Polymers of vinylphosphonic acid,acrylonitrile, and methyl acrylate and their nanofibers

In this study, a small amount of vinylphosphonic acid was used to produce fire-retardant copolymers and terpolymers from acrylonitrile and methyl acrylate. The structures of copolymer and terpolymers were elucidated by ¹H-NMR and phosphorous analysis. Thermal decomposition of vinylphosphonic acid-containing copolymers and terpolymers started at lower temperatures than of poly(acrylonitrile-co-methyl acrylate). Methyl acrylate contributes to the thermal resistance of the terpolymers. Poly(acrylonitrile-co-methyl acrylate-co-vinylphosphonic acid) with a phosphorous content about 0.25% burned at a slower rate and emitted less smoke compared to poly(acrylonitrile-co-methyl acrylate). The burning tests showed that both copolymer and terpolymers containing vinylphosphonic acid behaved as a fire-retardant polymer. The phosphonate and phosphonic acid groups in the copolymer and terpolymers accelerate the cyclization of nitrile groups and inhibit the fire in the gas phase. Nanofibers were successfully produced by the electrospinning method from the copolymers and terpolymers containing vinylphosphonic acid moiety.     

Terpolymers. III. Isochronal viscoelastic parameters for terpolymers of vinyl stearate,vinyl acetate,and vinyl chloride

Isochronal viscoelastic parameters were collected for many of the copolymers, terpolymers, and diluent mixtures whose mechanical properties at ambient temperatures were reported in the preceding paper. In the polymeric systems, vinyl stearate, acting as the primary internal plasticizer, was introduced into terpolymers by displacing vinyl acetate from base copolymers of vinyl acetate and vinyl chloride, across the range of composition. In the diluent mixtures, poly(vinyl chloride) was plasticized by di-2-ethylhexyl phthalate across the range of compositions. For direct comparison with the mixtures, vinyl chloride was plasticized by copolymerization with vinyl stearate across the same range of compositions. Moduli for the co- and terpolymers reached the low values characteristic of soft materials at room temperature only through a short range of vinyl stearate composition. At higher internal plasticizer compositions, side-chain crystallization stiffened the samples and raised their moduli. In contrast, moduli for the mixtures decreased steadily with increase in diluent at ambient temperature. The effective use temperature ranges were narrow for the co- and terpolymers but broad for the mixtures. Curve broadening was similar for both types of systems, but reached a maximum at about 40 weight-% plasticizer for the diluent mixtures. The slopes of the glassy modulus with decreasing temperature at 50°C below T_g for the vinyl stearate copolymers were relatively large. However, moduli close to that of poly(vinyl chloride) were reached only near the temperature range associated with the γ-transition. Consequently, this behavior was attributed to motions of the side chains in the glassy matrix. Room temperature moduli, which could be obtained before the onset of melting, were correlated with the fractional side-chain crystallinity for polymers having a high vinyl stearate content. From this relation, the modulus for the hexagonal crystal form of the side-chain crystallites of poly(vinyl stearate) was estimated to be 1.2×10¹⁰ dynes/cm². Moduli for the glassy amorphous phase of this same polymer appeared to have one sixth of this value at 40°C below the glass transition. The glass transition temperature occurred about 10° below the inflection temperature at 10⁹ dynes/cm², as an average for all of the systems studied.     

Comparison of thermomechanical properties of statistical, gradient and block copolymers of isobornyl acrylate and n-butyl acrylate with various acrylate homopolymers

Well-defined statistical, gradient and block copolymers consisting of isobornyl acrylate (IBA) and n-butyl acrylate (nBA) were synthesized via atom transfer radical polymerization (ATRP). To investigate structure-property correlation, copolymers were prepared with systematically varied molecular weights and compositions. Thermomechanical properties of synthesized materials were analyzed via differential scanning calorimetry (DSC), dynamic mechanical analyses (DMA) and small-angle X-ray scattering (SAXS). Glass transition temperature (T_g) of the resulting statistical poly(isobornyl acrylate-co-n-butyl acrylate) (P(IBA-co-nBA)) copolymers was tuned by changing the monomer feed. This way, it was possible to generate materials which can mimic thermal behavior of several homopolymers, such as poly(t-butyl acrylate) (PtBA), poly(methyl acrylate) (PMA), poly(ethyl acrylate) (PEA) and poly(n-propyl acrylate) (PPA). Although statistical copolymers had the same thermal properties as their homopolymer equivalents, DMA measurements revealed that they are much softer materials. While statistical copolymers showed a single T_g, block copolymers showed two T_gs and DSC thermogram for the gradient copolymer indicated a single, but very broad, glass transition. The mechanical properties of block and gradient copolymers were compared to the statistical copolymers with the same IBA/nBA composition.     

Rate dependent finite deformation stress-strain behavior of an ethylene methacrylic acid copolymer and an ethylene methacrylic acid butyl acrylate copolymer

The large strain deformation behaviors of an ethylene methacrylic acid (EMAA) copolymer and an ethylene methacrylic acid butyl acrylate (EMAABA) copolymer are evaluated and compared in compression over nearly eight orders of magnitude in strain rate, from 10⁻⁴ to almost 10⁴/s. Transition regimes are quantified using dynamic mechanical analysis. The stress-strain behavior of these copolymers exhibits a relatively stiff initial behavior followed by a rollover to a more compliant response. The low strain modulus, the rollover stress and the large deformation stress-strain behavior are strongly dependent on strain rate. The proximity of the material glass transition to the room temperature test conditions results in a substantial change in the nature of the rate sensitivity of the stress-strain behavior as one moves over the range of strain rates. The mechanical behavior of the EMAA is contrasted to that of a corresponding EMAABA terpolymer and to its sodium-neutralized counterpart (EMAABA_Na). The nature of the rate sensitivity of the room temperature stress-strain behavior of EMAA transitions from a behavior near the glassy end of the leathery regime at low rates to a near glassy behavior at high rates. The butyl acrylate content in the EMAABA lowers the glass transition temperature and leads to a more compliant mechanical behavior (reduced initial stiffness, reduced rollover stress, reduced post-rollover stress level) at room temperature. The EMAABA behavior transitions from a rubbery-like behavior at the lowest rates to a leathery-like behavior at the highest rates. Upon sodium neutralization, the overall stiffness and flow stress levels are enhanced likely due to the presence of the ionic aggregates; the glass transition of EMAABA_Na is broadened in comparison to the EMAABA, giving a rate dependent room temperature behavior that transitions through the leathery regime with increasing strain rate. A constitutive model that separately accounts for the distinct deformation resistances of the crystalline domains and the amorphous domains is able to capture the changes in rate dependent deformation behavior of the EMAA copolymers studied herein. The crystalline domains provide resistance to flow across a wide window in rate and temperature whereas the amorphous domains provide increasing resistance as the strain rate is increased and the material effectively transitions through the glass transition regime, providing a mechanism for changing rate sensitivity.     

Copolymerization of pentachlorophenyl acrylate with vinyl acetate and ethyl acrylate. Polymer-bound fungicides

Copolymers of pentachlorophenyl acrylate (M₁) with both vinyl acetate and ethyl acrylate were prepared (in benzene at 60°C initiated by t-butyl peroxypivalate) at a variety of M₁/M₂ ratios. The reactivity ratios for the vinyl acetate (M₂) copolymerizations were r₁ = 1.44 and r₂ = 0.039, while for ethyl acrylate copolymerizations r₁ = 0.21 and r₂ = 0.88. The glass transition temperatures were obtained as a function of the M₁/M₂ ratio. The values of T_g for the copolymers fell between those of poly(pentachlorophenyl acrylate) and either poly(vinyl acetate) or poly(ethyl acrylate). A series of bulk copolymers with low pentachlorophenyl acrylate content were studied as biocidal coatings using accelerated growth agar dish tests inoculated with Aspergillus sp., Pseudomonas sp., Alternaria sp., and Aureobasidium pullulans. The copolymers retarded or prevented growth but did not give a zone of inhibition around the coatings. Pentachlorophenol, when added to coating polymers, did exhibit a zone of inhibition due to migration of this biocide into the agar medium.     

Viscosity index. I. Evaluation of selected copolymers incorporating n-octadecyl acrylate as viscosity index improvers

Compositionally and structurally varied copolymers all containing n-octadecyl acrylate were prepared and evaluated as viscosity index improvers in a common base oil under conditions of low shear. Systems evaluated over a range of copolymer and blend composition were: copolymers of n-octadecyl acrylate with, respectively, methyl methacrylate, 2-ethylhexyl acrylate, and n-dodecyl acrylate; and homopolymers of poly(n-octadecyl acrylate), prepared with a wide range of molecular weights. Properties were compared with those of blends of commercial methacrylate copolymers (acryloids) which had been freed of their entraining liquid. Mixtures of base oil with copolymers of n-octadecyl acrylate and methyl methacrylate, compared at fixed SAE viscosities, were the most efficient of all blends studied. They had the smallest rate of change of viscosity with temperature (as measured by their ASTM slopes), particularly in the composition region of incipient polymer precipitation at room temperature. Efficiency of certain of these composition was somewhat greater than that of the acryloids. A parameter that related concentration and weight-average molecular weight was used to correlate all of the data for ASTM slope and viscosity. Empirical relations developed by using this parameter enabled rheological data to be estimated that agree within 6% of experimental values for the case of thermodynamically good base oil solvents. These data demonstrated the relatively small contributions of copolymer structure to viscosity index improvement.     

Synthesis and characterization of homopolymers and copolymers of various acrylates and acrylonitrile

Various homopolymers and copolymers of methyl acrylate, ethyl acrylate, butyl acrylate, and acrylonitrile in different feed ratios were synthesized. These were characterized by IR, ¹³C-NMR, DSC, DTA, and TGA. Spectroscopic characterization helped in differentiating copolymers of different mol ratios. Thermal analysis revealed different degradation patterns for homopolymers and copolymers. The temperature and energy changes associated with various phase transitions were dependent on the chemical composition of homo- and copolymers, as expected. © 1993 John Wiley & Sons, Inc.     

Copolymers of methyl methacrylate and acrylate comonomers: Synthesis and characterization

Methyl methacrylate (MMA) has been copolymerized with n-butyl acrylate (n-BA), ethyl acrylate (EA), and 2-ethylhexyl acrylate (2-EHA) in solution at 70°C using benzoyl peroxide as free radical initiator. The copolymer composition was estimated by the ¹H-NMR spectroscopic technique. The copolymers were further characterized by IR, XRD, TGA, DTA, DSC, GPC, and solubility. The adhesive characteristics of the copolymers to cellulosic substrate are also reported. © 1995 John Wiley & Sons, Inc.     

Terpolymers. II. Mechanical properties and transition temperatures of terpolymers of vinyl stearate,vinyl acetate,and vinyl chloride

Vinyl stearate was studied as a major internal plasticizer in terpolymers containing vinyl acetate and vinyl chloride. The terpolymers were prepared by systematically replacing vinyl acetate by close increments of vinyl stearate starting with combinations of vinyl acetate and vinyl chloride, in increments, over all compositions. For comparison of properties, a complete range of copolymers of vinyl stearate and vinyl chloride, as well as mixtures of poly(vinyl chloride) and di-2-ethylhexyl phthalate (DOP) were also made. The external plasticizer was more efficient in reducing the glass temperature than was vinyl stearate. The decline in T_g with weight fraction of plasticizer was linear for the copolymers and terpolymers but concave downward with the liquid diluent. The linear decline was shown to involve mere additivity of the free volume contributed by each side-chain methylene (or methyl) group in both vinyl esters to reducing T_g. The mechanism of the diluent system was more complex. However, the magnitude of the reduction of tensile modulus at a given weight fraction of DOP could be equaled or exceeded by the same amount of vinyl stearate, by increasing the vinyl acetate content of the base copolymer to 40 mole-% or more. Unfortunately, the ultimate strengths and elongations of internally plasticized systems were reduced more than those of the mixtures at comparable compositions. Vinyl stearate was found to markedly retard photolytic degradation compared to both vinyl acetate and the external plasticizer in unstabilized samples having nearly the same thermal treatment. The effect was greater than could be ascribed to dilution by the long alkyl group. The production of a stearoyl radical more stable than the radicals initiating dehydrochlorination is suggested as a possible mechanism.     

Study on modified phenolic resin. III. Modification with p-hydroxyphenylmaleimide/acrylic ester copolymer

The improvement of toughness and heat resistance of phenolic resin was examined by blend of novolac and copolymers prepared from p-hydroxyphenylmaleimide (HPMI) and acrylic ester. Copolymers of HPMI and acrylic esters, such as methyl acrylate, ethylacrylate, n-butylacrylate, or 2-ethylhexyl acrylate, were synthesized. Average molecular weights, glass transition temperatures (T_g) and thermal decomposition temperatures were measured. The miscibility of the copolymers with novolac was evaluated. It was found that these copolymers had higher average molecular weight and higher thermal decomposition temperature than those of novolac; they also had good miscibility with novolac. Molding compounds were prepared by hot roll-kneading of mixtures, which involved novolac, the copolymer, hexamethylenetetramine (hexamine), and glass fiber. Test pieces of the modified phenolic resins were prepared by transfer molding from the molding compounds. It was found that phenolic resin, modified with HPMI/ethylacrylate copolymer or HPMI/n-butylacrylate copolymer, which consisted of numerous units of acrylic ester, showed both good toughness and good heat resistance.     

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     

Internal plasticization of poly(vinyl chloride) by grafting acrylate copolymers via copper-mediated atom transfer radical polymerization

Internal plasticization of poly(vinyl chloride) (PVC) was achieved in one-step using copper-mediated atom transfer radical polymerization to graft different ratios of random n-butyl acrylate and 2–2-(2-ethoxyethoxy)ethyl acrylate copolymers from defect sites on the PVC chain. Five graft polymers were made with different ratios of poly(butyl acrylate) (PBA) and poly(2–2-(2-ethoxyethoxy)ethyl acrylate) (P2EEA); the glass transition temperatures (T_g) of functionalized PVC polymers range from − 25 to − 50°C. Single T_g values were observed for all polymers, indicating good compatibility between PVC and grafted chains, with no evidence of microphase separation. Plasticization efficiency is higher for polyether P2EEA moieties compared with PBA components. The resultant PVC graft copolymers are thermally more stable compared to unmodified PVC. Increasing the reaction scale from 2 to 14 g produces consistent and reproducible results, suggesting this method could be applicable on an industrial scale.     

Synthesis and thermoanalysis of emulsion terpolymers of N‐phenylmaleimide,styrene, and acrylonitrile

Terpolymers of N‐phenylmaleimide (PMI), styrene, and acrylonitrile (AN) were synthesized by emulsion polymerization. The thermal properties of terpolymers at different PMI and AN feed contents were investigated by differential scanning calorimetry, torsional braid analysis, thermogravimetric analysis, and a Vicat softening point test. The results showed the glass‐transition temperature and decomposition temperature of the terpolymers increased with increasing PMI feed content. Furthermore, the Vicat softening point of the terpolymers rose with PMI feed content. The weight‐ and number‐average molecular weights (M̄_w and M̄_n) of the terpolymers were also determined by gel permeation chromatography. The results showed that the M̄_w and M̄_n of the terpolymers decreased with increasing PMI feed content and increased with increasing AN feed content. The mechanical properties (tensile strength and impact strength) of the terpolymers decreased with increasing PMI feed content and increased with increasing AN feed content. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1067–1073, 2001     

Rheological behavior of acrylonitrile/ammonium acrylate copolymer solutions

Ammonium acrylate was first used as a comonomer to copolymerize with acrylonitrile. The viscosity behavior of dimethyl formamide solutions of acrylonitrile/ammonium acrylate copolymer was studied, and the rheological kinetics of the solutions were studied for comparison. It was shown that the solutions behaved the same as a Newtonian flow as the rotor speed increased beyond 12 rpm. With an increase in temperature, the apparent viscosity of acrylonitrile/ammonium acrylate copolymer solutions showed a trend of decreasing. The changes in the apparent flow‐activation energy of solutions (E_η) calculated by the Arrhenius equation became less prominent along with the changes in the molecular weight of the acrylonitrile/ammonium acrylate copolymers. E_η increased continuously with an increase in copolymer concentration. The viscosity of copolymer solutions decreased continuously as the concentrations of KCl and NaCl increased up to 0.015 mol/L, and then it increased. The E_η showed an obvious trend of decreasing with the addition of alkali salts, and the changes in the E_η containing NaCl were more prominent than those of solutions containing KCl. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2320–2324, 2007     

Pyrolysis of poly(methyl methacrylate co ethyl acrylate)

An investigation of the behavior of poly(methyl methacrylate co ethyl acrylate) with a commercially available filament-type pyrolysis unit and gas chromatogaph was conducted. It has been hypothesized that the quantity of ethyl acrylate monomer produced under the conditions of the experiment is dependent upon the number of ethyl acrylate–methyl methacrylate bonds contained in the copolymer. These observations were made possible by a standardized samples-handling technique in which a uniformsize disk was pyrolyzed at a maximum pyrolysis temperature of 600°C. This enabled reproducible pyrolysis gas chromatograms to be obtained and permitted pyrolysis products of copolymers containing different ratios of ethyl acrylate and methyl methacrylate to be compared. An examination of sequence distribution data, obtained with the aid of a sequence distribution program for copolymers, showed sufficient agreement with the pyrolysis data to support the hypothesis. It has been demonstrated that pyrolysis gas chromatography may be applied to experimentally determine the sequence distribution of copolymers.     

Graft polymerization of acrylonitrile and methyl acrylate onto hemicellulose

Graft polymerizations of acrylonitrile onto both a commercial larchwood hemicellulose and a purified (low lignin) wheat straw hemicellulose could be initiated by ceric ammonium nitrate. The resulting hemicellulose-g-polyacrylonitrile (PAN) copolymers were fractionated by extraction at room temperature with dimethylformamide and dimethylsulfoxide. Fractions were characterized by determining both the wt % PAN in each polymer fraction and the molecular weight of grafted PAN. Saponification of the PAN component of hemicellulose-g-PAN gave a water-dispersible graft copolymer with good thickening properties for water systems. An absorbent polymer, similar to the starch-based absorbents (Super Slurpers), was produced when saponified hemicellulose-g-PAN was isolated by methanol precipitation and then dried. Larchwood hemicellulose was also graft-polymerized with methyl acrylate using ceric ammonium nitrate initiation, and the hemicellulose-g-poly(methyl acrylate) was extrusion-processed into a tough, leathery plastic. Although ceric ammonium nitrate could be used as an initiator for graft polymerizations onto low-lignin hemicelluloses, it was inert with crude wheat straw hemicellulose containing 11% lignin. The ferrous sulfate–hydrogen peroxide redox system was used to initiate graft polymerizations onto this high-lignin material, and properties of the resulting hemicellulose-g-poly(methyl acrylate) and saponified hemicellulose-g-PAN graft copolymers were evaluated.     

Studies of the properties of a thermosetting epoxy modified with block copolymers

Poly[(n‐butyl acrylate)‐block‐poly(methyl methacrylate)‐co‐(glycidyl methacrylate)] (BMG) diblock copolymers incorporating an epoxy‐reactive functionality in one block have been synthesized and used as modifiers for the model epoxy resin E‐51 cured with 4,4′‐diaminodiphenyl methane (DDM). The properties and morphologies of the modified epoxy thermosets were investigated by dynamic mechanical analysis (DMA), impact testing and scanning electron microscopy (SEM). The results reveal that addition of the block copolymers leaves the glass transition temperatures of the blends relatively unchanged, with small decreases in the storage moduli at room temperature. The toughening effect is dependent on the chemical structures of the block copolymers and an increase in the impact strength by a factor of two was obtained by the addition of ‘relatively symmetrical’ block copolymers. Moreover, the impact test results are consistent with the morphologies of the fracture surfaces as evidenced by SEM. Copyright © 2005 Society of Chemical Industry     

Synthesis and thermal analysis of emulsion terpolymers of N‐phenylmaleimide,methyl methacrylate,and acrylonitrile

Terpolymers of N‐phenylmaleimide (PMI), methyl methacrylate (MMA), and acrylonitrile (AN) were synthesized by emulsion polymerization. The thermal properties of the terpolymers, at different PMI and AN feed contents, were investigated by TBA, TGA, and the Vicat softening point test. The results show that the glass transition temperature (T_g) and decomposition temperature of the terpolymers increase with increasing PMI feed content. Furthermore, the Vicat softening points of the terpolymers increase with the PMI feed content. The M?_w and M?_n of the terpolymers were also determined by GPC. The results show that the M?_w and M?_n of the terpolymers have a maximum value in the range of 0–30% PMI feed content and decrease with an increasing AN feed content. The mechanical properties (tensile strength and impact strength) of the terpolymers decrease with an increasing PMI feed content and increase with an increasing AN feed content. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2455–2462, 2001     

Blends containing polymers of epichlorohydrin and ethylene oxide. II. Polyacrylates

The phase behavior of blends of various polyacrylate homopolymers and two commercial ethyl acrylate (EA) and n-butyl acrylate (nBA) copolymers with polyepichlorohydrin (PECH), poly(ethylene oxide) (PEO), and a copolymer of epichlorohydrin and ethylene oxide [P(ECH/EO)] was examined using differential scanning calorimetry and optical indications of phase separation on heating, i.e., lower critical solution temperature (LCST) behavior. Poly(methylacrylate) (PMA) was shown to be miscible with PECH, PEO, and P(ECH/EO) while only PECH was found to be miscible with the higher polyacrylates: poly(ethyl acrylate), EA copolymer, poly(n-propyl acrylate), and nBA copolymer. However, even PECH was found to be only partially miscible with poly(n-butyl acrylate). In general, glass transitions observed by DSC for blends were not as broad as those found in corresponding polymethacrylate blends. All mixtures showed LCST behavior, and, based on this and excess volume measurements, to the extent possible, qualitative conclusions were made concerning the relative strength of the interactions among the various blend pairs. For PECH it appears that the interaction with polyacrylates decreases with increasing size of the alkyl group. The commercial copolymers seem to interact more exothermically with PECH than the corresponding homopolymers. The interaction with PMA is apparently larger for PECH than for PEO or for P(ECH/EO). Interactions for the latter two are about the same. The apparently exothermic interactions between ECH and EO units are not sufficiently strong to preclude miscibility of P(ECH/EO) with PMA. As for the polymethacrylates, it is clear that the chlorine moeity of PECH is needed for miscibility with higher polyacrylates.     

Resultant synergism in the shear resistance of acrylic pressure‐sensitive adhesives prepared by emulsion polymerization of n‐butyl acrylate/2‐ethyl hexyl acrylate/acrylic acid

Acrylic emulsion pressure‐sensitive adhesives (PSAs) were synthesized by the copolymerization of n‐butyl acrylate with various levels of 2‐ethyl hexyl acrylate (2EHA) and a small constant amount of acrylic acid. The effect of varying the n‐butyl acrylate/2EHA monomer composition on the kinetic behavior of the polymerization and the characteristics of the copolymers prepared in a batch process were investigated. The results showed that increasing the amount of 2EHA in the monomer caused the polymerization rate and the glass‐transition temperature of the acrylic copolymers to decrease. Increasing the amount of 2EHA caused the gel content of the copolymers to decrease, reaching a minimum at 50 wt %; thereafter, the gel content increased at higher 2EHA levels. For the acrylic emulsion, the peel‐fracture energy of the PSAs decreased as the amount of 2EHA in the monomer was increased up to 50 wt %. At higher 2EHA levels, the peel‐fracture energy was relatively constant. Interestingly, a synergistic effect of increased shear resistance at 25 wt % 2EHA was observed without a significant trade‐off in terms of the peel and tack properties. This behavior was attributed to a good interconnection between the microgels and the free polymer chains inside the contacting particles in the adhesive film. Cooperation between various levels of 2EHA in the copolymer structure simultaneously changed the crosslink molecular weight (M_c) of the microgels and the entanglement molecular weight (M_e) of the free chains in the adhesive network morphology. The adhesive performance of the PSAs was found to be correlated with their M_c/M_e values as the 2EHA proportion was varied. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008