chitosan, and poloxamer hydrogels. The influence of the polymer concentration, pH, and incorporation of additives such as glycerol, drug solution, or liposomes on the texture properties, as determined by Texture Analyzer, was evaluated. In addition, the new method was applied to determine the changes during the accelerated stability testing. While Carbopol and poloxamer gels showed a linear relationship between the polymer concentration and texture properties, for low molecular weight chitosan gels the properties increased in exponential manner with increasing polymer concentration. The effect of incorporated liposomes on the gel properties was found to be dependent on the type of hydrogel. The hydrogel hardness was affected by the temperature as seen in accelerated stability testing. The method represents a valuable tool in pharmaceutical and cosmetics formulation development. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Enzymatic synthesis of soluble phenol polymer in water using anionic surfactant as additive

In phosphate–citric acid buffer (pH = 8.0) containing sodium dodecylbenzenesulfonate (SDBS) as a surfactant, enzymatic polymerization of phenol catalyzed by horseradish peroxidase (HRP) is efficiently performed. The as‐synthesized phenol polymer is completely soluble in organic solvents such as dimethylfomamide, dimethylsulfoxide, acetone and tetrahydrofuran. The aqueous micelle system provides a new environmentally friendly method for HRP‐catalyzed phenol polymerization. The effects of the dosage of SDBS and reaction temperature on the yield of the target phenol polymer are investigated. The soluble phenol polymer is composed of phenylene and oxyphenylene units as determined using infrared and ¹ H NMR spectral analyses. The number‐average molecular weight calculated from gel permeation chromatography (GPC) is in the range 900–1500 g mol^?1 and the dispersity in the range 3.4–6.3. In all cases, the values of weight‐average molecular weight characterized using GPC–static light scattering are tens of thousands. It is concluded that a branched structure is produced in the aqueous micelle system. The phenol polymer prepared possesses good thermal stability for it is completely decomposed at a temperature as high as 628 °C in air.     

酸枣仁多组分鼻用温敏凝胶的制备、评价及其联合释放研究

以泊洛沙姆P407和泊洛沙姆P188为凝胶材料,甘油或聚乙二醇为保湿剂,制备了复方添加酸枣仁中主要有效成分酸枣仁皂苷a、酸枣仁皂苷b、斯皮诺素的复方多组分鼻用温敏凝胶。以无膜溶出法进行了凝胶体外释放评价,以渗透膜法考察了其活性成分的联合释放规律,通过f2检验法证实凝胶活性成为的体外释放行为具有协同性。     

Polymer gel electrolytes prepared from P(EG‐co‐PG) and their nanocomposites using organically modified montmorillonite

Polymer gel electrolytes were prepared by thermal crosslinking reaction of a series of acrylic end‐capped poly(ethylene glycol) and poly(propylene glycol) [P(EG‐co‐PG)] having various geometries and molecular weights. Acrylic end‐capped prepolymers were prepared by the esterification of low molecular weight (M_n: 1900–5000) P(EG‐co‐PG) with acrylic acid. The linear increase in the ionic conductivity of polymer gel electrolyte films was observed with increasing temperature. The increase in the conductivity was also monitored by increasing the molecular weight of precursor polymer. Nanocomposite electrolytes were prepared by the addition of 5 wt % of organically modified layered silicate (montmorillonite) into the gel polymer electrolytes. The enhancement of the ionic conductivity as well as mechanical properties was observed in the nanocomposite systems. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 894–899, 2004     

Properties of Polyisoprene-Based Pressure Sensitive Adhesives Crosslinked by Electron Beam Irradiation

Many pressure sensitive adhesives are based on partially-crosslinked blends of an elastomer and a tackifying resin. In this work, a model pressure sensitive adhesive system was studied based on anionically-polymerized polyisoprenes. The effects of the initial molecular weight of the polyisoprene and the degree of crosslinking on the adhesive properties were investigated. The adhesives were crosslinked by electron beam irradiation to achieve particular levels of gel content. The dependence of gel content on dose and molecular weight is in good agreement with statistical crosslinking theory. The molecular weight of the soluble fraction was always dominated by that of the initial elastomer. With regard to creep resistance, it was observed that high gel content could compensate for low molecular weight. This was not true of the peel behavior.     

Solute and solvent effects on the thermorheological properties of poly(oxyethylene)–poly(oxypropylene) block copolymers: Implications for pharmaceutical dosage form design

Despite their widespread use as platforms for topical drug delivery systems, there is a relative lack of information concerning the thermorheological and viscoelastic properties of poloxamer systems and the effects of formulation components on these properties. To address this deficit, we examined the effects of the poloxamer concentration (25 and 35% w/w), molecular weight blend (poloxamer 407 and poloxamer 188), cosolvents (ethanol, propylene glycol, and glycerol), and presence of inorganic and organic electrolytes (sodium chloride and tetracaine hydrochloride, respectively) on these properties. The rheological properties were examined with a rheometer (4‐cm‐diameter, stainless steel, parallel‐plate geometry) in either thermal sweep (0.5 Hz) or frequency sweep (0.01–1.0 Hz and 37°C) modes. Increasing the poloxamer concentration increased the elasticity [i.e., increased the storage modulus (G′) and reduced the loss tangent (tan δ)] and reduced the sol–gel transition temperature (T_m) of all the formulations. Decreasing the ratio (407:188) increased T_m and reduced the elasticity of all the formulations. Increasing the concentration of ethanol, propylene glycol, or glycerol in the solvent reduced T_m. The presence of ethanol reduced G′ and increased tan δ in a concentration‐dependent fashion, whereas the viscoelastic properties of the poloxamers were more tolerant of glycerol (in particular) and propylene glycol. The elasticity of the formulations containing up to 10% glycerol and 5% propylene glycol was increased with respect to their aqueous counterparts. The presence of sodium chloride reduced T_m and, at lower concentrations (1 and 3%), increased G′ and reduced tan δ for aqueous poloxamer systems. Conversely, the addition of a model therapeutic agent, tetracaine hydrochloride (5 and 7% w/w), significantly increased T_m and altered the viscoelastic character of the poloxamer system, notably reducing G′ and increasing the loss modulus and tan δ. Alterations in the viscoelastic and thermorheological properties of aqueous poloxamer systems will have implications for their clinical performance. This study, therefore, has highlighted the need for the rational selection of components in the formulation of poloxamer systems as platforms for topical drug delivery. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1016–1026, 2003     

Synthesis and aggregation behavior of four types of different shaped PCL‐PEG block copolymers

Biodegradable, amphiphilic, linear (diblock and triblock) and star‐shaped (three‐armed and four‐armed) poly[(ethylene glycol)‐block‐(ε‐caprolactone)] copolymers (PEG–PCL copolymers) were synthesized by ring‐opening polymerization of ε‐caprolactone (CL) with stannous octoate as a catalyst, in the presence of monomethoxypoly(ethylene glycol) (MPEG), poly(ethylene glycol) (PEG), three‐armed poly(ethylene glycol) (3‐arm PEG) or four‐armed poly(ethylene glycol) (4‐arm PEG) as an initiator, respectively. The monomer‐to‐initiator ratio was varied to obtain copolymers with various PEG weight fractions in a range 66–86%. The molecular structure and crystallinity of the copolymers, and their aggregation behavior in the aqueous phase, were investigated by employing ¹H‐NMR spectroscopy, gel permeation chromatography and differential scanning calorimetry, as well as utilizing the observational data of gel–sol transitions and aggregates in aqueous solutions. The aggregates of the PEG–PCL block copolymers were prepared by directly dissolving them in water or by employing precipitation/solvent evaporation technique. The enthalpy of fusion (ΔH_m), enthalpy of crystallization (ΔH_crys) and degrees of crystallinity (χ_c) of PEG blocks in copolymers and the copolymer aggregates in aqueous solutions were influenced by their PEG weight fractions and molecular architecture. The gel–sol transition properties of the PEG–PCL block copolymers were related to their concentrations, composition and molecular architecture. Copyright © 2006 Society of Chemical Industry     

转化率为65%的SBR1500丁苯橡胶基本特性的研究

对吉化有机合成厂试生产的单体聚合转化率为65％的丁苯橡胶SBR1500进行了基本特性研究,重点考核了生胶分子量、分子量分布和凝胶含量。结果表明,物性达到国际优级品指标,分子量、分子量分布和凝胶含量与转化率为62％的正常产品相当。     

Determination of molecular weight averages and molecular weight distribution by g.p.c. of N-trifluoroacetylated polyamides

To determine their molecular weight averages and molecular weight distribution, N-trifluoroacetylated (TFA) polyamides are studied using gel permeation chromatography in tetrahydrofuran at 25°C. Several calibration methods (calibration with polydisperse standards, universal calibration) are tested; among these, direct calibration of M_w of polydisperse samples vs. peak maximum of the corresponding g.p.c. chromatogram leads to the best results. Calculated molecular weight averages of nylon 6-TFA and Trogamid^R-TFA are compared with data from light scattering, viscometry and osmometry.     

Evolutionary computing approach for evaluating flory distribution curves in gel permeation chromatography: Study of the poly(1‐octene) system

We carried out deconvolution of the molecular weight distribution curves from gel permeation chromatography for polyolefins into individual active sites considering Flory distribution by an evolutionary‐computing‐based real‐coded genetic algorithm, a nonlinear multivariate optimization algorithm. We applied the deconvolution to homopolymers of 1‐octene synthesized using heterogeneous Ziegler–Natta catalysts with different amounts of hydrogen. The molecular weight distribution was deconvoluted in to five Flory distributions, which showed a sensitivity to hydrogen amounts. With no hydrogen presence, the peaks corresponding to high‐molecular‐weight fractions were intense. As the amount of hydrogen was increased, not only did the intensities of the high‐molecular‐weight peaks decrease, but also peaks corresponding to low‐molecular‐weight fractions were observed. The method allowed us to determine the active site distribution of the polymer molecular weight distribution obtained from gel permeation chromatography. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparative gel permeation chromatography of Athabasca asphaltene and the relative polymer-forming propensity of the fractions

Athabasca asphaltene has been separated according to molecular weight on Bio-Beads SX-1 gel. The number-average molecular weights of the five arbitrary fractions obtained by this fractionation range from 1200 to 17000. The chemical, spectral and thermal properties of the fractions are all similar but their polymer-forming propensities are markedly different. The significance of this latter property, which is defined in terms of the amount of CH₂Cl₂-insoluble material produced upon thermolysis at 300 °C, increases rapidly with increasing molecular weight of the fraction. In contrast the whole asphaltene does not form polymer at 300 °C under the same conditions and it is concluded that the chain propagating steps are terminated by a variety of inhibitors that are contained in the asphaltene agglomerate. During gel permeation chromatography separation the clay present in the asphaltene concentrates in the higher-molecular-weight fractions. This affinity to attract the clay is thought to be related to the physical, and not the chemical, properties of these higher-molecular-weight materials. The clay also exerts a catalytic effect on the polymerization of the asphaltene fractions which is most pronounced in the highest-molecular-weight fraction and gradually decreases with decreasing molecular weight.