Preparation and polymerization of N-(1,1-dimethyl-3-hydroxybutyl) acrylamide and N-(1,1-dimethyl-3-hydroxybutyl)methacrylamide

The syntheses of N-(1,1-dimethyl-3-hydroxybutyl)acrylamide and the corresponding methacrylamide by reduction of the oxobutyl acrylamides are described. These monomers are colorless liquids which are soluble in water and many organic solvents. They polymerize readily to form homopolymers and copolymers with other vinyl monomers. The preparation of polymers containing these repeating units by reduction of polymers of diacetone acrylamide and diacetone methacrylamide is also described.     

Graft polymerization of vinyl monomers inside macroporous polyacrylamide gel,cryogel, in aqueous and aqueous‐organic media initiated by diperiodatocuprate(III) complexes

Graft polymerization initiated by diperiodatocuprate(III) complex (Cu(III)) initiator was found to be an effective and convenient method for graft polymerization of vinyl monomers onto macroporous polyacrylamide gels, the so‐called cryogels (pAAm‐cryogels). The effect of time, temperature, monomer and initiator concentration during the graft polymerization in aqueous and aqueous‐organic media was studied. The graft polymerization of water‐soluble monomers as [2‐(methacryloyloxy)ethyl]‐trimethylammonium chloride, 2‐hydroxyethyl methacrylate, N‐isopropylacrylamide, and N,N‐dimethylacrylamide proceeds with higher grafting yield in aqueous medium, as compared with that in aqueous‐organic media. Graft polymerization in aqueous‐organic media such as water–DMSO solutions allows grafting of water‐insoluble monomers such as glycidyl methacrylate and N‐tert‐butylacrylamide with high grafting degrees of 100 and 410%, respectively. It was found that the deposition of initiator on the pore surface of cryogels promoted graft polymerization by facilitating the formation of the redox couple Cu(III)‐acrylamide group. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1952–1963, 2006     

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.     

Synthesis,photopolymerization and adhesive properties of new hydrolytically stable phosphonic acids for dental applications

Novel monomers 2‐(N‐methylacrylamido)ethylphosphonic acid, 6‐(N‐methylacrylamido)hexylphosphonic acid, 10‐(N‐methylacrylamido)decylphosphonic acid, and 4‐(N‐methylacrylamidomethyl)benzylphosphonic acid have been prepared in good yields for use in dental adhesives. They have been fully characterized by ¹H‐NMR, ¹³C‐NMR, ³¹P ‐ NMR, and by HRMS. All monomers are hydrolytically stable in aqueous solution. Free radical homopolymerizations of these monomers have been carried out in solution of ethanol/water (2.5/1:v/v), using 2,2′‐azo(2‐methylpropionamidine) dihydrochloride (AMPAHC) as initiator. They lead to homopolymers in moderate to excellent yields. Structure of the polymers has been confirmed by SEC/MALLS and ¹H‐NMR spectra. The photopolymerization behavior of the synthesized monomers with N,N′‐diethyl‐1,3‐bis(acrylamido)propane has been investigated by DSC. New self‐etch primers, based on these acrylamide monomers, have been formulated. Dentin shear bond strength measurements have shown that primers based on (N‐methylacrylamido)alkylphosphonic acids assure a strong bond between the tooth substance and a dental composite. Moreover, the monomer with the longest spacer group provides the highest shear bond strength. © Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7074–7090, 2008     

N,N′-(disubstitutedmethylene)bisacrylamides: Preparation and polymerization

Preparative methods for the previously unreported N,N′-(disubstitutedmethylene)-bisacrylamides are presented. The solubility and thermal stability of these new bisamides are compared to the well known N,N′-methylenebisacrylamide. N,N′-Isopropyl-idenebisacrylamide, one of these new compounds, readily copolymerizes with a variety of vinyl monomers. It forms high molecular weight copolymers by the conjugate polyaddition of alkanedithiols or piperazine.     

Kinetic Studies upon the Influence of Cyclodextrin on the Polymerization of Methacrylamides in Homogenous Aqueous Solution

Summary: N‐methacryloyl‐1‐aminopropane ( 1 ), N‐methacryloyl‐1‐aminobutane ( 2 ), N‐methacryloyl‐1‐aminopentane ( 3 ), and N‐methacryloyl‐1‐aminohexane ( 4 ) are synthesized and treated with an aqueous solution of randomly methylated β‐cyclodextrin (Me‐β‐CD) to form the water‐soluble host‐guest complexes 1a – 4a . In case of the aqueous polymerization of the free monomers 1 – 4 the initial polymerization rate increases with increasing water solubility. The opposite effect is observed in the case of the polymerizations of the Me‐β‐CD‐complexed methacrylamide monomers 1a – 4a . The polymerization rates are increased with increasing alkyl chain length of the complexed monomers 1a – 4a and decreasing water solubility of the free monomers 1 – 4 .

Initial polymerization rate v₀ of CD‐complexed monomers 1a – 4a (○) vs. water solubilities of monomers 1 – 4 (▪).     

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.     

Synthesis and polymerization of new styryl and methacryloyl monomers containing acidic saccharide moieties

New styryl‐type water‐insoluble and methacryloyl‐type water‐soluble monomers, N‐(p‐vinylbenzyl)‐1,2‐O‐isopropylidene‐6‐D ‐glucofuranuronamide and N‐(2‐methacryloylamino)ethyl‐1,2‐O‐isopropylidene‐6‐D ‐glucofuranuronamide, were synthesized from the most common acidic saccharide, D ‐glucuronic acid. Their radical homopolymerizations and copolymerizations with styrene and acrylamide were tried under various conditions. The isopropylidene groups in the resulting polymers were removed in a mixture of trifluoroacetic acid and water (2/1 v/v) to give the corresponding polymers with many pendant D ‐glucopyranuronyl groups with reactive reducing groups. The pendant reducing ends may be useful as potential binding sites under a hydrophilic atmosphere. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3893–3901, 2001     

Side‐Product of N‐Acryloyloxysuccinimide Synthesis or Useful New Bifunctional Monomer?

During the synthesis of the N‐acryloxysuccinimide (NAS) monomer, we observed the formation of a by‐product, resulting from the condensation of two NAS molecules via a Michael addition. Due to its bulky structure, this new bifunctional monomer shows a very poor ability to homopolymerize. On the contrary, it readily copolymerizes with N‐acryloylmorpholine (NAM), an hydrophilic acrylamide derivative, leading to functional polymer chains exhibiting a wide range of solubility and a high potential for biomolecule covalent binding.     

Access to Poly{N‐[3‐(dimethylamino)propyl](meth)acrylamide} via Microwave‐Assisted Synthesis and Control of LCST‐Behavior in Water

In the present paper, the microwave (MW)‐assisted synthesis of the alkaline N‐[3‐(dimethylamino)propyl]methacrylamide ( 4 ) and ‐acrylamide ( 5 ) monomers within minutes is described. The reaction was carried out by mixing and subsequent irradiation of 3‐dimethylamino‐1‐propylamine ( 3 ) and (meth)acrylic acid ( 1 / 2 ) without addition of solvent. After polymerization, the obtained homopolymers ( 6 / 7 ) exhibit lower critical solution temperature (LCST) behavior in water at 35 °C only at pH = 14. The LCST‐behavior can be influenced by N‐oxidation of the tertiary amino group with hydrogen peroxide or by formation of a polymer‐inclusion complex ( 6a ) of 6 and β‐cyclodextrin (β‐CD) by addition of randomly‐methylated β‐CD.

     

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.     

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.     

Controlled Synthesis and Degradation of Poly(N‐(isobutoxymethyl) acrylamide) Homopolymers and Block Copolymers

The homopolymerization of the water‐insoluble N‐(isobutoxymethyl)acrylamide (IBMA) is investigated for the first time by nitroxide‐mediated polymerization. The homopolymerization is characterized by a linear increase in number average molecular weight (M_n) versus conversion (X) to X > 0.80 while maintaining dispersities of M_w/M_n < 1.30. A strong Arrhenius relationship correlates the apparent rate constants and the homopolymerization temperatures between 105 and 120 °C. All poly(IBMA) homopolymers are then successfully chain‐extended with styrene (S) to form well‐defined block copolymers of poly(IBMA)‐b‐poly(S) suggesting a high degree of livingness of the poly(IBMA) macroinitiators. Thermogravimetric analysis and differential scanning calorimetry are both used to characterize the thermal properties of the homopolymers and block copolymers and identify possible unique degradation of the poly(IBMA) block through imide formation at elevated temperatures.

     

Synthesis and characterization of N-substituted 1,4,5,6-tetrahydropyrimidine containing functional polymers as SO2 and CO2 sorbents

Novel vinyl monomers containing 1,4,5,6-tetrahydropyrimidine were prepared by the reaction of N-substituted-1,3-diaminopropane with N,N-dimethyl-formamide dimethylacetal, which gave 1-alkyl or aryl substituted 1,4,5,6-tetrahydropyrimidines, Alkylation of the tetrahydropyrimidine derivatives by chloromethylstyrene produces the N-methyl-N′-vinyl benzyl-1,4,5,6-tetrahydropyrimidinium chloride in high yields. These monomers were readily polymerized in dimethylformamide by AIBN at 80°C. Homopolymers and soluble linear copolymers were prepared and copolymerization parameters were rationalized. Further, insoluble terpolymers prepared from these monomers, styrene and divinylbenzene were tested for the sorption of the weakly acidic gases gave excellent results. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 2411–2420, 1997     

Alternating copolymerization of methyl acrylate with donor monomers having a protected amine group

Attempts were made to copolymerize p-aminostyrene, p-acetamidostyrene, N-methyl-p-aceta-midostyrene, N-(4-vinylphenyl) phthalimide, N-vinyl succinimide, and N-vinyl phthalimide with methyl acrylate complexed with ethyl aluminum sesquichloride. Only reactions involving N-(4-vinylphenyl)phthalimide and N-vinyl phthalimide yielded alternating copolymers. N-vinyl succinimide gave nonalternating copolymers insoluble in common solvents and the other monomers did not copolymerize. In some cases, the conventional radical copolymers were prepared for comparison purposes. The reactivity ratios of the free-radical initiated copolymerization of methyl acrylate (I) with N-(4-vinylphenyl)phthalimide (II) were r₁ = 0.14 and r₂ 1.56. The alternating copolymers were studied by ¹H-NMR and ¹³C-NMR spectroscopy. The alternating copolymer of N-(4-vinylphenyl)phthalimide with methyl acrylate was hydrazinolyzed to form the alternating copolymer of methyl acrylate with p-aminostyrene. Hydrazinolysis of the alternating copolymer of methyl acrylate with N-vinyl phthalimide removed the phthalimide moiety and generated vinyl amine units which readily cyclized with neighboring methyl acrylate units to form copolymers that contained five-membered lactam rings. The infrared (IR) spectra of the hydrazinolyzed products contain bands due to amine or amide groups and are devoid of the characteristic bands of the phthalimide ring.     

High molecular weight polyacrylamides by atom transfer radical polymerization: Enabling advancements in water‐based applications

Through the use of copper (I) chloride (CuCl) and tris(2‐dimethylaminoethyl)amine (Me₆‐TREN) as a metal/ligand pair, conditions for the robust, fast, and controlled radical polymerization of high molecular weight N‐hydroxyethylacrylamide (HEAm),N‐isopropylacrylamide (NIPAm), N,N′‐dimethylacrylamide (DMAm), and acrylamide (Am) at ambient temperature are reported. Linear evolution of molecular weight and narrow molecular weight distribution was observed for all monomers with degrees of polymerization ranging from 50 to 5000. Random copolymers of several acrylamide‐based monomers are also reported with excellent control over molecular weight and polydispersity. Characterization of high molecular weight poly (NIPAm) demonstrated large changes in the lower critical solution temperature observed on heating and cooling, and this hysteresis was exploited for the controlled release of doxorubicin from poly(NIPAm) spheres. This study represents the first example of preparation of high molecular weight acrylamide polymers by a metal‐mediated controlled radical polymerization technique. Access to these materials, as well as to NIPAm polymers in particular, opens new doors for interesting applications in a variety of fields including tissue engineering, drug delivery, and controlled solution viscosity. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Esterification reactions on syndiotactic poly(methallylalcohol). IV. Homo- and copolymers of N-protected methallyl-(L)-histidinate

Syndiotactic poly(methylallylalcohol) is fully esterified with N^α-protected (L )-histidine by carbodiimide in pyridine to yield the corresponding homopolymers, i.e., N^α-protected 2-methylallyl-(L )-histidinate monomer units and unreacted 2-methylallyl alcohol units are obtained, which in a second exhaustive esterification step are reacted with N^α-(benzyloxycarbonyl)-(L )-aspartic acid anhydride. The resulting copolymers consist of N^α-protected 2-methylallyl-(L )-histidinate and 2-methylally-N^α-(benzyloxycarbonyl)-(L )-hydrogen-α-aspartate monomer units. They are polyampholytes containing both imidazole and carboxyl groups. The structure, including composition of the copolymers, is determined by ¹H- and ¹³C-NMR, while water solubility and apparent pK_aa values are investigated by potentiometry.     

Tailoring macromolecular architecture with imidazole functionality: A perspective for controlled polymerization processes

Controlled radical polymerization (CRP) allows for the design and synthesis of functional polymers with tailored composition and unique macromolecular architectures. Synthetic methods that are readily available for controlled radical polymerization include nitroxide-mediated polymerization, reversible addition–fragmentation chain transfer polymerization, and atom transfer radical polymerization. N-Vinyl monomers that are typically amenable to free radical methods are often difficult to synthesize in a controlled manner to high molecular weight due to the lack of resonance stabilization of the propagating radical. However, recent advances in the field of CRP have resulted in successful controlled polymerization of various N-vinyl heterocyclic monomers including N-vinylcarbazole, N-vinylpyrrolidone, N-vinylphthalimide, and N-vinylindole. The incorporation of the imidazole ring into homopolymers and copolymers using conventional free radical polymerization of N-vinylimidazole monomer is particularly widespread and advantageous due to facile functionalization, high thermal stability, and the relevance of the imidazole ring to many biomacromolecules. Copolymers prepared with methyl methacrylate displayed random incorporation according to differential scanning calorimetry and amorphous morphologies according to X-ray scattering. Imidazole- and imidazolium-containing monomers have shown recent success for CRP; however, the controlled polymerization of N-vinylimidazole has remained relatively unexplored. Future efforts focus on the development of tailored imidazole-containing copolymers with well-defined architectures for emerging biomedical, electronic and membrane applications.     

Synthesis and characterization of an azobenzene‐ and acrylamide‐based photoresponsive copolymer and gel

This article reports the synthesis and characterization of a new type of copolymer consisting of acrylamide and trans‐4‐methacroyloxyazobenzene and their gel. Free‐radical polymerization initiated with 2,2′‐azobisisobutyronitrile was used to conduct the synthesis although N,N′‐methylene bisacrylamide was used as a crosslinking agent for the gel synthesis. Despite the insolubility of the different monomers in a single solvent, a certain ratio of water/tetrahydrofuran (THF) enabled the propagating species to stay in the solution and thus to facilitate chain growth. The solubility, Fourier transform infrared spectra, and solid‐state ¹³C NMR investigations revealed that two monomers in the copolymer were chemically bonded. The compositions of the incorporated acrylamide and azobenzene in the copolymer and the gel were determined by NMR spectroscopy. Because the potential actuating behavior of such materials was due to the volume change involved in reversible solvent uptake, the sorption and evaporation of the gel were also investigated and showed that the gel could absorb about 460% water, which corresponded to a polymer content of the weight gel of 18% and was compatible with thermogravimetric analysis of a saturated gel that revealed about 83 wt % of a swollen gel was lost within 12 h. Finally, photoinduced trans–cis isomerization kinetics of the copolymer was investigated in a 30:70 mixture of water and THF against irradiation time. A photostationary state was reached within 5.5 min with a corresponding conversion of 70% of the trans isomer to the cis form. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2886–2896, 2004     

Synthesis of hydrophilic microspheres with LCST close to body temperature for controlled dual‐sensitive drug release

Novel stimuli‐responsive hydrophilic microspheres were prepared by free radical polymerization of hydroxyethyl methacrylate (HEMA) and methacrylic acid (MA), as hydrophilic monomers, and N‐isopropylacrylamide (NIPAAm) and N,N′‐ethylenebisacrylamide (EBA), as thermo‐sensitive monomer and crosslinker, respectively. Hydrophilic comonomers were introduced in the macromolecular network to synthesize materials with tunable thermal behavior. In addition, by introducing in the polymerization feed both a hydrophilic and a pH‐sensitive monomer, such as MA, dual stimuli‐responsive (pH and temperature) hydrogels were synthesized. The incorporation of monomers in the network was confirmed by infrared spectroscopy, while the network density and the shape of hydrogels was found to strictly depend on the concentration of monomers in the polymerization feed. Thermal analyses showed negative thermo‐responsive behavior with pronounced water affinity of microspheres at a temperature lower than lower critical solution temperature (LCST). In our experiment, the LCST values of the hydrogels were in the range 34.6–37.5°C, close to the body temperature, and the amount of hydrophilic moieties in the polymeric network allows to collect shrinking/swelling transition temperatures higher than the LCST of NIPAAm homopolymers. In order to test the preformed materials as drug carriers, diclofenac diethylammonium salt (DDA) was chosen and drug entrapment percent was determined. Drug release profiles, in media at different temperature and pH, depend on hydrogels crosslinking degree and drug–bead interactions. By using semi‐empirical equations, the release mechanism was extensively studied and the diffusional contribute was evaluated. Copyright © 2010 John Wiley & Sons, Ltd.