Synthesis and characterization of poly[methyl methacrylate‐co‐2‐ethylhexyl acrylate‐co‐poly(propylene glycol diacrylate)] latices

The emulsion polymerization of the monomers methyl methacrylate (MMA) and 2‐ethylhexyl acrylate (EHA) was studied to investigate the effect of the crosslinkable monomer poly(propylene glycol diacrylate) (PPGDA). IR spectroscopy, NMR, differential scanning calorimetry, gel permeation chromatography, and scanning electron microscopy were used to characterize the synthesized polymers. These polymers were coated on glass panels and cured at appropriate temperatures to study the physical properties, swelling behavior, surface tension, and contact angle of these polymer latices. The results show that as the concentration of EHA monomer increased, the surface tension of the latices decreased. The copolymers were characterized by ¹H‐NMR spectroscopy to ensure the absence of unreacted monomer, and the results confirm the incorporation of EHA units in the copolymer. The contact angle of the latices on the glass substrate was smaller than that on the metal. The swelling mechanism of the film showed that the Fickian diffusion coefficient with 10 wt % PPGDA was at a minimum value and was the most highly crosslinked polymer among the samples. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Three‐dimensional thermorheological behavior of isotactic polypropylene across glass transition temperature

The aim of this work was to determine the three‐dimensional thermorheological behavior of isotactic polypropylene (i‐PP) in the region of its glass transition temperature (T_g) by a master curve. The i‐PP is a widespread polymer with a T_g ～ 0°C. Dynamic mechanical analysis (DMA) at varying frequencies and temperatures and bulk tests at varying temperatures and times are carried out to obtain the relaxation spectra. Traditionally, the combination of time and temperature is done for thermorheological simple material by the creation of a master curve based on the Arrhenius or William–Landel–Ferry (WLF) equation. This investigation shows that these equations do not fit the behavior across the glass transition of i‐PP. Instead, a new arc tangent function is derived. Additionally, it can be shown that the shifting factors differ from shear to bulk load. Therefore, the mode of mechanical stress seems to have an influence on the thermorheological behavior. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 877–880, 2004     

Relation between microstructure and glass transition temperature of poly[(methyl methacrylate)‐co‐(ethyl acrylate)]

The glass transition temperature of a series of samples of the poly[(methyl methacrylate)‐co‐(ethyl acrylate)] copolymer, synthesized at low conversion, were calculated theoretically using the equations of Barton and Johnston. The values obtained are more precise when the probabilities of the compositional diads are derived from the ¹³C NMR data instead of the classical method utilizing reactivity ratios. This can be observed more clearly when the copolymer samples are synthesized at high conversion. Introduction of configuration (tacticity) at the diad level confirms the above observations and slightly improves the calculated values of T_g compared to the initial formulae which were only taking into account the compositional sequences of the copolymer. © 2001 Society of Chemical Industry     

Variations of the glass‐transition temperature in the imidization of poly(styrene‐co‐maleic anhydride)

The imidization of poly(styrene‐co‐maleic anhydride) (SMA) was conducted, and the glass‐transition temperatures (T_g's) of the resulting products were measured with differential scanning calorimetry. The contributions from functional groups of maleic anhydride, N‐phenylmaleamic acid, and N‐phenylmaleimide to T_g were examined. T_g increased in the order of SMA < styrene–N‐phenyl maleimide copolymer < styrene–N‐phenyl maleamic acid copolymer and followed the Fox equation. T_g of the imidized products of SMA could be controlled by the conversions of both ring‐opening and ring‐closing reactions. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2418–2422, 2007     

Glass‐transition temperature of poly(vinylidene fluoride)‐poly(methyl acrylate) blends: Influence of aging and chain structure

The glass‐transition temperature (T_g) of the poly(vinylidene fluoride) (PVF₂)‐poly(methyl acrylate) (PMA) blends increase with aging time. The T_g versus log(time) plots are straight lines whose slope values depend on the head to head (H–H) defect content of PVF₂ samples and on the composition of the blends. The values of polymer–polymer interaction parameters (χ) increase with an increase in the H–H defect of PVF₂ for a fixed composition of the blend. Consequently, the T_g of the blend decreases with an increase in the H–H defect of the PVF₂ sample. However, after aging for longer times this decrease of the T_g with H–H defects is lower than those of the unaged blends. The possible reasons are discussed. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1541–1548, 2001     

Microstructure and glass‐transition temperature of novel star N‐SIBR

In this study, a polymeric N‐functionalized mutilithium (N‐M‐Li) compound was prepared from commercial divinylbenzene (DVB) and lithiohexamethyleneimine (LHMI), and star‐shaped copoly(styrene–butadiene–isoprene) was obtained by anionic polymerization using preformed N‐M‐Li as initiator, tetramethylethlenediamine (TMEDA) as polar modifier, and cyclohexane as solvent. The microstructure and the glass–transition temperature (Tg) of copolymers were characterized by ¹H NMR and differential scanning calorimetry (DSC), respectively. It showed that the non‐1,4‐structure content and the Tg of copolymers increased with the increase of TMEDA dosage or the decrease of polymerization temperature; however, the effects of the initiator concentration and DVB dosage on them were not obvious. We also obtained the relationships between the non‐1,4‐structure content of copolymers and the Tg of copolymers respectively, and between the ln(T/Li) (TMEDA/N‐M‐Li, mole ratio) and the non‐1,4‐structure content of copolymers, as follows: Tg (°C) = 0.6258C_{non 1,4}?55.93 and C_{non 1,4} = 20.79 ln K+59.11, where K is T/Li value. Therefore on the basis of experimental results, we realize polymer design according to our practical requirements. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5848–5853, 2006     

Tris(trimethylsilyl)methyl functionalized 4‐chloromethyl styrene polymers: Effects of side chain modification on polymer structure and glass transition temperature

4‐Chloromethyl styrene was copolymerized with various molar ratio of methyl methacrylate or ethyl methacrylate by solution free radical polymerization method, at 70 ± 1°C using α,α′‐azobis(isobutyronitrile) as an initiator. Then, very highly sterically hindered tris(trimethylsilyl)methyl substituent was covalently linked to the obtained copolymers with liberation of chlorine atoms. The structure of all polymers was characterized and confirmed by FT‐IR, ¹H and ¹³C NMR spectroscopy techniques. The average molecular weight and glass transition temperature of polymers were determined using gel permeation chromatograph and differential scanning calorimeter instruments, respectively. Study of differential scanning calorimetry analyses showed that chemical modification of 4‐chloromethyl styrene copolymers with tris(trimethylsilyl)methyl substituents leads to an increase in the rigidity and glass transition temperature of polymers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 633–639, 2006     

Synthesis and characterization of N‐ and O‐alkylated poly[aniline‐co‐N‐(2‐hydroxyethyl) aniline]

Poly[aniline‐co‐N‐(2‐hydroxyethyl) aniline] was synthesized in an aqueous hydrochloric acid medium with a determined feed ratio by chemical oxidative polymerization. This polymer was used as a functional conducting polymer intermediate because of its side‐group reactivity. To synthesize the alkyl‐substituted copolymer, the initial copolymer was reacted with NaH to obtain the N‐ and O‐anionic copolymer after the reaction with octadecyl bromide to prepare the octadecyl‐substituted polymer. The microstructure of the obtained polymers was characterized by Fourier transform infrared spectroscopy, ¹H‐NMR, and X‐ray diffraction. The thermal behavior of the polymers was investigated by thermogravimetric analysis and differential scanning calorimetry. The morphology of obtained copolymers was studied by scanning electron microscopy. The cyclic voltammetry investigation showed the electroactivity of poly [aniline‐co‐N‐(2‐hydroxyethyl) aniline] and N and O‐alkylated poly[aniline‐co‐N‐(2‐hydroxyethyl) aniline]. The conductivities of the polymers were 5 × 10^?5 S/cm for poly[aniline‐co‐N‐(2‐hydroxyethyl) aniline] and 5 ×10^?7 S/cm for the octadecyl‐substituted copolymer. The conductivity measurements were performed with a four‐point probe method. The solubility of the initial copolymer in common organic solvents such as N‐methyl‐2‐pyrrolidone and dimethylformamide was greater than polyaniline. The alkylated copolymer was mainly soluble in nonpolar solvents such as n‐hexane and cyclohexane. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Curing of epoxy systems at sub‐glass transition temperature

Three epoxy‐amine thermoset systems were cured at a low ambient temperature. Evolution of the reaction kinetics and molecular structure during cure at the sub‐glass transition temperature was followed by DSC and chemorheology experiments. The effect of vitrification and the reaction exotherm on curing and final mechanical properties of the epoxy thermosets was determined. Thermomechanical properties of the low‐temperature cured systems depend on the reaction kinetics and volume of the reaction mixture. Curing of the fast‐reacting system in a large volume (12‐mm thick layer) resulted in the material with T_g exceeding the cure temperature by 70–80°C because of an exothermal temperature rise. However, the reaction in a too large volume (50‐mm layer) led to thermal degradation of the network. In contrast, thin layers (1.5 mm) were severely undercured. Well‐cured epoxy thermosets could be prepared at sub‐T_g temperatures by optimizing reaction conditions. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3669–3676, 2006     

Conversion analysis of acrylated hyperbranched polymers UV‐cured below their ultimate glass transition temperature

The photo‐curing behavior of reactive blends of dipentaerythritol penta/hexaacrylate (DPHA) with an acrylated hyperbranched polyester and an acrylated hyperbranched polyether was investigated by means of photo differential scanning calorimetry. The chemical conversion data was analyzed using an autocatalytic model with close attention paid to the influence of composition, UV intensity, and vitrification. The autocatalytic model was found to be relevant to describe autoacceleration and diffusion controlled reaction stages, as long as the polymers were not vitrified. It was shown that the reaction order and the autocatalytic exponent were independent of UV intensity, whereas the rate constant showed strong intensity dependence, and the maximal conversion showed weak intensity dependence. A criterion for vitrification onset was proposed as the occurrence of a third stage in the conversion process. The ultimate conversion was found to be 0.16 higher than the conversion at vitrification for all investigated multifunctional acrylates independent of composition and UV intensity. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2366–2376, 2007     

Swelling behavior of poly(MMA‐co‐BA‐co‐PPGDA) polymers

The kinetics of emulsion polymerization of monomers MMA/BA was studied to investigate the effect of cross‐linkable monomer PPGDA. The results showed that by the incorporation of PPGDA, rate constant of reaction decreased. The IR and differential scanning calorimetry were used to characterize the presence of PPGDA in the synthesized polymers. These polymers were coated on glass panels and cured at appropriate temperature. The results showed that the polymer containing 15 wt % PPGDA had minimum value of Fickian diffusion coefficient, thus showing highest level of cross‐linking among all the polymers studied. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation and characterization of inherently heat‐sealable polyimides with high glass transition temperatures

A series of inherently heat‐sealable copolyimides (CPIs) with high glass transition temperatures were synthesized from 2,3,3′,4′‐oxydiphthalic anhydride (aODPA) and bicomponent diamines, 4,4′‐oxydianiline (ODA) and para‐phenylenediamine (PDA). The PI chain rigidity was manipulated by the regulation of the diamine ratio, and its effects on the heat sealability and thermal resistance of the derived CPI films were investigated in detail. The results show that these films are in possession of both good heat sealability and thermal resistance due to the synergetic effect of the asymmetry of aODPA and the rigidity of PDA. It is also found that there exists one critical PDA content that distinguishes the heat‐sealing behaviors of the CPI films, and the relevant mechanism was established. Especially for CPI‐5, the heat‐sealing strength is up to 350 N m^?1 simultaneously with a relatively high T_g of 310°C. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43058.     

A novel copolymer of methyl methacrylate with N-pentafluorophenyl maleimide: High glass transition temperature and highly transparent polymer

N-pentafluorophenyl maleimide (PFPMI) was synthesized. The homo and copolymers of PFPMI with methyl methacrylate (MMA) were prepared. The monomer reactivity ratio, r₁ (PFPMI) and r₂ (MMA) were 0.389 and 1.06 respectively. Q and e values for PFPMI were calculated as 1.00 and 1.30. The refractive indexes of poly(PFPMI) and PMMA were found to be similar; 1.4989 and 1.4953 at 532 nm, respectively. The copolymers exhibited no light scattering, and the film was very transparent. The glass transition temperatures of the PFPMI-co-MMA were in the range of 140 °C-180 °C with the PFPMI content from 18.8 to 65 mol% and the copolymers obtained have high thermal stability (∼370 °C). The water absorption of PFPMI-co-MMA was greatly reduced as compared with that of pure PMMA.     

Effect of glass transition temperature and saturation temperature on the solid‐state microcellular foaming of cyclic olefin copolymer

Effect of glass transition temperature and saturation temperature on the solid‐state microcellular foaming of cyclic olefin copolymer (COC)—including CO₂ solubility, diffusivity, cell nucleation, and foam morphology—were investigated in this article. COCs of low T_g (78°C) and high T_g (158°C) were studied. Solubilities are 20–50% higher in high T_g COC than in the low T_g COC across the saturation temperature range. Diffusivities are about 15% higher on average in high T_g COC for temperatures up to 50°C. A much faster increase of diffusivity beyond 50°C is observed in low T_g COC due to it being in the rubbery state. Under similar gas concentration, high T_g COC starts foaming at a higher temperature. And the foam density decreases faster in low T_g COC with foaming temperature. Also, high T_g COC foams show about two orders of magnitude higher cell nucleation density than the low T_g COC foams. The effect of saturation temperature on microcellular foaming can be viewed as the effect of CO₂ concentration. Nucleation density increases and cell size decreases exponentially with increasing CO₂ concentration. Uniform ultramicrocellular structure with an average cell size of 380 nm was created in high‐T_g COC. A novel hierarchical structure composed of microcells (2.5 μm) and nanocells (cell size 80 nm) on the cell wall was discovered in the very low‐density high‐T_g COC foams. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42226.     

Preparation and characterization of novel hyperbranched poly(amine‐ester) films crosslinked by glutaraldehyde

Novel films based on hydroxyl terminated hyperbranched poly (amine‐ester) (HPAE‐OH) of different generation were prepared by crosslinking the terminal hydroxyl groups of HPAE with glutaraldehyde (GA). The progress of crosslinking reaction was characterized by Fourier transform infrared (FTIR) and viscosity measurement. The surface morphology of the crosslinked HPAE films was characterized by field emission scanning electron microscope (FE‐SEM) and atomic force microscopy. The results suggested that the films have homogenously dense interior matrices and smooth surface. The hydrophilicity/hydrophobicity of the crosslinked HPAE films was characterized by the water contact angle measurement. Variable swelling behavior in different solvents was also studied. The in vitro biocompatibility of the film was investigated by the bovine hemoglobin (Hb) adsorption measurement. And these results showed that these crosslinked HPAE films had excellent hydrophilicity, variable swelling behavior in different solvents, and relative low protein absorption. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and characterization of soluble poly(arylene ether ketone)s with high glass transition temperature based on 3,6‐bi(4‐fluorobenzoyl)‐N‐alkylcarbazole

3,6‐bi(4‐fluorobenzoyl)‐N‐methylcarbazole and 3,6‐bi(4‐fluorobenzoyl)‐N‐ethylcarbazole were synthesized and used to prepare poly(arylene ether ketone)s (PAEKs) with high glass transition temperatures (T_g) and good solubility. High molecular weight amorphous PAEKs were prepared from these two difluoroketones with hydroquinone, phenolphthalein, 9,9‐bis(4‐hydroxyphenyl)fluorene and 4‐(4‐hydroxylphenyl)‐2,3‐phthalazin‐1‐one, respectively. All these polymers presented high thermal stability with glass transition temperatures being in the range 239–303 °C and a 5% thermal weight loss temperature above 460 °C. Compared with the T_g of phenolphthalein‐based PAEK (PEK‐C), fluorene‐based PAEK (BFEK) and phthalazinone‐based PAEK (DPEK) not containing a carbazole unit, these polymers presented a 30–50 °C increase in T_g. Meanwhile, PAEKs prepared from N‐ethylcarbazole difluoroketone showed good solubility in ordinary organic solvents, and all polymers exhibited excellent resistance to hydrochloric acid (36.5 wt%) and sodium hydroxide (50 wt%) solutions. In particular, phthalazinone‐based PAEK bearing N‐ethylcarbazole afforded simultaneously a T_g of 301 °C with good solubility. Tensile tests of films showed that these polymers have desirable mechanical properties. The carbazole‐based difluoroketones play an important role in preparing soluble PAEKs with high T_g by coordinating the relationship between chain rigidity resulting from the carbazole unit and chain distance from the side alkyl. © 2014 Society of Chemical Industry     

Free radical copolymerization of N,N‐dimethylaminoethyl methacrylate with styrene and methyl methacrylate: monomer reactivity ratios and glass transition temperatures

BACKGROUND: The properties of copolymers depend strongly on their composition; therefore in order to tailor some for specific applications, it is necessary to control their synthesis, and, in particular, to know the reactivity ratios of their constituent monomers. Free radical copolymerizations of N,N‐dimethylaminoethyl methacrylate (DMAEM) with styrene (ST) and methyl methacrylate (MMA) in toluene solution using 1‐di(tert‐butylperoxy)‐3,3,5‐trimethylcyclohexane as initiator at 70 °C were investigated. Monomer reactivity ratios were determined for low conversions using both linear and nonlinear methods. RESULTS: For the DMAEM/ST system the average values are r₁ = 0.43 and r₂ = 1.74; for the DMAEM/MMA system the average values are r₁ = 0.85 and r₂ = 0.86. The initial copolymerization rate, R_p, for DMAEM/ST sharply decreases as the content of ST in the monomer mixture increases up to 30 mol% and then attains a steady value. For the DMAEM/MMA copolymerization system the composition of the feed does not have a significant influence on R_p. The glass transition temperatures (T_g) of the copolymers were determined calorimetrically and calculated using Johnston's sequence length method. A linear dependence of T_g on copolymer composition for both systems is observed: T_g increases with increasing ST or MMA content. CONCLUSION: Copolymerization reactivity ratios enable the design of high‐conversion processes for the production of copolymers of well‐defined properties for particular applications, such as the improvement of rheological properties of lubricating mineral oils. Copyright © 2009 Society of Chemical Industry     

Predictors of glass transition in the biodegradable poly‐lactide and poly‐lactide‐co‐glycolide polymers

The biodegradable polylactide (PLA) and polylactide‐co‐glycolides (PLGAs) are being widely investigated for use as scaffolds in bone and ligament reconstruction. The glass transition temperatures (T_g) for these polymers are generally greater than 37°C, causing PLA and PLGA devices to possess brittle characteristics in physiological conditions. To evaluate the possibility of obtaining PLGA polymers with T_g values below 37°C, we evaluated the determinants of T_g in PLA and PLGA copolymers. The T_g, changes in specific heat capacity (ΔC_p), and enthalpic relaxation (ΔH_g) in two consecutive heating cycles were correlated with lactide/glycolide content and intrinsic viscosity [η] for PLA, PLGAs 90:10, 75:25, 65:35, and 50:50. A linear correlation was observed between T_g and intrinsic viscosity, with 0.1 dL/g increase in viscosity resulting in an increase in T_g by about 3.55°C. The selection of PLA and PLGA copolymers with [η] values <0.19 dL/g, corresponding to a viscosity average molecular weight of <70 kDa, will obtain PLA/PLGA polymers with T_g values below 37°C. The lowest attainable T_g values were found to be 28–30°C. Intrinsic viscosity also correlated with ΔC_p differences between aged and rapidly cooled polymers, and is therefore important in predicting free volume changes within these polymers upon aging. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1983–1987, 2006     

Preparation and characteristic of electric stimuli responsive hydrogel composed of polyvinyl alcohol/poly (sodium maleate‐co‐sodium acrylate)

Maleic anhydride was used to preparare polyvinyl alcohol/poly (sodium maleate‐co‐sodium acrylate) hydrogels (PVA/poly(SMA‐SAA)) by a repeated frost‐defrost process because of its higher charge density and potential electric stimuli sensitivity. The bending angle was measured in a noncontact electric field using carbon as plate electrodes. It was found that the bending angle was dependent on various factors, including composition of hydrogel, concentration of NaCl solution, types of electrolyte solution, and electric voltage. It exhibited that the bending angle increased when the concentration of NaCl solutions and the electric voltages increased. An abnormal bending direction was observed, and it was affected not only by the kinds of hydrogels, but also by the exterior variations. The hydrogel showed good reversibility in on‐off electric field and could be a candidate for practical application. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008