Rate Of Photocrosslinking Research Articles

Photoinitiator Free Resins Composed of Plant-Derived Monomers for the Optical µ-3D Printing of Thermosets.

In this study, acrylated epoxidized soybean oil (AESO) and mixtures of AESO and vanillin dimethacrylate (VDM) or vanillin diacrylate (VDA) were investigated as photosensitive resins for optical 3D printing without any photoinitiator and solvent. The study of photocross-linking kinetics by real-time photorheometry revealed the higher rate of photocross-linking of pure AESO than that of AESO with VDM or VDA. Through the higher yield of the insoluble fraction, better thermal and mechanical properties were obtained for the pure AESO polymer. Here, for the first time, we validate that pure AESO and mixtures of AESO and VDM can be used for 3D microstructuring by employing direct laser writing lithography technique. The smallest achieved spatial features are 1 µm with a throughput in 6900 voxels per second is obtained. The plant-derived resins were laser polymerized using ultrashort pulses by multiphoton absorption and avalanche induced cross-linking without the usage of any photoinitiator. This advances the light-based additive manufacturing towards the 3D processing of pure cross-linkable renewable materials.

Photoresins based on acrylated epoxidized soybean oil and benzenedithiols for optical 3D printing

PurposeThe purpose of this paper is the design and investigation of novel acrylated epoxidized soybean oil-based photocurable systems as candidate materials for optical 3D printing.Design/methodology/approachAromatic dithiols, benzene-1,3-dithiol or benzene-1,4-dithiol, were used as cross-linking agents of acrylated epoxidized soybean oil in these systems. Kinetics of photocross-linking was investigated by real-time photorheometry using two different photoinitiators, 2, 2-dimethoxy-2-phenylacetophenone or 2-hydroxy-2-methylpropiophenone, in different quantities. The effect of the initial composition on the rate of photocross-linking, mechanical, thermal properties and swelling of obtained polymers was investigated.FindingsThe rate of photocross-linking was higher, more cross-links and shorter polymer chains between cross-linking points of the network were formed when benzene-1,4-dithiol and 2, 2-dimethoxy-2-phenylacetophenone were used in compositions. The higher yield of insoluble fraction, glass transition temperatures and values of compressive modulus were obtained when benzene-1,3-dithiol and 2, 2-dimethoxy-2-phenylacetophenone were used in compositions.Originality/valueThis is the first study of acrylated epoxidized soybean oil-based thiol-ene system by real-time photorheometry. The designed novel photocurable systems based on acrylated epoxidized soybean oil and benzenedithiols are promising renewable photoresins for rapid optical 3D printing on demand.

Biodegradable photocross-linked polymers of glycerol diglycidyl ether and structurally different alcohols

Structurally different alcohols, e.g. 1,4-cyclohexanedimethanol, 1,1,1-tris(hydroxymethyl)propane, hydroquinone, and bisphenol A, were used for photocross-linking of glycerol diglycidyl ether on purpose to study structure-properties relationship of the resulting polymer films. Kinetics of photocross-linking was investigated by photorheometry. Dependencies of chemical structure and amount of alcohol used on mechanical, thermal, rheological properties, and biodegradability of the synthesized polymers were studied. The addition of alcohol resulted in an increase of the rate of photocross-linking of glycerol diglycidyl ether. The amount of alcohol used had more considerable effect on properties of polymers than chemical structure of alcohol. The higher amount (>20mol%) of alcohol led to the easier association of alcohol molecules with released protons and thus deteriorated the properties of the cross-linked polymers. However, the addition of alcohols increased the biodegradability of resulted polymers.

Photochemical Acceleration of DNA Strand Displacement by Using Ultrafast DNA Photo‐crosslinking

DNA strand displacement is an essential reaction in genetic recombination, biological processes, and DNA nanotechnology. In particular, various DNA nanodevices enable complicated calculations. However, it takes time before the output is obtained, so acceleration of DNA strand displacement is required for a rapid-response DNA nanodevice. Herein, DNA strand displacement by using DNA photo-crosslinking to accelerate this displacement is evaluated. The DNA photo-crosslinking of 3-cyanovinylcarbazole (CNV K) was accelerated at least 20 times, showing a faster DNA strand displacement. The rate of photo-crosslinking is a key factor and the rate of DNA strand displacement is accelerated through ultrafast photo-crosslinking. The rate of DNA strand displacement was regulated by photoirradiation energy.

Photocrosslinkable polymer based on 4-(3-(2,4-dichlorophenyl)-3-oxoprop-1-enyl) phenylacrylate: synthesis, reactivity ratio, and crosslinking studies

Abstract The acrylate monomer was synthesized by two step process. 2,4-dichloro-1-ene(4-hydroxyphenyl)phenone (DHP) was synthesized using 4-hydroxy benzaldehyde and 2,4-dichloro acetophenone. 4-[3-(2,4-dichloro-phenyl)3-oxoprop-1-en-1-yl]phenylacrylate (DCP) was prepared by reacting DHP with acryloyl chloride. The synthesized monomer was copolymerized with 2-hydroxyethyl acrylate and styrene using solution polymerization technique. Monomer and polymers were characterized by IR, NMR and UV techniques. The average molecular weight of the polymer was around 4000 g/mol. First and second decomposition temperature of the polymers was around 320 °C and 430 °C, respectively. The reactivity ratio of the polymers was calculated by Fineman-Ross, Kelen-Tudos and extended Kelen-Tudos methods. The synthesized monomer has been less reactive than the commercial monomer. The rate of photocrosslinking increased from 39 % to 99 % due to the using of copolymerization technique.

UV Cross‐Linkable Polymer Based on Triazine: Synthesis, Characterization and Crosslinking Studies

Summary3‐(4‐((4‐(4‐Acetylphenoxy)‐6‐((4‐nitrophenyl)amino)‐1,3,5‐triazin‐2‐yl)oxy)phenyl)‐1‐(2,4‐dichlorophenyl)prop‐2‐en‐1‐one (TAP) is synthesized using cynuric chloride, 2,4‐Dichloro‐1‐ene(4‐hydroxyphenyl)phenone,4‐nitroaniline and 4‐aminoacetophenone. 1‐(2,4‐dichlorophenyl)‐3‐(4‐((4‐(4‐(3‐(4‐hydroxyphenyl)acryloyl)phenoxy)‐6‐((4nitrophenyl)amino)‐1,3,5‐triazin‐2‐yl)oxy)phenyl)prop‐2‐en‐1‐one (TCC) is synthesized using TAP and 4‐hydroxybenzaldehyde. 4‐(3‐(4‐((4‐(4‐(3‐(2,4‐dichlorophenyl)‐3‐oxoprop‐1‐en‐1‐yl)phenoxy)‐6‐((4‐nitrophenyl)amino)‐1,3,5‐triazin‐2‐yl)oxy)phenyl)‐3‐oxoprop‐1‐en‐1‐yl)phenyl acrylate (TCP) is synthesized using TCC and acryloyl chloride. Copolymers of the TCP are prepared using vinyl acetate, styrene, and acrylamide are carried out by solution polymerization technique by using benzoyl peroxide (BPO) under a nitrogen atmosphere. Monomer and polymers are characterized by using IR and NMR techniques. The photocrosslinking property of the polymers was done by using the UV absorption spectroscopic technique. The rate of photocrosslinking was enhanced compared to that of the homopolymers, when the TCP was copolymerized with the VA, AM and S. Thermal stability and molecular weights (Mw and Mn) are determined for the polymer samples and molecular weights of the polymers are found to be around 10000 g/mol.

New generation of photosensitive poly(azomethine)esters: Thermal behaviours, photocrosslinking and photoluminescence studies

Three new series of soluble photosensitive poly(azomethine)esters with even methylene spacers in their backbone and various substituents on their side chain were synthesized. Their molecular structures were elucidated with various spectroscopic methods. The different substituents and length of the methylene spacers were found to influence the thermal stability of the polymers. The –OCH3 substituted side chain poly(azomethine)esters showed highest thermal stability, followed by –Cl and –H. Meanwhile, poly(azomethine)esters with longer methylene spacers exhibited lower thermal stability. The photoreactivity of these poly(azomethine)esters revealed that the chalcone moiety dimerized and led to photocrosslinking. The rate of photocrosslinking increased with longer methylene spacers and in the order of –H < –Cl < –OCH3. Photoluminescence intensity was found to be enhanced upon UV irradiation. This could be due to the arrangement of the phenyl rings in the position that promoted effective π–π stacking interaction and hence led to aggregation of the polymer chains which was confirmed via TEM analysis.

Synthesis, spectral, and thermal characterization of photosensitive poly(ether-ester)s containing α,β-unsaturated ketone moieties in the main chain derived from 2,6-bis[4-(3-hydroxypropyloxy)-3-methoxybenzylidene]cyclohexanone

A series of photosensitive poly(ether–ester)s containing α,β-unsaturated ketone moieties in the main chain were synthesized from 2,6-bis[4-(3-hydroxypropyloxy)-3-methoxybenzylidene]cyclohexanone (BHPMBCH) and aliphatic and aromatic diacid chlorides. The diol precursor, BHPMBCH, was synthesized from 2,6-bis(4-hydroxy-3-methoxybenzylidene)cyclohexanone and 3-bromo-1-propanol. The solubility of the polymers was tested in various solvents. The intrinsic viscosity of the synthesized polymers, determined by an Oswald viscometer, was found to be 0.06–0.80 g/dL. The molecular structures of the monomer and polymers were confirmed by Fourier transform infrared, ultraviolet–visible, 1H-NMR, and 13C-NMR spectral analyses. The thermal properties were studied with thermogravimetric analysis and differential scanning calorimetry. The thermogravimetric analysis data revealed that the polymers were stable up to 220°C and started degrading thereafter. The thermal stability initially increased with increasing spacer length and then decreased due to negative effects of the spacer. The self-extinguishing properties of the synthesized polymers were studied by the determination of the limiting oxygen index values with Van Krevelen's equation. In addition, the photocrosslinking properties of the polymer chain were studied with UV spectroscopy, and we observed that the rate of photocrosslinking increased significantly with increasing methylene carbon chain length of the acid spacer. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011

Photoactive liquid crystalline polymers: A comprehensive study of linear and hyperbranched polymers synthesized by A2B2, A2B3, A3B2, and A3B3 approaches

AbstractA series of linear and hyperbranched polyester epoxies, with varied structural parameters such as kinked structure and different dendritic architectures, were synthesized by A2 + B2, A2 + B3, A3 + B2, and A3 + B3 approaches. The structures of synthesized monomers and polymers were confirmed by Fourier transform infrared, 1H NMR, and 13C NMR spectroscopic techniques. The effect of varied structural parameters on phase behavior and photoresponsive properties was investigated by using differential scanning calorimeter, thermal optical polarized microscope, UV–visible spectroscopy, photoviscosity, and refractive index studies. The transition temperatures of hyperbranched polymers were higher than that of the corresponding linear analogues. All the polymers showed nematic phase (nematic droplets) over a broad temperature range. The effect of kinked structural unit on photoresponsive property is less in both linear and hyperbranched architectures. Although the effect of architectural nature is highly considerable within the hyperbranched architectures, the polymer (HPE–33) synthesized by A3 + B3 approach showed highest rate of photocrosslinking, followed by HPE–I 32; HPE–T 32, and HPE–23, which were synthesized by A3 + B2 and A2 + B3 approaches, respectively. The findings in photoresponsive properties were further supported by molecular modeling studies. Substantial variation of refractive index (0.015–0.024) indicates that these polymers could be used for optical recording. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011

Synthesis and properties of novel photosensitive poly(arylene ether sulfone) containing chalcone moiety in the main chain

A new series of photosensitive poly(arylene ether sulfone)s containing chalcone moiety in the main chain were synthesized from 4,4′-dihydroxychalcone (4DHC), 4,4′-difluorodiphenylsulfone (DFDPS) and bisphenol A (BPA). This series of polymers were characterized by 1H NMR, FT-IR, UV spectroscopy, thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The polymers were stable up to 400 °C, which indicates that the polymers possess good thermal properties. The polymers were found to be soluble in polar solvents and chlorinated solvents. However, the polymers were insoluble in hydrocarbons and in hydroxyl group-containing solvents. After the irradiation of UV light, the thin polymer film was crosslinked to give an insoluble film in the absence of a photoinitiator or sensitizers. The rate of photocrosslinking was also examined and discussed.

Stilbene-based liquid crystalline and photocrosslinkable polynaphthylphosphate esters

A series of liquid crystalline and photocrosslinkable polymers were synthesized from 4,4′-bis(m-hydroxyalkyloxy)stilbene (m = 2, 4, 6, 8, 10) with naphthylphosphorodichloridate. The synthesized polymers were characterized by spectroscopic techniques. Thermogravimetric analysis revealed that the polymers were stable between 283 and 341 °C, then underwent two-stage decomposition, and char yield increased with decreasing spacer length. DSC and HOPM analysis disclosed that the polymers III–V (m = 6, 8, 10) exhibited LC phases wherein flexible methylene spacer separates mesogenic alignment and reduces overall rigidity of polymers, while polymers I and II are unable to show LC phase. The photolysis was studied by UV–visible and fluorescence spectroscopy. The rate of photocrosslinking increases with increase in methylene chain. The fluorescence property decreased with successive UV irradiation in the polymers.

Photocrosslinkable phosphorus containing homo‐ and copolyesters: Synthesis, characterization, and photosensitive properties

AbstractA new series of homo‐ and copolyphosphoramide esters containing pendant chlorine group was synthesized from dihydroxy chalcones, N‐(4‐chlorophenyl)phosphoramidic dichloride, and terephthaloyl chloride by interfacial polycondensation technique. The diol monomers were prepared by condensing 4‐hydroxy benzaldehyde and 3‐methoxy‐4‐hydroxybenzaldehyde with 4‐hydroxy acetophenone. The synthesized monomers and polymers were characterized by UV, IR and 1H, 13C, and 31PNMR spectroscopic techniques. Molecular weight of the polymers was determined by gel permeation chromatography. The thermal properties of the polymers were studied by thermogravimetric analysis and differential scanning calorimetry under nitrogen atmosphere. The photo‐crosslinking ability of the polymers in various solvents was observed with UV spectrophotometer. The photocrosslinking proceeds via 2π +2π cycloaddition reaction of α, β‐unsaturated carbonyl group. The comparison study on the rate of photocrosslinking of homo and copolymers was also carried out. The chemical and physical properties of these polyesters are compared with those of the unsubstituted polyesters and the results are discussed herein. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009

Synthesis, Characterization and Photocrosslinking Properties of Poly(1‐(4‐Methacrylamidophenyl)‐1‐(4‐nitrophenyl)prop‐1‐en‐3‐one)

The phenylmethacrylamide monomer, 1‐(4‐methacrylamidophenyl)‐1‐(4‐nitrophenyl)prop‐1‐en‐3‐one (MPNP) containing a photosensitive group was synthesized by reacting 4‐nitrocinnamoylaniline with methacryloyl chloride in the presence of triethylamine at 0–5°C. The functional monomer, MPNP was polymerized in ethyl methyl ketone (EMK) under nitrogen atmosphere at 70°C using benzoyl peroxide (BPO) as the initiator. The synthesized polymer was characterized by UV, IR, 1H‐NMR and 13C‐NMR spectroscopy. The molecular weight data of the polymer as obtained from gel permeation chromatography suggests a higher tendency for chain termination by radical recombination than disproportionation. The thermal studies of the polymer were obtained from thermogravimetric analysis. The glass transition temperature of the polymer was determined by differential scanning calorimetry. The solubility of the polymer was tested in various organic solvents at room temperature. The photosensitivity of the polymer was investigated in various solvents in the presence and absence of triplet photosensitizers. The effect of the different solvents nature and concentration on the rate of photocrosslinking of the polymer were also examined for using the polymer as negative photoresist materials.

Homopolymer and copolymers of 4‐methacrylamidophenyl‐4‐methoxystyryl ketone with methyl methacrylate: Synthesis, characterization, reactivity ratios, and photocrosslinkable properties

Abstract4‐Aminophenyl‐4‐methoxystyryl ketone (APMSK) was prepared by reacting 4‐aminoacetophenone and 4‐methoxybenzaldehyde in the presence of sodium hydroxide as base catalyst. The methacrylamide monomer, 4‐methacrylamidophenyl‐4‐methoxystyryl ketone (MPMSK), was synthesized by reacting APMSK with methacryloyl chloride in the presence of triethylamine. Free‐radical solution polymerization technique was used to prepare the homo‐ and copolymers of different feed compositions of MPMSK with methyl methacrylate in methyl ethyl ketone solution at 70°C, using benzoyl peroxide as the initiator. The polymers were characterized by UV, IR, 1H‐NMR, and 13C‐NMR spectral techniques. The reactivity ratios of both comonomers were calculated using Fineman–Ross, Kelen–Tüdös, extended Kelen–Tüdös, and a nonlinear error‐in‐variables model (EVM) method using a computer program, RREVM. The molecular weights (M̄w and M̄n) and polydispersity indices of the polymers were determined using size exclusion chromatography. The glass‐transition temperatures of the polymers were determined by differential scanning calorimetry. The thermal stability of the polymers was measured by thermogravimetric analysis in air. The photoreactivity of the polymers was studied in chloroform solutions in the presence and absence of various triplet sensitizers. The effect of concentration of homopolymer and composition of the copolymers on the rate of photocrosslinking of the polymers was investigated. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci, 2006

Synthesis, Characterization, and Photocrosslinking Properties of Poly(4‐Methacrylamidophenyl‐2′,3′‐benzostyryl Ketone)

A new methacrylamide monomer, 4‐methacrylamidophenyl‐2′,3′‐benzostyryl ketone (MPBSK) having a free‐radical polymerizable group and a photocrosslinkable functional group, was synthesized by reacting 4‐(2′,3′‐benzocinnamoyl)aniline with methacryloyl chloride in the presence of triethyl amine. The monomer, MPBSK was polymerized in methyl ethyl ketone (MEK) at 70°C using benzoyl peroxide (BPO) as the initiator. The polymer was characterized by UV, IR, 1H‐NMR, and 13C‐NMR spectroscopy. The polymer was found to be soluble in several polar aprotic solvents and in chlorinated solvents but insoluble in aliphatic and aromatic hydrocarbons and in alcohols. The molecular weight data of the polymer as obtained from gel permeation chromatography suggests a higher tendency for chain termination by disproportionation than dimerization. The glass transition temperature of the polymer was determined by differential scanning calorimetry. Thermogravimetric analysis of the polymer carried out in air reveals that it possesses good thermal stability required of a negative photoresist. The photocrosslinking property of the polymer was investigated by irradiating the polymer solution with UV light in the presence and absence of triplet photosensitizers. The effect of the solvent on the rate of photocrosslinking of the polymer was also studied.

Effect of UV-irradiation on poly(vinyl chloride) modified by methyl methacrylate–butadiene–styrene copolymer

The influence of methyl methacrylate–butadiene–styrene copolymer (MBS) on poly(vinyl chloride) (PVC) photodehydrochlorination and photooxidative degradation was investigated by UV–vis, FTIR and fluorescence spectra. The gel amount formed in exposed samples was estimated gravimetrically. It was found that MBS decelerates PVC photodehydrochlorination and photocrosslinking; the effect is caused by the fact that the Cl radicals react with H atoms at tertiary atoms in polystyrene of MBS and initiate the depolymerisation of the PMMA chains of MBS, then leads to reinitiation of PVC dehydrochlorination. The surface free energy of PVC/MBS blends was calculated on the basis of contact angle measurements. The rate of photocrosslinking and photodegradation distinctly influenced the surface free energy, which can reach a maximum value at an appropriate irradiation time.

Synthesis and characterization of new photoresponsive acrylamide polymers having pendant chalcone moieties

New acrylamide monomers, 4-acrylamidophenyl-2′,3′-benzostyryl ketone (APBSK) and 4-acrylamidophenyl-4′- N, N′-dimethylstyryl ketone (APDSK) having a free-radical polymerizable group and a photocrosslinkable functional group, were synthesized by reacting the corresponding aminochalcones with acryloyl chloride in the presence of triethyl amine. The monomers were polymerized in methyl ethyl ketone at 70 °C using benzoyl peroxide as the initiator. The resulting polymers were characterized by UV, IR, 1H NMR and 13C NMR spectroscopy. The polymers were found to be soluble in several polar aprotic solvents and in chlorinated solvents but insoluble in aliphatic and aromatic hydrocarbons and in alcohols. The molecular weight data of the polymers as obtained from gel permeation chromatography suggests a higher tendency for chain termination by dimerization than disproportionation. The glass transition temperature of the polymers was determined by differential scanning calorimetry. Thermogravimetric analysis of the polymers carried out in air reveals that the polymers possess good thermal and thermo-oxidative stability required of a negative photoresist. The photosensitivity of the polymer was investigated in various solvents in the presence and absence of triplet photosensitizers. The effect of the different solvents and concentration on the rate of photocrosslinking of the polymers were also examined for using the polymers as negative photoresist materials.

Synthesis, characterization and photocrosslinking properties of polyacrylamides having bromo substituted pendant cinnamoyl moieties

New 3- and 4-bromocinnamoyl aniline were synthesized condensing 4-aminoacetophenone and the respective bromobenzaldehydes in the presence of sodium hydroxide. The monomers, 4-(3′-bromocinnamoyl) phenyl acrylamide (4,3′-BCPA) and 4-(4′-bromocinnamoyl) phenyl acrylamide (4,4′-BCPA) were prepared by reacting the respective chalcones and acryloyl chloride in the presence of triethylamine at 0–5 °C. Homopolymers of 4,3′-BCPA and 4,4′-BCPA was carried out in methyl ethyl ketone using benzoyl peroxide (BPO) under nitrogen atmosphere at 70 °C. The prepared polymers were characterized by UV, IR, 1H-NMR and 13C-NMR techniques. The molecular weights ( M w and M n) of the polymers were determined by gel permeation chromatography. The thermogravimetric analysis (TGA) of the polymers in nitrogen atmosphere reveals that they possess very good thermal stability required of a negative type photoresist. The glass transition temperature of poly(4,3′-BCPA) and poly (4,4′-BCPA) were found to be 55 and 64 °C respectively. The solubility of the polymers was tested in various polar and non-polar solvents. Photocrosslinking nature of the polymer samples was carried out in the presence and absence of various triplet photosensitizers in solution phase using chloroform solvent under medium frequency UV light. For using the polymers as negative photoresist materials the rate of photocrosslinking of the polymers was measured under the influence of different solvents, concentrations and position of the substituent.

Photocrosslinkable copolymers based on 4‐acryloyloxyphenyl‐3′‐chlorostyryl ketone and methyl methacrylate: synthesis, comonomer reactivity ratios and UV photosensitivity

AbstractA new photosensitive acrylate monomer having a pendant chlorocinnamoyl moiety (APCSK) was copolymerized with methyl methacrylate (MMA) in different feed compositions in ethyl acetate solution at 70°C using benzoyl peroxide as a free‐radical initiator. The newly synthesized copolymers were characterized by FTIR, 1H and 13C nuclear magnetic resonance (NMR) spectral techniques, as well as by size‐exclusion chromatography. Their thermal behaviour was assessed by thermogravimetric analysis in air and differential scanning calorimetry under nitrogen atmosphere. The copolymers exhibit no phase separation since there is only one glass transition temperature (Tg) value in the region of copolymer composition studied. The reactivity ratios of the comonomers were calculated by adopting linearization methods such as the Fineman–Ross (F‐R), Kelen–Tudos (K‐T) and extended Kelen–Tudos (ExtK‐T) methods, and by a non‐linear error‐in‐variables model method (EVM) using a computer program (RREVM). The results suggest that MMA is more reactive than APCSK and that their copolymerization leads to the formation of random copolymers. The photosensitivity of the copolymer samples was studied in solution as well as in thin films through UV irradiation. The influence of different factors, including solvent nature, concentration, temperature, photosensitizer and copolymer composition, on the rate of photocrosslinking of the photoreactive copolymers was investigated for effective industrial application of these polymers as negative photoresists. Copyright © 2004 Society of Chemical Industry

The influence of comonomer (2‐hydroxyethyl acrylate) and keto group on photocrosslinking property of arylidene polymers

AbstractTwo types of arylidene compounds were synthesized by reacting p‐hydroxybenzaldehyde with acetone [1,5‐bis(4‐hydroxyphenyl)penta‐1,4‐dien‐3‐one] (PBHP) and cyclohexanone [2,6‐bis(4‐hydroxybenzylidene)cyclohexanone] (HBC). 1,4‐Pentadien‐3‐one‐1‐p‐hydroxyphenyl‐5‐p‐phenyl methacrylate (PHPPMA) and 4‐{[‐3‐(4‐hydroxybenzylidene)‐2‐oxocyclohexylidene]methyl}phenyl acrylate (HBA) were prepared by reacting PBHP and HBC with methacryloyl chloride and acryloyl chloride in the presence of triethylamine, respectively. Copolymerization of different feed compositions of PHPPMA and HBA with 2‐hydroxyethyl acrylate (HEA) was carried out using a free‐radical solution polymerization technique in ethyl methyl ketone (MEK) using benzoyl peroxide (BPO). All the monomer and polymers were characterized by IR and NMR (1H/13C) spectroscopic techniques. The reactivity ratio of the monomers were obtained using Fineman–Ross (FR), Kelen–Tudos (KT), and extended Kelen–Tudos (exKT) methods. The photocrosslinking properties of the polymers were done using a UV absorption spectroscopy technique. Homopolymers of both the arylidene polymers shows similar trend towards the rate of photocrosslinking. The rate of photocrosslinking was enhanced when the cyclohexanone based arylidene monomer was copolymerized with HEA. Thermal stability and molecular weights (Mw and Mn) of the polymers were determined. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3433–3444, 2004