The influence of N‐vinyl pyrrolidone on polymerization kinetics and thermo‐mechanical properties of crosslinked acrylate polymers

Polymerization of multifunctional acrylate monomers generates crosslinked polymers that are noted for their mechanical strength, thermal stability, and chemical resistance. A common reactive diluent to photopolymerizable formulations is N‐vinyl pyrrolidone (NVP), which is known to reduce the inhibition of free radical photopolymerization by atmospheric oxygen. In this work, the copolymerization behavior of NVP was examined in acrylate monomers with two to five functional groups. At concentrations as low as 2 wt %, NVP increases the polymerization rate in copolymerization with multifunctional acrylate monomer. The relative rate enhancement associated with adding NVP increases dramatically as the number of acrylate double bonds changes from two to five. The influence of NVP on polymerization kinetics is related to synergistic cross‐propagation between NVP and acrylate monomer, which becomes increasingly favorable with diffusion limitations. This synergy extends bimolecular termination into higher double bond conversion through reaction diffusion controlled termination. Copolymerizing concentrations of 5–30 DB% NVP with diacrylate or pentaacrylate monomer also increases Young's modulus and the glass transition temperature (T_g) in comparison to neat acrylate polymers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4062–4073, 2007     

Preparation of polystyrene/poly (4-butyltriphenylamine) composite particles by chemical oxidative seeded dispersion polymerization

Polystyrene (PSt)/poly (4-butyltriphenylamine; PBTPA) composite particles was prepared by a chemical oxidative seeded dispersion polymerization of (4-butyltriphenylamine) with PSt seed particles that were prepared by nonaqueous dispersion polymerization of styrene. Monodisperse composite particles were obtained when the ratio of monomer to seed, the rate of monomer feed, and poly(N-vinyl pyrrolidone; PVP) concentration was appropriately selected. The introduction of PBTPA was confirmed by the presence of the characteristic absorption band attributed to PBTPA from a Fourier transform infrared spectra. The solvent extraction with ethyl acetate revealed that composite particles consisted of PSt core and PBTPA shell. Then two-dimensional arrays of composite particles were also fabricated.     

Polymerization Kinetics of Water-Soluble N-Vinyl Monomers in Aqueous and Organic Solution

Summary: Free-radical batch polymerization (FRP) of N-vinyl pyrrolidone (NVP) and N-vinyl formamide (NVF) monomers in aqueous solution as well as NVP polymerization in organic (n-butanol) solution has been studied. The differences found in rate of monomer conversion with monomer and solvent choice correlates well with the differences in values of the propagation rate coefficients (k_p) and their variation with monomer concentration measured in independent pulsed-laser polymerization studies, a result demonstrating that a generalized understanding of water-soluble vinyl monomers can be obtained once their k_p differences have been accounted for. A reasonable representation of polymer molecular mass averages and the complete molecular mass distributions for the three systems was obtained by assuming that the rate coefficient for transfer to monomer, polymer, and organic solvent also vary as a function of monomer concentration.     

REVERSE ATOM TRANSFER RADICAL POLYMERIZATION OF STYRENE WITH COPPER-BASED CATALYST

 "Living"/controlled radical polymerization of styrene was carried out with diethyl 2,3-dicyano-2,3-diphenylsuccinate (DCDPS)/CuCl₂/bipyridine (bipy) initiation system at 120℃. The molecular weights of resultant PSt increased with the monomer conversion and the polydispersities were in the range of 1.37 ～ 1.52. A linear ln([M]o/[M])versus time plot was also obtained indicating the constant concentration of growing radicals during the polymerization with this initiation system. End group analysis by ¹H-NMR spectroscopic studies showed that the end groups of the polymer obtained is cω-functionalized by a chlorine group from the catalyst and a-functionalized by a (carbethoxy-cyano-phenyl)methyl group from the fragments of the initiator. Having C1 atom at the chain end, the PSt obtained can be used as a macroinitiator to promote a chain-extension reaction with fresh St and block copolymerization reaction with a second monomer, such as methyl methacrylate, in the presence of CuC1/bipy catalyst via a conventional ATRP process.     

Phosphate‐Loaded Hydrogel Nanoparticles for Sepsis Prevention Prepared via Inverse Miniemulsion Polymerization

Local depletion of intestinal phosphate triggers changes in bacterial phenotypes that adversely affect the health of the host. This article describes a process for encapsulating phosphates in crosslinked poly(ethylene glycol) diacrylate (PEGDA) nanoparticles using inverse miniemulsion polymerization as a drug delivery approach for sustained release of phosphates to the intestinal epithelium. The effects of crosslinker, PEGDA co‐monomer, N‐vinyl pyrrolidone, (NVP) and surfactant concentrations on the nanoparticle size distribution, swelling ratio and monomer conversion are investigated. Increased surfactant and PEGDA concentrations result in smaller particle size and swelling ratio. A copolymerization model of crosslinking is used to predict conversion and gelation dynamics as a function of polymerization conditions. The model assumes that bulk polymerization can be used to approximate inverse miniemulsion polymerization with an aqueous‐phase initiator. The initiator efficiency is used as an adjustable parameter to simulate the conversion dynamics, thus accounting for radical confinement effects and interaction with emulsifier molecules.     

Atom Transfer Radical Polymerization of Styrene with 5‐Chloromethyl‐2‐hydroxy‐benzaldehyde as Initiator

Abstract

Atom transfer radical polymerization (ATRP) of styrene (St) proceeded using 5‐chloromethyl‐2‐hydroxy‐benzaldehyde as initiator, CuCl as catalyst, and N,N,N′,N′,N′‐pentamethyldiethyltriamine (PMDETA) as ligand. The results show that the polymerization is a first order reaction with respect to monomer concentration. The polymerization displayed living character as evidenced by a liner increase of monomer weight with conversation and a relatively narrow distribution (M _n/M _w ranges from 1.25 to 1.50). The end structure of PSt was analyzed by ¹H‐NMR, and PSt initiated MMA to form block copolymer (PSt‐b‐PMMA), which also proved that the polymerization could be controlled. The effects of reaction temperature and monomer to initiator mole ratio on the polymerization displayed living character were discussed.     

The hydrolysis of N-vinylpyrrolidone in the presence of polyacrylic acid and potassium persulphate

The vinyl monomer N-vinyl pyrrolidone (NVP) hydrolyses in aqueous solution in the presence of both polyacrylic acid and potassium persulphate. The rates of these hydrolyses have been measured; in the former case, the rate is the same as in the presence of acetic acid. In addition polyacrylic acid is cross-linked by potassium persulphate although the cross-linked polymer is still capable of interacting with complexing molecules such as polyvinylpyrrolidone. The mechanism of the NVP hydrolysis is shown to agree with that proposed by other workers although the dimeric product 1,1′bis(1′-pyrrolidonyl) ethane was not found.     

Living free-radical copolymerization of allyl glycidyl ether with methyl acrylate

An investigation of the copolymerization of allyl glycidyl ether (AGE) with methyl acrylate (MA) was performed in the presence of benzyl imidazole-1-carbodithioate (BICDT) on the thermal initiation condition. Results showed that the process has good characteristics of living free radical polymerization, i.e. the molecular weight of the obtained polymer increases linearly with monomer conversion, molecular weight distribution is very narrow, and a linear relationship between ln([M]₀/[M]) and polymerization time is found. The copolymer structure containing epoxy groups was demonstrated from the ¹H nuclear magnetic resonance (1H NMR) spectrum. It was found that the content of AGE in the copolymer increases with the increase in monomer conversion and molar faction of the AGE in the monomer feed. However, the polymerization could slow down when the fraction of AGE increases in the monomer feed. Taking advantage of living polymerization character, functional block copolymers PSt-b-P (MA-co-AGE) were prepared in the presence of PSt RAFT agent. __________ Translated from Journal of Anhui University of Science and Technology, 2006, 26(3): 56–61 [译自: 安徽理工大学学报]     

Determination of N-vinyl-2-pyrrolidone and N-methyl-2-pyrrolidone in drugs using polypyrrole-based headspace solid-phase microextraction and gas chromatography-nitrogen-phosphorous detection

A headspace solid-phase microextraction and gas chromatography-nitrogen-phosphorous detection (HS-SPME-GC-NPD) method using polypyrrole (PPy) fibers has been introduced to determine two derivatives of pyrrolidone; N-vinyl-2-pyrrolidone (NVP) and N-methyl-2-pyrrolidone (NMP). Two types of PPy fibers, prepared using organic and aqueous media, were compared in terms of extraction efficiency and thermal stability. It was found that PPy film prepared using organic medium (i.e. acetonitrile) had higher extraction efficiency and more thermal stability compared to the film prepared in aqueous medium. To enhance the sensitivity of HS-SPME, the effects of pH, ionic strength, extraction time, extraction temperature and the headspace volume on the extraction efficiency were optimized. Using the results of this research, high sensitivity and selectivity had been achieved due to the combination of the high extraction efficiency of PPy film prepared in organic medium and the high sensitivity and selectivity of nitrogen-phosphorous detection. Linear range of the analytes was found to be between 1.0 and 1000 μg L⁻¹ with regression coefficients (R²) of 0.998 and 0.997 for NVP and NMP, consequently. Limits of detection (LODs) were 0.074 and 0.081 μg L⁻¹ for NVP and NMP, respectively. Relative standard deviation (R.S.D.) for five replications of analyses was found to be less than 6.0%. In real samples the mean recoveries were 94.81% and 94.15% for NVP and NMP, respectively. The results demonstrated the suitability of the HS-SPME technique for analyzing NVP and NMP in two different pharmaceutical matrices. In addition, the method was used for simultaneous detection of NVP, 2-pyrrolidone (2-Pyr), γ-butyrolactone (GBL) and ethanolamine (EA) compounds.     

Free-radical crosslinking copolymerization of acrylamide and N,N-methylenebis acrylamide by used Ce(IV)/polyethylene glycol and Ce(IV)/diethylmalonate redox initiator systems

Acrylamide and N,N^′-methylenebis (acrylamide) (AAm-Bis) copolymerization has been investigated in water at a total monomer concentration of the 0.5 M. Conversion of monomer was measured as a function of the reaction time up to the onset of macrogelation. Experimental results indicate that the critical conversion at the gel point shows a minimum at 6 mol.% Bis when the monomer concentration was kept constant at 0.5 M and it was found that polymer formed with different Bis% are not dissolved in water, acetic acid, toluene or chloroform.     

Side Reactions in Aqueous Phase Polymerization of N‐Vinyl‐Pyrrolidone as Possible Source for Fouling

An improved kinetic model for the radical polymerization of N‐vinyl‐pyrrolidone (NVP) in aqueous medium is developed. Quantum chemical simulations reveal that the transfer to polymer is of minor importance whereas the transfer to monomer by hydrogen abstraction in 3‐position of the pyrrolidone ring leads to a radical with a double bond which initiates a new chain bearing a terminal double bond (TDB). The resulting dead chains with one, two, or more TDB are the main source for a strong increase of molar mass in batch reactors at high conversion due to long chain branching and crosslinking. This can be a source for gel formation and fouling in continuous reactors.     

Alternating copolymerization of ethylene with maleic anhydride

The copolymerization of ethylene with maleic anhydride was carried out with γ-radiation and a radical initiator, i.e., 2,2′-azobisisobutyronitrile and diisopropyl peroxydicarbonate under pressure at various reaction conditions. The homopolymerization of neither monomer was observed in this system. In the γ-ray-initiated copolymerization the G value (polymerized monomer molecules per 100 e.v.) was shown to be between 10³ and 10⁴. It was found that the dose rate exponent of the rate is approximately unity, and the rate is proportional to the amount of ethylene monomer. Apparent activation energies of 1.8 and 27.5 kcal./mole were obtained for γ-ray-initiated and AIBN-initiated copolymerization, respectively. Since the composition of copolymer is independent of monomer molar ratio and the molar ratio of ethylene to maleic anhydride in the polymer is approximately unity, the monomer reactivity ratios were obtained as r_E ? 0 and r_M ? 0 for γ-ray-initiated polymerization at 40°C. Alternating copolymerization was, therefore, concluded to occur. Infrared analysis of the copolymer is almost consistent with this. The copolymer in the solid state is amorphous. It is soluble in water, cyclohexane, and dimethylformamide and insoluble in lower alcohols, ether, and aromatic hydrocarbons. The aqueous solution of polymer gave a strong acid.     

Synthesis of poly(p-phenylene)s having alternating sugar and alkyl substituents by Suzuki coupling polymerization and evaluation of their main-chain conformations

This paper reports synthesis of poly(p-phenylene)s (PPPs) having alternating sugar and alkyl substituents by Suzuki coupling polymerization of a 1,4-dibromobenzene monomer having peracetylated glucose residues with a 1,4-benzene bis(boronic acid) having alkyl chains using Pd(PPh₃)₄ in a mixed solvent of THF and NaHCO₃ aq. at reflux temperature. The polymerization proceeded with the progress of frequent deacetylation, and thus, the crude product was acetylated, followed by the isolation procedures, giving the PPP having alternating peracetylated glucose and alkyl substituents. The structure of the isolated product was confirmed by the ¹H and ¹³C NMR measurements to be the desired PPP derivative. The M_n values were estimated by GPC analysis with DMF as the eluent to be 5400-12,700. The deacetylation of the polymer completely took place using sodium methoxide in methanol/THF. The conformation of the main-chain was evaluated by the CD spectrum in comparison with that of PPP only with the glucose substituents, indicating that the present PPP derivative had the flexible nature of the main-chain by introduction of the alkyl-substituted units between glucose-substituted units. The Suzuki coupling of a 1,4-dibromobenzne monomer having disaccharide substituents with the benzene bis(boronic acid) monomer was also performed under the similar conditions. The product was precipitated from the reaction mixture, which was simply isolated by filtration. The isolated polymer was purified further by reprecipitation into diethyl ether and its structure was a PPP having free disaccharide or monosaccharide residues. This indicated occurrence of complete deacetylation as well as partial degradation of the glycosidic linkages in the disaccharides during the polymerization. The main-chain of the obtained polymer had also the flexible nature. The fluorescence spectra of the obtained PPP derivatives in this study were also measured.     

自组装效应对AM/NVP共聚的影响

研究了丙烯酰胺(AM)与N-乙烯基吡咯烷酮(NVP)在水/四氢呋喃(THF)溶液中的自由基共聚。发现,当水溶液中含THF,AM的聚合速率下降,NVP的聚合速率提高。黏度测定发现,在THF质量分数为28%,AM/NVP物质的量比为5∶1的水/THF体系中,共聚物的黏度达到最大值,与该体系中NVP的聚合速率达到最大值相一致。溶液中加入氯化钠,AM的聚合速率提高,但随THF的含量增加而降低。加入尿素,在含水率达到较大值,NVP聚合速率最大。用透射电子显微镜(TEM)和核磁共振谱(NMR)对聚合物结构进行了表征。在水/THF中,共聚物链自组装形成"核―壳"状微聚体。NVP上的五元环聚集成"核"状,共聚物链的酰胺基团尽量舒展,形成"壳"状。溶剂的组成变化伴随"核―壳"状微聚体半径的改变,影响AM和NVP的聚合速率。     

Room temperature synthesis and mechanical properties of two kinds of elastomeric interpenetrating polymer networks based on castor oil

Two kinds of interpenetrating polymer networks (IPNs) composed of two-component polyurethane (PU) and vinyl or methacrylic polymer (PV), namely, (polyether-castor oil)PU/PV IPN(I) and (polybutadiene-castor oil)PU/PV IPN(II), were synthesized at room temperature using benzoyl peroxide and N,N-dimethylaniline as redox initiator and dibutyltin dilaurate as catalyst. The former IPN was prepared by polymerization of castor oil, NCO-terminated polyether and vinyl or methacrylic monomer together and the latter IPN was obtained by polymerization of castor oil, NCO-terminated polybutadiene, NCO-terminated castor oil and vinyl or methacrylic monomer together. Various synthesis conditions affecting mechanical properties of the two kinds of IPNs were studied. Acrylonitrile (AN) is a good monomer for synthesizing IPN(I), but is a poor monomer for preparing IPN(II). At optimum conditions for the synthesis, both the (polyether-castor oil)PU/PAN IPNs and the (polybutadiene-castor oil)PU/polystyrene (PSt) IPNs possess permanent set about 10%, tensile strength over 13 and 11 MPa and ultimate elongation over 240% and 270%, respectively, thus behaving as elastomers. TEM micrograph of a (polybutadiene-castor oil)PU/PSt IPN showed a microphase separation in the IPN.     

Ring-opening polymerization of ε-caprolactone initiated by diphenylzinc

In the present work the polymerization of ε-caprolactone (ε-CL) using Ph₂Zn as initiator is reported. The effects of reaction temperature, molar ratio of monomer/initiator and reaction time on the yield and the molecular weight are investigated. The temperature is varied between 20 and 120 °C and the molar ratio of monomer to initiator between 200 and 800 mol/mol. The results indicate that the Ph₂Zn induces the polymerization of ε-CL to high conversion and produces polymer with high molecular weight at temperatures around 40-60 °C.     

Novel method for the preparation of core-shell nanoparticles with movable Ag core and polystyrene loop shell

Core/shell nanoparticles with movable silver (Ag) core and polystyrene (PSt) shell (Ag@PSt nanoparticle) were successfully synthesized at room temperature and under ambient pressure via two steps: γ-irradiation and interfacial-initiated polymerization. Firstly, mono-dispersed Ag nanoparticles with diameters 20 nm were synthesized in inversed microemulsion by reducing silver nitrate under γ-irradiation. Then, Ag nanoparticles were coated with PSt via interfacial-initiated polymerization with cumene hydroperoxide/ferrous sulfate/disodium ethylenediaminetetraacetate/sodium formaldehyde sulfoxylate (CHPO-Fe²⁺-EDTA-SFS) as the redox initiation pair. The resulted Ag@PSt nanoparticles were identified by transmission electron microscopy (TEM), dynamic light scattering (DLS), X-ray powder diffraction (XRD) and X-ray photoelectron spectroscopy (XPS).     

Stabilizer-free precipitation copolymerization of renewable bio-based α-methylene-γ-butyrolactone and styrene

Stabilizer-free precipitation copolymerization of α-methylene-γ-butyrolactone (MBL) and styrene (St) was carried out in isoamyl acetate with BPO as initiator at 80°C. The influence of monomer feed ratio, initiator concentration and reaction time on the size and morphology of the obtained polymer particle was investigated in details. It was found that the monomer feed ratio play an important role on the particle formation process. When the monomer feed ratio of MBL to St was 1:2, narrow size distributed spherical polymer particles were formed with number average diameters in the range of 785–2620 nm. The formation process of polymer particle was studied to get a deep insight into the polymerization process of this reaction system. It was found that the formation mechanism of the poly(MBL-co-St) particles was similar to that of conventional precipitation polymerization. After a short nucleation stage (10 min), the amount of polymer particles remained constant and the particle growth mainly came from the capturing of newly formed polymer chains. The chemical composition and thermal property of the poly(MBL-co-St) were fully characterized by FTIR, ¹H-NMR spectra, and DSC.     

Copolymerization behavior of direct polycondensation of AB2 and AB monomers that forms hyperbranched aromatic polyamide copolymers

The copolymerization behavior of the one‐step direct polycondensation of 3,5‐bis‐(4‐aminophenoxy)benzoic acid (AB₂ monomer) and 3‐(4‐aminophenoxy)benzoic acid (AB monomer) was investigated by IR and ¹³C NMR measurements. IR measurements revealed that the content of the AB₂ units in the polymer was higher in the early stages of polymerization. ¹³C NMR spectra of the polymers indicated that the number of dendritic units increased slowly with increasing reaction time. The stepwise copolymerization of the AB₂ and AB monomers was also carried out, and the structure was analyzed by ¹³C NMR measurements. Copolymer synthesized stepwise by adding AB₂ monomer first (polymer II ) had more dendritic units and less terminal units as compared with the one‐step copolymer (polymer I ). Copolymer synthesized stepwise by adding AB monomer first gave a resulting copolymer (polymer III ) composed of long AB chains. The solubility of the stepwise copolymers was low, and the inherent viscosity was high in comparison with the one‐step copolymer as a result of the difference in architecture of the copolymers. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3304–3310, 2001     

Experimental studies on the ring opening polymerization of p-dioxanone using an Al(OPr)3-monosaccharide initiator system

The ring opening polymerization (ROP) of p-dioxanone using a protected monosaccharide (1,2;3,4-di-O-isopropylidene-α-d-galactopyranose)/Al(OⁱPr)₃ initiator system to yield polydioxanone with a protected monosaccharide end-group is described. The products were synthesized at 60-100 °C and characterized by ¹H and ¹³C NMR, and MALDI-TOF mass spectrometry. Besides the desired polydioxanone functionalised with a monosaccharide end-group, also polydioxanone with an OⁱPr end-group was formed (20-30%). Systematic studies showed that the polymer yield is a function of the reaction temperature and the reaction time, with higher temperatures (100 °C) leading to lower yields. The average chain length of the polymers is between 7 and 58 repeating units and may be tuned by the monomer to monosaccharide ratio (at constant Al(OⁱPr)₃ intake). A statistical model has been developed that successfully describes the experimentally observed relation between the average chain length of the functionalized polymer and reaction parameters.