Reaction Of Acryloyl Chloride Research Articles

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.

Chitosan-g-poly(4-acrylamidobenzenesulfonamide) copolymers: synthesis, characterization, and bioactivity

The monomer, 4-acrylamidobenzenesulfonamide (ABS), was synthesized via reaction of acryloyl chloride with 4-aminobenzenesulfonamide in acetone at 0 °C. This monomer was then grafted onto chitosan using solution containing 2% acetic acid and mixture of K2S2O8 and Na2SO3 as the redox promoter. An optimal G% of 150% was obtained when the process is conducted at 60 °C for 3 h employing 3.0 × 10−3 M K2S2O8 and 1.5 × 10−3 M Na2SO3. The graft copolymers, chitosan-g-poly(4-acrylamidobenzenesulfonamide), were characterized by using FTIR, XRD, and SEM. The results were shown that the crystallinity of chitosan is enhanced by increasing the monomer content through the grafting process. Potential Antimicrobial activities of the permethyl ammonium salt forms of chitosan and its grafted copolymers against selected microorganisms were evaluated. The results show that the graft copolymers display better inhibitory effects on the growth of bacteria and some fungi than does chitosan.

Synthesis of chitosan‐graft‐poly[2‐cyano‐1‐(pyridin‐3‐yl)allyl acrylate] copolymer from a novel monomer, prepared using a Morita–Baylis–Hillman reaction, and characterization of its antimicrobial activity

AbstractA novel method has been developed to modify the natural polymer chitosan. The process utilizes a monomer prepared by employing a Morita–Baylis–Hillman (MBH) reaction. Specifically, the vinyl monomer 2‐[hydroxy(pyridin‐3‐yl)methyl]acrylonitrile (HPA) was synthesized using a high‐yielding MBH reaction of acrylonitrile with pyridine‐3‐carboxaldehyde in the presence of 1,4‐diazabicyclo[2.2.2]octane. Conversion of HPA to 2‐cyano‐1‐(pyridin‐3‐yl)allyl acrylate (CPA) was then carried out by reaction of acryloyl chloride. The highly functionalized monomer CPA was grafted onto chitosan through a reaction in 2% acetic acid containing a persulfate and a sulfite (K2S2O8/Na2SO3) as redox promoter. An optimal grafting percentage of 123% is obtained when the grafting process is conducted at 60 °C for 4 h employing a 1:0.5 ratio of K2S2O8 and Na2SO3 at a concentration of 2.5 × 10−3 mol L−1. Chitosan‐graft‐poly[2‐cyano‐1‐(pyridin‐3‐yl)allyl acrylate] graft copolymers, having various grafting percentages, were characterized using Fourier transform infrared, 1H NMR and 13C NMR spectroscopies, X‐ray diffraction, thermogravimetric analysis and scanning electron microscopy. Finally, the results of studies probing the antimicrobial activities of the polymers against selected microorganisms show that the graft copolymers display higher growth inhibition activities against bacteria and fungi than does chitosan. © 2014 Society of Chemical Industry

Synthesis and Characterization of New Polyimide by Curing Poly Acryloyl Chloride with Different Amides

The present work involved preparation of new substituted and unsubstituted and poly imides (1-17) using reaction of acryloyl chloride with different amides (aliphatic ,aromatic) in the presence of a suitable solvent and amount tri ethyl amine (Et3N) with heating – the structure confirmation of all polymers were proved using FT-IR,1H-NMR,C13NMR and UV spectroscopy ,thermal analysis (TG) for some polymers confirmed their thermal stabilities . Other physical properties including softening and melting points, PH and solubility of the polymers were also measured

Synthesis and Characterization of New Polyimide by Curing Poly Acryloyl Chloride with Different Amides

The present work involved preparation of new substituted and unsubstituted and poly imides (1-17) using reaction of acryloyl chloride with different amides (aliphatic ,aromatic) in the presence of a suitable solvent and amount tri ethyl amine (Et3N) with heating – the structure confirmation of all polymers were proved using FT-IR,1H-NMR,C13NMR and UV spectroscopy ,thermal analysis (TG) for some polymers confirmed their thermal stabilities . Other physical properties including softening and melting points, PH and solubility of the polymers were also measured

Synthesis of multifunctional acrylate monomers (MFAMs) and their applications

Novel multifunctional acrylate monomers (MFAMs) were synthesized by reaction of acryloyl chloride with 3,4,5-trihydroxybenzoic (Gallic) acid and diethanolamine in the presence of triethylamine as catalyst. The prepared multifunctional acrylate monomers were used as cross-linkers for the synthesis of polyacrylic acid by precipitation polymerization using 2,2'-azobisisobutyronitrile (AIBN) as free radical initiator. Differential scanning calorimetry studies showed that the glass transition temperature behavior is significantly affected by the type and amount of MFAM employed. Viscosity measurements showed that the thickening effect depend upon the cross-linker type and concentration.

Synthesis of Chiral Polysiloxane via Hydrosilylation between Synthesized Hydrogen-Containing Polysiloxane and a Chiral Unsaturated Amide

In this article, we synthesized some hydrogen-containing polysiloxanes by ring-openging polymerization of cyclosiloxanes and studied their viscosity-average molecular weights (η) and active hydrogen content respectively. Then we prepared a chiral amide compound by condensation reaction of acryloyl chloride and (1S)-1-phenylethanamine. Subsequently, we successfully carried out hydrosilylation reaction with the chiral amide and one of hydrogen-containing polysiloxane. In addition, the structures of the target molecules have been confirmed by IR and 1H NMR spectra, elemental analysis and polarimetric analysis.

Synthesis and Reactions of 2-(N-tetrabromophthalimido) Ethyl Acrylate Polymer with Hydroxy and Amino Compounds

N-(2-HYDROXYETHYL)tetrabromophthalimide (HETP) was ……prepared by heating tetrabromophthalic anhydride dissolved in dimethyl formamide (DMF) with ethanol amine. 2- (N-tetrabromophthalimido) ethyl acrylate (TPEA) was prepared by the reaction of acryloyl chloride (AC) with N-(2-hydroxyethyl) tetrabromophthalimide (HETP) in presence of triethyl amine(TEA). The resulting monomer was polymerized. The exchange reactions were carried out in solution at 60ºC The structure of prepared polymers and copolymers was investigated by bromine analysis, IR and

Intermolecular radical addition of alkoxyamines onto olefins: An easy access to advanced macromolecular architectures precursors

Novel “second generation” alkoxyamines, derived from N-(2-methylpropyl)-N-(1-diethylphosphono-2,2-dimethylpropyl)-N-oxyl (so-called SG1) as initiators for nitroxide-mediated polymerization (NMP) were synthesized by intermolecular radical 1,2-addition (IRA) of a high dissociation rate constant alkoxyamine (BlocBuilder®, also called MAMA-SG1) onto various activated olefins, such as n-butyl acrylate, acrylic acid, dimethylacrylamide, 2-hydroxyethylacrylate and styrene. The potential of this radical addition was further applied to the synthesis of multifunctional alkoxyamines as precursors for complex macromolecular architectures, namely 3- and 4-arm star polymers. For this, tri- and tetra-acrylates were synthesized by reaction of acryloyl chloride with the 1,1,1-tris(hydroxymethyl)ethane and pentaerythritol, respectively, in the presence of triethylamine. The addition of MAMA-SG1 onto these olefins led to the tri- and tetra-functional SG1-based alkoxyamines which were further used to prepare polystyrene stars of controlled molecular weights and polydispersity values not exceeding 2. The individual arms were recovered by hydrolysis of the ester groups of the star core originating from the alkoxyamine initiator under basic conditions. The decreasing molecular weight determined by GPC during hydrolysis demonstrated the star architecture of the polymers.

Synthesis, characterization, and ligating behavior of poly[N,N‐p‐phenylene bisacryl (methacryl)amide

AbstractMonomers of diacylated amine were synthesized by the reaction of acryloyl chloride or methacryloyl chloride with p‐phenylenediamine. Heating DMF solution of these monomers at 75°C in the presence of AIBN as an initiator gave the corresponding polymer. The solid metallopolymer complexes with different metal salts were isolated either by the in situ addition of the monomer, metal salt, and initiator at 75°C or by the reaction of the isolated polymer with the metal salt at 150°C. The monomers, polymers, and their metallopolymer compounds were characterized using elemental analysis, IR, NMR (1H and 13C), and MS spectral measurements in addition to thermal analysis. The IR data showed that the coordinating atoms of the polymer are dependent on the reaction temperature. The ion selectivity of the isolated polymers toward different metal ions either for a single metal ion or in a mixture as aqueous solutions are studied by the batch techniques. Energy dispersive spectroscopy (EDS) measurements showed that both polymers are more selective to Hg2+ and Pb2+. The morphology of the polymers and their metallopolymer complexes at different temperature was also studied. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2412–2422, 2006

Synthesis of organic–inorganic hybrid hydrogels using rodlike polysiloxane having acrylamido groups as a new cross-linking agent

In this study, we synthesized organic–inorganic hybrid hydrogels using rodlike polysiloxane having acrylamido groups as a new cross-linking agent which had a regular higher-ordered structure. The cross-linking agents were prepared by reaction of acryloyl chloride with amino groups of the rodlike polysiloxane in the presence of triethylamine in water/methanol mixed solvent. The structures of the cross-linking agents were characterized by IR and 1H NMR spectra, as well as by XRD measurement. Free-radical polymerization of acrylamide monomer in the presence of these cross-linking agents was performed using potassium persulfate as an initiator in degassed water under argon atmosphere at 60 °C to form transparent and elastic organic–inorganic hybrid hydrogels, which contained water weighing more than 90% of the materials. The obtained hybrid hydrogels sustained compressive stresses in the range of 237–696 kPa and their fracture strains were 81–93%.

New poly(amidoamine)s containing disulfide linkages in their main chain

AbstractNovel poly(amidoamine)s (PAAs) containing disulfide linkages regularly arranged along their backbones were synthesized by the stepwise polyaddition of 2‐methylpiperazine to N,N′‐bis(acryloyl)cystamine (BACy1) or N,N′‐bis(acryloyl)‐(L)‐cystine (BACy2). Both bisacrylamides had, in turn, been obtained by the reaction of acryloyl chloride with the corresponding amines. All the products were characterized with 1H and 13C NMR spectroscopy, and the average molecular weights of the polymers were determined by size exclusion chromatography. Both PAAs showed different solubility properties. In particular, PAA‐Cy1, derived from BACy1, was sparingly soluble in water, whereas PAA‐Cy2, derived from BACy2, was very soluble in aqueous media. The polymerization rates were investigated with 1H NMR spectroscopy. In both cases, the experimental data were consistent with pseudo‐second‐order kinetics. The calculated kinetic constants were 5.96 × 10−3 and 5.90 × 10−2 min−1 L mol−1 for the polyaddition of BACy1 and BACy2, respectively. The observed hydrolytic degradation rate of PAA‐Cy2 in a pH 7.4 tris(hydroxymethyl)aminomethane (TRIS) buffer was comparable to that of conventional amphoteric PAAs, that is, PAAs containing carboxyl groups in their repeating unit. Degradation experiments carried out in the presence of 2‐mercaptoethanol with both PAAs demonstrated that the disulfide groups contained in its repeating units were susceptible to reductive cleavage in the presence of thiols. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1404–1416, 2005

Preparation of new polymer from podophyllotoxin derivative

The new monomer, 4α-acrylpodophyllotoxin(APPT) was synthesized from reaction of acryloyl chloride with the 4α-hydroxy of podophyllotoxin. The homo- and copolymer of new monomer with NIPAAm/AAm have been prepared by free radical polymerization. The new monomer and polymers have been characterized by IR, 1H- and 13C-NMR spectra. The homopolymer have low the molecular weight but it is not oligomer, and the molecular weight of copolymer increased with decreasing new monomer content. The composition of copolymers was close to the original monomer composition. The distinction of antitumor activity among podophyllotoxin, new monomer and homopolymer was smaller. The copolymer with NIPAAm (The PAPPT content (mol-%) =43.7%) did not exhibit any antitumor activity at present condition of experimentation.

Novel refreshable N‐halamine polymeric biocides containing imidazolidin‐4‐one derivatives

AbstractA novel cyclic‐amine monomer, 1‐acryloyl‐2,2,5,5‐tetramethylimidazolidin‐4‐one (ACTMIO), was synthesized in a good yield through the reaction of acryloyl chloride with 2,2,5,5‐tetramethylimidazolidin‐4‐one and was fully characterized with Fourier transform infrared and 1H NMR studies. ACTMIO was copolymerized with several widely used acrylic and vinyl monomers under ordinary conditions. In the presence of triallyl‐1,3,5‐triazine‐2,4,6(1H,3H,5H)‐trione, ACTMIO was easily grafted onto most textile fabrics. After regular chlorine bleach treatment, N‐halamine derivatives of the corresponding polymeric materials exhibited antibacterial properties against Escherichia coli, and these properties were durable and refreshable with chlorine bleaching. The relationship between the structures and antibacterial properties of the samples is further discussed. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3073–3084, 2001

Syntheses, antitumour activities and antiangiogenesis of 1,2,3-tris(ethoxycarbonyl)-2-propyl acrylate and its polymers

A new monomer, 1,2,3-tris(ethoxycarbonyl)-2-propyl acrylate (TPA), was synthesized by reaction of acryloyl chloride and triethyl citrate. The homopolymer of TPA and its copolymers with acrylic acid (AA), vinyl acetate (VAc) and maleic anhydride (MAH) were prepared by polymerization using lauroyl peroxide (LPO) at 70 °C for 24 h. The structures of TPA and its polymers were identified by FTIR, 1H NMR, 13C NMR spectroscopies, and elemental analysis. The number average molecular weights and polydispersity indices of the synthesized polymers determined by GPC were in the range 4200–23 000 g mol−1 and 1.1–2.1, respectively. The IC50 values of the synthesized samples against cancer cell lines were greater than those of 5-fluorouracil (5-FU). The percentage inhibition values of SV40 DNA replication were 82.2 for TPA, 34.3 for poly (TPA), 81.9 for poly(TPA-co-AA), 82.0 for poly(TPA-co-VAc), 35.6 for poly(TPA-co-MAH) and 12.7 for 5-FU. The inhibitions of SV40 DNA replication and antiangiogenesis for the synthesized TPA and its polymers are much greater than those of the control. © 2001 Society of Chemical Industry

Poly(N-acryl amino acids): a new class of biologically active polyanions.

Poly(N-acryl amino acids) bearing side groups with a lipophilic character or having charged functional groups (i.e. -NH(2), -COOH, -SH, -OH, and phenols) were synthesized from the radical polymerization of N-acryl amino acid monomers. Monomers were prepared from the reaction of acryloyl chloride and amino acid esters in dry solvents. Polymers of a broad molecular weight ranging from 3 000 to 60 000 Da were obtained. The polymers were optically active, and their structures were confirmed by (1)H NMR and IR spectra and elemental analysis. Hydroxyl-containing polymers were sulfated in high conversion yields by SO(3)/pyridine complex. The newly synthesized linear homopolyanions were tested for heparin-like activities: (i) inhibition of heparanase enzyme, (ii) release of basic fibroblast growth factor (bFGF) from the extracellular matrix (ECM), and (iii) inhibition of smooth muscle cell (SMC) proliferation. Polymers based on tyrosine and leucine were highly active in all three tests (microgram level). Polymers based on phenylalanine, tert-leucine, and proline were active as heparanase inhibitors and FGF release, and polymers of trans-hydroxyproline, glycine, and serine were active only as heparanase inhibitors. The polymer of cis-hydroxyproline was inactive. It was found that a net anionic charge (i.e. carboxylic acid) is essential for biological activity. Thus, methyl ester derivatives of the active polymers, zwitterionic amino acid dependent groups (lysine, histidine), and decarboxylated amino acids (tyramine, ethanolamine) were inactive. The above active polymers did not exhibit anticoagulation activity which is considered the main limitation of heparin and heparinomimetics for clinical use. These synthetic poly(N-acryl amino acids) may have potential use in the inhibition of heparanase-mediated degradation of basement membranes associated with tumor metastasis, inflammation, and autoimmunity.

Synthesis of N-alkyl- and N-arylalkylacrylamides and micellar copolymerization with acrylamide

Different series of alkyl- and arylalkylacrylamide have been synthesized, the number of methylen units of the side chain varying from 2 to 10. They were obtained by the reaction of acryloyl chloride and the corresponding amine. The arylalkylacrylamide containing hexyl and decyl chains were prepared from the appropriate halogenous compounds by a multi-step synthesis. These monomers were then copolymerized, in low proportion (≤2 mol%) with acrylamide under micellar conditions. Copolymers were taken to a conversion of about 30%. This method is known to lead to multiblocks copolymers in which the number and the length of the hydrophobic blocks could be monitored by the initial number of hydrophobes per micelle. The copolymers composition was established by NMR and elemental analysis. The hydrophobic level indicates an increase of the apparent reactivity of the hydrophobic monomer due to the solubilization of this latter in micelles. This drift in composition increases upon increasing the number of hydrophobes per micelle.

Synthesis of novel compatibilizers and their application in PP/nylon-66 blends. I. Synthesis and characterization

A series of novel compatibilizers with different length of oligocaprolactone branch chains, which are capped with one, two or three carboxyl groups at one of these branch chains’ extremities, were synthesized by a three-step approach involving: (1) the oligomerization of ϵ-caprolactone initiated by various of hydroxy acids (glycollic acid, dl-malic acid, or citric acid); (2) the reaction of acryloyl chloride with α-hydroxyl-ω-carboxyl (1,2,3)-oligocaprolactone (HCPCL); and (3) the graft copolymerization of α-acryloyl-ω-carboxyl (1,2,3)-oligocaprolactone (ACPCL) with polypropylene. Effects of various parameters such as monomer ACPCL and initiator benzoyl peroxide concentration, reaction time, and ACPCL kinds on the grafting percentage of ACPCL onto polypropylene (PP) in xylene solution were studied. The grafting of ACPCL onto PP in a laboratorial single screw extruder was also investigated. The maximum extents of grafting achieved in solution and melt were about 10.2 and 12.3%, respectively. The intermediate products, HCPCL and ACPCL were characterized by acid–base titration, hydroxyl value titration, Fourier transform infrared spectroscopy (FTIR), 1H- and 13C-nuclear magnetic resonance analyses, respectively. The grafting copolymers were also characterized by electrometric titration, FTIR analysis, and differential scanning calorimetric, respectively.

Structure reassignment of the major isomer from the Diels-Alder reaction of acryloyl chloride and 4,5,6,6a-tetrahydropentalene

After hydrogenation and hydrolysis, the two adducts formed from the Diels-Alder reaction of acryloyl chloride and 4,5,6,6a-tetrahydropentalene were originally assigned 7-exo- and 7-endo-carboxylic acid structures 3 and 4. Based on unexpected results in using these acids as starting materials for a superacid carbocation study, a reinvestigation of these structural assignments was carried out. From an extensive series of 2D NMR experiments, we conclude that 4 is correctly assigned, but that the other isomer is the 9-endo carboxylic acid 8. The formation of these two isomers (out of eight possible modes of addition) can be rationalized. Finally, an X-ray study of 8 was carried out as a final proof of structure.Key words: Diels-Alder reaction, facial selectivity, regioselectivity, X-ray structure, MO calculation.

Synthesis and exchange reactions of poly-N-acryloyloxytetrabromophthalimide as activated polymer

The synthesis of N-acryloyloxytetrabromophthalimide was accomplished in fair yield by the reaction of acryloyl chloride with N-hydroxytetrabromophthalimide in the presence of triethylamine. Following polymerization of the monomer, exchange reactions of the resulting polymer with amines, amino acids, alcohols, phenols and hydroxybenzoic acids were studied.