Radical-induced ionic polymerization in the presence of maleic anhydride. III. Polymerization of isobutyl vinyl ether initiated by trapped radicals in poly(maleic anhydride)

In a previous paper¹ it was mentioned that trapped radicals in poly(maleic anhydride) (Poly-MAH) have the ability to initiate cationic polymerization. In this paper, the cationic polymerization of isobutyl vinyl ether (IBVE) is described using Poly-MAH as the initiator. These radicals show different behavior during polymerization depending upon their structure. In particular, large conjugated radicals initiate ionic polymerizations.     

Catalytic polymerization of maleic anhydride

This study examined the polymerizations of maleic anhydride in solution and in the bulk phase catalyzed by nanocrystalline titania or sodium acetate. Through IR and ¹H‐NMR, the monomer and polymer were characterized, and the structure of the polymer was confirmed. Moreover, the polymer molecular weight was measured to be 400–800 in solution and 2000–3000 in the bulk phase. The mechanism of the catalytic polymerization was also investigated. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2868–2874, 2003     

Surface photografting polymerization of vinyl acetate,maleic anhydride,and their charge‐transfer complex. IV. Maleic anhydride

In general, it has been accepted that maleic anhydride (MAH) cannot be homopolymerized under normal conditions. However, MAH can be grafted onto substrates under UV irradiation rather easily. In this study, the photografting polymerization of MAH was examined with low‐density polyethylene (LDPE) film as a substrate. The initiating performances of different photoinitiators, including benzophenone (BP), Irgacure 651, and benzoyl peroxide (BPO), were examined. The effects of some principal factors, such as the temperature, solvent, and UV intensity, on the grafting polymerization of MAH were also investigated. The results show that MAH can be smoothly grafted onto LDPE film by UV radiation. Enhancing the intensity of UV radiation and elevating the irradiation temperature facilitate the grafting polymerization of MAH. Among BP, Irgacure 651, and BPO, Irgacure 651 can initiate the polymerization of more MAH, but BP is more effective for the initiation of surface grafting polymerization. Solvents of MAH also have a great influence on the grafting polymerization; some of them even seem to take part in the reaction. The occurrence of photografting polymerization was verified with Fourier transform infrared and electron spectroscopy for chemical analysis spectra. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 2318–2325, 2003     

Step-growth polymerization of maleic anhydride and 1,2-propylene glycol

The NMR (nuclear magnetic resonance) and GPC (gel permeation chromatography) studies of the polymerization of maleic anhydride and 1,2-propylen glycol are reported. Assignment of individual groups was made and their concentration dependence on reaction time was established. The first step of the reaction is the formation of monoesters, which, immediately after the temperature increased, reacted to diesters. The reactivity ratio between the primary and the secondary hydroxyl group of 1,2-propylene glycol was 2.6:1. The concentration of water formed was followed as a function of reaction time by the Karl–Fischer method.     

球形PE粒子的合成与马来酸酐固相接枝反应

采用负载型高效球形催化剂催化乙烯淤浆聚合得到了高孔隙率的球形聚乙烯(PE)颗粒。用光学显微镜、扫描电子显微镜等方法对所得PE的形貌、结构、粒径分布等进行了表征。实验表明,PE颗粒的粒径分布窄、形貌规整、孔隙率高。以球形PE为基体,研究了马来酸酐在PE颗粒中的接枝反应,考察了反应条件对接枝率和酸值的影响。     

Surface photografting polymerization of vinyl acetate (VAc), maleic anhydride (MAH), and their charge transfer complex (CTC). III. VAc(3)

Vinyl acetate (VAc) was grafted onto low‐density polyethylene (LDPE) substrates by UV irradiation with benzophenone (BP) as the photoinitiator. BP preabsorbed film samples and BP precoated film samples were prepared in advance and applied as the substrates onto which VAc was photografted, together with the method in which BP was dissolved in VAc directly. In addition, the efficiency of the polymerizations applying the preirradiation technology was examined. The conversion percent, grafting percent, and grafting efficiency were determined by a gravimetric method. The contact angles of the grafted films against water were also measured. The results show that BP preabsorbing and precoating were favorable to grafting polymerization, especially the BP precoating method, which was due to its simple operation and the ease of controlling the amount of BP. The diffusion of BP and VAc through the substrates proved to be an important factor for grafting polymerization. Through UV irradiation, dormant groups can be introduced onto LDPE film, which may be activated again by UV irradiation or by heating, leading to the formation of free radicals. Grafting polymerization can be initiated during the activation process in the presence of monomer. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1426–1433, 2001     

Surface photografting polymerization of vinyl acetate,maleic anhydride,and their charge‐transfer complex. VIII. Charge‐transfer complex (4)

In view of the complexity of surface photografting polymerization of vinyl acetate/maleic anhydride (VAC/MAH) binary monomer systems, a novel method was adopted in the present article to obtain insight into the relevant grafting copolymerization mechanism. This method includes two steps: semibenzopinacol dormant groups were first introduced onto LDPE film by UV‐irradiation and then thermally reactivated to produce LDPE macromolecular free radicals, which initiated the grafting copolymerization of VAC and MAH. It was demonstrated that, in the first step, the solvent used to introduce benzophenone (BP) to LDPE film largely affected the subsequent grafting copolymerization, which was closely related to the affinity of the solvent toward the substrate. The monomer feed composition had considerable influence on both the grafting and nongrafting copolymerization; however, the maximum copolymerization rates did not appear in the polymerization system with [VAC]/[MAH] being 1 : 1, but, in the system with a bit more VAC than MAH, as the total monomer concentration was raised, the maximum copolymerization rates tended to appear in the system with [VAC] equal to [MAH]. The relationship between the total copolymerization rate (RP) and monomer concentration was determined to be LnRP ∝ [VAC + MAH]^1.83. All of these results indicated that both charge transfer (CT) complex formed by VAC and MAH and free monomers took part in grafting copolymerization. This feature differentiated the surface grafting copolymerization of VAC/MAH from the well‐studied thermally induced alternating copolymerization of VAC/MAH. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Surface photografting polymerization of vinyl acetate (VAc), maleic anhydride,and their charge transfer complex. I. VAc(1)

Photografting of vinyl acetate (VAc) onto LDPE films was carried out with lamination technology and simultaneous method, using BP as photoinitiator. Some principal factors affecting the grafting polymerization were investigated in detail. The experimental results showed that oxygen dissolved in monomer solution had great influence on grafting polymerization. Compared with other routine monomers (St, MMA, AN, AA, and AAm), VAc exhibited higher photografting reactivity. It was observed that the reaction temperature affected the graft polymerization markedly. To film samples with a given diameter, there exists optimum thickness of monomer solution. Adding a pertinent amount of water to the photografting polymerization system could accelerate the polymerization. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1513–1521, 2000     

Radical-induced ionic polymerization in the presence of maleic anhydride. II. Cationic polymerization of 1,2-butylene oxide by benzoyl peroxide and α,α′-azobisisobutyronitrile in the presence of maleic anhydride

The cationic polymerization of 1,2-butylene oxide initiated by radical catalysts has been investigated in detail in the presence of maleic anhydride. The active species of this ionic polymerization was thought to be a conjugated radical of poly(maleic anhydride).     

Surface photografting polymerization of vinyl acetate,maleic anhydride,and their charge‐transfer complex. VI. Charge‐transfer complex (2)

The photografting copolymerization of a low‐density polyethylene/vinyl acetate (VAC)–maleic anhydride (MAH) binary monomer system was studied from the perspective of dynamics. The total conversion percentage (CP) and grafting conversion percentage (CG) were measured by gravimetry. On the basis of plots of CP and CG as functions of the polymerization time, the total polymerization rate (RP) and grafting polymerization rate (RG) were calculated. In addition, the apparent activation energy (E_a) and the reaction orders of the photografting polymerization under different reaction conditions, such as the total monomer concentration and the concentration of benzophenone (BP), were determined also. The results showed that, in comparison with the photografting polymerization of the two single monomers (VAC and MAH), RP and RG noticeably increased for the VAC–MAH binary monomer system. When the total monomer concentration was kept at 4M, the apparent E_a's of the three photografting polymerization systems were as follows: for VAC ([MAH]/[VAC] = 0/4), E_a's for the total polymerization and grafting polymerization were 41.00 and 43.90 kJ/mol, respectively; for MAH ([MAH]/[VAC] = 4/0, E_a's were 39.65 and 43.23 kJ/mol, respectively; and for the VAC–MAH binary monomer system, E_a's were 34.35 and 40.32 kJ/mol, respectively. These results suggested that the polymerization of the binary system occurred more readily than the other two. The reaction orders of RP with respect to the total monomer concentration of the monomers and the concentration of BP were 1.34 and 0.81, respectively. According to these investigations, it could be inferred that in the binary monomer system, both the free monomers and charge‐transfer complex took part in the polymerization; to the termination of the propagating chains, two possible pathways, unimolecular termination and bimolecular termination, coexisted in this binary monomer system. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 910–915, 2005     

Polystyrene/calcium carbonate nanocomposites prepared by in situ polymerization in the presence of maleic anhydride

Polystyrene (PS)/calcium carbonate (CaCO₃) nanocomposites were prepared by in situ polymerization in the presence of maleic anhydride (MA). The composites were characterized by Fourier transform infrared spectra, gel permeation chromatography, differential scanning calorimetry, controlled stress rheometer, scanning electron microscope (SEM), small‐angle X‐ray scattering (SAXS), and mechanical test. Results show that the copolymer of styrene (St) and MA formed during the polymerization acts as a compatibilizer between PS and nanometer calcium carbonate (nano‐CaCO₃) particles, resulting in an increase in the glass transition temperature of the composite. The complex modulus and the impact strength of the PS/nano‐CaCO₃ composite show an increase with the addition of MA on account of the enhanced interfacial adhesion and the increased molecular weight. SEM and SAXS analyses indicate that a finer dispersion of nanoparticles and an increased homogeneity of the PS/nano‐CaCO₃ composites are obtained with application of a small amount of MA. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci., 2013     

Vinyl polymerization by metal complexes. XVIII. Kinetics of the polymerization of acrylonitrile initiated by imidazole-copper-(II) complexes

A study on the kinetics and mechanism of the polymerization of acrylonitrile initiated by imidazole and 2-substituted imidazole-copper-(II) complexes was made in dimethyl sulfoxide solution at 40–70°C. The rate of polymerization, Rp, could be expressed as follows: The overall activation energies of these polymerization processes are in a range from 14.2 to 69.1 KJ mole^-1. From the data of electronic spectra and electron paramagnetic resonance, it was confirmed that the polymerization in question could be initiated by free radicals which were formed by the reduction of copper-(II) complex to copper-(I) complex, and the latter formed a new complex with polyacrylonitrile resulted.     

马来酸酐改性聚醋酸乙烯酯乳液的研究

以马来酸酐(MA)作为醋酸乙烯酯(VAc)的改性共聚单体,采用半连续种子乳液聚合法合成了改性聚醋酸乙烯酯(PVAc)乳液,并考察了MA含量对VAc/MA共聚乳液性能的影响。结果表明:当w(MA)=0.3%～0.4%(相对于VAc质量而言)时,改性乳液的聚合稳定性、储存稳定性和稀释稳定性良好;随着MA含量的不断增加,种子反应阶段回流时间延长,共聚速率变慢,最终合成的改性乳液黏度逐渐增大;当w(MA)=0.4%时,改性乳液的综合性能相对最好,其粘接强度(9.70 MPa)比VAc均聚乳液增加了70%。     

Investigation of the surface area and polarity of porous copolymers of maleic anhydride and divinylbezene

Porous copolymers of maleic anhydride (MA) and divinylbezene (DVB) in the form of regular microspheres were prepared by suspension polymerization. During copolymerization the mixture of 1,4-dioxane and n-dodecane as a pore-forming diluent was used. It was found that specific surface area of the obtained beads is strongly dependent on the diluent system and polymerization medium and achieves a value from 4 to 535 m²/g. To determine the influence of polymerization medium on the selectivity and polarity of the copolymers, inverse gas chromatography (IGC) was applied. To determine these parameters, three procedures were applied: overall polarity, the selectivity triangle, and the ΔC method. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Melt functionalization of EVA copolymers with maleic anhydride

Ethylene vinyl acetate (EVA) copolymers with different amounts of vinyl acetate were melt‐functionalized with maleic anhydride. The effect of benzoyl peroxide, t‐butyl perbenzoate, and dicumyl peroxide (DCP) as free‐radical initiators on the functionalization performance was studied. The crosslinking reactions occur to a larger extent than in polyethylene, indicating that the vinyl acetate groups favor the formation of free radicals. From all the experiments performed in this study, the recommended initiation system to achieve the best values of the functionalization degree and the lower gel content involves the use of DCP in a concentration of about 0.3 wt % and a maleic anhydride concentration around 5.0 wt %. From FTIR and TGA analyses, it is suggested that the hydrogen abstraction in the EVA copolymers occurs both in the methyl group of the acetate moiety and in the tertiary C—H. The free radicals generated in the tertiary C—H react with maleic anhydride in a higher proportion. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1799–1806, 1999     

Studies of reactions with polymers. II. The reaction of maleic anhydride with acrylonitrile onto PVA and the properties of the resultant

Graft terpolymers were prepared by graft polymerization of a mixture of acrylonitrile (AN) and maleic anhydride (MA) onto PVA in DMSO solution using KPS as an initiator. Structure and solubility of graft terpolymers varied with the concentrations of KPS and MA. Both lower and upper critical values of KPS concentration varied with MA concentration, and the resulting reaction could be divided into three regions—crosslinked, hydrophobic, and hydrophilic regions. Structures of graft terpolymers were considered to be composed of homopolymer side chain grafted onto PVA while gelation occurred from the surplus radicals in PVA backbone to carry on the coupling reaction. The mechanical properties and viscosities increased with the increase of the wt % of AN in graft terpolymers; however, to increase AN content in PVA by increasing KPS concentration would bring about the oxidation scission and do damage to mechanical properties. Thus it becomes obvious that KPS can only be used at a suitable amount.     

Synthesis and polymerization of lignin macromonomers. II. Effects of lignin fragments on methyl methacrylate radical polymerization

In the course of a study on the synthesis and polymerization of lignin macromonomers, the effect of lignin fragments and acetylated lignin ones on the radical polymerization of methyl methacrylate has been investigated. Kinetics show that lignin moieties act first as inhibitors of the MMA polymerization. The inhibition process has been attributed to the phenolic groups, which primarily react through hydrogen transfer with free radicals issued from benzoyl peroxide dissociation, thus leading to a series of lignin free radicals inactive towards ethylenic groups. The derivatization of lignin hydroxyl groups into ester groups totally suppresses the inhibition process. Besides, it was also shown that both lignin and acetylated lignin units act as chain limiting agents towards MMA polymerization. As indicated both by the chemical composition of the polymers produced and the kinetic data, the latter process might involve the formation of a new type of lignin free radicals, able to initiate MMA polymerization. A reaction scheme is proposed.     

Amphiphilic polyperoxide based on an alternating copolymer of 1-octene and maleic anhydride for interface modification

A new water-soluble amphiphilic polyperoxide (APP) based on alternating copolymer poly(1-octene-co-maleic anhydride) and tert-butylperoxymethanol has been synthesized. Kinetic parameters of APP peroxide groups decomposition are determined to show APP capability to initiate radical polymerization. A “grafting to” approach was used for the modification of poly(methyl methacrylate) (PMMA) latex with APP macromolecules. The covalent attachment of the APP to the surface of PMMA particles is found to be beneficial in enhancing latex aggregative stability.At the same time, the emulsifying capability of APP has been observed during the emulsion polymerization of styrene. Furthermore, because they are able to decompose at elevated temperatures, APP peroxide groups generate free radicals initiating the polymerization.To this end, it can be concluded that the new amphiphilic polyperoxide possesses properties of an inisurf (initiator–surfactant), opening new experimental pathways for interface modification processes.     

Bulk grafting of poly(styrene‐alt‐maleic anhydride) onto preirradiated polyolefin membranes in supercritical carbon dioxide

To take advantage of the property of supercritical carbon dioxide as both a solvent and swelling agent, the bulk grafting of poly(styrene‐alt‐maleic anhydride) [P(MAH‐alt‐St)] onto preirradiated polyolefin membranes was performed by a combination of γ‐ray‐preirradiation‐induced graft copolymerization and supercritical fluid‐swollen polymerization. The trapped radicals on the polyolefin backbones were uniformly distributed by γ‐ray irradiation under a nitrogen atmosphere. Subsequently, these polymeric trapped radicals initiated the alternating copolymerization of styrene (St) and maleic anhydride (MAH) infused into the swollen polymer matrix with the aid of supercritical CO₂. It was important that the graft copolymers were relatively pure without any contaminants, including homopolymers, monomers, and initiators. The experimental results show that the degree of grafting could be easily controlled. In addition, St/MAH could synergistically promote the bulk grafting process and strongly effect on the alternating trend; this was confirmed by element analysis and differential scanning calorimetry. Soxhlet extraction, X‐ray diffraction, and Fourier transform infrared spectroscopy indicated that the P(MAH‐alt‐St) was covalently bonded to the polymeric backbones. Scanning electron microscopy showed that the alternating graft chains were uniformly dispersed throughout the 5‐mm thickness of the polymer membranes on the nanometer scale. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Surface photografting polymerization of vinyl acetate,maleic anhydride,and their charge‐transfer complex. V. Charge‐transfer complex (1)

In previous studies, the photografting polymerization of vinyl acetate (VAC) and maleic anhydride (MAH) was investigated systematically. After that, to increase the grafting rate and efficiency and make the project more practicable, a VAC–MAH binary monomer system was employed for simultaneous photografting onto the surface of low‐density polyethylene film. The effects of several crucial factors, including the composition and total concentration of the monomer solution and different types of photoinitiators and solvents, on the grafting polymerization were investigated in detail. The conversion percentage (CP), grafting efficiency (GE), and grafting percentage were measured by gravimetry. The results showed that the monomer composition played a big part in this binary system; appropriately increasing the content of MAH in the monomer feed was suited for grafting polymerization. The growth of the total monomer concentration, however, made the copolymerization faster and was unfavorable for grafting polymerization. The three photoinitiators—2,2‐dimethoxy‐2‐phenylacetophenone (Irgacure 651), benzoyl peroxide, and benzophenone (BP)—led to only slight differences in CP, but for GE, BP was the most suitable. As for the different solvents—acetone, ethyl acetate, tetrahydrofuran (THF), and chloroform—using those able to donate electrons (acetone and THF) resulted in relatively higher CPs; on the contrary, the use of the other solvents made GE obviously higher, and this should be attributed to the charge‐transfer complex (CTC) that formed in this system. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 903–909, 2005