Synthesis and characterization of graft copolymer of polyacrylonitrile‐g‐polyethylene glycol‐maleic acid monoester macromonomer

A novel solid–solid phase‐change energy storage material was synthesized by the aqueous phase precipitation polymerization. The amphiphilic polyethylene glycol‐maleic acid monoester macromonomer (MAPEG) with a double bond and a terminal carboxyl was the side chain and the polyacrylonitrile (PAN) was a skeleton. The chemical structure and thermal properties of the graft copolymer were investigated. The results indicated that the MAPEG chains were successfully grafted onto the PAN backbone. The graft copolymer possess good thermal reliability and the phase‐transition temperature is in the temperature range of human comfort, meanwhile, the melting enthalpy could reach 74.16 J/g and the crystallization enthalpy could reach 65.40 J/g, accounting for theoretical enthalpy value of 89 and 93%, respectively. Besides, optimum conditions of synthesizing the graft copolymer were determined by orthogonal experiment. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40152.     

Cellulose/acrylic acid copolymer blends for films and coating applications

Enzymatically treated cellulose was dissolved in a NaOH/ZnO solvent system and mixed together with poly(ethylene‐co‐acrylic acid) (PE‐co‐AA) or poly(acrylamide‐co‐acrylic acid) (PAA‐co‐AA) polymers, in order to improve the properties of dissolved cellulose and to prepare homogeneous cellulose‐based blends for films and coatings. The solution stage properties of the blends were evaluated by rheological methods and the precipitated dry blends were characterized by dynamic mechanical analysis, differential scanning calorimetry, and scanning electron microscopy. Paperboard coating tests done at laboratory scale showed dissolved cellulose/acrylic acid copolymer‐based blends function well as coating materials. All of the tested blends showed a good resistance against grease in the coating trials, having grease resistance from 60 to 69 days despite a very thin (～2 µm) coating layer. In addition, cellulose/PE‐co‐AA coating showed improved water vapor and oxygen barrier properties when compared with neat dissolved cellulose‐coated paperboard. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40286.     

Vapor deposition of stable copolymer thin films in a batch iCVD reactor

This study demonstrates the deposition of poly(ethylhexyl acrylate-co-ethylene glycol dimethacrylate) (P(EHA-co-EGDMA)) copolymer thin films in a batch type initiated chemical vapor deposition (iCVD) reactor. Crosslinked copolymers are desired for many applications because of their high stable properties. iCVD polymers derived by monomers bearing only one vinyl bond are usually linearly structured polymers and hence they are not durable, which is unfavorable for many real-world applications. Robust crosslinked iCVD films can be produced with the help of crosslinkers. In a typical iCVD process, copolymer thin film is produced by constantly feeding monomer vapor and crosslinker into the reactor. The monomer/crosslinker ratio should be precisely controlled for fabrication of reproducible thin films. In order to eliminate problems caused by adjusting the flowrates of precursors, a closed-batch type iCVD reactor was used for the first time in this study to produce copolymer thin films. The variation of precursors' partial pressures allowed control over the copolymer thin film structures. As compared with homopolymer, copolymers showed the better chemical and thermal stable properties. Almost 40% of the copolymer thin film remained on the substrate surface at an annealing temperature of 300°C, whereas the homopolymer film was completely removed at an annealing temperature of 280°C.     

Functional coatings for anti-biofouling applications by surface segregation of block copolymer additives

Temperature responsive or bactericidal coatings with poly(n-butyl methacrylate) (PBMA) as bulk material and surface segregated poly(n-butyl acrylate)-block-poly-(N-isopropylacrylamide) (PBA-b-PNIPAAm) or poly(n-butyl acrylate)-block-quaternized poly(2-(dimethylamino)ethyl methacrylate) (PBA-b-PDMAEMAq) as additive were prepared via sequential solvent evaporation of polymer solutions in a solvent mixture. The degree of enrichment at the air surface of the coating and the functionality were examined for different molecular weight additives with different block ratios obtained via Atom Transfer Radical Polymerization (ATRP). The design of the block copolymers with an anchor block (PBA) which is compatible with the bulk polymer (PBMA) and water-compatible functional blocks (PNIPAAm and PDMAEMAq) along with the selection of suited solvent mixtures based on pre-estimation of the selective solubility and sequential evaporation via the Hansen solubility parameters and vapor pressures, respectively, were found to work very well. A small fraction of water in the solvent mixture had been crucial to obtain surface segregation of the functional block, e.g., a PNIPAAm surface with temperature-switchable wettability. Reversible temperature dependent wettability and long term stability of the functionalization, based on contact angle data, were obtained for an optimized PBA-b-PNIPAAm additive. Surface charge density, estimated from dye binding and zeta potential measurements, and killing efficiency against Staphylococcus aureus were investigated for PBA-b-PDMAEMAq as additive. Both block copolymer additives were found to dominate the surface properties and the functionality of the PBMA coating.     

Synthesis and characterization of maleated rosin‐modified fluorosilicone resin and its fluorosilicone rubber

Imide‐containing vinyl fluorosilicone resin (MR‐VFS) was synthesized from maleated rosin (MR). And then, with MR‐VFS as a new polar cross‐linking agent in a heat curable fluorosilicone rubber composition, a series of maleated rosin‐modified fluorosilicone rubbers (MR‐FSR) were obtained. The effects of MR‐VFS on the mechanical properties, oil resistance, thermal stability, and low‐temperature performance were studied in detail. It was found that MR‐VFS could increase the tearing strength and high‐temperature thermal stability of fluorosilicone rubber. When the MR‐VFS weight content reached to 2 wt %, the tearing strength of MR‐FSR increased by 20.1% compared with that of common fluorosilicone rubber. However, MR‐FSR showed a similar low‐temperature resistance and a little worse oil resistance. The morphological study showed that incorporation of maleated rosin could intensify the microphase separation of fluorosilicone rubber. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41888.     

Synthesis and application of a new vinyl copolymer superplasticizer

A new vinyl graft copolymer superplasticizer was synthesized by copolymerization of polyethylene glycol acrylate (PEGAA), polyethylene glycol biester of maleic acid and citric acid (PEGMC), acrylic acid (AA), sodium allylsulphonate (SAS), and methyl acrylate (MA). The effects of the vinyl monomers' molar ratio, initiator, reaction temperature, and reaction time on its application properties were investigated. The results show that the new vinyl graft copolymer superplasticizer has excellent application properties when the molar ratio of PEGAA, PEGMC, AA, SAS, and MA is 0.5 : 0.10 : 0.20 : 0.05 : 0.03 and the initiator ammonium persulfate [(NH₄)₂S₂O₈, APS] is 0.8 wt % at 80°C for 3 h. The vinyl monomers' conversion is 98.7%. The applied results show that the water‐reducing ratio and retardation solidification time of the superplasticizer reach 33.5% and 4 h, respectively. The applied concrete has excellent mechanical properties. Its molecular structure was characterized by nuclear magnetic resonance, Fourier transform infrared spectra, and gel permeation chromatography. It is characteristic of the new vinyl graft copolymer superplasticizer that citric acid (CA) and MA are introduced into the copolymer molecules. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

双尾型丙烯酰胺类疏水缔合共聚物的合成与表征

通过光引发自由基聚合的方式,将双尾型丙烯酰胺类疏水单体(N-苯乙基-N-十四烷基甲基丙烯酰胺,PETMAM),与丙烯酰胺(AM)、丙烯酸(AA)等水溶性单体进行共聚,制备出双尾型疏水缔合水溶性共聚物(DTHAP),来解决丙烯酰胺类聚合物耐温抗盐性以及稳定性差的难题。通过测定聚合物溶液的表观黏度作为评价其性能的主要手段,考察了丙烯酸加量、盐、表面活性剂(SDS)含量、疏水单体含量等因素对聚合物性能的影响,从而确定了比较理想的反应条件。实验中发现:丙烯酸加量和表面活性剂含量的变化会影响聚合物的临界缔合行为;盐的引入能够显著降低表面活性剂的用量,提高聚合物的增黏效果;疏水单体含量较低时[0.35%～0.45%(mol)],聚合物可以表现出明显的增黏效果。当聚合物浓度为1 g·L^-1时,聚合物的黏度可以达到141.5 mPa·s,其临界缔合浓度(CAC)为0.75 g·L^-1左右。聚合物在120 g·L^-1的NaCl溶液和120 g·L^-1 NaCl、0.4 g·L^-1 CaCl₂溶液中,80℃下老化90 d,黏度分别为47.6 mPa·s和45.9 mPa·s。采用红外光谱、扫描电镜两种手段,表征了聚合物的结构。     

Synthesis,characterization, and properties of a polyhedral oligomeric octadiphenylsulfonylsilsesquioxane

A novel polyhedral oligomeric octadiphenylsulfonylsilsesquioxane (ODPSS) was synthesized from octaphenylsilsesquioxane and benzenesulfonyl chloride via a Friedel–Crafts reaction with a high yield. ODPSS was identified by Fourier transform infrared spectroscopy, ¹H‐NMR, ¹³C‐NMR, ²⁹Si‐NMR, matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry (MALDI–TOF MS), wide‐angle X‐ray diffraction, and elemental analysis to be a kind of polyhedral oligomeric silsesquioxane of a T₈R₈ structure. ODPSS exhibited superior thermal stability according to thermogravimetric analysis. Its initial thermal decomposition temperature (T_onset) was at 491°C in air and 515°C in nitrogen. Thermal and mechanical properties of epoxy resin (EP) composites with ODPSS added were studied by differential scanning calorimetry and tensile testing. The results show that the incorporation of ODPSS at a low loading content not only improved the glass‐transition temperature of the EP composites but also enhanced their tensile strength. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40892.     

Synthesis and performance of a novel nitrogen‐containing cyclic phosphate for intumescent flame retardant and its application in epoxy resin

A novel nitrogen‐containing cyclic phosphate (NDP) was synthesized and well characterized by ¹H, ¹³C, ³¹P NMR, mass spectra and elemental analysis. NDP was used as an additive intumescent flame retardant (AIFR) to impart flame retardancy and dripping resistance for diglycidyl ether of bisphenol‐A epoxy resin (DGEBA) curied by 4,4′‐diaminodiphenylsulfone (DDS) with different phosphorus content. The flammability, thermal stability, and mechanical properties of NDP modified DGEBA/DDS thermosets were investigated by UL‐94 vertical burning test, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and Izod impact strength and flexural property tests. The results showed that NDP modified DGEBA/DDS thermosets exhibited excellent flame retardancy, moderate changes in glass transition temperature and thermal stability. When the phosphorus content reached only 1.5 wt %, the NDP modified DGEBA/DDS thermoset could result in satisfied flame retardancy (UL‐94, V‐0). The TGA curves under nitrogen and air atmosphere suggested that NDP had good ability of char formation, and there existed a distinct synergistic effect between phosphorus and nitrogen. The flame retardant mechanism was further realized by studying the structure and morphology of char residues using FT‐IR and scanning electron microscopy (SEM). It indicated that NDP as phosphorus‐nitrogen containing flame retardant worked by both of the condensed phase action and the vapor phase action. Additionally, the addition of NDP decreased slightly the flexural strength of the flame retarded DGEBA epoxy resins, and increased the Izod impact strength of these thermosets. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41859.     

Synthesis and analysis of phase segregation of polystyrene-block-poly(methyl methacrylate) copolymer obtained by Steglich esterification from semitelechelic blocks of polystyrene and poly(methyl methacrylate)

Here, an alternative route to successfully synthesize polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) is reported. Steglich esterification was used as an effective, metal free approach for coupling carboxylic terminated PS and the hydroxyl end-functionalized PMMA chains obtained by nitroxide-mediated polymerization and atom transfer radical polymerization, respectively. α-Functionalization was obtained using 4,4′-azobis(4-cyanovaleric acid) and 2,2,2-tribromoethanol as initiators. The synthesis of PS-b-PMMA was confirmed by gel permeation chromatography and nuclear magnetic resonance (NMR), while the dependence of the diffusion coefficients of the polymers (PS, PMMA, PS/PMMA blend, and PS-b-PMMA) with their corresponding molecular weights was discussed based on the results of atomic force microscopy-based infrared spectroscopy, differential scanning calorimetry, and spectra of diffusion-ordered NMR spectroscopy. Differently from PS-b-PMMA, a partial segregation was observed for the PS/PMMA blend, affecting its thermal behavior and diffusion coefficient. The study here presented provides an easier and efficient strategy for the synthesis of PS-b-PMMA and new insights into the diffusion of polymers.     

Preparation of polyacrylate/paraffin microcapsules and its application in prolonged release of fragrance

The purpose of the present work was to develop a fragrance encapsulation system using polyacrylate/paraffin microcapsules. The Polyacrylate/paraffin microcapsules were fabricated by the method of suspension polymerization in Pickering emulsion. Morphology, size distribution, and thermal resistance of polyacrylate/paraffin microcapsules were investigated by scanning electron microscopy, light scattering particle size analyzer, and thermogravimetric analyzer. Results indicated that the crosslinked PMMA/paraffin microcapsules and P(MMA‐co‐BMA)/paraffin microcapsules prepared under optimal conditions presented regular spherical shape and similar size distribution. The crosslinked P(MMA‐co‐BMA)/paraffin microcapsules exhibited better thermal stability, with a thermal resistance temperature up to 184 °C. Fragrance microcapsules were prepared by encapsulating fragrance into crosslinked P(MMA‐co‐BMA)/paraffin microcapsules. The prolonged release performance of fragrance microcapsules was measured by ultraviolet‐visible near‐infrared spectrophotometer. 63.9% fragrance was retained after exposing fragrance microcapsules in air for 3 months, and the fragrance continued to release over 96 h in surfactant solution (sodium lauryl sulfonate, 20 wt %). © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44136.     

Synthesis,polymerization, and properties of the allyl‐functional phthalonitrile

A novel bisphthalonitrile monomer containing allyl groups (DBPA‐Ph) had been synthesized via the reaction of diallyl bisphenol A (DBPA) and 4‐nitrophthalonitrile. The chemical structure of DBPA‐Ph was confirmed by ¹HNMR, ¹³CNMR, and FTIR spectroscopy. The curing behaviors and processability of DBPA‐Ph were studied by differential scanning calorimetry (DSC) and dynamic rheological analysis. The monomer manifested a two‐stage thermal polymerization pattern. The first stage was attributed to the polymerization of allyl groups and the second to the ring‐form polymerization of cyano groups. The result of dynamic rheological analysis indicated the monomer had wide curing window and the self‐catalyzed curing behavior. DBPA‐Ph polymers were prepared from the thermal polymerization with short curing time, showing high glass transition temperature (>350°C) and attractive thermal decomposition temperature (>430°C). The outstanding glass transition temperature, desirable thermo‐oxidative stabilities, good processability and sound process conditions could provide more applications to the DBPA‐Ph polymers. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41203.     

Soluble network polymers based on trifluoropropyl-substituted open-cage silsesquioxane: Synthesis,properties, and application for surface modifiers

Fluorinated completely condensed polyhedral oligomeric silsesquioxanes (F-CC-POSSs) are widely utilized as surface modifiers for polymeric materials because of their polyhedral and fluorine-rich structures, which generate polymers with lower surface energies under molecular-level control. In contrast, their derivatives, fluorinated incompletely condensed or open-cage POSSs (F-IC-POSSs), have similarly intriguing structures, but their utilization for polymer synthesis remains undeveloped. Herein, fluorinated network polymers were prepared based on a 3,3,3-trifluoropropyl-substituted IC-POSSs via hydrosilylation polymerization with isobutyl- and phenyl-substituted IC-POSS under optimized conditions. In addition to their good thermal stability and tunable refractive indices, these polymers exhibited solution processability and their casting films showed excellent optical transparency, indicating their potential for constructing fluorinated polymers. Their utilization as surface modifiers was examined by addition to poly(methylmethacrylate) (PMMA) films. Intriguingly, modified PMMA films with 2.0 and 0.5 wt% addition showed similar hydrophobicity and surface energies to the films prepared with only fluorinated network polymers.     

松香基功能性单体的合成及应用

松香是我国重要的林业生物质资源,主要成分为松香树脂酸。由于松香分子结构中含有双键和羧基,可经多种反应途径合成功能性单体制备高分子材料,广泛应用在涂料、胶黏剂、航空航天等领域中。由于松香价格低廉、力学性能与热性能优越,同时具有环境友好、可再生等优点,在高分子领域引起了广泛的关注。论文分别对丙烯酸酯类、乙烯基酯类及烯丙基类的改性松香功能性单体的合成进行了综述,重点论述了在聚氨酯树脂、环氧树脂、酚醛树脂、有机硅树脂和不饱和聚酯等领域的应用。针对松香基功能性单体的深度研究,探讨了一系列由松香基衍生物参与的新型材料的应用,为新型表面活性剂、交联剂、形状记忆类材料等领域的发展提供了新的视角。最后,论文对未来松香基高分子材料合成研究的方向进行了展望。     

Combination of temperature and saturated vapor annealing for phase separation of block copolymer

Phase separation of block copolymer films is a perspective technique for the creation of nanostructured templates. The phase separation can be induced by thermal or vapor solvent annealing. However, a standardized and reproducible technique of the phase separation is still missing, even though many papers describing various experimental conditions. In this article we have tried to develop standardized and reproducible technique of the phase separation, which can be easily scaled up. For this purpose we used the combination of the thermal and vapor annealing of poly(styrene‐b‐4‐vinylpyridine) copolymer films on a glass substrate under static conditions. The technique was tailored by the choice of optimal solvent for the vapor annealing, based on the solvent–polymer interaction. Finally, the films were reconstructed by immersing in methanol or ethanol and stretching of the P4VP component during the reconstruction was investigated by the angle‐resolved X‐ray photoelectron spectroscopy. Morphology of the films was investigated by the atomic force microscopy and confocal microscopy. The kinetics of the phase separation was also studied. The presented combined technique of the thermal and vapor annealing can be easily temperature‐controlled for reproducibly obtaining the films of a desired morphology. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41853.     

Synthesis of hydroxyethylcellulose‐g‐methoxypoly (ethylene glycol) copolymer and its application for protein separation in CE

Hydroxyethylcellulose‐g‐methoxypoly (ethylene glycol) (HEC‐g‐PEG) graft copolymers were synthesized through the etherification reaction between the hydroxyl group of hydroxyethylcellulose (HEC) and iodinated methoxypoly (ethylene glycol) (PEG‐I), which was prepared on the basis of two‐step reaction. Fourier transforms infrared spectrum (FTIR), nuclear magnetic resonance (NMR), thermal gravimetric analysis (TGA), differential scanning calorimetry (DSC), and iodide oxidation method were used to prove the success of synthesis of graft copolymer. Furthermore, the comparative studies of electro‐osmotic flow (EOF) and protein separation in bare‐fused silica, HEC and HEC‐g‐PEG‐coated capillary were performed in capillary electrophoresis (CE). The results showed that HEC‐g‐PEG‐coated capillary presented efficient EOF suppression ability and excellent resisting protein adsorption ability. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis of a melamine‐cyclotriphosphazene derivative and its application as flame retardant on cotton gauze

The halogen‐free flame retardance of natural fiber is an everlasting challenge due to the well‐known poor solubility of phosphazene in water. In this case, a new cyclotriphosphazene derivative (MCP) was synthesized. It was etherized hexamethylolmelamine (HMMM) and hexachloro‐cyclotriphosphazene (HCCP) by one pot reaction. It was characterized by ¹H NMR, ¹³C NMR, ³¹P NMR, FT‐IR, TGA, SEM, limited oxygen index (LOI) and vertical flame testing. The MCP has good solubility in water and thermosetting MCP has compact structure which can expand several times after burning. Cotton gauze was soaked in six different concentration of aqueous solutions of MCP (0 wt %, 5 wt %, 10 wt %, 15 wt %, 20 wt % and 25 wt %, respectively) to obtain the flame retardant cloth. The cloth was soaked in 20 wt % MCP solution had higher char yield and LOI. They had no any afterflame and afterglow, and gauze 2‐ gauze 5 cannot be burned out in 12s ignition time. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43555.     

Synthesis,optical, and thermal properties of polyimides containing flexible ether linkage

The goal of this article was to synthesize a series of flexible polyimides containing ether linkage in main chain and clarified the effect of this ether linkage on some physical properties such as optical and thermal decomposition. Also, different functional group effects such as carbonyl (? C?O), hexa‐fluoro‐isopropylidene [? C(CF₃)₂? ] and phenyl (? C₆H₅) on these physical properties were evaluated. The structural characterization of poly(ether imide)s was performed using Fourier transform infrared, ¹H‐nuclear magnetic resonance (NMR), and ¹³C‐NMR techniques. Optical band gap of polyimides was calculated in the range from 2.57 to 2.81 eV. Thermal characterization of poly(ether imide)s was carried out using thermogravimetry–differential thermal analysis and differential scanning calorimetry. Thermal stability of poly(ether imide)s was evaluated by initial decomposition temperature (T_on) and char. T_on value of polymers was determined in the range from 100 to 195 °C. In addition, glass transition temperatures of poly(ether imide)s were found between 144 and 148 °C. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46573.     

Crosslink network and phenyl content on the optical,hardness, and thermal aging of PDMS LED encapsulant

This work aims to synthesize new series of polysiloxane copolymer through hydrosilylation reaction based on different level of crosslink densities and phenyl content. The results revealed that polysiloxanes resins with phenyl rings increased viscosity up to 3800 cps while displaying a relatively high refractive index of 1.531. The asymmetric phenyl substitution onto chain backbone led to formation of densely packed structure resulting in reduced water absorption and gas permeability of PDMS resins. High level of crosslinking contributed to a high shore A hardness and adhesion strength. It displayed transparency of 97% whose percentage reduction was 1.6% under thermal and 0.6% UV aging. No obvious discoloration was observed during accelerated thermal aging up to 210 min at 80 °C. These results are key attributes that make the synthesized polysiloxane series as ideal candidate for high brightness LED encapsulant. © 2019 Wiley Periodicals, Inc. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47895.     

Thermal stability and dynamic mechanical behavior of acrylic resin and acrylic melamine coatings

Acrylic polyols of different hydroxyl numbers consisting of hydroxy ethyl methacrylate, methyl methacrylate, butyl acrylate, and styrene were prepared by free‐radical solution as well as suspension polymerization techniques in the presence of benzoyl peroxide initiator. These polyols were crosslinked with butoxy methyl melamine at a ratio of 85 : 15 in the presence of acid catalyst. The thermal stability of polyols and their corresponding crosslinked films was studied by thermogravimetric (TG) technique. The Broido and Coats–Redfern methods were used to calculate the activation energy of thermal decomposition from standard TG curves. Dynamic mechanical thermal analysis was used to study the dynamic mechanical properties and determination of glass‐transition temperature of acrylic/melamine crosslinked films. The results indicate that the thermal stability of polyols and crosslinked films strongly depends on the hydroxyl number of the acrylic polyols. It was found that acrylic polyols synthesized by suspension polymerization methods upon crosslinking yield more thermally stable and flexible films than polyols prepared by solution polymerization methods. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 27–34, 2004