Acryloyl Chloride Research Articles

Preparation of novel side-chain fluoroalkyl polyether oligomers with terminal acrylate for emulsion copolymerization and application on cotton fabric finishing

Three novel side-chain fluoroalkyl polyether oligomers with different molecular weight were synthesized base on the ring-opening polymerization of 3-perfluoro-n-butyl-1,2-epoxypropane, followed by terminal esterification using acryloyl chloride. The oligomer intermediates were used as functional monomers for emulsion copolymerization with methyl methacrylate, butyl acrylate, and hydroxyethyl methacrylate. The produced latexes were used for hydrophobic and oil-phobic finishing on cotton fabric surface and the treated cotton fabrics were tested by scanning electron microscopy and energy-dispersive spectroscopy, combined with chemical composition analysis by X-ray photoelectron spectroscopy. The result showed that fluorinated copolymers were successfully coated on the cotton fibers’ surface. Water contact angles was used to evaluate the wettability and the results showed that treated cotton fabrics possessed good hydrophobicity with the contact angle of 139.1 ± 1°, and the heat resistance of treated cotton fabrics was identified improved through the thermogravimetric analyses (TGA).

Preparation and characterization of a novel antibacterial acrylate polymer composite modified with capsaicin

Abstract A novel antibacterial acrylate polymer composite modified with capsaicin was successfully synthesized by a two-step reaction. Capsaicin and acryloyl chloride were firstly esterified, and then applied to solution polymerization with acrylate monomers and styrene. The yield of the esterified products was about 85.3%. The polymer was characterized by Fourier transform infrared spectroscopy (FTIR), gel permeation chromatography (GPC), thermogravimetric analysis (TGA), contact angle (CA) and antibacterial ring tests. The number-average molecular weight (Mn) of the polymer was 27214, based on the capsaicin-acrylate dosage of 6.5 wt%. The TGA revealed a stable thermal property. The contact angles of the polymers films on tinplate increased from 77.5° to 86.2° with the increasing amount of capsaicin-acrylate. The antibacterial tests demonstrated excellent antimicrobial capability of the polymers.

Acrylated Eudragit® E PO as a novel polymeric excipient with enhanced mucoadhesive properties for application in nasal drug delivery

Eudragit® E PO (EPO) is a terpolymer based on N,N-dimethylaminoethyl methacrylate with methylmethacrylate and butylmethacrylate, produced by Evonik Industries AG as a pharmaceutical excipient. In this work, EPO was chemically modified through reaction with acryloyl chloride. The successful modification of EPO was confirmed by FTIR, NMR-spectroscopy, elemental and thermal analysis. The degree of acrylation was determined by permanganatometric titration. The slug mucosal irritation test was used to demonstrate non-irritant nature of EPO and its acrylated derivatives (AEPO). The mucoadhesive properties of EPO and AEPO were evaluated using freshly excised sheep nasal mucosa and it was demonstrated that acrylated polymers facilitated greater retention of sodium fluorescein on mucosal surfaces compared to solution mixture of this dye solution with EPO as well as free dye.

The effect of substituents on the stability of the central four-member ring of unsymmetrical squaraine derivatives

Two unsymmetrical squaraines (SQ-OH and SQ-OPA) have been synthesized. SQ-OPA was gained by esterification of acryloyl chloride and hydroxyl group on SQ-OH. Based on the investigation of the UV–vis, fluorescent, time-dependent 1H NMR and mass spectra, SQ-OPA was demonstrated to have two response sites to biothiols: the central four-member ring and acryloyl group. SQ-OPA is the first “turn-on” fluorescent squaraine thiol probe, and can probe the biothiols (Cys, Hcy, and GSH) simultaneously by naked-eye. However, SQ-OH bearing similar squaraine molecular framework with SQ-OPA, showed good chemical stability during the addition of biothiols. Therefore, for unsymmetrical squaraines, the substituent attached in benzene ring, far away from the central four-member ring, can signficantly affect the stability of squaraine central four-member ring against the nucleophilic attack, which could provide a new strategy for designing “turn-on” fluorescent SQ probes.

Synthesis of New 2′-(2- and 3-Aminopropanoyl)-6′,7′-dimethoxy-2′,3′-dihydro-1′H-spiro[cyclopentane-1,4′-isoquinoline]-1′-carboxamides

6′,7′-Dimethoxy-N-methyl-2′,3′-dihydro-1′H-spiro[cyclopentane-1,4′-isoquinoline]-1′-carboxamide reacted with 2-bromopropanoyl chloride to give the corresponding 2-bromopropanamide which was converted to substituted 2-aminopropanoyl derivatives via reactions with cyclic secondary amines. The reaction of 6′,7′-dimethoxy-N-methyl-2′,3′-dihydro-1′H-spiro[cyclopentane-1,4′-isoquinoline]-1′-carboxamide with acryloyl chloride, followed by treatment of the resulting acrylamide with amines, afforded 3-aminopropanoyl derivatives.

IRMOF‐3 Biological Activity Enhancement by Post‐Synthetic Modification

The growing resistance of pathogens to conventional antibiotics has become a public health problem requiring novel effective solutions. In this context, metal‐organic frameworks (MOFs) are attracting attention because they can act as reservoirs releasing metal ions with antibacterial properties. This action is reminiscent of that proposed for metal‐ and metal oxide‐nanoparticles but different from the action of antibiotics. These features make MOFs promising candidates for pharmaceutical and biomedical applications. Here, IRMOF‐3 was modified with 2,5‐dimethoxytetrahydrofuran, N,N′‐disuccinimidyl carbonate, acryloyl chloride, and phthalaldehyde to produce, respectively, IRMOF‐3‐FU, IRMOF‐3‐SU, IRMOF‐3‐AC, IRMOF‐3‐DL in 38 to 90 % yields. Remarkably, the biological activity of these compounds evaluated against various bacterial and fungal strains is higher than the activity of commercial antibiotics.

Controlled synthesis of thermoresponsive polymers derived from l‐Lysine, a biorenewable resource

ABSTRACTRenewable lysine was cyclized to its corresponding α‐amino‐ε‐caprolactam and then underwent the reaction with acryloyl chloride to harvest a 2‐acrylamido‐caprolactam (ACL) monomer. Subsequent reversible addition–fragmentation chain transfer copolymerization of the obtained monomer with oligo(ethylene glycol)acrylate (OEGA) gave well‐defined P(ACL‐co‐OEGA) with low distribution. Nuclear magnetic resonance , size exclusion chromatography, and matrix‐assisted laser desorption ionization–time‐of‐flight–mass spectrometry measurements indicated the controlled feature of the polymerization. Moreover, the resultant copolymers demonstrated thermoresponsiveness, and the cloud points (Tcp) can be adjusted from 34 to 79 °C, by changing pH values, and the fraction of cyclic lysine. These results suggested that these lysine‐based thermoresponsive polymers might be used as new materials in biomedical fields. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 862–868

The Influence of Composition of Thermo- and pH-Sensitive Copolymers of N-(3-(Diethylamino)propyl)-N-methylacrylamide and N,N-Diethylacrylamide on Their Behavior in Aqueous Solutions

Buffer solutions of random copolymers of N-(3-(diethylamino)propyl)-N-methylacrylamide and N,N-diethylacrylamide containing 7.5 and 5.0 mol % units of N-(3-(diethylamino)propyl)-N-methylacrylamide with molecular masses of 3.07 × 104 and 1.45 × 104, respectively, have been studied by methods of light scattering and turbidimetry. The synthesis of copolymers has been performed via reaction of poly(acryloyl chloride) with N,N-diethyl-N′-methyl-1,3-propanediamine and diethylamine. Aqueous solutions have been studied in the concentration range of 0.0003–0.04 g/cm3 at pH 7.0–13.0. The intensities of scattered light I and optical transmittance I* have been measured. Phase separation temperatures have been determined. The results obtained have been compared with the data for a copolymer of the same structure, but with 20 mol % N-(3-(diethylamino)propyl)-N-methylacrylamide units. It has been shown that the characteristics of aqueous solutions of copolymers depend on their composition. An increase in the fraction of N-(3-(diethylamino)propyl)-N-methylacrylamide leads to formation of aggregates in the copolymer solutions and to a gain in the phase separation temperatures.

A NEW APPROACH TO SYNTHESIS METHACRYLIC MONOMERS N-ALKYLMETHACRYLAMIDE USING AN ECOLOGIC AND FRIENDLY CATALYST MAGHNITE H+

In this paper, we have developed a novel procedure to synthesize four monomers formulated as 1,4-bis(Methacryloyl)Piperazine, N-Methacryloylmorpholine, N-Phenylmethacrylamide and N-Formyldimethacrylamide. N-Alkylmethacrylamide monomers are synthesized by the condensation of primary amine aniline and formamide or heterocyclic secondary amines such as piperazine and morpholine with methacrylic anhydride using an ecologic and friendly catalyst “Maghnite H+”, a proton exchanged montmorillonite clay by replacing a toxic reactant acryloyl chloride and triethylamine which are using in previously published studies. This new approach is even more interesting since this synthesis is carried out in bulk (without solvent) and at 0 °C for 2 hours, obtaining a better yield around 70% and selectivity to the product 100%. These monomers are characterized and confirmed by Infrared Spectroscopy (FTIR), 1H and 13C nuclear magnetic resonance (NMR) spectroscopy.

End group modification of polyethylene glycol (PEG): A novel method to mitigate the supercooling of PEG as phase change material

Polyethylene glycol (PEG) is a kind of phase change material with high phase change enthalpy and good compatibility with the environment. However, there is relatively large supercooling for PEG, limiting their practical applications. To reduce their supercooling degree, herein we use three different small molecules (acryloyl chloride, acetyl chloride, and thionyl chloride) to modify PEG and study the effects of different end group modification on their phase change properties. Fourier-transform infrared (FTIR) and proton nuclear magnetic resonance (1H-NMR) spectroscopy are used to confirm the molecular structure of the PEG with different molecular weights and functionalities after chemical modification. Crystal structures of the PEG before and after the modification are verified by X-ray diffractometry (XRD) method and show no change. Differential scanning calorimetry (DSC) results show that the end group modification is quite effective for mitigating the supercooling of PEG with double -OH end groups but not effective for PEG with mono -OH end group. The mechanism for the change of supercooling behavior is proposed. The costs of different modification methods are estimated and compared.

Novel palladium nanoparticles supported on β‐cyclodextrin@graphene oxide as magnetically recyclable catalyst for Suzuki–Miyaura cross‐coupling reaction with two different approaches in bio‐based solvents

A novel nanocatalyst was designed and prepared. Initially, the surface of magnetic graphene oxide (M‐GO) was modified using thionyl chloride, tris(hydroxymethyl)aminomethane and acryloyl chloride as linkers which provide reactive C═C bonds for the polymerization of vinylic monomers. Separately, β‐cyclodextrin (β‐CD) was treated with acryloyl chloride to provide a modified β‐CD. Then, in the presence methylenebisacrylamide as a cross‐linker, monomers of modified β‐CD and acrylamide were polymerized on the surface of the pre‐prepared M‐GO. Finally, palladium acetate and sodium borohydride were added to this composite to afford supported palladium nanoparticles. This fabricated nanocomposite was fully characterized using various techniques. The efficiency of this easily separable and reusable heterogeneous catalyst was successfully examined in Suzuki–Miyaura cross‐coupling reactions of aryl halides and boronic acid as well as in modified Suzuki–Miyaura cross‐coupling reactions of N‐acylsuccinimides and boronic acid in green media. The results showed that the nanocatalyst was efficient in coupling reactions for direct formation of the corresponding biphenyl as well as benzophenone derivatives in green media based on bio‐based solvents. In addition, the nanocatalyst was easily separable, using an external magnet, and could be reused several times without significant loss of activity under the optimum reaction conditions.

Synthesis of Bisthiacalix[4]arene: Reaction of Piperazine with Monoacrylamide Derivative of p-tert-Butylthiacalix[4]arene

The reaction of acryloyl chloride with the monoamine derivative of p-tert-butylthiacalix[4]arene was used to synthesize p-tert-butylthiacalix[4]arene monoacrylamide in the 1,3-alternate conformation. The effect of the nature of the amine on the result of its Michael reaction with the synthesized p-tert-butylthiacalix[4]arene monoacrylamide was studied. The latter was reacted with piperazine to obtain bisthiacalix[4]arene with the macrocyclic fragments in the 1,3-alternate conformation.

Evaluation of antibacterial and anticancer properties of poly(3-hydroxybutyrate) functionalized with different amino compounds

The chemical modification of biodegradable poly(3-hydroxybutyrate) (PHB) is useful for biomedical applications. In this study, the transesterification reaction of PHB was carried out under reflux conditions in the presence of 1,4-butanediol to form telechelic PHB-diol. Further modification of PHB-diol into PHB-diacrylate was carried out by the reaction of PHB-diol with acryloyl chloride. PHB-diacrylate was grafted with amino compounds such as 1,4-butanediamine, 1,3-propanediamine, 1,2-ethylenediamine, piperazine, cyclohexylamine, 2,2′-(ethane-1,2-diylbis(oxy)) diethanamine (jeffamine EDR 148) and morpholine via Michael-type addition reaction. The functionalized amino-PHB polymers were characterized by using FTIR and 1H NMR techniques. XRD showed that amino-PHB polymers have different crystallinity compared with neat PHB. Some biological activities of amino-PHB polymers were determined such as antibacterial, antioxidant and anticancer activities. In this regard, the results showed that PHB-ethylenediamine revealed a potent antibacterial activity against Staphlococcus aureus, Escherichia coli, Klebsiella pneumoniae and Pseudomonas aeruginosa. All amino-PHB polymers under the study showed reasonable antioxidant activity. Among these polymers, PHB-piperazine showed a potent anticancer effect against in vivo Ehrlich ascetic carcinoma bearing mice.

Highly Effective Removal of Methylene Blue Using a Chemi-Mechanical Pretreated Cellulose-based Superabsorbent Hydrogel

Eucalyptus bleached chemical pulp was fibrillated using a PFI pulp beater and ball mill method and was modified by acryloyl chloride. A novel porous cellulose-based hydrogel was prepared from the modified cellulose and acrylic acid for the removal of methylene blue (MB) from aqueous solution. The structure and morphology of the hydrogel were characterized by Fourier transform infrared spectroscopy (FT-IR) and scanning electron microscopy (SEM), respectively. The influence of various parameters, such as pH value, hydrogel dosage, initial MB concentration, and contact time on the dye adsorption, were investigated. The equilibrium experimental data fitted well to the Langmuir isotherm model, and the maximum adsorption capacity of the hydrogel reached 3003 mg/g. In addition, the reusability study suggested that the hydrogel showed great adsorption capacity and a high removal ratio, even after the 5th adsorption-desorption cycle. Thus, the modified cellulose-based hydrogel is a potential superabsorbent for the removal of MB from wastewater.

Synthesis, characterization, conformational equilibrium and intramolecular hydrogen bond analysis of Novel Azocalix[4]arenes including acryloyl moiety using DFT studies

Azocalix[4]arenes were synthesized via diazo-coupling reaction with aniline in 1:1, 1:2, 1:3 and 1:4 molar ratio. Novel Azocalix[4]arenes having Acryloyl moiety were prepared esterification reaction with metallic sodium and Acryloyl chloride with the same molar ratio of Azocalix[4]arene derivatives. The spectroscopic characterizations of the compounds were made by using IR, UV–Vis, 1H NMR and 13C NMR spectroscopies. In our study, the validation of the exact conformation of Azocalix[4]arene existing in a Cone, Partial Cone, 1,2-Alternate and 1,3-Alternate was realized by spectroscopic and DFT analyses. These results reveal that the compounds exist in the Cone conformation because of the existence of Intramolecular Hydrogen Bonds (IHBs) in the calixarene core. According to the conformational analysis, Cone conformation corresponds to the minimum energy for compounds 6, 7 and 8, as well. Both DFT and NMR results confirmed that a conformational rearrangement of compound 9 is 1,3-Alternate conformer. The experimental results were correlated with the theoretical calculations. In addition, Natural Bond Orbital (NBO) calculations were used to examine the electronic characteristics of the intramolecular hydrogen bonds. NBO energies show that the main contributions to energy stabilization correspond to LP → σ* interactions for IHBs, O⋅⋅⋅OH and the delocalisation LP → π* for OCO.

Preparation of photoluminescent grafted polymers, having a polyethylene matrix and pyrene units linked via oligo(ethylene glycol) spacers, using gamma radiation

New polymers were prepared by grafting of low density polyethylene films (PE). Firstly, PE was reacted with acryloyl chloride in the presence of gamma radiation to give the precursor grafted polymers (PE-g-AC). These polymers were further esterified with a new pyrene derivative having a tetra (ethylene glycol) side chain, [2-(2-(2-(2-(pyren-1-yloxy)ethoxy)ethoxy)ethoxy)ethan-1-ol] (PyTEG), leading to the obtainment of a series of luminescent polymers bearing pyrene units (PE-g-AC-PyTEG). The influence of the irradiation dose on the structure and the percentage of grafting of the produced polymers has been studied in detail. These materials have been characterized by FTIR spectroscopy, and their thermal properties have been determined by TGA and DSC. The optical properties of the grafted polymers have been studied by UV–vis and fluorescence spectroscopy.

Spruce xylan/HEMA-SBA15 hybrid hydrogels as a potential scaffold for fibroblast growth and attachment

A hybrid hydrogel (GHC-SBA15) based on spruce xylan (HC), 2-hydroxyethyl methacrylate (HEMA), and mesoporous silica (SBA15) was prepared with the intended use of fibroblast attachment and growth. Xylan was functionalized with acryloyl chloride to introduce vinyl groups and was crosslinked by radical polymerization with HEMA in presence of SBA15. Infrared spectroscopy and nuclear magnetic resonance confirmed the copolymerization of HEMA with xylan. Up to 20 wt.% addition, SBA15 was homogenously incorporated in the structured hydrogel network as observed by SEM. Moreover, nitrogen adsorption–desorption, small angle X-ray scattering and transmission electron microscopy indicated that the mesoporous SBA15 framework was maintained and that the hybrid hydrogel was a physical mixture of SBA15 with the copolymer HC/HEMA. Rheological analysis revealed that addition of 20% w/w SBA15 into hydrogel enhanced significantly the mechanical properties. In addition, we demonstrate that fibroblast L929 cells grew and spread on GHC-SBA15. Cell viability was within the expected range.

Preparation of photosensitive polyimides (PSPIs) and their feasible evaluation for lithographic insulation patterns (LIPs) of integrated circuits (ICs) without negative photoresists

A photosensitive polyimide (PSPI) with high glass transition temperature (Tg; 259 ℃), good inherent viscosity (I.V.; 0.31 dL/g), and superb decomposition temperature (Td; 368 ℃) has been manufactured by the appropriate prescription of diamine monomer (i.e. 2,2-bis (3-amino-4- hydroxyphenyl)-hexafluoropropane; APAF), dianhydride monomer (i.e. 4,4′-(4,4′- isopropylidenediphenoxy)bis(phthalic anhydride); BPADA), cyclodehydating agent (i.e. p-xylene), base (i.e. N,N,N-triethylamine; TEA), and photosensitive monomer (i.e. acryloyl chloride; AOC). In order to explore the applying feasibility, we have prepared lithographic insulation pattern resin (LIPR) of integrated circuit (IC) with PSPI (i.e. APAF/BPADA/AOC polyimide), solvent (i.e. N-methyl-2-pyrrolidone; NMP), photoinitiator (i.e. I-305), crosslinking agent (i.e. CLA-1), co-photoinitiator (i.e. I-309) as well as coupling agent (i.e. vinyltrimethoxysilane; VTES) and utilized it without negative photoreist by silicon wafer, i-line (wavelength: 365 nm; optical density: 1200 mW/cm2), and photomask. Experimental results reveal that lab-made LIPR of IC based on PSPI is a promising IC package material with high tensile strength of 106 MPa, excellent adhesion on silicon wafer (i.e. eligible of cross-cut examination), great coefficient of thermal expansion (CTE) of 17.9 ppm/℃, low dielectric constant (Dk) of 3.5, high surface electric resistance of 8.3 × 1011 Ω/sq., low dielectric loss (Df) of 0.01, moderate hygroscopicity of 2.9% (23 ℃, 24 h), and low residual stress of 32.0 MPa.

Functionalization of poly(3‐hydroxybutyrate) with different thiol compounds inhibits MDM2–p53 interactions in MCF7 cells

ABSTRACTHigh‐molecular‐weight poly(3‐hydroxybutyrate) (PHB) has a low reactivity toward its terminal functional groups. Thus, the chemical reactivity of PHB was enhanced by the chemical degradation that occurred via β‐elimination through the functionalization of PHB with ethylene glycol to give a low‐molecular‐weight PHB–diol. The reaction of PHB–diol with acryloyl chloride gave PHB–diacrylate, which was grafted by thiol compounds, such as ethane dithiol, 2‐mercaptoethanol, ethane thiol, dithiothreitol, butane thiol, and thioglycolic acid, via a Michael‐type addition reaction. The chemical and thermal properties of the functionalized PHB–thiol products were characterized with Fourier transform infrared spectroscopy, 1H‐NMR, gel permeation chromatography, differential scanning calorimetry, and thermogravimetric analysis techniques. X‐ray diffraction showed that the PHB–thiol polymers had slight differences in crystallinity compared with neat PHB. The biological activities of the neat polymer and new PHB–thiol polymers, including the antibacterial and anticancer activities, were tested, and some of these products showed antibacterial and anticancer activities. These anticancer activities were attributed to the ability of these PHB–thiol polymers to induce apoptosis (as revealed by the higher expression of Bax and caspase 9 and the lower expression of Bcl2) and cell‐cycle arrest in the G0/G1 phase, which is associated with the higher expression of p53 and p21 and the lower expression of the p53 inhibitor, MDM2. Thus, the anticancer effect of these PHB–thiol polymers may have been due to their ability to inhibit MDM2–p53 interactions. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019, 136, 46924.

Monomers with a High Refraction Index Based on Acryloyl Derivatives of Spirocyclic Piperidin-4-One Thioacetals

Dithioazaspiroheterocyclic derivatives are synthesized by condensing dithiols with piperidin-4-one in the presence of catalytic amounts of Lewis acids. Acrylic dithioazaspiroheterocyclic derivatives are obtained by the reaction with acryloyl chloride. The polymerization of monomers yields transparent polymer films of optical quality. The refractive indices for the synthesized monomers and polymers are in the range of n = 1.59–1.64.