The molar heat of polymerization is determined as 141 kcal. Styrene maleic anhydride sma or smanh is a synthetic polymer that is builtup of styrene and maleic anhydride monomers. Maleic anhydride appears as colorless crystalline needles, flakes, pellets, rods, briquettes, lumps or a fused mass. Introduction preparation and characterization of maleic. On heating selenophene with maleic anhydride, selenium and the diene 74 are formed. Whereas the product of the reaction o f acetic anhydride with pyridine was not proved 10 the reaction of maleic anhydride with n,ndimethyl aniline undoubtedly takes place. Synthesis and characterization of styrene maleic anhydride copolymer derivatives thesis presented in partial fulfillment of the requirements for the degree of master of science polymer chemistry by khotso mpitso university of stellenbosch faculty of science department of. Nevertheless, the underlying mechanism of the copolymerization is still a point of debate. Heuts, laboratory of polymer chemistry, eindhoven university of technology, p. The copolymerization of styrene sty with maleic anhydride manh has received. Pure butane, stream 2, and compressed air, stream 3, are mixed and fed to r101, an adiabatic reactor, where butane reacts with oxygen to form maleic anhydride. 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, fourier transform. Styrenemaleic anhydride copolymer chemical compound. Vema an grades are the anhydrous form of the polymer, which can be reacted with water to form the acid form, or reacted with alcohols to form half esters or crosslinked.
Free radical copolymerization of styrene and maleic. Sodium ions and pyridine are particularly effective, even at concentrations below 0. Controlled radical copolymerization of styrene and maleic. As esterification process involves hazardous mineral acids, ecofriendly solid. The copolymerization of styrene and maleic anhydride has received. A rigid, heatresistant, and chemicalresistant plastic, it is used in automobile parts, small appliances, and foodservice trays. The monomers in these cases must contain two or more functional groups. Styrenemaleic anhydride copolymer, a thermoplastic resin produced by the copolymerization of styrene and maleic anhydride. Synthesis of terpolymers with homogeneous composition by free.
The deposited plasma polymer layers have been characterized by xray photoelectron spectroscopy and transmission infrared spectroscopy. Process description figure 1 shows a pfd for the overall process. The terpolymerization reactions were performed in analogy to the previously described polymerization of maleic anhydride and 1h,1h,2h,2h. Be as complete as possible and show electron flow for all steps. 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. 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. Endfunctional styrenemaleic anhydride copolymers via. It was used for work in 1928, on the reaction between maleic anhydride and 1,3butadiene, for which otto paul hermann diels and kurt alder were awarded the nobel prize in 1950. Pdf towards controlled graft polymerization of poly. The high ratio of maleic anhydride to furfuryl alcohol 1. Polymerization of maleic anhydride and vinyl acetate. Us4250289a us06074,067 us7406779a us4250289a us 4250289 a us4250289 a us 4250289a us 7406779 a us7406779 a us 7406779a us 4250289 a us4250289 a us 4250289a authority us united states prior art keywords maleic anhydride copolymers parts dispersant polymerization prior art date 19780918 legal status the legal status is an assumption and is not a legal conclusion.
The monomers can be almost perfectly alternating, making it an alternating copolymer, citation needed but random copolymerisation with less than 50% maleic anhydride content is also possible. Investigation of graft polymerization of maleic anhydride. The free radical polymerization of maleic anhydride. Abstract maleic anhydride mah was grafted onto polycisbutadiene rubber pcbr. Addition of chain transfer reagents yields low mn, narrow pdi polymer samples. Synthesis of end and midphthalic anhydride functional. Stellenbosch university, department of chemistry and polymer science. Ringopening copolymerization of maleic anhydride with.
Styrenemaleic anhydride copolymers have been successfully synthesized using catalytic chain transfer polymerization employing the low spin bisdifluoroboryldimethylglyoximatocobaltii cobf complex. Under the given reaction conditions the electrolytic reduction products of the salt might have initiated the polymerization. Reactions in monolayers of drying oils iipolymerization. Homopolymerization of maleic anhydride occurs only at very high concentrations of peroxides 5% wv and is a slow reaction 33% of conversion after 48 h at 70. Surface photografting polymerization of binary monomers. Cathodic polymerization of maleic anhydride with n. Durham etheses new applications for polyethylenealt. Plasma polymerization of maleic anhydride has been studied using continuouswave and pulsed glow discharges. Polymaleic anhydride having a weight average molecular weight by gel permeation chromatography of between 450 and 800 and a polydispersivity of between 1. 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. Towards controlled graft polymerization of polystyrenecomaleic anhydride on functionalized silica mediated by oxoaminium bromide salt. A combination of these processes should be important. Further reaction of 74 and maleic anhydride gives the adduct 75. Maleic anhydride is a cyclic dicarboxylic anhydride that is the cyclic anhydride of maleic acid.
The maleinized soybean oil soma was then polymerized with diols to the halfester stage. Quantitative isomerization of the cismaleate form of all polymers affords the transfumarate analogues. The second type of polymerization reaction produces condensation polymers, which are formed when monomers are linked together with the release of a smaller molecule, such as water or hydrogen chloride. Adducts of maleic anhydride with methyl oleate, methyl linoleate, and monomeric distillate have been prepared. The bulk polymerization is characterised by the high chain.
Polyethylenealtmaleic anhydride average m w 100,000500,000, powder. Publishers pdf, also known as version of record includes final. Graft copolymers of maleic anhydride and its isostructural. Diethyl maleate is manufactured by reacting maleic anhydride with ethanol in the presence of catalytic quantities of sulphuric acid makowka et al 1989. Production of maleic anhydride biomedical engineering. The molar heat of polymerization is determined as 14 i 1 kcal. Pdf mechanistic considerations on styrenemaleic anhydride. We report the ringopening copolymerization of maleic anhydride with a variety of epoxides catalyzed by a chromiumiii salen complex. In this study soybean oil triglycerides were reacted with maleic anhydride in an ene reaction to introduce more than two maleate residues per triglycerides.
Maleic anhydride is a classic substrate for dielsalder reactions. Poly4styrenesulfonic acidcomaleic acid sodium salt average m w 20,000. Box 5, 5600 mb eindhoven, the netherlands dutch polymer institute dpi, john f. Anhydride functionality incorporation into the growing films is found to be greatest during pulsed plasma polymerization with low duty cycles. Styrenemaleic anhydride ma copolymerization was carried out using. The reaction of vegetable oils with maleic anhydride is widely known, and the final product can be obtained by a thermal conventional route, which requires 3 h for total reaction. The free radical polymerization of maleic anhydride wiley online. Endfunctional styrene maleic anhydride copolymers via. This was achieved by copolymerising ma in the presence of excess styrene using a raft. Maleic anhydride copolymers miscellaneous hydrophilic. The polymer is formed by a radical polymerization, using an organic peroxide as. Mechanistic considerations on styrene maleic anhydride.
The effect of hbonding on radical copolymerization of. Maleic anhydride released into the atmosphere will degrade by reaction with ozone and photochemically. Pdf synthesis and chemical modification of maleic anhydride. Nevertheless, the underlying mechanism of the copolymerization is still a point. The reaction rate can be followed roughly by the rate of ethylene consumption note 7 with 1 mol of ethylene being consumed for each mol of maleic anhydride note 8. Pulsed plasma polymerization of nanocellulose maleic. Results showed that bpo was superior to aibn as an initiator, and oxygen had an inhibiting effect on the reaction. Facile synthetic pathway using nitroxide chemistry a. It is through this reaction that maleic anhydride converted to many pesticides and pharmaceuticals. The homopolymerization of liquid maleic anhydride at 74. It is a cyclic dicarboxylic anhydride and a member of furans. The copolymerization of styrene and maleic anhydride has received significant attention in academia as well as in industry.
Similarly, polymer chemistry is exemplified in a variety of ways by reactions of maleic anhydride, including its role in chargetransfer, addition. Process for copolymerization of maleic anhydride with 1. Polymers bearing the phthalimide group as a pendant. Write a mechanism for the reaction of aniline with maleic anhydride to form maleanilic acid 24a. The free radical copolymerization of electronacceptor and electrondonor vinyl monomers represents a particular case of sequencecontrolled polymerization. Between 1940 and 1978 its production has increased seventyfivefold.
The reactions of maleic anhydride ma or related compounds acceptor comonomers with. Poly4styrenesulfonic acidcomaleic acid sodium salt average m w 20,000, powder. Maleic anhydride released into water will hydrolyze rapidly halflife 0. Grafted starches by in situ solid phase polymerization. Maleic anhydride mla cautionary response information common synonyms molten. Mechanistic considerations on styrenemaleic anhydride. Heat of polymerization poses certain problems during copolymerization of styrenedivinylbenzenemaleic anhydride, and also divinylbenzene and maleic. The complex formed in the reaction system might be the active intermediate for the dielsalder reaction, but not for the polymerization reaction.
Pdf polymerization of maleic anhydridemodified plant. Preparation and characterization of maleic anhydride grafted poly. Reaction of the adducts with ethylene diamine gave a linear, soluble polyamide in the case of the oleate adduct, but gelation occurred at a low degree of reaction with other adducts. Therefore, to test this in situ solid phase polymerization method, maleic anhydride, lactic acid, and methyl acrylate were used as graft monomers to prepare hydrophobically modi. Maleic anhydride ma occupies a unique position in a large family of monomers. Free radical copolymerization of styrene and maleic anhydride.
The evidence that the reaction subsequent to the formation of the peroxide is a species of polymerization is based upon the following observations. Maleic anhydride decomposes exothermically, evolving carbon dioxide, in the presence of alkali or alkaline earth metal or ammonium ions, dimethylamine, triethylamine, pyridine, or quinoline, at temperatures above 150c 1. Preparation and characterization of maleic anhydride based resins. It was suggested that the hyperbranched polyesteramides formed via a mechanism of a combination of esterification and addition reactions. In this paper, an overview is given that provides compelling evidence in favor of the penultimate unit model as the correct choice to describe the process of chain growth.
Maleic anhydride copolymers via catalytic chain transfer polymerization gemma c. The fact that more than half of all maleic anhydride produced in the united states is consumed in a single application tends to obscure the great. Radical polymerization of furan with maleic anhydride. Effect of maleic anhydride content and ethanol dilution on.
Living radical copolymerization of styrenemaleic anhydride. This method provides access to a range of new unsaturated polyesters with. The linoleate adduct was separated into monomeric and polymeric components. In termsof the history of polymer chemistry one might call free radical. Evidence of this is the intensively orange coloration appearing after the anhydride, nor n,ndimethyl aniline absorb in the visible part of the spectrum. Polymerization of maleic anhydridemodified plant oils. Application maleic anhydride may be used in the synthesis of unsaturated polyester resins and as a reactant in synthesizing important products such as agricultural chemicals, lubricant.
1358 1414 764 626 40 78 824 446 1533 1356 288 230 1475 824 1246 1205 1047 1535 1283 1103 798 1212 182 1421 778 348 1499 1428 1258