Polymerization and copolymerization of an isocyanate blocking agent. N-(1,1′-dimethyl-3-oxobutyl) acrylamide oxime. Mechanical and thermal properties

The bulk polymerization and copolymerization of N-(1,1′-dimethyl-3-oxobutyl) acrylamide oxime have been studied. Polymerization of diacetone acrylamide oxime was carried out with different initiating systems. The rate of polymerization of diacetone acrylamide oxime with azoisobutyronitrile as the initiating system was much higher than with peroxides. However, in the case of perester initiating systems (t-butyl perbenzoate and t-butyl per ethyl-2-hexanoate), cobalt salt promoted the polymerization rate markedly. Diacetone acrylamide oxime readily formed copolymers with a variety of comonomers (crosslinking agents and reactive diluents). Gel permeation chromatography has shown a higher reactivity of diacetone acrylamide oxime with trimethylol propane trimethacrylate as crosslinking agent and N-vinyl-pyrrolidone as reactive diluent. Therefore, the dynamic mechanical analyses presented an increase in T_g with trimethylolpropane trimethacrylate and N-vinyl-pyrrolidone as comonomers. The terpolymer formed with diacetone acrylamide oxime, trinethylolpropane trimethacrylate, and N-vinyl-pyrrolidone exhibited interesting mechanical properties and high temperature behavior.     

Preparation and polymerization of some N-(dialkylaminoalkyl)acrylamides

A series of N-(dialkylaminoalkyl)acrylamides was synthesized by reductive amination of N-(1,1-dimethyl-3-oxobutyl)acrylamide (diacetone acrylamide) and by the reaction of either an alkenylamine or an amino alcohol with acrylonitrile. These monomers homopolymerize and copolymerize readily to form high molecular weight products. The solubility of the monomers and their homopolymers in water ranges from soluble to insoluble at room temperature. The insoluble materials can be quaternized readily to produce water-soluble products. The solubility of the homopolymers in water decreases with increasing temperature. Glass transition and decomposition temperatures of the homopolymers are reported.     

Effect of association processes on polymerization of N-[3-(dimethylamino)propyl]methacrylamide salts in aqueous solutions

The effect of associative interactions of monomers and propagating macroradicals in homopolymerization of N-[3-(dimethylamino)propyl]methacrylamide salts and their copolymerization with acrylonitrile and acrylamide in aqueous solution was studied.     

Analyzing the surface properties of acrylic-based water-soluble polymers

The surface properties of newly synthesized N-methoxy isopropyl acrylamide, N-methoxy isopropyl methacrylamide, cyclo propyl acrylamide, and cyclo propyl methacrylamide polymers were investigated using inverse gas chromatography. The highest dispersive component of the surface energy value was obtained for cyclo propyl methacrylamide at 30°C. The values obtained for all polymers were decreasing with the increasing temperature. The values obtained for the acidic and the basic parameters revealed strong basic characters for the surface of N-methoxy isopropyl methacrylamide and cyclo propyl methacrylamide polymers and weak basic characters for the surface of N-methoxy isopropyl acrylamide and cyclo propyl acrylamide polymers.     

New carbazole-containing monomers and polymers

Five novel vinyl monomers, all of which contain 3-substituted carbazolyl groups [i.e., N-(9-ethyl-3-carbazolyl)-maleimide, 9-ethyl-3-carbazolyl acrylamide, 9-ethyl-3-carbazolyl methacrylamide, 9-ethyl-3-hydroxymethylcarbazolyl acrylate, and 9-ethyl-3-hydroxymethylcarbazolyl methacrylate], and their corresponding polymers were synthesized. Two methods were used for the synthesis of the last two monomers.     

Synthesis and Characterization of Catechol-Containing Polyacrylamides with Adhesive Properties

In this study, a row of four analogous dopamine acryl- and methacrylamide derivatives, namely N-(3,4-dihydroxyphenyethyl) acrylamide, N-(3,4-dihydroxyphenyethyl) meth acrylamide, N-phenethyl methacrylamide, N-(4-hydroxyphenethyl) methacrylamide were synthesized and characterized by ¹H-NMR and ¹³C-NMR, followed by further solvent-based radical polymerization with N-hydroxyethyl acrylamide. All copolymers were characterized by ¹H-NMR, dynamic differential calorimetry, and gel permeation chromatography. The dependency of the used comonomer ratios to the molecular mass of the corresponding copolymers has been described. The synthesis of the various polymers serves as a feasibility study and provides important data for a future biometric application in the medical field. We synthesized N-(3,4-dihydroxyphenyethyl) acrylamide copolymer up to 80 mol% by free radical polymerization without using any protecting groups. All polymers show identical perfect adhesive properties by a simple scratch test. Further, the monomers were used as a photo reactive glue formulation to test its adherence to a medical titanium surface sample by tensile shear test.     

Vinyl polymerization by a manganese(III) complex

Bis(diethanolamine) manganate(III) was prepared. The polymerization of acrylamide and methacrylamide initiated by this complex in aqueous solution at pH 0.9 was studied at 45°. The rate of polymerization was followed by bromometry, the rate of complex disappearance spectrophotometrically and the molecular weights of the polymers were determined viscometrically. The rate of polymerization was found to be proportional to [Monomer]^1.0. The order with respect to initiator was found to be 0.5 for acrylamide and 0.3 for methacrylamide. The apparent overall activation energies for the polymerizations are ?87 kJ mol^?1 and ?59 kJ mol^?1 for acrylamide and methacrylamide respectively. A kinetic reaction scheme is proposed on the basis of the experimental data; kinetic parameters have been evaluated.     

Water-soluble copolymers. IX. Copolymers of acrylamide with N-(1,1-dimethyl-3-oxybutyl)acrylamide and N,N-dimethylacrylamide: Synthesis and characterization

The copolymerizations of acrylamide (AM) with N-(1,1-dimethyl-3-oxybutyl)acrylamide (DAAM) and with N,N-dimethylacrylamide (DMAM) have been studied. The values of r₁,r₂ have been determined to be 0.75 for the AM-DAAM pair and 0.86 for the AM-DMAM pair. The molecular weights of the copolymers were found to decrease with an increase in the feed composition of DAAM or DMAM. The microstructure was predicted for a wide range of feed compositions through a knowledge of reactivity ratios. These model structures are utilized for assessment of structure/dilute solution relationships reported in a subsequent paper in this series.     

Water-soluble copolymers. X. Copolymers of acrylamide with N-(1,1-dimethyl-3-oxybutyl)acrylamide and N,N-dimethylacrylamide: Solution properties

Dilute solution properties of copolymers of acrylamide (AM) with N-(1,1-dimethyl-3-oxybutyl)acrylamide (DAAM) and with N,N-dimethylacrylamide (DMAM) have been studied as a function of composition, temperature, time, and added electrolytes sodium chloride and calcium chloride. Unlike the AM-DMAM copolymers, the AM-DAAM copolymers show solution viscosity increases in the presence of added NaCl and CaCl₂ and decreases with increasing temperature which are related to copolymer composition. The unusual viscosity behavior of the DAAM-AM copolymers is suspected to be due to chain extension resulting from intramolecular hydrogen bonding and other cooperative associations along the macromolecular backbone.     

Polymerization behavior of N-(p-vinyl)phenylacrylamide

The polymerization behavior of N-(p-vinyl)phenylacrylamide, synthesized from p-aminostyrene and acryloyl chloride by means of the Schotten-Baumann reaction was studied. Due to a marked difference in electron density between the two double bonds, this monomer provided soluble polymers by both cationic and anionic polymerization procedures, the cationic and anionic polymers mainly carrying, as side chains, the acrylamide and styrene moieties, respectively. The polymerization behavior of the residual double bonds was also investigated for both polymers, leading to crosslinked, insoluble products.     

Synthesis and free-radical polymerization of water-soluble acrylamide monomers

Water-soluble acrylamide monomers N-(hydroxymethyl)acrylamide, N-(hydroxymethyl)methacrylamide, N,N-diethanolacrylamide, N,N-diethanolmethacrylamide, N,N-methylethanolacrylamide, and N,N-methylethanolmethacrylamide have been synthesized and characterized. The kinetics and thermodynamics of the free-radical polymerization of these monomers and of the model compounds N-isopropylacrylamide and acrylamide have been studied by the methods of isothermal and scanning calorimetry. The structure and the solubility of the said polymers in water and organic solvents have been investigated and their molecular-mass characteristics and temperatures of glass transition (T _g) and melting (T _m) have been examined by DSC, liquid chromatography, ¹H NMR and IR spectroscopy, and chemical analysis of functional groups. Hydrogels and amphiphilic network polymers based on acrylamide monomers have been prepared and characterized.     

Polymerization of N-(fluoro phenyl) maleimides

Poly(N-aryl maleimide)s of characteristic structures have been synthesized and some of their physical properties studied. These include N-(2-fluoro phenyl), N-(3-fluoro phenyl), N-(4-fluoro phenyl), N-(2,4-difluoro phenyl), N-(2,5-difluoro phenyl), N-(2,3,5,6-tetrafluoro phenyl), and N-(pentafluoro phenyl). The polymerization of N-(fluoro phenyl) maleimides by free-radical initiation in bulk or in solution and by anionic catalyst have been studied to compare the characteristics of polymerization by γ-ray irradiation with that by free-radical initiation. The polymers were characterized by elemental analysis, intrinsic viscosity, spectroscopy (IR and NMR), programmed thermogravimetric analysis, and x-ray diffraction. Spectra of polymers prepared by radiation and anionic polymerization were nearly identical with those of polymers prepared by free-radical polymerization initiated by AIBN in bulk or in solution and by the self-initiated thermal polymerization. A variety of reaction conditions were tried, but all attempts to change the molecular structure of the polymers were unsuccessful. Rates of thermal degradation for poly[N-(fluoro phenyl) maleimide]s have been analyzed by using a multiple-heating-rate procedure. Overall activation energy, order of reaction, and frequency factor have been evaluated. On the basis of the comparison between the overall activation energy of the thermal degradation of poly[N-(fluoro phenyl) maleimide]s and NMR spectra of their corresponding monomers, it can be concluded that the ¹H shifts due to ethylenic protons are so characteristic in sign and magnitude as to be useful in thermal stability elucidation. Some qualitative explanations were given on the stability of these polymers as affected by the type and size of the substituent. The x-ray diffractograms of all samples show two rather broad peaks indicative of noncrystalline structures. The location of the peaks does not depend upon preparation conditions and temperature. Poly(N-maleimide)s of fluoroanilines have not been hitherto described.     

Complexation of anionic copolymers of acrylamide and N-(2-hydroxypropyl)methacrylamide with aminoglycoside antibiotics

The complexation of aminoglycoside antibiotics neomycin, gentamicin, kanamycin, and amikacin in the form of free bases with carboxyl- and sulfo-containing copolymers of acrylamide and N-(2-hydroxypropyl)methacrylamide (HPMA) in water and water-salt solutions is studied by means of viscometry, equilibrium dialysis, potentiometric titration, and molecular hydrodynamics. Factors influencing the stability of formed copolymer-antibiotic complexes and determinations of their toxicity are established.     

N-(P-羟甲基苯基)咔唑丙烯酸酯的合成和聚合

<正> 为了深入认识含咔唑基单体的光敏性与聚合性的关系,在本系列含咔唑基化合物的基础上,合成了两个新单体:N-(p-羟甲基苯基)咔唑丙烯酸酯和N-(P-羟甲基苯基)咔唑甲基丙烯酸酯,并研究了其聚合行为。 化合物Ⅰ、Ⅱ、Ⅲ和聚合物的合成,反应式如下:     

Arrangement of fullerene above the poly(methyl methacrylate) surface with fluoroalkyl end-capped N-(1,1-dimethyl-3-oxobutyl)acrylamide polymers

Fluoroalkyl end-capped N-(1,1-dimethyl-3-oxobutyl)acrylamide polymers were found to be a convenient tool for the arrangements of fullerenes above the poly(methyl methacrylate) [PMMA] surface, and the higher fluorescent intensity of fullerene was obtained in the modified PMMA surface, although the reverse side of this modified film surface afforded an extremely weak fluorescent intensity.     

Hydrogen-transfer polymerization of methyl-substituted acrylamides

Base-catalyzed hydrogen-transfer polymerization and copolymerization of acrylamide and its methyl-substituted derivatives were studied in pyridine at 110°C. n-Butyllithium was used as an initiator. The observed rates of these homopolymerizations were found to decrease in the following order: acrylamide > crotonamide > methacrylamide > N-methylacrylamide > N-methylcrotonamide > tiglinamide > N-methylmethacrylamide ? α-chlorocrotonamide ? α-cyanocrotonamide = 0. Acrylamide gave the polymer with the highest degree of polymerization among the monomers examined. It was found that the number and the position of the methyl substituent in acrylamide affected significantly both the rate of polymerization and the molecular weight of the polymer. Although all polymers obtained, except the N-methyl derivatives, contained both methanol-soluble and methanol-insoluble fractions, a polyamide structure with unsaturated terminal monomer unit was confirmed by both infrared and NMR determinations. From the NMR determination of the saturated and terminal unsaturated units, the degree of polymerization of the resulting polyamides were also obtained. The monomers were also found to copolymerize by a hydrogen-transfer mechanism. However, the main chain of the resulting copolymers was composed of the more reactive monomer unit, and the less reactive monomer was incorporated only as a terminal unit when a less reactive monomer was copolymerized with a more reactive one. From these results, it was concluded that these polymerizations proceeded via an intermolecular hydrogen-transfer mechanism (i.e., stepwise mechanism).     

Water‐soluble acrylamide copolymers. IX. Preparation and characterization of the cationic derivatives of poly(acrylamide‐co‐n,n‐dimethylacrylamide), poly(acrylamide‐co‐methacrylamide), and poly(acrylamide‐co‐n‐t‐butylacrylamide)

This article extends the preparative details of a series of nonionic copolymers of acrylamide with N,N‐dimethylacrylamide, methacrylamide, and N‐t‐butylacrylamide to the synthesis of cationic derivatives of these new copolymers. The described procedures gave products with cationicities of 14–26 mol %. We measured the mean squared radii of gyration and intrinsic viscosities of aqueous solutions of these products at several different pHs and NaCl concentrations to compare these values with those determined for the nonionic precursors and related commercial cationic polymers. Because the molecular weights of the examples measured varied widely, it was difficult to establish definite trends. However, the large values obtained for the mean squared radii of gyration and intrinsic viscosities, relative to the nonionic precursors of these polymers, demonstrated that the charged groups had a qualitatively greater effect on polymer extension than the nonpolar bulky groups. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2525–2535, 2001     

Monolayers and Multilayers of Amphiphilic Phospholipid Analogous Poly(Acrylamide)s

Abstract

A series of amphiphilic phospholipid analogous acrylamide monomers and homopolymers containing long alkyl chains as the hydrophobic groups and phosphatidylcholine analogues as the hydrophilic groups were used to study the properties of monolayers and multilayers. The P-A isotherms of the monolayers for these monomers and polymers were measured at different temperatures. The temperature and length dependence of alkyl chains, and the difference between monomers and polymers were investigated, respectively. On the other hand, the LB multilayers of all monomers and polymers were prepared. The contact angles of LB films obtained with pure water were also measured.     

Acid‐labile,thermoresponsive (meth)acrylamide polymers with pendant cyclic acetal moieties

Acid‐labile, thermoresponsive polymers with pendant six‐membered cyclic acetal groups were prepared by radical polymerization of two monomers, N‐(2,2‐dimethyl‐1,3‐dioxan‐5‐yl) methacrylamide (NDMM) and N‐(2,2‐dimethyl‐1,3‐dioxan‐5‐yl) acrylamide (NDMA). The aqueous solution properties of the polymers, PNDMM and PNDMA, were studied by turbidimetry, ¹H NMR, fluorescence, and DSC measurements. It is found that both polymers show sensitive and reversible phase transitions with distinct lower critical solution temperatures (LCST). Below their LCSTs, there are still some polymer aggregates as evidenced by measurements of pyrene excitation spectra and urea effects on the cloud points (CP) of polymers. The salting effect of six inorganic sodium salts on the phase transition behavior of PNDMM was investigated by turbidimetric approach. The salting‐out to salting‐in effect is in the order of SO₄^2? > F^? > Cl^? > Br^? > I^? > SCN^?, following the Hofmeister's series. pH‐dependent hydrolysis of PNDMM and PNDMA was studied by turbidimetric and ¹H NMR methods. They are both pH‐sensitive and their hydrolysis rates significantly increase with decreasing pH value. The CP of PNDMM gradually increases with the acid‐triggered hydrolysis of the acetal groups and the hydrolyzed polymer with ～ 30% hydrolysis degree does not show thermally induced phase transition. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4332–4343, 2008     

Helix—Sense—Selective Polymerization of N,N—Diphenyl （Meth） acrylamide by Anionic Catalysts

In this paper, the helix-sense-selective polymerization of N,N-diphenyl acrylamide (DPAA) and N,N-diphenyl methacrylamide (DPMAA) were studied with living helix prepolymer as anionic initiator, and the chiral optical properties of the obtained polymers were investigated too. It was shown that optically active polymers of DPAA and DPMAA could be obtained under the experimental condition, and exhibited the same screw sense as that of the prepolymer.