Nanoporous Crosslinked Copolymers Prepared by Thermal Degradation of Poly(Methacryl‐N,N′‐diisopropylurea‐co‐ethylene Glycol Dimethacrylate)

Abstract

Copolymers of methacryl‐N,N′‐diisopropylurea (MA‐DiPrU) with ethylene glycol dimethacrylate (EDMA) at monomer‐to‐monomer ratios in the feed: 0.3/0.7; 0.5/0.5; 0.7/0.3; 0.8/0.2 were prepared in butanone in the presence of 2% of dibenzoyl peroxide (Bz₂O₂) at 70°C for 48?hr. Copolymers regardless of the ratio of comonomers in the feed decompose thermally at 200–250°C under the separation of isopropylisocyanate (iPrNCO). Residues after the removal of iPrNCO are thermally stable nanoporous crosslinked copolymers of methacryl‐isopropylamide (MA‐iPrA) with EDMA which decompose by a one‐step mechanism between 280°C and 450°C. Nonporous model copolymers poly(MA‐iPrA‐co‐EDMA) of similar composition, prepared by copolymerization of MA‐iPrA with EDMA, also decomposed by a one‐step mechanism as shown by TGA measurements.     

Copolymerization of N‐tert‐Butylacrylamide with Ethylene Glycol Dimethacrylate

N‐tert‐butylacrylamide (NtBA) was copolymerized with ethylene glycol dimethacrylate (EDMA) in butanone solution over a wide composition and conversion range, using dibenzoyl peroxide (Bz₂O₂) as a free‐radical initiator. The copolymer composition was determined from the nitrogen content. Using only low conversion (≤20%) collected for the copolymerization reactions, monomer reactivity ratios were estimated using the Kelen‐Tüdos graphical method and were found to be r₁=0.26 (NtBA) and r₂=7.05 (EDMA). In order to get a better insight into the mechanism of nanoporous copolymers of NtBA with EDMA preparation by thermal degradation of copolymers of N‐acryl‐N,N′‐di‐tert‐butylurea (A‐DitBuU) with EDMA, nonporous copolymers (model compound), of the same chemical structure and composition, were prepared by performing copolymerization of NtBA with EDMA up to the high conversion of 97–100%. Thermal behavior of nanoporous and nonporous copolymers of NtBA with EDMA was studied.     

Synthesis and Characterization of Hydrogels Based on Gamma Radiation Copolymerization of N‐isopropylacrylamide and Ethylene Glycol Dimethacrylate Monomers

Hydrogels based essentially on N‐isopropylacrylamide (NIPAAm) and different ratios of ethylene glycol dimethacrylate (EGDMA) monomer were synthesized by gamma radiation copolymerization. The thermal decomposition behavior of NIPAAm/EGDMA hydrogels was determined by thermogravimetric analysis (TGA). The effect of temperature and pH on the swelling behavior was also studied. The results showed that the ratio of EGDMA in the comonomer feeding solution has a great effect on the yield product, gel fraction and water content in the final hydrogel. In this regard, it was observed that the increase of EGDMA ratio decreased these properties. The TGA study showed that all the compositions of NIPAAm/EGDMA hydrogels displayed higher thermal stability than the hydrogel based on pure PNIPAAm hydrogel. The swelling kinetics in water showed that pure PNIPAAm and NIPAAm/EGDMA hydrogels reached equilibrium after 6 h. However, NIPAAm/EGDMA hydrogels show swelling in water lower than pure PNIPAAm. The results showed that the swelling character of pure PNIPAAm and NIPAAm/EGDMA hydrogels was affected by the change in temperature within the temperature range 25–40°C, and showed a reversible change in swelling in the pH range 4–7 depending on composition.     

Polyimide‐Polydimethylsiloxane Copolymers. Evaluation of the Thermal and Electrical Properties

Poly(dimethylsiloxane‐amic‐acid)s have been prepared starting from a fluorinated dianhydride, namely 4,4′‐(hexafluoroisopropylidene)diphthalic anhydride, and a mixture of an aromatic diamine and bis(aminopropyl)‐oligodimethylsiloxane of controlled molecular weight, in different ratios. A solution imidization procedure was used to convert them quantitatively to the corresponding polyimides. The polymers, easily soluble both in polar (N‐methylpyrrolidone) and less polar (chloroform) solvents, were prepared for film‐forming by casting from solution. The thermal behavior in dependence on composition was evaluated by thermogravimetric analysis and differential scanning calorimetry. The kinetic processing of thermogravimetric data was carried out using the Flynn‐Wall‐Ozawa and Kissinger methods. Electrical insulating properties of some polymer films were evaluated on the basis of dielectric constant and dielectric loss tangent and their variation with frequency.     

Molecular Architecture of Non-Linear Polymers: Kinetic Modeling and Experimental Characterization of the System Methyl Methacrylate + Ethylene Glycol Dimethacrylate

A general kinetic approach allowing the prediction of the molecular architecture of non-linear polymers is applied to the study of the copolymerization of methyl methacrylate (MMA) with ethylene glycol dimethacrylate (EGDMA). Dynamic predictions of molecular weight distributions, sequence length distributions and mean square radius of gyration are possible before and after gelation. A set of experiments concerning the copolymerization of MMA and EGDMA was carried out in toluene solution at 60 °C for which classic radical kinetics is a good approximation. The time evolution of key polymer properties was followed using a SEC system with a refractive index detector coupled with MALLS allowing the determination of absolute weight average molecular weight and apparent molecular size distributions as well as z-average radius of gyration. Special focus was given to assess the influence of the initial amount of cross-linker on the dynamics of the non-linear structure build-up of these products. A kinetic scheme comprising 23 different chemical species and 76 chemical reactions was used in the modeling studies of this chemical system. Most of the kinetic parameters used in the simulations have been collected from previous studies. For experiments at low monomer conversion (up to about 0.5) a good agreement between predictions and experimental measurements is observed for molecular weights and z-average radius of gyration by fitting a small number of parameters describing gel effect (with a conversion dependent but chain length independent termination rate parameter) and the relative propagation on pendant double bonds. However, predicted values of weight-average molecular weights and z-average radius of gyration before gelation are too low at higher monomer conversions with non-linear systems. The likely cause is the presence of intramolecular reactions which should not be neglected in these circumstances.     

Differences between smectic homo‐ and co‐polysiloxanes as a consequence of microphase separation

This paper compares smectic phases formed from LC‐homo‐ and LC‐co‐polysiloxanes. In the homopolysiloxane, each repeating unit of the polymer chain is substituted with a mesogen, whereas in the copolysiloxanes mesogenic repeating units are separated by dimethylsiloxane units. Despite a rather similiar phase sequence of the homo‐ and co‐polysiloxanes—higher ordered smectic, smectic C* (SmC*), smectic A (SmA) and isotropic—the nature of their phases differs strongly. For the copolymers the phase transition SmC* to SmA is second order and of the ‘de Vries’ type with a very small thickness change of the smectic layers. Inside the SmA phase, however, the smectic thickness decreases strongly on approaching the isotropic phase. For the homopolymer the phase transition SmC* to SmA is first order with a significant thickness change, indicating that this phase is not of the ‘de Vries’ type. This difference in the nature of the smectic phases is probably a consequence of microphase separation in the copolymer, which facilitates a loss of the tilt angle correlation between different smectic layers. This has consequences for the mechanical properties of LC‐elastomers formed from homo‐ and co‐polymers. For the elastomers from homopolymers the smectic layer compression seems to be rather high, while it seems to be rather small for the copolymers.     

Novel Copolymers of Vinyl Acetate with Alkyl and Alkoxy Ring‐Disubstituted 2‐Phenyl‐1,1‐dicyanoethylenes

Electrophilic trisubstituted ethylene monomers, alkyl and alkoxy ring‐disubstituted 2‐phenyl‐1,1‐dicyanoethylenes, RC₆H₃CH?C(CN)₂ (where R is 2,4‐(CH₃)₂, 2,5‐(CH₃)₂, 2,3‐(CH₃O)₂, 2,4‐(CH₃O)₂, 2,5‐(CH₃O)₂, 3,4‐(CH₃O)₂, 3‐C₂H₅O‐4‐CH₃O, 4‐CH₃O‐3‐CH₃), were synthesized by piperidine catalyzed Knoevenagel condensation of ring‐disubstituted benzaldehydes and malononitrile, and characterized by CHN elemental analysis, IR, ¹H‐ and ¹³C‐NMR. Novel copolymers of the ethylenes and vinyl acetate were prepared at equimolar monomer feed composition by solution copolymerization in the presence of a radical initiator (ABCN) at 70°C. The composition of the copolymers was calculated from nitrogen analysis, and the structures were analyzed by IR, ¹H and ¹³C‐NMR, GPC, DSC, and TGA. High T _g of the copolymers, in comparison with that of polyvinyl acetate, indicates a substantial decrease in chain mobility of the copolymer due to the high dipolar character of the trisubstituted ethylene monomer unit. The gravimetric analysis indicated that the copolymers decompose in the 190–700°C range.     

Regio‐ and Diastereoselective Ring‐Opening Reaction of Epoxides with Nitric Oxide

Ring‐opening reactions of epoxides with nitric oxide afforded syn or anti α‐hydroxy nitrates in high regio‐ and diastereoselectivities in good yields.     

Synthesis and Characterization of Water‐Soluble Cellulose Derivatives with Thermo‐ and pH‐Sensitive Functional Groups

A series of water‐soluble cellulose derivatives with thermo‐ and pH‐sensitive properties were prepared in aqueous solutions by the graft copolymerization of N‐isopropylacrylamide (NIPAAm) on carboxymethylcellulose (CMC). Ceric ammonium nitrate (CAN) was used in combination with nitric acid as the initiator system. The effects of various factors such as CAN concentration, NIPAAm and CMC amounts as well as reaction temperature on the grafting percentage and efficiency were studied. The resultant cellulose derivatives were characterized with respect to their structure and aqueous solution properties by IR spectra, thermogravimetric analyses and optical transmittance measurements.     

O‐Alkylation of Pyridine Aldo‐ and Ketoximes with Dihalohydrins under Phase‐Transfer Conditions

Phase‐transfer‐catalyzed alkylation of (E)‐pyridine aldo‐ and (E)‐ketoximes with dihalohydrins in the benzene (or DMSO)/10% aq. NaOH system in the presence of tetradecylammonium bromide proceeds regiospecifically to afford the corresponding O‐halohydrins in good yields. In this study, first O‐halohydrin derivatives were converted into glycidyl ether derivatives, and then a new series of amino alcohols were synthesized by the condensation of amines with these glycidyl ethers.     

Synthesis,Characterization and Thermal Degradation of Oligo‐2‐[(4‐hydroxyphenyl) Imino Methyl]‐1‐naphtol and Oligomer‐Metal Complexes

The oxidative polycondensation of 2‐[(4‐hydroxyphenyl) imino methyl]‐1‐naphtol (4‐HPIMN) has been accomplished by using NaOCl, H₂O₂ and air O₂ oxidants in aqueous alkaline medium. Optimum reaction conditions of the oxidative polycondensation and the main parameters of the process were established. At optimum reaction conditions, yield of the products were found to be 77.0%, 91.6% and 99.0% for H₂O₂, air O₂ and NaOCl oxidants, respectively. The structures of the obtained monomer and oligomer were confirmed by FT‐IR, UV‐Vis, ¹H‐ and ¹³C‐NMR and elemental analysis. The characterization was made by TG‐DTA, SEC and solubility tests. The ¹H‐ and ¹³C‐NMR data shows that the polymerization proceeded by the C–C coupling of ortho positions according to –OH group of 4‐HPIMN. The molecular weight distribution values of the product were determined by using size exclusion chromatography (SEC). The number‐average molecular weight (M_n), weight‐average molecular weight (M_w) and polydispersity index (PDI) values of O‐4‐HPIMN were found to be 1777, 2225 and 1.252; 1790, 2250 and 1.257; 4540, 5139 g mol^?1, and 1.132 for NaOCl, H₂O₂ and air O₂ oxidants, respectively. According to TG analyses, the carbonaceous residue of 4‐HPIMN and O‐4‐HPIMN was found to be 28.02% and 44.22% at 1000°C, respectively. Thermal analyses of O‐4‐HPIMN‐Cd, O‐4‐HPIMN‐Co, O‐4‐HPIMN‐Cu, O‐4‐HPIMN‐Fe, O‐4‐HPIMN‐Mg, O‐4‐HPIMN‐Mn, O‐4‐HPIMN‐Ni, O‐4‐HPIMN‐Pb and O‐4‐HPIMN‐Zn oligomer‐metal complex compounds were investigated in N₂ atmosphere between 15–1000°C.     

Copolymers of 2‐[(5‐Methylisoxazol‐3‐yl)amino]‐2‐oxo‐ethyl Methacrylate with Ethyl Methacrylate: Monomer Reactivity Ratios,Thermal Properties and Antimicrobial Activity

We report the monomer reactivity ratios for copolymers of ethyl methacrylate (EMA) and a reactive monomer, 2‐[(5‐methylisoxazol‐3‐yl)amino]‐2‐oxo‐ethyl methacrylate (IAOEMA), using the Fineman‐Ross, Kelen‐Tüdös, and a nonlinear error invariable model method using a computer program RREVM. Copolymers were obtained by radical polymerization initiated by α,α'‐azobisisobutyronitrile in 1,4‐dioxane solution and were analyzed by FTIR, ¹H‐NMR, and gel permeation chromatography. Elemental analysis was used to determine the molar fractions of EMA and IAOEMA in the copolymers. The reactivity ratios indicated a tendency toward ideal copolymerization. The polydispersity indices of the polymers determined using gel permeation chromatography suggest a strong tendency for chain termination by disproportionation. Thermal behaviors of copolymers with various compositions were investigated by differential scanning calorimetry and thermogravimetric analysis. It was observed that glass transition temperature of copolymers increased with increasing of IAOEMA content in copolymers. Also, the apparent thermal decomposition activation energies (ΔE_d) were calculated by Ozawa method using the SETARAM Labsys TGA thermobalance. The homo‐ and copolymers were tested for their antimicrobial properties against selected microorganisms. All the products show moderate activity against different strains of bacteria, fungi and yeast.     

Crosslinking of Polydimethyl Siloxane Copolymers with Aromatic Dianhydrides: The Study of Thermal and Flame Retardant Properties †

Aromatic dianhydrides have been identified as potential candidates for crosslinking with biocatalytically synthesized siloxane copolymers containing a functional amino group on the isophthalate moieties. We present the synthesis, characterization, thermal and flame retardant properties of this novel class of crosslinked organo-siloxane copolymers. We also discuss the effect of the concentration of one of the crosslinkers, 1,2,4,5-benzenetetracarboxylic dianhydride (DAH), on thermal decomposition and flame retardant properties using thermogravimetric analysis (TGA) and pyrolysis combustion flow calorimetry (PCFC) studies. The char yields were improved in all the polymers crosslinked with the various aromatic dianhydrides. The heat release capacity of a polymer crosslinked with 20% DAH, compared to the pure polymer, was tremendously reduced from 190 J/gK to 100 J/gK. The decomposition kinetics from TGA showed that the crosslinked polymer is thermally more stable than the non-crosslinked polymer.     

Microbial Screening of Copolymers of N‐Vinylimidazole with Phenacyl Methacrylate: Synthesis and Monomer Reactivity Ratios

N‐vinylimidazole (VIM), and phenacyl methacrylate (PAMA) copolymerized with different feed ratios using 1,4‐dioxane as a solvent and α,α'‐azobisisobutyronitrile (AIBN) as an initiator at 60°C. Structure and composition of copolymers for a wide range of monomer feed were determined by elemental analysis (content of N for VIM‐units) and by Fourier transform infrared spectroscopy through recorded analytical absorption bands for VIM (670 cm^?1 for C‐N of imidazole ring) and PAMA (1730 cm^?1 for C?O of ester group) units, respectively. Monomer reactivity ratios for VIM (M₁)‐PAMA (M₂) pair were determined by the application of conventional linearization methods such as Fineman‐Ross (F‐R) and Kelen‐Tüdös (KT) and a nonlinear error invariable model method using a computer program RREVM. The molecular weights (_w and _n) and polydispersity indices of the polymers were determined using gel permeation chromatography (GPC). Thermal behaviors of copolymers with various compositions were investigated by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Also, the apparent thermal decomposition activation energies (ΔE_d) were calculated by Ozawa method using the SETARAM Labsys TGA thermobalance. The antibacterial and antifungal effects of polymers were also tested on various bacteria, fungi and yeast.     

Unexpected Rearrangement in the Reaction of 7‐Mercapto‐4‐methylcoumarin with 1‐Mono‐ and 1,1‐Dimethyl Propargyl Alcohols

The reaction of 7‐mercapto‐4‐methylcoumarin (4) with 1‐mono‐ and 1,1‐dimethyl propargyl alcohols in H₃PO₄ afforded the corresponding β‐(7‐coumarinthio)ketones with a rearrangement of the carbon chain of propargyl. A possible mechanism of this rearrangement was proposed.     

N‐Arylation of Heterocycles with Chloro‐ and Fluoroarenes using Resin‐Supported Sulfonato‐Cu(salen) Complex

Sulfonato‐Cu(salen) complex immobilized onto a Merrifield's resin was found to be an efficient catalyst for the N‐arylation of heterocycles with electron‐withdrawing hloro‐ and fluoroarenes. The reactions were carried out in the presence of an inexpensive mild base, K₂CO₃, and N‐arylated compounds were obtained in good to excellent yields. The catalyst was recovered by simple filtration and reused for three cycles with almost consistent activity.     

Novel Copolymers of Alkyl and Alkoxy Ring‐Substituted Ethyl 2‐Cyano‐3‐phenyl‐2‐propenoates and Styrene

Abstract

Electrophilic trisubstituted ethylenes, ring‐substituted ethyl 2‐cyano‐3‐phenyl‐2‐propenoates, RC₆H₄CH?C(CN)CO₂C₂H₅ (where R is 2‐CH₃, 3‐CH₃, 4‐CH₃, 2‐OCH₃, 3‐OCH₃, and 4‐OCH₃) were prepared and copolymerized with styrene (ST). The monomers were synthesized by the piperidine catalyzed Knoevenagel condensation of ring‐substituted benzaldehydes and ethyl cyanoacetate, and characterized by CHN analysis, IR, ¹H and ¹³C NMR. All the ethylenes were copolymerized with ST (M₁) in solution with radical initiation (AIBN) at 70°C. The compositions of the copolymers were calculated from nitrogen analysis and the structures were analyzed by IR, ¹H and ¹³C NMR. The order of relative reactivity (1/r ₁) for the monomers is 3‐OCH₃ (0.88)?>?4‐CH₃ (0.71)?>?2‐OCH₃ (0.68)?>?3‐CH₃ (0.55)?>?2‐CH₃ (0.47)?>?4‐OCH₃ (0.40). Higher T _g of the copolymers in comparison with that of polystyrene indicates a decrease in chain mobility of the copolymer due to the high dipolar character of the TSE structural unit. Gravimetric analysis indicated that the copolymers decompose in the 257–287°C range.     

Structure Investigation of Xylenols and Their Redox Products by Thermal and Spectral Methods of Analyses

The structures of 2, 6- and 3,4-xylenols together with their iodine redox products Ⅰ-Ⅲwere studied and critically investigated. Characterization of these matrials involves elemental, the-rmogravimetric, differential thermogravimetric and differential thermal analyses. IR and NMRspectrometry were used for the study of structural formulae of the obtained redox products. Theidentification and characterization of these materials confirm the proposed schemes representingredox reactions of xylenols with iodine. It also explained the schemes representing fragmentationof the investigated compounds by thermal analyses. Thin layer chromatography was also used forseparation and identification of redox products obtained in the reaction media.     

Thermal degradation of bromine-containing polymers. Part 9—Copolymers of 2,3-dibromopropyl methacrylate and 2,3-dibromopropyl acrylate with styrene

The products of the thermal degradation of copolymers of styrene (S) with 2,3-dibromopropyl methacrylate (2,3-DBPM) and 2,3-dibromopropyl acrylate (2,3-DBPA) have been analysed quantitatively using thermal analysis, infra-red spectroscopy, mass spectrometry and gas-liquid chromatography. The products are generally similar to those which result from the degradation of the two homopolymers and no significant interaction occurs between the two types of units in the polymer chains. The only abnormal feature is the fact that the yield of 2,3-DBPA increases as the 2,3-DBPA content of copolymers of 2,3-DBPA and S decreases but this is consistent with previous observations in related copolymer systems.