Controlled radical polymerization guide sigmaaldrich. The chemical structure of the obtained copolymers from a wide range of monomer feeds was determined by elemental analysis content of n for ntba units. Despite its age, it is a polymerization tecbnique whose use is widespread. The molar heat of polymerization is determined as 141 kcal. Freeradical polymerization frp is a method of polymerization by which a polymer forms by the successive addition of freeradical building blocks. Melt freeradical grafting of maleic anhydride onto biodegradable polylactic acid by using styrene as a comonomer piming ma, long jiang, tao ye, weifu dong and mingqing chen the key laboratory of food colloids and biotechnology, ministry of education, school of chemical and material engineering, jiangnan university, 1800 lihu road. A method of polymerizing maleic anhydride and vinyl acetate in a solvent selected from the group consisting of toluene and benzene comprising carrying the polymerization out in the presence of a stabilizing agent comprising a copolymer of maleic anhydride and an alphaolefin containing from four to 18 carbon atoms, the amount of stabilizing agent being from 0. First, the diblock copolymers mpegbpnipaam were synthesized by atom transfer radical polymerization atrp and functionalized with one molecule of maleic anhydride ma by atrp, and then reacted. The effects of comonomer composition, crosslinker content, and variation of ph solutions on the swelling. The polymerization of citraconic acid ca was also performed in the same manner. Abstract maleic acidma was found to polymerize easily by potassium persulfate kps in water in the presence of polyvinylpyrrolidone pvp, and to form a. Living freeradical polymerization by reversible addition. Hydrogels copolymers n,ndimethylacrylamide dma and maleic acid ma were prepared by freeradical polymerization at 56c in aqueous solution, using n,nmethylenebisacrylamide nmba as crosslinking agent and potassium persulfate kps as initiator. Dft modeling of the alternating radical copolymerization.
S3252, ascorbic acid,14 glucose,9 hydrazine,10 or cu0. One key benefit of radical polymerization, which is difficult to achieve through anionic means, is the ease of copolymerization with other monomers, generating polymers with unique and varying properties. The effect of hbonding on radical copolymerization of maleic. From the results of radical polymerization of def with aibn and isomerization of dem with mor, the radical polymerization of dem in the presence of both aibn and mor is considered to proceed via a. Relationship between lnln12 x21 and 1t for styrene maleic anhydride copolymerization by bpotempo system. Recent developments in maleic acid synthesis from bio.
Maleic anhydride copolymers via catalytic chain transfer polymerization gemma c. Controlled radical copolymerization of styrene and maleic. Substituted maleimides underwent homopolymerization to give high molecular weight polymers, which have high thermal stability. Heuts, laboratory of polymer chemistry, eindhoven university of technology, p. The aim of this work was to modify poly lactic acid pla via free radical grafting with maleic anhydride ma by using supercritical carbon dioxide scco2.
Radical polymerization of unsaturated organic acids and their. Free radicals can be formed by a number of different mechanisms, usually involving separate initiator molecules. Living radical copolymerization of styrenemaleic anhydride. Pdf mechanistic considerations on styrenemaleic anhydride. Sfrp stable free radical polymerization sty styrene ssma styrene sulfonate maleic anhydride ssmi styrene sulfonatemaleimide sma styrene maleic anhydride smi styrenemaleimide thf tetrahydrofuran atrp transfer radical polymerization tea triethylamine ph 3p triphenyl phosphine vac vinyl acetate mwd molecular weight distribution. Maleic anhydride ma and its isostructural analogues maleic, fumaric, citraconic and itaconic acids and their amide, imide, ester and nitril derivatives as polyfunctional monomers are being widely used in the synthesis of reactive macromolecules with linear, hyperbranched and selfassembled structures to prepare high performance. The solubility of ma in scco2 was first determined to estimate the suitable grafting conditions and equilibrium. Aqueous polymerization of maleic acid and crosslinking of.
Surface photografting polymerization of binary monomers maleic anhydride and nbutyl vinyl ether on polypropylene film ii. Maleic acid may be used to form acid addition salts with drugs to make them more stable, such as indacaterol maleate. Melt freeradical grafting of maleic anhydride onto. Polymaleic anhydride having a weight average molecular weight by gel permeation chromatography of between 450 and 800 and a polydispersivity of between 1. Unseparated part of polyma seems to be grafted onto pvp. A slurry polymerization process for preparing uncrosslinked copolymers of maleic anhydride and acrylic acid or methacrylic acid, optionally including a c 1c 4 alkyl vinyl ether, having a predetermined weight average molecular weight of about 10,000 to one million which comprises. Melt free radical grafting of maleic anhydride onto biodegradable polylactic acid by using styrene as a comonomer piming ma, long jiang, tao ye, weifu dong and mingqing chen the key laboratory of food colloids and biotechnology, ministry of education, school of chemical and material engineering, jiangnan university, 1800 lihu road. Improving application performance of in situ polymerization and crosslinking system of maleic aciditaconic acid for cotton fabric. Cas form alternating headtotail copolymers when radically copolymerized with electronrich monomers, such as vinyl ethers 69,70. Maleic acid and its anhydride are prepared industrially by the catalytic oxidation of benzene. Graft copolymers of maleic anhydride and its isostructural. The recent developments and the technical drawbacks in the gas and the liquid phases are also.
Intramolecular association of polymaleic acidoctyl vinyl. Box 5, 5600 mb eindhoven, the netherlands dutch polymer institute dpi, john f. Maleic acid is also used as an adhesion promoter for different substrates, such as nylon and zinc coated metals e. Melt freeradical grafting of maleic anhydride onto biodegradable polylactic acid by using styrene as a comonomer by piming ma, long jiang, tao ye, weifu dong and mingqing chen the key laboratory of food colloids and biotechnology, ministry of education, school of chemical and material engineering, jiangnan university, 1800 lihu road. This can induce chain branching through the terminal double bond propagation reaction.
Plasma polymerization of maleic anhydride has been studied using continuouswave and pulsed glow discharges. Melt free radical grafting of maleic anhydride onto biodegradable polylactic acid by using styrene as a comonomer by piming ma, long jiang, tao ye, weifu dong and mingqing chen the key laboratory of food colloids and biotechnology, ministry of education, school of chemical and material engineering, jiangnan university, 1800 lihu road. The free radical polymerization of maleic anhydride. The introduction of azo groups onto the carbon black. This is due to interactions of carboxylic acid functionality with the catalyst. Us3534122a free radical polymerization of bulk liquid. A copolymerization of maleic anhydride with ally1 chloride gives a high monomer reac tivity ratio of about 0. Catalytic polymerization of maleic anhydride request pdf. Following its generation, the initiating free radical adds nonradical monomer. Radical polymerization of maleic acid by potassium persulfate. Paper open access related content grafting of poly lactic. The chain transfer constant of cobf was determined for the di.
Radical polymerization of maleic acid by potassium. It was found to increase 2 orders of magnitude from a purely styrene. Free radical polymerization frp is a method of polymerization by which a polymer forms by the successive addition of free radical building blocks. Process for polymerizing and curing methyl methacrylate monomerpolymer sirups in thepresence of metal salts of hemiperesters of maleic acid. Following its generation, the initiating free radical adds nonradical monomer units, thereby growing the polymer chain. Characterization of phresponsive hydrogels of polyitaconic. Preparation of water based polymeric binders for paper. A fatty acidinspired tetherable initiator for surfaceinitiated atom transfer radical polymerization jiajun yan, xiangcheng pan, zongyu wang, zhao lu, yi wang, li liu, jianan zhang, chien ho, michael r. Fumaric acid derivatives, dialkyl fumarates, alkyl n,n. The bulk polymerization of maleic anhydride initiated with acylperoxides, ditertbutyl peroxide, aibn, or pyridine proceeds with evolution of co2.
Before polymeriza tion, 70% of the carboxylic acid charge of. Anhydride functionality incorporation into the growing films is found to be greatest during pulsed plasma. Recent developments in maleic acid synthesis from biobased. Effect of comonomer composition on the controlled free. Radical high polymerization of fumaric and maleic acid. It was shown that polymerization was faster and quality of control. Further interesting developments include the proposed participation of excited maleic anhydride in the polymerization process and of poly. Polymerization reactivities of the monomers and some properties of the resulting polymers are described and discussed.
Polymerization of maleic anhydride and vinyl acetate. Microstructure of the copolymer of 2vinylnaphthalene 2vn with maleic anhydride obtained by radical initiation over a wide range of monomer feeds has been characterized by fluorescence. Effect of polymerization temperature on the behavior of the styrenemaleic anhydride copolymerization sample code polymerization temperature c conversion % m n m w m w m n tpsm08 90 7 5,300 8,100 1. Polymaleic anhydride or the hydrolyzed water soluble polymer has. Maleic acid is the cisisomer of butenedioic acid, whereas fumaric acid is the transisomer. Radical copolymerization of n,ndiallyln,ndimethylammonium chloride with maleic acid in various solvents was studied. It is mainly used as a precursor to fumaric acid, and relative to its parent maleic anhydride, maleic acid has few. Maleic acid or cisbutenedioic acid is an organic compound that is a dicarboxylic acid, a molecule with two carboxyl groups. Kinetics and mechanism 11 ciocco italy, september 38, 2006 preface fundamentals of radical polymerization the cutthroat competition between termination and transfer to shape the kinetics of radical. Synthesis and characterization of maleic acid polymer for use as. The bulk polymerization is characterised by the high chain. However this tendency is weaker than for maleic anhydridestyrene system. Free radical copolymerization of styrene and maleic anhydride.
The deposited plasma polymer layers have been characterized by xray photoelectron spectroscopy and transmission infrared spectroscopy. Maleic acid, also called cisbutenedioic acid ho 2 cchchco 2 h, unsaturated organic dibasic acid, used in making polyesters for fibrereinforced laminated moldings and paint vehicles, and in the manufacture of fumaric acid and many other chemical products. The recent developments and the technical drawbacks in the. Radical copolymerization of maleic acid with styrene. Note that the styrene radical that is generated is stabilized by resonance delocalization, which is why styrene is such a good polymerization substrate see bottom of next page.
For example, aminocaproic acid has an amine group at one end and a carboxyl group at the other. Polymerization of maleic acid and itaconic acid studied by ftraman spectroscopy. The solvent effect on the relative activity of the monomers and the possibility of preparing copolymers of preset composition were examined. Free radical polymerization is one of the processes of polymer formation. The radical copolymerization of maleic acid with styrene shows an alternating tendency. It is based on the most recent publications on the topic, which are discussed in details with respect to the observed catalytic performances. Polymaleic acid was synthesized by a free radical solution polymerization process.
Today free radical polymerization accounts for a large portion of massproduced polymers. Malditof mass spectroscopy and lightscattering study charles q. However, in recent years it has been demonstrated that maleic anhydride readily undergoes polymerization under gamma and uv radiation as well as in the presence of free radical catalysts and various organic bases. Jul 25, 2009 radical copolymerization of n,ndiallyln,ndimethylammonium chloride with maleic acid in various solvents was studied. Similar results were obtained, though the polymerization of ca was slower as compared with that of ma.
Free radical polymerization frp is a type of chain growth polymerization, along with anionic, cationic and coordination polymerization. Characterization of phresponsive hydrogels of poly. The free radical polymerization of maleic anhydride wiley online. Endfunctional styrene maleic anhydride copolymers via. Controlled radical polymerization has branched into three fundamental techniques which are listed below. Surface photografting polymerization of binary monomers.
The free radical polymerization of maleic anhydride researchgate. The structure of maleic acid consists of four carbon molecules along with carboxylate groups on either ends, with a double bond between the central carbon atoms. The polymerization process was pronounced at different ratios of maleic anhydride. In termsof the history of polymer chemistry one might call free radical copolymerization an ancient phenomenon.
Synthesis and characterization of styrene maleic anhydride. The free radical polymerization of maleic anhydride joshi. Polymerization of maleic anhydride and vinyl acetate nalco. Study of swelling properties and thermal behavior of poly. The anhydride of maleic acid has five atoms in its cyclic molecule, the unsaturated bond undergoes free radical polymerization in the presence of an initiator.
Insitu polymerization of maleic acid and itaconic acid on. Radical copolymerization of maleic anhydride and substituted styrenes by reversible additionfragmentation chain transfer raft polymerization. Slurry polymerization of maleic anhydride and acrylic acid. Free radical copolymerization of styrene and maleic. Radical polymerization of maleic acid by potassium persulfate in the presence of polyvinylpyrrolidone in water. The effects of comonomer composition, crosslinker content, and variation of ph solutions on the swelling behavior of polymers were. These polymers were characterized as a new rigid polymer. Radical copolymerization of 2vinylnaphthalene with maleic. Maleic acid ma is able to establish an esterification reaction with cotton but is. The effect of monomer feed ratio on copolymerization kinetics and on control over molar mass distribution was examined. Controlled freeradical copolymerization of styrene and maleic anhydride was performed in 1,4dioxane or tetrahydrofurane solution at 60 c using the raft technique.
The effect of hbonding on radical copolymerization of. Us2789099a polymerization of acrylic acid in aqueous. Us3534122a us3534122da us3534122a us 3534122 a us3534122 a us 3534122a us 3534122d a us3534122d a us 3534122da us 3534122 a us3534122 a us 3534122a authority us united states prior art keywords room temperature phosphine monomer butyl peroxy polymerization prior art date 19670310 legal status the legal status is an assumption and is. The radical graft polymerization of vinyl monomers from carbon black initiated by azo groups introduced onto the surface was investigated. Publishers pdf, also known as version of record includes final page, issue. The importance of chainlength dependent kinetics in freeradical polymerization. Study of swelling properties and thermal behavior of polyn,n. Improving application performance of in situ polymerization and crosslinking system of maleic acid itaconic acid for cotton fabric. The properties of the resulting copolymer will be different from those of o o o maleic anhydride m.
The homopolymerization of liquid maleic anhydride at 74. Some mechanistical aspects some mechanistical aspects changmin xing 1, 2. Methyl methacrylate polymerinmonomer polymerization in the presence of a peroxymaleate and an amine. Insitu polymerization of maleic acid and itaconic acid on cotton. A method of polymerizing maleic anhydride and vinyl acetate in a solvent selected from the group consisting of toluene and benzene comprising carrying the polymerization out in the presence of a stabilizing agent comprising a copolymer of maleic anhydride and an alphaolefin containing from four to 18 carbon atoms, the amount of. Maleic acid is an industrial raw material for the production of glyoxylic acid by ozonolysis. Radical polymerization of unsaturated organic acids and. Anhydride functionality incorporation into the growing films is found to be greatest during pulsed plasma polymerization with low duty cycles.
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