Crosslinking of poly(vinyl alcohol) and poly(vinyl acetate) using poly(maleic anhydride‐alt−2,4‐dimethyl‐1,3‐pentadiene) as polyfunctional crosslinker and decrosslinking by ozone degradation

Crosslinking and decrosslinking reactions of poly(vinyl alcohol) (PVA) and poly(vinyl acetate) (PVAc) using an alternating copolymer of maleic anhydride and 2,4‐dimethyl‐1,3‐pentadiene (PMAD) as the polyfunctional crosslinker and subsequent ozone degradation are reported. PVA and PVAc are heated at 200 °C for 0.5 to 3 h in the presence of 5 to 30 wt % of PMAD in the solid state to obtain the corresponding crosslinked polymers. The reactions of a hydroxy group of PVA and an acetate group of PVAc with an anhydride group of PMAD slowly proceed to give insoluble polymers with a loose crosslinking structure. Almost no change in the thermal decomposition temperatures and the IR spectra is observed during the crosslinking reactions. The crosslinked PVA produces hydrogels with a high swelling ratio of 500 to 1700%, which are readily degradable during a reaction with ozone in water at 0 °C. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44229.     

Preparation and Molecular Structure of Poly(Vinyl Alcohol) by Low Temperature Bulk Polymerization of Vinyl Acetate and Saponification

Abstract

Vinyl acetate (VAc) was bulk-polymerized at 30, 40 and 50°C using a low temperature initiator, 2,2′-azobis(2,4-dimethylvaleronitrile) (ADMVN), and effects of polymerization temperature and initiator concentration were investigated in terms of polymerization behavior and molecular structures of poly(vinyl acetate) (PVAc) and corresponding poly(vinyl alcohol) (PVA) obtained by saponifying it with sodium hydroxide. Low polymerization temperature and low conversion by adopting ADMVN proved to be successful in obtaining PVA of high molecular weight. PVAc having number-average degree of polymerization (P_n ) of 6,800–10,100 was obtained, whose degree of branching for acetyl group of 0.6–0.7 at 30°C, 0.8–1.1 at 40°C, and 1.0–1.9 at 50°C at conversion of below 40%. Saponifying so prepared PVAc yielded PVA having P_n of 3,100–6,200, and syndiotactic diad (S-diad) content of 51–53%. The whiteness, S-diad content, and crystal melting temperature were higher with PVA prepared from PVAc polymerized at lower temperatures.     

Crosslinking reaction and properties of two‐component waterborne polyurethane from terpene‐maleic ester type epoxy resin

A two‐component waterborne polyurethane (2K‐WPU) is prepared with the terpene‐maleic ester type epoxy resin‐based polyol dispersion and a hydrophilically modified hexamethylene diisocyanate tripolymer. Laser particle size analyzer and transmission electron microscopy are used to characterize the particle size distribution and the micromorphology of the 2K‐WPU. Crosslinking reaction kinetics of the 2K‐WPU is examined by fourier transform infrared spectrometry (FTIR) spectra. In the preliminary stage of the crosslinking reaction, it shows a very good fit with a second order reaction kinetics, and the apparent activation energy is 94.61 kJ mol^?1. It is also shown from the FTIR spectra that the complete crosslinking reaction of the 2K‐WPU needs 7 h at 70°C. The crosslinked products of the 2K‐WPU have good thermal resistant properties, with glass‐transition temperatures (T_g) in the range of 35–40°C and 10% weight loss temperatures (T_d) in the range of 275–287°C. The films obtained from the crosslinked products have good water‐resistance, antifouling, blocking resistance properties and impact strength of >50 cm, flexibility of 0.5 mm, adhesion of 1 grade, pencil hardness of HB‐2H. The pencil hardness and thermal‐resistant properties of the crosslinked products increase with the molar ratio of isocyanate (? NCO) group to hydroxyl (? OH) group. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Properties of poly(vinyl chloride) fibers crosslinked by 2-dibutylamino-4,6-dimercapto-1,3,5-triazine

PVC fibers, fastened to a needle frame, were crosslinked by 2-dibutylamino-4, 6-dimercapto-1,3,5-trizine in the presence of tetra-n-butylammonium bromide and alkali in water at 96°C. Solvent resistance, characterized by the gel fraction of THF, improves markedly. Mechanical properties of the fibers investigated by tensile tests at 20°C show that both the modulus and tensile strength at break increase, while elongation at break decreases over 40% gel content. Creep tests indicate that the resistance to heat deformation improves by crosslinking. The heat distortion temperature increases by 12°C at 75% gel content. Results of dynamic tests show that the T_g of PVC fibers determined by a peak in the loss modulus (E'') increases from 40% gel content. Dynamic modulus (E') increases by 74% at 23°C and the T_g by 37°C in the case of crosslinked PVC fibers having a 92% gel content. The shrinkage of PVC fibers in hot water at 94°C for 30 min decreases more than 50% over 75–80% gel content indicating the improved resistance to heat deformation.     

Fabrication and characterization of electrospun polybutadiene fibers crosslinked by UV irradiation

Crosslinked electrospun polybutadiene (BR) fibers were made using electrospinning and UV curing methods. The crosslinked BR fibers were obtained by irradiating UV light on the electrospun BR fibers containing a photoinitiator and a crosslinker. Although uncrosslinked electrospun BR fibers did not retain the fiber morphology at room temperature due to a cold flow resulting from the very low glass transition temperature (T_g) of BR (below ?80°C), the crosslinked electrospun BR fibers retained the fiber morphology. The crosslink density increased with increase of the content of crosslinking agent. The crosslinked BR fibers had higher T_g than the raw BR. Tensile strength, modulus, and elongation at break of the electrospun BR fiber mats increased with increase of the crosslinker content. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2233–2337, 2006     

A convenient crosslinking method for sulfonated poly(ether ether ketone) membranes via friedel–crafts reaction using 1,6‐dibromohexane and aluminum trichloride

In this study, sulfonated poly(ether ether ketone) (SPEEK) was very efficiently crosslinked via a Friedel–Craft reaction using 1,6‐dibromohexane and AlCl₃. The resulting crosslinked SPEEK (c‐SPEEK) membranes exhibited improved dimensional stability, thermal and chemical stability, and mechanical strength with slight reduction in the elongation. The methanol permeability was reduced by approximately two orders of magnitude by the crosslinking reaction. The proton conductivities of c‐SPEEK membranes were greater than Nafion‐212 in the temperature range of 30–90°C. Overall, this new crosslinking method can be conveniently and efficiently applicable to most aromatic hydrocarbon polymer membranes. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40695.     

Electrospinning of solvent‐resistant nanofibers based on poly(acrylonitrile‐co‐glycidyl methacrylate)

This article reports on the preparation of novel solvent‐resistant nanofibers by electrospinning of poly(acrylonitrile‐co‐glycidyl methacrylate) (PANGMA) and subsequent chemical crosslinking. PANGMA nanofibers with diameters ranging from 200 to 600 nm were generated by electrospinning different solutions of PANGMA dissolved in N,N‐dimethylformamide. Different additives were added to reduce the fiber diameter and improve the morphology of the nanofibers. The as‐spun PANGMA nanofibers were crosslinked with 27 wt % aqueous ammonia solution at 50°C for 3 h to gain the solvent resistance. Swelling tests indicated that the crosslinked nanofibers swelled in several solvents but were not dissolved. The weight loss of all the crosslinked nanofibrous mats immersed in solvents for more than 72 h was very low. The characterization by electron microscopy revealed that the nanofibrous mats maintained their structure. This was also confirmed by the results of the pore size measurements. These novel nanofibers are considered to have a great potential as supports for the immobilization of homogeneous catalysts and enzymes. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Cationic copolymerization behavior of a bicyclic orthoester having hydroxy group with glycidyl phenyl ether and volume change on their copolymerization

This article describes cationic ring‐opening copolymerization of a bicyclic orthoester having hydroxy group (BOE‐OH) and glycidyl phenyl ether (GPE), and the volume shrinkage behavior during the copolymerization. THF soluble polyethers [poly(BOE‐OH‐co‐GPE)] were obtained by the copolymerizations at 80–180°C, while crosslinked poly(BOE‐OH‐co‐GPE) was obtained by the copolymerizations at 220–250°C. This crosslinking reaction may originate from the dehydration of methylol groups in the side chain of poly(BOE‐OH‐co‐GPE). The volume shrinkage during the cationic copolymerization reduced as the increase of the BOE‐OH feed ratio. By contrast, the volume shrinkage on the crosslinking polymerization was almost independent on the BOE‐OH feed ratio. Poly(BOE‐OH‐co‐GPE)s with higher BOE‐OH composition showed lower thermal weight loss temperature owing to the release of H₂O by dehydration of methylol groups. The BOE‐OH component in the THF soluble poly(BOE‐OH‐co‐GPE)s lowered the glass transition temperature (T_g), while that in the crosslinked poly(BOE‐OH‐co‐GPE) increased the T_g probably because of the higher crosslinking density. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1356–1361, 2006     

Investigations of water and high energy radiation interactions in an epoxy

Differential scanning calorimetry (DSC) and infrared spectroscopy (IR) have been used to study the crosslinked epoxy system tetraglycidyl-4,4′-diaminodiphenyl methane cured with diaminodiphenyl sulfone. Samples cured at various temperatures were soaked in distilled water for extended periods or irradiated with 0.5 Me V electrons and ⁶⁰Co gamma. DSC results show that the standard-cured (137°C for 2 h and 160°C for 5 h) dry samples have a T_g around 190°C and a large exothermic reaction at about 260°C. The latter is attributed to further reaction of curing agent with the epoxide rings. The exothermic energy is about 124 cal/g for an uncured specimen, 42 cal/g for standard cured specimen, and 20 cal/g for soaked samples containing 4% H₂O. The exothermic energy is shown to decrease monotonically with the ionizing radiation dosage. IR results show a reduction in the intensity of the epoxide band as the exothermic energy is decreased.     

Effects of nuclear radiations on structure and molecular motions in some crystalline stereoregular polymers

Young's modulus and the mechanical damping factor have been determined between ?180 and +280°C. (at a frequency of several kilocycles), in samples of isotactic polypropylene, isotactic polystyrene, and trans-1,4-polybutadiene, subjected to pile irradiation (γ-rays and neutrons) at γ-doses from 90 to 4000 Mrad. In isotactic polypropylene no important structural changes are produced by the irradiation, except for a partial destruction of crystallinity. The samples receiving high radiation doses exhibit a low temperature loss region, which is attributed to the formation of a certain number of branches. Isotactic polystyrene shows very slight modifications of the dynamic mechanical properties at room temperature. At low temperature an increase of intensity of the δ relaxation phenomenon (probably due to oscillations of phenyl rings) with increasing radiation dose is observed. Important structural modifications produced by the radiation, destruction of crystallinity accompanied by crosslinking, which transform the material into a crosslinked rubber, are observed in trans-1,4-polybutadiene. Unlike conventional (sulfur) vulcanization, crosslinking by radiation does not cause a marked shift of the glass transition point. A secondary low-temperature relaxation effect, not existing in the unirradiated material, appears in the mechanical loss curves of the irradiated samples; it is attributed to the formation of ? CH₂? sequences in the main chains through saturation of C?C bonds. The mechanical spectrum of irradiated polybutadiene is very similar to those shown by crosslinked ethylene–butadiene copolymers.     

Synthesis of a novel difunctional NLO azo‐dye chromophore and characterizations of crosslinkable copolymers with stable electrooptic properties

The synthesis and the nonlinear optical (NLO) properties of crosslinkable copolymers based on a novel NLO azo‐dye chromophore bearing two functions: one used the free‐radical copolymerization, that is, the methacrylate group, and the other one used for the crosslinking process, that is, the carboxylic acid function, are described. Copolymerization of this new monomer with glycidyl methacrylate leads to novel soluble crosslinkable NLO copolymers bearing free epoxy and carboxylic groups. The poling process, before crosslinking, is achieved at a temperature (T_p) close to the glass transition temperature, T_g (<70°C), of the copolymers. At this temperature, no reaction takes place between epoxy and carboxylic acid functions. In fact, crosslinking begins to start at a higher temperature, T_c (T_c ≫ T_p ≈ T_g). After the optimization of the poling and crosslinking processes, the NLO crosslinked polymer with 30 mol % of the chromophore exhibits a T_g of 157°C and a high quadratic susceptibility (d₃₃) of 30 pm/V at 1320 nm. This coefficient is stable at 85°C for several weeks. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 974–982, 1999     

Partially constrained recovery of (meth)acrylate shape‐memory polymer networks

The purpose of this study was to characterize the partial strain recovery of a thermoset shape‐memory polymer under a constraining stress. Three polymer networks were synthesized from tert‐butyl acrylate and poly(ethylene glycol) dimethacrylate (PEGDMA) solutions. The molecular weight and the weight fraction of the PEGDMA crosslinking monomer was altered systematically to maintain a constant glass transition temperature (T_g = 54°C) but tailorable rubbery moduli, which varied by almost an order of magnitude for the three polymer networks (E = 1.8–11.3°MPa). The shape‐recovery behavior of the polymers under a constraining stress was characterized for programming temperature below (20°C) and above (70°C) the T_g. The experiments revealed a peak in the recovered strain for samples programmed at 20°C. Recovered strain scaled linearly with the constraining stress by the rubbery modulus. The work performed by the shape‐memory polymer networks was observed to be primarily a function of constraining stress and crosslinking density, while programming temperature had a relatively mild influence; however, the efficiency of the shape‐memory effect was shown to be a function of constraining stress and programming temperature, but was independent of crosslinking density. Maximum work efficiencies (up to 45%) were observed for programming temperature of 70°C. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Preparation and characterization of biodegradable polymer blends from poly(3‐hydroxybutyrate)/poly(vinyl acetate)‐modified corn starch

Biodegradable polymer blends prepared by blending poly(3‐hydroxybutyrate) (PHB) and corn starch do not form intact films due to their incompatibility and brittle behavior. For improving their compatibility and flexibility, poly(vinyl acetate) (PVAc) was grafted from the corn starch to prepare the PVAc‐modified corn starch (CSV). The resulting CSV consisted of 47.2 wt% starch‐g‐PVAc copolymer and 52.8 wt% PVAc homopolymer and its structure was verified by FT‐IR analysis. In comparison with 35°C of the neat PVAc, the glass transition temperature (T_g) of the grafted PVAc chains on starch‐g‐PVAc was higher at 44°C because of the hindered molecular mobility imposed from starch on the grafted PVAc. After blending PHB with the CSV, structure and thermal properties of the blends were investigated. Only a single T_g was found for all the PHB/CSV blends and increased with increasing the CSV content. The T_g‐composition dependence of the PHB/CSV blends was well‐fitted with the Gordon‐Taylor equation, indicating that the CSV was compatible with the PHB. In addition, the presence of the CSV could raise the thermal stability of the PHB component. It was also found that the presence of the PHB and PVAc components would not hinder the enzymatic degradation of the corn starch by α‐amylase. POLYM. ENG. SCI., 55:1321–1329, 2015. © 2015 Society of Plastics Engineers     

Effect of gamma irradiation on the interpenetrating networks of gelatin and polyacrylonitrile: Aspect of crosslinking using microhardness and crosslink density measurements

The present article reports the effect of gamma irradiation on the hardness behavior of the interpenetrating polymer networks (IPNs) of gelatin and polyacrylonitrile (PAN). Various compositions of gluteraldehyde‐crosslinked gelatin and N, N′‐methylene bis acrylamide (MBA)‐crosslinked PAN were prepared and investigated for microhardness studies. The pre‐ and post‐irradiated IPNs were characterized for their crosslinking density, determined with swelling ratio measurements. It was found that the crosslinked IPNs get further hardened because of radiational hardening at specific doses in the range from 2 to 250 kGy. The role of acrylonitrile and crosslinker (MBA) in the IPNs, as a consequence of irradiation, has also been explained. A fair consistency has been observed between the microhardness results and crosslinking density measurements. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2581–2586, 2006     

Study on the properties of crosslinking of poly(ethylene oxide) and hydroxyapatite–poly(ethylene oxide) composite

This study covers the crosslinking of poly(ethylene oxide) (PEO) and its composite with calcium hydroxyapatite (HA), their mechanical and swelling properties, and morphology. Sheets of the composites of PEO (two different grades with M_v: 5 × 10⁶ and 2 × 10⁵) and HA and neat PEO were prepared by compression molding. The prepared composite and PEO (0.1‐mm‐thick) sheets were crosslinked with exposure of UV‐irradiation in the presence of a photoinitiator, acetophenone (AP). This simple method for crosslinking, induced by UV‐irradiation in the presence of AP, yielded PEO with gel content up to 90%. Gel content, equilibrium swelling ratio, and mechanical and morphological properties of the low molecular weight polyethylene oxide (LMPEO)–HA crosslinked and uncrosslinked composites were evaluated. Although the inclusion of HA into LMPEO inhibits the extent of crosslinking, the LMPEO–HA composite with 20% HA by weight shows the highest gel content, with appreciable equilibrium swelling and mechanical strength. The growth of HA in simulated body fluid solutions on fractured surfaces of LMPEO and also LMPEO–HA was found to be very favorable within short times. The dimensional stability of these samples was found to be satisfactory after swelling and deposition experiments. The good compatibility between the filler hydroxyapatite and poly(ethylene oxide) makes this composite a useful tissue‐adhesive material. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 488–496, 2003     

Size‐controlled gold nanoparticles inside polyacrylamide microgels

Gold nanoparticles (AuNPs) of different sizes were synthesized into a crosslinked network of polyacrylamide (PAAm) microgels. PAAm was prepared by means of semicontinuous inverse heterophase polymerization under monomer‐starving conditions with a z‐average particle size of 384 ± 18 nm. AuNPs with controlled size were obtained by a reduction reaction of Au⁺³ to Au⁰ from a gold(III) chloride trihydrate (HAuCl₄) solution inside microgel the crosslinked network (AuNP‐PAAm). The reduction reaction was verified for 2 h by ultraviolet–visible spectroscopy (UV–vis). AuNP–PAAm exhibited a particle size between 288 ± 12 and 230 ± 15 nm at HAuCl₄ concentrations of 0.4 and 1.3 mM, respectively. The AuNP–PAAms were observed by transmission electron microscopy, and their sizes were determined to be 19 ± 2 nm (1.3 mM) and 17 ± 2 nm (1.1 mM). With UV–vis spectroscopy, we detected the formation of AuNPs at a wavelength of 552 nm, and with X‐ray diffraction analysis, we proved that the crystal arrangement was face‐centered cubic. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43560.     

The effect of photodegradation of polystyrene on its permeability characteristics

The diffusion (D) and permeability (P) coefficients for ¹⁴CO₂ in polystyrene films which had been irradiated by short-wave ultraviolet (253.7 nm) radiation under vacuum and in oxygen were determined in the temperature range of 20° to 55°C. Both D and P decreased with increasing exposure, the vacuum-irradiated sample showing significantly greater decreases, presumably on account of a larger extent of crosslinking which was possible in the absence of oxidation. A good correlation was observed between crosslinking and decreasing P and D values. The solubility coefficients for all irradiated samples increase with increasing dose. Activation energies for diffusion increase with increasing irradiation, particularly for the vacuum-irradiated samples. Reductions in P and D values are interpreted in terms of free-volume decreases due to crosslinking and other modifications, while the increasing activation energies are attributed to the increasing energy requirements for creation of free volume in modified polymers.     

Depth-gradient and photoinitiator-free photocrosslinking of poly(ethylene oxide)

Poly(ethylene oxide) (PEO) films are photocrosslinked by continuous UV irradiation without photoinitiators. Maximum gel fraction and swelling of the photocrosslinked PEO films reach up to about 38.8% and 2824%, respectively. From NMR analysis, the photocrosslinking mechanism of PEO can be attributed to recombination between methine radicals, which are generated from the polymer chain by hydrogen abstraction. However, the relatively low degree of crosslinking is attributed to more facile photooxidation of the generated radicals and concomitant photo-scission of the crosslinks. Depth-gradient crosslinked structure can be formed by inherent UV absorption and successive photoscission of the crosslinked polymer surface, which can be made uniform by adjusting UV energy. The photocrosslinked PEO shows the higher glass transition temperature as much as 7.3°C coupled with significantly enhanced storage modulus and thermal stability. The lower crystallinity causes by the reduced recrystallizability of the crosslinked polymer chains in melt. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Preparation of melting‐free poly(lactic acid) by amorphous and crystal crosslinking under UV irradiation

The poly(lactic acid) (PLA) with 3.6% mol of benzophenone (BP) per repeat unit of PLA can be crosslinked to a gel fraction of 98.5% at UV energy of 160 J/cm². From NMR analysis, the photocrosslinking of PLA was attributed to the recombination of primary and tertiary carbon radicals in the repeating units which were generated by the hydrogen abstraction of BP. With increasing crosslinking, melting peak disappeared and glass transition temperature elevated with loss of crystallinity, indicating that the crosslinking occurred in the crystalline region as well as in the amorphous region. The thermal stability of the crosslinked PLA also improved as shown by higher onset temperature as much as 56°C and higher maximum decomposition temperature compared with the pristine PLA. The higher toughness of the crosslinked PLA film was obtained together with the improvement in tensile strength and modulus with increasing crosslinking density. In addition to photocrosslinking of amorphous region, the crosslinking of crystalline region can have significant influence in the improvement of thermal and mechanical properties. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Dynamic Mechanical Properties of Carbon Black Filled Ethylene Vinyl Acetate Rubber

Abstract

The dynamic mechanical properties of ethylene vinyl acetate (EVA) rubber filled with different loadings of carbon black and at different degrees of crosslinking were studied over a wide range of temperatures (-150° to +200°C). The loss tangent (tan δ) versus temperature plots indicated presence of different transitions. The α-transition (or the glass-rubber transition) corresponding to the maximum in tan δ value, occurred at ?17°C, which is the principal glass-transition temperature (abbreviated as T _g) of EVA rubber. The γ-transition occurred in the temperature region of ?125° to ?135°C, while the β-transition appeared as a shoulder in the temperature region of ?65° to ?75°C. Besides, there was also a high tempeature transition around +62°C which is known as liquid to liquid transition (T _1.1). Incorporation of carbon black filler did not cause any shift of T _g, while the tan δ peak values at T _g decreased sequentially with increase in filler loading. The γ- and β-relaxations were found to be insensitive to filler loading. The T _1.1 transition, however, was found to be suppressed by incorporation of carbon black filler particularly at high loading. Extent of crosslinking did not influence the T _g But, the T _1.1 transition, which was prominent with the lightly crosslinked system was found to be suppressed at high level of crosslinking. Strain dependent dynamic mechanical properties under isothermal conditions showed that the secondary structure breakdown of carbon black filler under the effect of strain amplitude is influenced by the degree of crosslinking of EVA rubber.