Polyphosphazene membranes. II. Solid-state photocrosslinking of poly[(alkylphenoxy)(phenoxy)phosphazene] films

The solid-state UV photocrosslinking mechanism and the properties of dense crosslinked films composed of poly [(methylphenoxy)(phenoxy)phosphazene], poly[(ethylphenoxy)(phenoxy)phosphazene], and poly[(isopropylphenoxy)(phenoxy)phosphazene] were investigated, where the alkyl substituent was in either the meta- or para-position. Solution-cast films containing dissolved benzophenone photoinitiator (at a concentration of 1–25 mol %) were crosslinked at either 25 or 70°C. The ordering of benzophenone disappearance during polymer irradiation was methylphenoxy > ethylphenoxy > isopropylphenoxy, indicating that the rate controlling step for photoinitiator disappearance was the consumption of benzophenone, either by benzopinacole formation (with the creation of a polymer crosslink) or by reaction of a benzophenone-derived ketyl radical with a polymer macro-radical. The presence of such a ketyl adduct in crosslinked ethylphenoxy/phenoxy and isopropylphenoxy/phenoxy phosphazene films was verified by solid-state NMR. The ordering of crosslinked polymer swelling (for a given initial benzophenone concentration) when films were equilibrated in dimethylacetamide (DMAc) was isopropylphenoxy/phenoxy > ethylphenoxy/phenoxy > methylphenoxy/phenoxy, indicating that steric effects of the alkyl group were playing a role during crosslink formation. The methylphenoxy/phenoxy phosphazenes were the best materials for crosslinking; the glass transition temperature increased by approximately 25°C (from −15 to 10°C) and the film swelling (in DMAc) decreased from infinity (complete solubilization) to 35% as the benzophenone concentration was increased from 0 to 25 mol %. © 1998 John Wiley & Sons, Inc.

1 This article is a U.S. Government work and, as such, is in the public domain in the United States of America.

J Appl Polym Sci 68:827–836, 1998     

Crosslinking of poly(vinyl acetate) nanolatices by gamma and UV radiation

Poly(vinyl acetate) PVAc, in nanolatices with 10% polymer content, prepared by microemulsion polymerization was crosslinked by gamma and UV radiation. PVAc colloidal nanoparticles (average diameter, Dp = 58 nm) had M_w = 562,000 g/mol and about 95% conversions. PVAc nanolatices irradiated by gamma rays (1–13 kGy) at room temperature without crosslinking agent and by UV light (30–300 s exposure times) in the presence of divinylbenzene and allyl methacrylate showed crosslinking of up to 96% (high gel content), Dp < 100 nm and did not degrade as shown by FTIR spectroscopy. DSC and TGA characterization of irradiated PVAc samples indicated that T_g temperatures increased from 28°C for PVAc to 42°C and 39°C for UV and gamma rays crosslinked PVAc, respectively, whereas 10% weight losses occurred at 261°C for uncrosslinked PVAc and at 320 and 313°C for UV and gamma rays crosslinked PVAc. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis of polymer materials by low energy electron beam. I. Polyurethane–acrylate materials prepared by the EB and the UV solid-state polymerization

Structure and properties of films obtained by the electron beam (EB) and the ultraviolet light (UV) solid-state polymerization of polyurethane–acrylate prepolymer were examined to reveal the characteristics of these radiation polymerizations. The prepolymer was synthesized by the reaction of poly(butylene adipate)diol, 4,4′-diphenylmethane diisocyanate, and 2-hydroxyethyl acrylate. EB polymerization behaviors of the prepolymer produced a unique polymer film different from that obtained by UV irradiation. Although polyurethane–acrylate films from the EB and the UV solid-state polymerizations consisted mainly of amorphous and crystalline phases, it was proved that the film from 10 Mrad of EB irradiation at 25°C had higher crystallinity and larger crystallite size than the film from UV irradiation. This is assumed to be due to the reason that EB irradiation below the melting point of the polyurethane–acrylate can lead to crosslinking without the destruction of the original crystalline structure. On the other hand, the UV polymerization proceeded with the melting of the crystalline structure by absorbing other lights than the UV absorbed by a photoinitiator. The EB-polymerized film which was crosslinked more densely than the UV-polymerized film showed higher mechanical strength than the latter film.     

Synthesis and characterization of novel photo‐crosslinkable fluorinated poly(phthalazinone ether)s for optical waveguides

A series of novel photo‐crosslinkable fluorinated poly(phthalazinone ether)s containing 1,1‐diphenylethylene segments in the polymer main chain, used for optical waveguide materials, were synthesized by polycondensation reaction of decafluorobiphenyl with a mixture of 4‐(4‐hydroxylphenyl)(2H)‐phthalazin‐1‐one (DHPZ), 4,4‐(hexafluoroisopropylidene)diphenol and 1,1‐bis(4‐hydroxyphenyl)ethylene (BHPE) as co‐reactant. The feed ratio of DHPZ to total bisphenols varied from 0 to 80 mol%, while that of BHPE remained at 20 mol% for all polymers. The obtained copolymers show good solubility in some common polar organic solvents. The resulting polymers were photo‐crosslinked after UV irradiation for 10 min in the presence of a photoinitiator. The cured polymers show good chemical resistance, high thermal stability (temperatures of 1% mass loss after curing of 472–496 °C under nitrogen) and high glass transition temperatures (160–249 °C) which could be further increased by about 10 °C after photochemical crosslinking. By adjusting the copolymerizing bisphenol content, the refractive indices of transverse electric and transverse magnetic modes (at 1550 nm) of films of the polymers were exactly tuned in the range 1.5029–1.5661 and 1.4950–1.5502, respectively. The propagation losses of the cured films were measured and found to be less than 0.3 dB cm^?1 at 1550 nm, indicating the promise of these materials for passive optical waveguide devices. Copyright © 2011 Society of Chemical Industry     

UV‐curable methacrylic epoxy dispersions for cationic electrodeposition coating

UV‐curable epoxy dispersions were prepared for cationic electrodeposition coating. Sequential reactions were used to introduce methacrylate groups to the epoxy‐amine polymer as coupling agents to the multifunctional acrylates. The molecular weight values of the prepared epoxy‐amine polymer were M_n = 2800 and M_w = 4300. The neutralized epoxy‐amine polymer containing photoinitiator with or without multifunctional acrylate (pentaerythritol triacrylate, PETA) could be dispersed into a stable dispersion without any phase separation. The size of the particles in these epoxy dispersions was approximately 77.7 nm, and increased with the incorporation of PETA. The electrodeposition process was introduced to the prepared epoxy dispersions, and the electrodeposited films were cured by UV irradiation after a 10‐min flash off at 80°C. Studies of the kinetics using photo‐DSC revealed that the crosslinked films containing PETA gave a higher conversion rate than those without PETA, resulting in better resistance to methyl ethyl ketone. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:5566–5570, 2006     

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     

Characterization of hydrogels based on chitosan and copolymer of poly(dimethylsiloxane) and poly(vinyl alcohol)

Copolymers composed of poly(vinyl alcohol) (PVA) and poly(dimethylsiloxane) (PDMS) were crosslinked with chitosan to prepare semi‐interpenetrating polymer network (IPN) hydrogels by an ultraviolet (UV) irradiation method for application as potential biomedical materials. PVA/PDMS copolymer and chitosan was cast to prepare hydrogel films, followed by a subsequent crosslinking with 2,2‐dimethoxy‐2‐phenylacetophenone as a nontoxic photoinitiator by UV irradiation. Various semi‐interpenetrating polymer networks (semi‐IPNs) were prepared from different weight ratios of chitosan and the copolymer of PVA/PDMS. Photocrosslinked hydrogels exhibited an equilibrium water content (EWC) in the range of 65–95%. Swelling behaviors of these hydrogels were studied by immersion of the gels in various buffer solutions. Particularly, the PCN13 as the highest chitosan weight ratio in semi‐IPN hydrogels showed the highest EWC in time‐dependent and pH‐dependent swelling. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2591–2596, 2002     

Surface photocrosslinking of ethylene–vinyl acetate copolymer films

Surface photocrosslinking of ethylene–vinyl acetate (EVAc) copolymer films containing benzophenone (BP) was investigated for the purpose of replacing a poly(vinyl chloride) floor. The photogelatin in the EVAc films was effectively observed after UV radiation in the presence of oxygen. The crosslinking reaction was initiated from the surface of the irradiated film, which was mainly due to the dehydrogenation and generation of macroradicals of polymer by the light absorption of BP. The experiments of polyethylene–VAc with BP showed that the VAc‐rich amorphous part in the EVAc copolymer works as a crosslinking site. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1741–1745, 2000     

Photocrosslinking of styrene–isoprene–styrene; effect of benzoin and ethylene glycol dimethacrylate on physical properties

Crosslinking reaction of polymer by ultraviolet (UV) irradiation has been important in industries. In this work, photocrosslinking of styrene–isoprene–styrene (SIS) triblock copolymer in the presence of benzoin photoinitiator and a dimethacrylate monomer as crosslinking agent was investigated. Curing of samples was initiated under UV irradiation. Benzoin was used as photoinitiator because it contains chromophore group that could absorb UV irradiation. Ethylene glycol dimethacrylate (EGDMA) was used as crosslinking agent, since it has alkene functional groups that could react with the alkene group of SIS. ATR-FTIR spectra of samples show that absorption band of double bond at 1500–1600?cm^?1 decreases after UV exposure. Increasing the concentration of benzoin (0.1–1?phr) and EGDMA (1–10?phr) leads to an increase in gel content and hardness, while swelling ratio decreases. After 5?min heating at 150?°C, about 20%wt of the unirradiated compound became insoluble, because heating of compound at 150?°C causes crosslinking reaction without any irradiation.     

Interpenetrating polymer networks. I. Photopolymerization of multiacrylate systems

The light-induced polymerization of a triacrylate monomer (TMPTA) has been carried out in a polymer matrix to generate a semi-interpenetrating polymer network (IPN). The reaction kinetics was followed by IR spectroscopy for the various polymer binders studied: poly(vinyl chloride) (PVC), poly(methyl methacrylate), polystyrene, and crosslinked polyurethane. Under intense illumination, crosslinking occurred extensively within a fraction of a second, with formation of a hard and highly resistant polymer material. These semi-IPNs were found to be essentially insoluble in the organic solvents, thus indicating that the acrylate network is grafted onto the polymer matrix, probably because of an efficient chain transfer process. The monomer and photoinitiator concentration, as well as the light intensity were shown to have a great influence on both the rate of polymerization and the final degree of conversion. By using an acylphosphine oxide photoinitiator, PVC–;TMPTA blends have been cured within a few minutes in an accelerated QUV-A weatherometer, which emits low-intensity UV radiation similar to sunlight. © 1994 John Wiley & Sons, Inc.     

UV light copolymerization of dimethyl vinylphosphonate with bisphenol A ethoxylate dimethacrylate

Dimethyl vinylphosphonate (DMVP), a very promising monomer, was copolymerized with acrylic monomer bisphenol A ethoxylate dimethacrylate (BEMA), in different molar ratios, by radical photoinitiated polymerization in the presence of photoinitiator Darocur 4265 (3 wt%) and in the absence of solvent. The UV light polymerization was an efficient method to obtain polymers in a green procedure. The molar ratio between DMVP and acrylic monomer BEMA varied between 1:1 and 5:1. The copolymers were characterized by FTIR, thermal analysis, water uptake and conductivity. From the ATR-FTIR spectra of DMVP-BEMA copolymers at the molar ratios of 1:1–5:1, it was observed that the intensity of P-O-C aliphatic band increased with increases in DMVP content. The synthesized copolymers showed good thermal stability in the range of 335–390 °C. DMVP:BEMA copolymer at 1:1 molar ratio displayed the highest stability, with decomposition temperature above 390 °C, the highest temperature in the series. The water uptake decreased with increases in DMVP content and this behavior was correlated with the ionic conductivity. Based on the Bode diagrams, the ionic conductivity of DMVP:BEMA of 1:1 molar ratio was 6.15 × 10^?8 S cm^?1 and that of DMVP:BEMA of 2:1 molar ratio was 3.69 × 10^?8 S cm^?1 which were considered promising as valuable conducting materials.     

Synthesis of a diacetylene-containing polyisophthalate and its third-order nonlinear optical susceptibility

In order to obtain amorphous thin films of a polydiacetylene, a polyisophthalate containing a push–pull diacetylene chromophore was synthesized by the reaction of p-(N,N-diethanolamino)-p’-nitrodiphenylbutadiyne with isophthaloyl chloride in anhydrous 1-methyl-2-pyrrolidone. The polymer was soluble in organic solvents, such as chloroform, tetrahydrofuran, dimethylformamide, etc., and films with good optical quality were obtained by spin coating from its N-methyl-2-pyrrolidone solution. It was characterized by ¹H-NMR, IR, DSC, UV–Visible, X-ray, etc. The diacetylene groups underwent polymerization in the film when irradiated with UV light at 120 °C under Ar atmosphere, and it contained free radicals with a radical concentration of 10¹⁶ radicals/g. The third-order nonlinear optical susceptibility, χ⁽³⁾, of the polymer film measured by the Z-scan technique at 1064 nm was not noticeable, but when the film was heated and irradiated with UV light, a χ⁽³⁾ value of 6.4?×?10^?10 esu was obtained due to increase in π-conjugation by the formation of polydiacetylene in the side chain.     

Synthesis and properties of novel soluble and high Tg poly(ether imide)s from diamine containing 4,5‐diazafluorene and trifluoromethyl units

The synthesis and properties of soluble, high T_g and transparent aromatic polyimides containing 4,5‐diazafluorene and trifluoromethyl units in the polymer backbone on the basis of a novel diamine monomer, 9,9‐di[4‐(4‐amino‐2‐trifluoromethyl phenoxy)phenylene]‐4,5‐diazafluorene, are described. Incorporation of 4,5‐diazafluorene and trifluoromethyl groups into rigid polyimides improves their solubility and transparency without decreasing their physical properties. All of the thermal imidization polyimides are soluble at room temperature in aprotic and protic polar solvents such as N,N‐dimethylacetamide, N,N′‐dimethylformamide, dimethylsulfoxide, pyridine and m‐cresol and can be solution cast into transparent, flexible and tough films. These films have a UV–visible absorption cutoff wavelength at 386–407 nm and light transparencies of 73%–84% at a wavelength of 550 nm. In addition, the polymers exhibit high thermal stability with a glass transition temperature (T_g) of 305 to 362 °C and 5% weight loss at temperatures ranging from 525 to 543 °C in nitrogen and from 521 to 538 °C in air. The polyimide films possess tensile strengths in the range 79 ? 113 MPa, a tensile modulus of 1.75 – 2.10 GPa and elongations at break of 7% ? 16%. © 2014 Society of Chemical Industry     

UV crosslinking of Fe3+‐doped poly(vinyl alcohol)—Characterization of optical properties and swelling behavior

The effects of UV irradiation on iron(III)chloride doped poly(vinyl alcohol) (PVA) films, using a high molar mass polymer, have been studied. It has been found that the polymer is oxidized and crosslinked during UV irradiation. UV/VIS spectra reveal an exponential loss of absorption at λ = 360 nm, and the refractive index of the PVA:FeCl₃ films decreases significantly during UV irradiation (Δn^D = ?0.09). The effects of crosslinking have been studied using the sol–gel technique, which revealed high gel contents due to doping and UV‐exposure. Photolithographic patterning of doped PVA films using a medium‐pressure mercury‐vapor UV source has been carried out, leading to good contrast behavior before and after development in aqueous media. A photobleaching effect was observed, therefore the curing of thicker films is feasible. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Mechanism and kinetics of curing of diglycidyl ether of bisphenol a (DGEBA) resin by chitosan

Crosslinking behavior of Diglycidyl Ether of Bisphenol A (DGEBA) resins cured by chitosan was isothermally studied by Fourier Transform Infrared (FTIR) Spectroscopy for various molar ratios of chitosan at different temperatures. Results indicated that oxirane undergoes nucleophilic attack by the primary amine groups in chitosan to form crosslinked structure. Epoxy fractional conversion (α ) was calculated by following the change in area of oxirane peak at 914 cm^?1. Value of α and reaction rate (dα /dt ) increased with increase in curing temperature and chitosan concentration. The maximum epoxy fractional conversion of 70% was obtained for 1:4 molar ratio (Epoxy:Chitosan) at 200°C. A four parameter kinetic model with two rate constants was employed to simulate the experimental data. Overall reaction order and activation energy for all compositions were in the range of 2.5–3 and 25–50 kJ mol^?1, respectively. Results indicated that cure reaction is autocatalytic and does not follow simple n th order cure kinetics. Thermogravimetric analysis (TGA) performed on chitosan cured DGEBA films and compared against neat epoxy and neat chitosan films. Results showed that the degradation of chitosan crosslinked epoxy network occurred in the temperature range of 450–550°C. POLYM. ENG. SCI., 57:865–874, 2017. © 2016 Society of Plastics Engineers     

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     

Fumaryl chloride and maleic anhydride–derived crosslinked functional polymers for nonlinear optical waveguide applications

The synthesis, processing, and characterization of new crosslinked functional polymer thin films derived from fumaryl chloride and maleic anhydride is presented. Experimental data demonstrated that this is a versatile, convenient, and cost‐effective method of fabricating ultrastructure crosslinked and functional polymer thin films for potential nonlinear optical (NLO) or other applications where molecular orientation is required. The unsaturated and processable polyester thin films are capable of crosslinking in air to form a hardened lattice under a variety of conditions, including both thermal and photoinitiated crosslinking. The thermal stability of the second harmonic (SHG) signal for a crosslinked NLO thin film was stable at temperatures up to 150°C, which is in contrast to uncrosslinked polymers whose SHG signals typically decreased over 50% below 100°C. Because of the lack of NH/OH groups and their vibrational overtones in the polymer, these crosslinked polyester systems have a great potential for low optical loss applications at 1550 nm communication wavelength. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 317–322, 2004     

Photopolymerization synthesis of poly(N-isopropylacrylamide) hydrogels

Poly(N-isopropylacrylamide) (NIPAAm) gels were formed by photopolymerization of NIPAAm in the absence of a crosslinker using a water solvent at 25°C. Factors affecting formation were the wavelength region of irradiated light, the type of photoinitiators, and the concentrations of the photoinitiator and monomer. A high-pressure mercury lamp (400 W) was used as a light source. An NIPAAm concentration of 10 wt % and irradiation time of 15 h was used for the photopolymerization. The gel (68% yield) was formed when the quartz glass system was used, but no gelation was observed for the Pyrex glass system that transmits light with π > 290 nm. The gel (100% yield) was easily formed, even in the latter system, when 30 mmol/L of hydrogen peroxide and potassium persulfate were used as the photoinitiator. Water soluble photoinitiators such as ferric chloride and sodium anthraquinone-2,7-disulfonate were not effective for the gel formation. Yield of the gel increased with increasing the potassium persulfate concentration (1–30 mmol/L), but it decreased when a high concentration of hydrogen peroxide (60 mmol/L) was used. The gel yield increased with the NIPAAm concentration (5–20 wt %). The degree of swelling of the resultant poly(NIPAAm) gels, which was measured by immersing the gels in water at various temperatures (0–50°C) for 24 h, steeply decreased at about 30°C with increasing temperature, exhibiting a temperature-responsive character. The gels swelled and shrank in water below and above the temperature, respectively. The extent of the character depended on the concentrations of hydrogen peroxide and monomer. The formation mechanism of the gel in the photopolymerization of NIPAAm using hydrogen peroxide photoinitiator was discussed. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65:1313–1318, 1997     

Light‐control birefringence of oriented poly(vinyl cinnamate) by UV irradiation

The research focused on realizing the birefringence of light‐control polymer films. The photoelastic birefringence exhibits when Poly (vinyl cinnamate) (PVCi) films are stretched below their glass transition temperature (T_g). The birefringence of PVCi decreases when the UV irradiation happens because the side chains of the PVCi photo‐react when the oriented films are exposed to UV light. A method to quantify the birefringence ability of the polymer films is created and verified. Using this method, the decrease of the birefringence through the UV irradiation is quantified. The result shows the birefringence of PVCi can be controlled by altering the UV irradiation time. In addition, oriented PVCi films of different esterification degrees were prepared and irradiated at different time, and the birefringence of them was studied to clarify the birefringence mechanism of light‐control polymer films. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Diacetylene-containing polymers. XI. Synthesis and characterization of poly(hexa-2,4-diynylene-1,6-dioxydibenzoate) and poly(octa-3,5-diynylene-1,8-dicarboxylate) containing p-nitroaniline groups

Summary Two novel polymers containing p-nitroaniline group in the side chain and diacetylene groups in the main chain, were synthesized, and characterized. The polymers gave films of excellent optical quality by spin coating from DMF or chloroform. The one containing benzoate had a T_g of 103°C and its thermal cross-linking through the diacetylene group started at around 160°C. The one containing pentynoate had a T_g of 35°C and its cross-linking started at around 120°C. It was shown that thermosetting resins with functional groups could be obtained by using diacetylene-containing polymers. Although these two polymers have a same polar dye molecule, the second order nonlinear optical property was so different, showing that the main chains are very important for nonlinear optical property. Irradiation of UV light converted the polymer films to completely insoluble thermoset resins. Received: 13 February 2001/Revised version: 25 July 2001/Accepted: 30 July 2001