Acrylate–vinylidene chloride copolymers derived from corresponding water‐borne latexes: Influence of acrylate units on their potential as heavy‐duty anticorrosive coating materials

A series of aqueous latexes with solid contents of 56%–59% were synthesized by binary emulsion copolymerization of vinylidene chloride (VDC) with an acrylate, namely methyl acrylate (MA), ethyl acrylate (EA), butyl acrylate (BA), hexyl acrylate (HA), or 2‐ethylhexyl acrylate (EHA). Differential scanning calorimetry (DSC) and Fourier‐transform infrared (FTIR) spectroscopy showed that the acrylate units with short ester side‐chains, such as MA and EA, made the copolymers hard and the crystallization tendency of their PVDC segments was reduced. Hydrophobic acrylates with relatively long ester groups, such as HA and EHA, gave flexible copolymers, and favored the crystallization of their PVDC segments. BA endowed the copolymers with medium flexibility and crystallization tendency. As coating materials, the copolymers bearing MA and EA adhered poorly to the tinplate before or after 100 hr of salt‐spray corrosion, whereas those bearing BA, HA, or EHA showed good adhesion to tinplate when they had little or no crystallinity. After 100 hr of salt‐spray corrosion, only BA–VDC80, containing 80% VDC, retained both excellent adhesion to metal and excellent barrier performance. Further study demonstrated that BA–VDC80 could protect tinplate from rusting for at least 250 hr under harsh salt‐spray corrosion. Scanning electron microscopy, FTIR‐attenuated total reflectance spectroscopy and DSC were used to evaluate the corroded BA–VDC80 film. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40192.     

Surface Energy and Thermal Stability Studies of Poly(dimethyl siloxane)–Poly(alkyl(meth)acrylate) Copolymers

The correlation between the surface energy and thermal stability of polymers plays an important role in engineering of plastic materials. In this work, microstructural characteristics of copolymers of poly(dimethyl siloxane) with benzyl methacrylate, ethyl methacrylate, and methyl acrylate are correlated with their surface energy and thermal stability. The poly(dimethyl siloxane) segments in the copolymer chains affected the hydrophobic behavior. The surface energy of the synthesized copolymers decreased by increasing segments of alkyl methacrylates. The thermal stability of copolymers suggesting that heat resistance of poly(dimethyl siloxane) copolymers used in this correlation can be improved by adjusting the units of alkyl methacrylates in copolymers.     

Morphologies and dynamic mechanical properties of core‐shell emulsifier‐free latexes and their copolymers for P(BA/MMA)/P(MMA/BA) and P(BA/MMA)/PSt systems in the presence of AHPS

Different poly(methyl methacrylate/n‐butyl acrylate)/poly(n‐butyl acrylate/methyl methacrylate) [P(BA/MMA)/P(MMA/BA)] and poly(n‐butyl acrylate/methyl methacrylate)/polystyrene [P(BA/MMA)/PSt] core‐shell structured latexes were prepared by emulsifier‐free emulsion polymerization in the presence of hydrophilic monomer 3‐allyloxy‐2‐hydroxyl‐propanesulfonic salt (AHPS). The particle morphologies of the final latexes and dynamic mechanical properties of the copolymers from final latexes were investigated in detail. With the addition of AHPS, a latex of stable and high‐solid content (60 wt %) was prepared. The diameters of the latex particles are ～0.26 μm for the P(BA/MMA)/P(MMA/BA) system and 0.22–0.24 μm for the P(BA/MMA)/PSt system. All copolymers from the final latexes are two‐phase structure polymers, shown as two glass transition temperatures (T_gs) on dynamic mechanical analysis spectra. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3078–3084, 2002     

Effects of shearing and comonomer content on the crystallization behavior of poly(butylene succinate‐co‐butylene 2‐ethyl‐2‐methyl succinate)

Poly(butylene succinate‐co‐butylene 2‐ethyl‐2‐methyl succinate) (PBSEMS) random copolymers were prepared with different comonomer compositions. The effects of shearing and comonomer content on the crystallization behavior of these copolymers were investigated at 80 °C. The thermal and morphological properties of the resulting samples were also discussed. The copolymers showed a longer induction time and a slower crystallization rate with increasing comonomer content. The promoting effect of shear on the overall crystallization behavior was more notable for those copolymers containing more 2‐ethyl‐2‐methyl succinic acid (EMSA) units. The melting temperature of ‘as‐prepared’ poly(butylene succinate) (PBS) was ca. 115 °C, while that of the copolymers varied from 112 to 102 °C. Higher comonomer contents in the copolymers gave rise to lower melting temperatures and broader melting peaks. In addition, the isothermally crystallized samples showed multiple melting endothermic behavior, the extent of which depended on the comonomer content. The copolymers showed different wide‐angle X‐ray diffraction (WAXD) patterns from that of neat PBS, depending on the comonomer content and shear applied during crystallization. With increasing comonomer content, the copolymers crystallized without shearing, showing the shifting of a diffraction peak to a higher angle, while those crystallized under shear did not show any peak shift. Copyright © 2004 Society of Chemical Industry     

Synthesis and characterization of fluorocarbon‐modified poly(N‐isopropylacrylamide)

Poly(N‐isopropylacrylamide) copolymers (PNIPAMs) containing pendent perfluoroalkyl (R_F) or dodecyl groups have been synthesized by copolymerization of NIPAM with small amounts of R_R‐acrylates or ‐methacrylates containing a sulfonamido moiety between the acrylate and R_F groups or with dodecyl acrylate. Evidence for strong intermolecular hydrophobic association of the fluorocarbon groups is provided by large viscosity increases with copolymer concentration and upon addition of NaCl and surfactants. These interactions appear to be much stronger than that of the corresponding copolymers of poly(N,N‐dimethylacrylamide) with similar comonomer contents. Hydrophobic association between the R_F groups is found to be much stronger than that of the corresponding dodecyl groups. The viscosity of some of the copolymer solutions, particularly in the presence of perfluorocarbon surfactants, was unusually temperature sensitive, decreasing by a factor of at least 1000 upon increasing the temperature from 10 to 20 °C. This large decrease is most probably related to the collapse of the copolymer coils near the lower critical solution temperature. This is in sharp contrast to the corresponding polyacrylamide or poly(N,N‐dimethylacrylamide) R_F‐acrylate copolymers that show viscosity increases with increasing temperature in the 40–60 °C range. The NIPIAM copolymers were also found to be different from the acrylamide or N,N‐dimethylacrylamide perfluorocarbon acrylate copolymers in that they were found to be Newtonian at a low R_F content but dilatant at a higher comonomer content. © 2000 Society of Chemical Industry     

AUTOADHESION OF HIGH DENSITY POLYETHYLENE (HDPE) TO HDPE BY ULTRAVIOLET GRAFTING OF METHACRYLATES AND ACRYLATES

A study has been made on the effect of the presence of grafted acrylic layers on the autoadhesion of polyethylene. Methyl methacrylate (MMA), ethyl methacrylate (EMA), methyl acrylate (MA), ethyl acrylate (EA), and butyl methacrylate (BMA) were grafted onto high density polyethylene (HDPE). The grafting reaction was faster at higher temperature and methacrylates graft more easily than acrylates. For methacrylates and acrylates, the grafted amount increases with increasing length of the pendant alkyl chain. The grafting temperature is a crucial factor affecting the adhesion of grafted PE samples. For the samples grafted at lower temperature (in a room temperature water bath), the adhesion is very low (less than 50 N/m), even for very thick grafted layers. But for the samples grafted at higher temperature, much higher adhesion can be obtained. The presence of homopolymer was another factor affecting the adhesion of PE samples. When homopolymer is removed from the surface of the grafted sample, higher adhesion can be obtained. For some samples, the highest peel strength of more than 1000 N/m has been obtained. The low adhesion of the samples grafted at low temperature is attributed to the high branching of grafted chains.     

Poly(acrylonitrile‐co‐methyl acrylate) copolymers: Correlation between copolymer composition,morphology and positron annihilation lifetime parameters

A series of poly(acrylonitrile‐co‐methyl acrylate) copolymers of differing copolymer compositions are synthesized through free radical emulsion copolymerisation of methyl acrylate (MA) and acrylonitrile (AN) and by variation of the monomer feed ratios. The copolymers are characterized by NMR, SEC, WAXD, DMA, and positron annihilation lifetime spectroscopy. Results show that, there is a linear decrease in the glass transition temperature (T_g) of the copolymers and the MA content. There is also a progressive decrease in the crystallinity of the copolymers with increasing MA content. Positron results show a sigmoidal variation in the ortho positronium lifetime with an increasing MA content. The low MA content, semi‐crystalline copolymers show a positive deviation from the linear additive relationship between the o‐Ps lifetime and MA content, whereas the higher MA content amorphous copolymers show a negative deviation from the linear additive behavior. The o‐PS intensity shows a linear behavior with MA content with a slight deviation from the additive linear behavior for the very high‐content MA copolymer. These variations in the measured positron lifetime parameters are interpreted in terms of the copolymer morphology. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of structure and composition on physico-mechanical properties of methyl methacrylate/alkyl (meth)acrylate copolymers

The paper describes the fabrication of cast acrylic sheets by copolymerizing a prepolymer syrup of methyl methacrylate (MMA) with varying amounts (1-20 wt.-%) of 2-ethylhexyl methacrylate (EHMA), n-hexyl methacrylate (HMA), 2-ethylhexyl acrylate (EHA) and n-hexyl acrylate (HA). The effect of structure of copolymer on light transmittance, density and mechanical properties was evaluated. Tensile strength and storage modulus decreased with increasing comonomer content. Strain increased significantly in the case of MMA/EHA and MMA/HA copolymer sheets having 15 and 20 wt.-% of comonomer. Softening temperature of copolymer samples was determined using dynamic mechanical thermal analysis. Heat deflection temperature under flexural load and softening temperature decreased with increasing comonomer content in copolymer.     

Homo-and copolymers of vinyl esters,acrylates, and methacrylates of some derivatives of fatty acids

Vinyl esters of some undecylenic acid derivatives and acrylates and methacrylates of undecyl and undecylenyl alcohols, which may be considered as derivaties of castor oil, have been polymerized and copolymerized with vinyl chloride to provide a variety of new polymers. The acrylate and the methacrylate of undecylenyl alcohol have been epoxidized to yield two new polymerizable monomers of potential usefulness as crosslinking agents in finished copolymers.     

Autoadhesion of high density polyethylene (HDPE) to HDPE by ultraviolet grafting of methacrylates and acrylates

A study has been made on the effect of the presence of grafted acrylic layers on the autoadhesion of polyethylene. Methyl methacrylate (MMA), ethyl methacrylate (EMA), methyl acrylate (MA), ethyl acrylate (EA), and butyl methacrylate (BMA) were grafted onto high density polyethylene (HDPE). The grafting reaction was faster at higher temperature and methacrylates graft more easily than acrylates. For methacrylates and acrylates, the grafted amount increases with increasing length of the pendant alkyl chain. The grafting temperature is a crucial factor affecting the adhesion of grafted PE samples. For the samples grafted at lower temperature (in a room temperature water bath), the adhesion is very low (less than 50 N/m), even for very thick grafted layers. But for the samples grafted at higher temperature, much higher adhesion can be obtained. The presence of homopolymer was another factor affecting the adhesion of PE samples. When homopolymer is removed from the surface of the grafted sample, higher adhesion can be obtained. For some samples, the highest peel strength of more than 1000 N/m has been obtained. The low adhesion of the samples grafted at low temperature is attributed to the high branching of grafted chains.     

Characterization of surgical adhesives from UV-polymerized poly(PEG dimethacrylate-co-2-hydroxyethyl methacrylate) copolymers

Polymer samples that could be used as wound adhesives were prepared from poly(ethylene glycol)dimethacrylate (PEGDMA) and 2-hydroxyethyl methacrylate (HEMA) copolymers in concentrations from 0 to 50 mol %. The UV copolymerization was initiated by 2,2-dimethoxy-2-phenylacetophenone (DMPA) and ultraviolet light intensities ranged from 0.1 to 0.5 m W/cm. The volume shrinkage during photopolymerization was observed using a dilatometric technique. The overall volume shrinkage was affected by the comonomer ratio and the nature of the PEGDMA comonomer. The rate of volume shrinkage was higher at higher ultraviolet light intensities. PEG(400)DMA-based copolymers exhibited lower glass transition temperatures than those of PEG(200)-based copolymers. The introduction of HEMA to the copolymers reduced both their glass transition and degradation temperatures. The equilibrium water-swelling ratio increased with increasing PEGDMA molecular weight and HEMA content. © 1995 John Wiley & Sons, Inc.     

Synthesis and property behavior of dioctyl phthalate plasticized styrene–acrylate particles by Shirasu porous glass emulsification and subsequent suspension copolymerization

Two‐phase model styrene–acrylate copolymers were synthesized with a soft phase consisting of methyl acrylate, butyl acrylate, and butyl methacrylate. Besides the styrenic copolymers, copolymers containing a hard phase of methyl methacylate and methyl acrylate were also synthesized. Comonomer droplets with a narrow size distribution and fair uniformity were prepared using an SPG (Shirasu porous glass) membrane having pore size of 0.90 μm. After the single‐step SPG emulsion, the emulsion droplets were composed mainly of monomers, hydrophobic additives, and an oil‐soluble initiator, suspended in the aqueous phase containing a stabilizer and inhibitor. These were then transferred to a reactor, and subsequent suspension polymerization was carried out. Uniform copolymer particles with a mean diameter ranging from 3 to 7 μm, depending on the recipe, with a narrow particle size distribution and a coefficient of variation of about 10% were achieved. Based on the glass‐transition temperatures, as measured by differential scanning calorimetry, the resulting copolymer particles containing a soft phase of acrylate were better compatibilized with a hard phase of methyl methacrylate than with styrene with dioctyl phthalate (DOP) addition. Glass‐transition temperatures of poly(MMA‐co‐MA) particles were strongly affected by the composition drift in the copolymer caused by their substantial difference in reactivity ratios. Incorporation of DOP in the copolymer particles does not significantly affect the glass‐transition temperature of MMA‐ or MA‐containing copolymer particles, but it does affect the St‐containing copolymer and particle morphology of the copolymers. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3037–3050, 2003     

Polymerization of alkyl acrylates and alkyl methacrylates with starch

A series of C₄-C₁₂ alkyl acrylates and methacrylates was polymerized with starch by irradiating starch–monomer mixtures with ⁶⁰Co. Homopolymers were extracted with cyclohexane. The amounts of insoluble versus soluble synthetic polymer in polymerization run with alkyl acrylates varied less with the chain length of the alkyl substuent than in the polymerizations run with alkyl acrylates varied less with the chain length of the alkyl substituent than in the polymerizations run with alkyl methacrylates; and the poly(alkyl acrylate) contents of cyclohexane-insoluble fractions were all in the 38–45% range. Synthetic polymer contents of the products from butyl, hexyl, and decyl methacrylates were also close to this range. Octyl and lauryl methacrylate, however, gave high conversions to cyclohexane-soluble poly(alkyl methacrylate) along with little or no unextractable synthetic polymer in the starch-containing fractions. Poly(lauryl methacrylate) could be rendered insoluble by incorporating a small amount of tetramethylene glycol dimethacrylate in the polymerization mixture. In a series of polymerizations run with hexyl acrylate and hexyl methacrylate, lower irradiation doses led to more cyclohexane-soluble polymer and less synthetic polymer in the starch-containing fractions. Enzymatic digestion of starch-soluble polymer and less synthetic polymer in the starch-containing fractions. Enzymatic digestion of starch-containing polymers gave synthetic polymer fractions that were largely insoluble in cyclohexane. Crosslinking is, therefore, probably taking place during these polymerizations; however, we could not eliminate the possibility that reduced solubility was caused by small amounts of residual carbohydrate in these polymer fractions. Ceric ammonium nitrate-initiated polymerizations of butyl acrylate, hexyl acrylate, and butyl methacrylate with starch gave cyclohexane-insoluble polymers that contained 33–39% synthetic polymer. The higher alkyl acrylates and methacrylates produced little or no polymer under these conditions. Starch-containing fractions were tested as absorbents for hydrocarbons. Products prepared from decyl acrylate and lauryl acryle acrylate absorbed about 9 g of isooctane per 1 g of polymer, whereas the lowrer alkyl monomers gave polymers with lower absorbency.     

Studies on the preparation of stable and high solid content emulsifier‐free latexes and characterization of the obtained copolymers for MMA/BA system with the addition of AHPS

3‐Allyloxy‐2‐hydroxyl‐propanesulfonic (AHPS) salt was synthesized and used as a hydrophilic comonomer for the methyl methacrylate (MMA) and n‐butyl acrylate (BA) emulsifier‐free emulsion copolymerization system to obtain latices of stable and high‐solid content. Properties of the latices, such as flow behavior, stability, and final diameter of the latex particles were studied. In addition, physical properties of the obtained copolymers, such as glass transition temperature (T_g), stress–strain behavior, and water resistance were investigated. With the addition of AHPS, the latices of stable and high‐solid content (as high as 60%) were prepared. Flow of the latices follows the law of the Bingham body. The final diameter of the latex particles is 0.3–0.5 μm in diameter, which is larger than that of the conventional latex particles and decreases with the increase of AHPS and potassium persulfate (KPS) concentration. All the copolymers are atactic polymers, showed as single T_g on dynamic mechanical analysis spectrum. Compared with the copolymers that were prepared by surfactant emulsion polymerization, tensile strength, as well as water resistance is greatly improved. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 21–28, 2001     

Morphology and mechanical properties of polypropylene and poly(ethylene‐co‐methyl acrylate) blends

The morphology and mechanical properties of isotactic polypropylene (iPP) and poly(ethylene‐co‐methyl acrylate) (EMA) blends were investigated. Various EMA copolymers with different methyl acrylate (MA) comonomer content were used. iPP and EMA formed immiscible blends over the composition range studied. The crystallization and melting reflected that of the individual components and the crystallinity was not greatly affected. The size of the iPP crystals was larger in the blends than those of pure iPP, indicating that EMA may have reduced the nucleation density of the iPP; however, the growth rate of the iPP crystals was found to remain constant. The tensile elongation at break was greatly increased by the presence of EMA, although the modulus remained approximately constant until the EMA composition was greater than 20%. EMA with a 9.0% MA content provided the optimum effect on the mechanical properties of the blends. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 175–185, 2003     

Miscibility of polycarbonate with poly(methyl methacrylate-co-cyclohexyl methacrylate)

Summary Miscibility of bisphenol-A polycarbonate, PC, with methyl methacrylate/cyclohexyl methacrylate, PMCHM, copolymers were examined by glass transition temperature and lower critical solution temperature, LCST, behavior. PMCHM copolymers were found to be miscible with PC at levels of below 4% or less of CHM in weight. Relatively small amount of the comonomer markedly raised phase separation temperature on heating. This result can be rationalized by intramolecular repulsion effect reported earlier.     

Compatibilization of poly(methyl acrylate) with poly(methyl methacrylate) through charge transfer interactions

Summary Copolymers of methyl acrylate (MA) with an electron-donor comonomer (N-vinylcarbazole) (NVC) are mixed with copolymers of methyl methacrylate (MMA) with a electron-acceptor comonomer (2-(3,5-dinitrobenzoyl) oxyethyl methacrylate) (DNBM) such that 1:1 mol ratios of NVC:DNBM are present at all times. The blends obtained are phase separated up to an average of 27 mol% donor/acceptor structural unit in the copolymer. Above 27 mol% perturbation, poly(MA) and poly(MMA) become compatible.     

Triple crystallization behavior of fractionated ethylene/α-olefin copolymers of different catalyst type

Non-isothermal crystallization processes in fractions of Ziegler-Natta (ZN) and single site (SS) based ethylene/1-butene and ethylene/1-hexene copolymers have been studied by differential scanning calorimetry (DSC). Fractionation of used copolymers was done according to molar mass (MM) and composition (comonomer content). It was observed in DSC scans that for fractions with high MM (larger than 10 kg/mol) in addition to the main high-temperature crystallization peak (HTCP), a very-low temperature crystallization peak (VLTCP) is present at temperatures in between 60–75 °C. Such peak is absent for the first fractions having very-low MM. The partial crystallinity and peak temperatures, obtained from VLTCP, increase with MM and level off at MM around 60–100 kg/mol. It was found that the crystallinity as related to the area of the VLTCP is catalyst type dependent, and is higher for the SS catalyst compared to the ZN. Peak temperature of VLTCP linearly decreases with increasing comonomer content at fixed MM while the partial crystallinity practically does not change with comonomer content.     

Studies on the polyblends of poly(vinyl chloride) with various methacrylate copolymers,physical and mechanical properties. I

The effect of blending various methacrylate copolymers on the physical and mechanical properties of poly(vinyl chloride) (PVC) has been investigated. Copolymers of methylmethacrylate with methylacrylate, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate in 80:20 and 50:50 wit methylmethacrylate have been prepared and characterized by nuclear magnetic resonance spectroscopy. Polyblends of PVC and such polyacrylates have been prepared in 80:20 ratio by melt blending technique and characterized by thermomechanical analysis to study the glass transition behavior vis-à-vis the compatibility of these blends. Mechanical properties of these blends revealed a substantial increase in impact strength particularly when long chain acrylate polymers like butyl acrylate and 2-ethyl hexyl acrylates are used; however, there is a decrease in the yield stress and initial modulus. A shift from brittle failure to ductility has been observed in blends of PVC on incorporation of these acrylate copolymers. Scanning electron microscopic studies have been carried out to support these observations.     

Multivariate analysis of C NMR spectra of methacrylate copolymers and homopolymer blends

¹³C NMR spectra of copolymers of methyl methacrylate and tert-butyl methacrylate with various chemical compositions, the homopolymers of the two methacrylates, and blends of the homopolymers with various blend ratios were subjected to principal component analysis. The first and second principal components correlated chemical composition and the randomness of comonomer sequence, respectively. Chemical composition of the copolymers was determined with high accuracy and precision by the partial least-squares regression without assignment of individual resonance peaks.