Radical copolymerization of optically active l-menthyl vinyl ether with maleic anhydride,dimethyl maleate,and dimethyl fumarate

The copolymerizations of l-menthyl vinyl ether (l-MVE) with the monomers, that is, maleic anhydride (MAn), dimethyl maleate (DMM), and dimethyl fumarate (DMFu), were undertaken to obtain optically active copolymers. The optically active l-menthyl group in the side chain of copolymers was removed by the ether cleavage reaction with dry-hydrogen bromide gas. The ethercloven copolymers were still optically active. Hence it was concluded that asymmetric carbon atoms were introduced into the copolymer main chain, the reason given being that l-MVE and comonomers (MAn, DMM, and DMFu) made the stereoselective charge-transfer complex one another and copolymerized stereospecifically. From the results of the measurements of optical rotatory dispersion (ORD) and circular dichroism (CD) for copolymers before and after the ether cleavage reaction, the mode of bond opening for α,β-substituted monomers (MAn, DMM, and DMFu) was discussed and the microstructures of copolymers were prepared.     

Anti-microbial activity of anhydride copolymers and their derivatives prepared by ionizing radiation

Methyl methacrylate/maleic anhydride (MMA/MAn) copolymers were synthesized using gamma rays. Preparation conditions such as irradiation dose, comonomer composition and type of diluent affecting the degree of comonomer conversion were investigated. The suitable diluent for obtaining reasonable MMA/MAn copolymer yield was acetone. The higher copolymer yield was achieved when the amount of methyl methacrylate in comonomer feed solutions as well as irradiation dose increased. The effect of ZnCl₂ on the MMA/MAn copolymer yield and structure was studied. Characterization of the prepared MMA/MAn copolymers was performed using FTIR, and thermogravimetric and viscometric analysis. The derivatives of MMA/MAn copolymers were obtained by treating them with different reagents such as sulpha-drugs, hydroxylamine hydrochloride and 4-amino sodium salyciliate. The antimicrobial activity of MMA/MAn copolymers and their derivatives was examined. The activity of such copolymers against Staphylococcus aureus and Escherichia coli increased by increasing MAn content in the copolymer. The MMA/MAn copolymers treated with sulpha-drugs exhibited particularly high biological activity against different microorganisms. These results revealed that the prepared MMA/MAn copolymer and its derivatives have a broad antimicrobial activity.     

POLYMERIC ACID FOR THIN FILM APPLICATIONS

ABSTRACT

Propyl and butyl half esters of the alternating copolymer isobutylene/maleic anhydride (IB/MAn) are polymers of high acid content (4.67 and 4.38 milliequivalent acid/g polymer). These polymers exhibit good physical performance in thin films, such as absence of cracking and minimal curl. The anhydride ring of the copolymer IB/MAn is opened in refluxing alcohol at atmospheric or elevated pressure; conversion is monitored by an IR probe (1783 vs. 1733 cm?1). The polymers are stable up to about 50 °C. Weight loss corresponding to the reversion to the anhydride structure is observed at higher temperature, with concurrent increase of anhydride resonances in the IR. Thermal stability of the half esters is similar to that of alkyl half esters of the alternating copolymers ethylene/maleic anhydride (EMA) and methyl vinyl ether/maleic anhydride (Gantrez® AN 119). The 1-propanol solution of the propyl half ester of IB/MAn copolymer is a shear thinning fluid, a significant advantage when coating at high speeds.     

反应性高分子抗菌剂的合成及对棉织物的抗菌整理

通过三元共聚将马来酸酐活性基团引入大分子链中,制备了两个系列的反应性高分子抗菌剂poly(DMAEMA-BC/AAm/MAn)和poly(DMAEMA-DB/AAm/MAn),并用FT-IR对合成的反应性高分子抗菌剂进行了结构表征,用酸碱滴定法测定了其酸值,通过平板活菌计数法测定了反应性高分子抗菌剂的抗菌活性,并表征了它们的抗菌活性对抗菌时间与浓度的依赖关系。通过热整理工艺将三元共聚物与棉织物反应,制得抗菌织物。之后,通过改良振荡烧瓶法测定了抗菌整理后棉织物的抗菌效果,并进一步考察了织物抗菌效果的耐洗性。研究结果表明,少量的马来酸酐(单体摩尔比5%)有助于提高共聚单体的反应活性,共聚物中含少量马来酸酐时,抗菌活性增强。用马来酸酐单体摩尔比5～35%的poly(DMAEMA-BC/AAm/MAn)或5～25%的poly(DMAEMA-DB/AAm/MAn)整理的抗菌织物均具有良好的抗菌效果,且前者经过100次水洗,后者经200次水洗后,仍表现良好的抗菌效果。     

Vinylhydroquinone. V. Tri-n-butylborane-initiated copolymerization of maleic anhydride and redox property of copolymers

Tri-n-butylborane (TBB) was found to be capable of initiating the copolymerization of vinylhydroquinone (VHQ) with maleic anhydride (MAn) and diethyl fumarate (DEF) in cyclohexanone at 30°C under nitrogen. Redox potentials of the VHQ–MAn copolymer obtained were examined. These results, along with spectroscopic data, indicate that the copolymers are of a highly alternating character.     

羧基化环氧丙烯酸酯合成及在光成像阻焊油墨中的应用

树脂;多元羧酸酐;光固化;碱显影;羧基化环氧丙烯酸酯合成及在光成像阻焊油墨中的应用     

A polarity‐activation strategy for the high incorporation of 1‐alkenes into functional copolymers via RAFT copolymerization

A new synthetic methodology for the preparation of copolymers having high incorporation of 1‐alkene together with multifunctionalities has been developed by polarity‐activated reversible addition‐fragmentation chain transfer (RAFT) copolymerization. This approach provides well‐defined alternating poly(1‐decene‐alt‐maleic anhydride), expanding the monomer types for living copolymerizations. Although neither 1‐decene (DE) nor maleic anhydride (MAn) has significant reactivity in RAFT homopolymerization, their copolymers have been synthesized by RAFT copolymerizations. The controlled characteristics of DE‐MAn copolymerizations were verified by increased copolymer molecular weights during the copolymerization process. Ternary copolymers of DE and MAn, with high conversion of DE, could be obtained by using additive amounts (5 mol %) of vinyl acetate or styrene (ST), demonstrating further enhanced monomer reactivities and complex chain structures. When ST was selected as the third monomer, copolymers with block structures were obtained, because of fast consumption of ST in the copolymerization. Moreover, a wide variety of well‐defined multifunctional copolymers were prepared by RAFT copolymerizations of various functional 1‐alkenes with MAn. For each copolymerization, gel permeation chromatography analysis showed that the resulting copolymer had well‐controlled M_n values and fairly low polydispersities (PDI = 1.3–1.4), and ¹H and ¹³C NMR spectroscopies indicated strong alternating tendency during copolymerization with high incorporation of 1‐alkene units, up to 50 mol %. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3488–3498, 2008     

Copolymerization and Charge-Transfer Interaction of Methyl Isopropenyl Ketone Cyclodimer with Maleic Anhydride and Maleimide

The copolymerizations of methyl isopropenyl ketone cyclodimer(MIPKD: 2-acetyl-2,5,6-trimethyl-2,3-dihydropyran) with maleic anhydride (MAn) and with maleimide (MI) in the presence of α,α′-azobisisobutyronitrile were investigated at 60 and 80°C. It was found that the copolymerizations were performed in both systems to give rather low molecular weight copolymers consisting of less than 50% MIPKD units. It was also observed from IR and NMR spectral determinations of the systems of MIPKD with MAn and with MI that 1:1 charge-transfer complexes with a small equilibrium constant were formed. Formation of these complexes seemed to affect the copolymerizations. Finally, the copolymerization of MIPKD with MAn was studied kinetically. The mechanism of copolymerization is discussed.     

Synthesis and characterization of ether derivatives of brominated poly(isobutylene‐co‐isoprene)

Variations of the Williamson ether synthesis were employed to prepare a range of new derivatives of brominated poly(isobutylene‐co‐isoprene) (BIIR). Unambiguous characterization of the polymeric products was accomplished by spectroscopic comparisons to low‐molecular‐weight analogues derived from brominated 2,2,4,8,8‐pentamethyl‐4‐nonene, which served as a model for the reactive functionality found within BIIR. The substitution of bromide from BIIR occurred at moderate temperatures with stoichiometric amounts of quaternary ammonium phenoxide to yield O‐alkylation products in high yields. Simple mixtures of BIIR, KOH, and aliphatic alcohols generated the desired allylic ethers when heated above 110 °C in the absence of quaternary ammonium salts. Knowledge gained from these small‐molecule alkylations was used to prepare graft copolymers from BIIR and poly(ethylene oxide) through the exploitation of the apparent ability of polyethers to activate potassium alkoxides in nucleophilic substitutions. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 983–992, 2006     

Cyclocopolymerization of d-limonene with maleic anhydride

d-Limonene (Lim), a nonconjugated 1,5-diene, was copolymerized with maleic anhydride (MAn) in tetrahydrofuran with α,α′-azobisisobutyronitrile as initiator. The composition, spectral analyses, and other physical properties of the resulting copolymer and its hydrolysed product suggest that Lim readily undergoes an inter-intramolecular cyclocopolymerization with MAn, leading to a 1:2 alternating copolymer. The findings and the proposed cyclocopolymerization mechanism are consistent with participation of a charge-transfer complex of the comonomers in the propagation step. The copolymers are optically active and their CD spectra are characterized by dichroic bands attributable to electronic transitions of carbonyl or carboxylic chromophores.     

Copolymerization of Maleic Anhydride with Benzofuran,Indole, and Benzothiophene

Abstract

Maieic anhydride (MAn) forms alternating copolymers with benzofuran (BF), indole, and benzothiophene (BT) under the influence of azobisisoburyronitrile. In all three cases the yield and molecular weight were highest when equimolar amounts of both monomers were used. The association constants of charge-transfer complex formation of MAn with the three comonomers have been measured at various temperatures by NMR. The following values were obtained (at 20°C):

MAn-BF ca. 0.01 liter/mole (in cyclohexanone)

MAn-indole 0.28 liter/mole (in chloroform)

MAn-BT 0.30 liter/mole (in chloroform)

The results indicate that the reactivity of the comonomers to form copolymers with MAn is governed by the resonance stabilization of the monomer and to a lesser extent by complex formation. The rate of copolymerization is much higher for the MAn-BF system than for the two other systems. In the former case it is not necessary to invoke charge-complex formation to explain the copolymerization.     

Radiation-induced copolymerization of phenylvinyl alkyl ethers and maleic anhydride

Alternating copolymers of phenylvinyl ethyl ether ( I ) and phenylvinyl sec-butyl ether ( II ) with maleic anhydride (MAn) were prepared in bulk or in benzene solution by high-energy irradiation at dose rates of 42, 160, and 540 Gy/h, respectively. The overall energies of activation in copolymerization of I and II with MAn were 15.5 and 18.8 kJ/mol, respectively. The reaction proceeds by the free-radical mechanism and was found to be largely dependent on the bulkiness of the alkyl group. In the copolymerization of I and MAn, the molecular weight increases with conversion. By applying the model described by Shirota and co-workers, it was established that participation of charge-transfer-complex monomers increases with the increase of the total monomer concentration and with the bulkiness of the alkyl group in electron donor monomer.     

FREE-RADICAL-INITIATED COPOLYMERIZATION OF 2-CHLOROSTYRENE, 4-CHLOROSTYRENE,AND 2,6-DICHLOROSTYRENE WITH MALEIC ANHYDRIDE

The title copolymers have been prepared by the free-radical-initiated copolymerization of 2-chlorostyrene (2-ClSt), 4-chlorostyrene (4-ClSt) and 2,6-dichlorostyrene (2,6-DClSt) with maleic anhydride (MAn) in toluene at 65°C. Copolymers of chlorinated styrenes with MAn prepared under different monomer-to-monomer ratios in the feed have alternating composition. In all cases, the mixture of comonomers forms charge-transfer complex monomers (CTC). The initial rate of copolymerization increases with the increase of electron donors in the comonomer feed, and the highest rates were at the equimolar ratios of comonomers in the feed. The thermal stability of the polymers was measured by thermogravimetric analysis in nitrogen. Homopolymers decompose by a one-step mechanism, while copolymers are more thermostable and decompose by a two-step mechanism. Glass transition temperatures (T_gs) of homopolymers are lower than T_gs of copolymers. The number and weight average molecular weights of chlorinated copolymers are higher than those of the corresponding homopolymers.     

Photoinduced polymerization of maleic anhydride in dioxane

Maleic anhydride (MAn) was irradiated with ultraviolet light in dioxane at 35°C without initiator, and predominantly a MAn oligomer was obtained with a small quantity of cyclic dimer of MAn. Mass spectrometric, NMR, and elementary analysis investigation of the oligomer showed that it is composed of about four MAn units and one dioxane molecule per molecule.     

Stereochemistry of alternating methacryloyl-L-valine methyl ester–maleic anhydride copolymer

The stereochemical composition of an alternating methacryloyl-L -valine methyl estermaleic anhydride (L-MAVM/MAn) copolymer which was prepared by the photocopolymerization of L-MAVM and MAn in dioxane at 25°C without initiator was investigated by proton magnetic resonance spectroscopy. The resonance of the ester methyl protons of the L-MAVM unit appeared as three split peaks at 3.65, 3.76, and 3.82 ppm, which could be assigned to those of the coisotactic (di-threo-tri-isotactic), coheterotactic and cosyndiotactic triads, respectively. The triad cotacticity determined according to these assignments indicated that the copolymer was composed predominantly of di-threo-tri-isotactic triad. Similarly PMR spectroscopic investigation of the acryloyl-L -valine methyl ester–maleic anhydride (L-AVM/MAn) copolymer with a 1:1 molar ratio of the monomers showed that the main tactic fraction of the copolymer was also di-threo-tri-isotactic one. Nevertheless, the circular dichroic investigation of the L-AVM/MAn copolymer before and after hydrolysis denied asymmetric induction into the polymer main chain. These results suggest that the propagation step in the photocopolymerization of L-MAVM or L-AVM with MAn proceeds by the trans-trans opening of the complexmer composed of a 1:1 molar ratio of L-MAVM or L-AVM and MAn.     

Dual monomer grafting of styrene and maleic anhydride onto model hydrocarbon substrates

Styrene and maleic anhydride (MAn) were successfully grafted, alone and simultaneously, onto various model hydrocarbon substrates at 180 °C with 2,5‐dimethyl‐2,5‐di‐(t‐butyl peroxy)hexane (L101) as a free‐radical initiator. Dodecane, 1‐dodecene, and 2,6,10,14‐tetramethylpentadecane were selected as model compounds to investigate the effects of terminal unsaturation and branching on grafting and crosslinking. These compounds were chosen to mimic the aforementioned microstructural characteristics that are commonly observed in polyethylene. The results demonstrate that terminal unsaturation increases the amount of crosslinked material in the presence of L101. With respect to grafting, for the single monomer systems, MAn prefers to graft as single saturated units, whereas styrene prefers to graft as long chains of polystyrene oligomers. However, when both monomers are grafted simultaneously, graft yields are drastically reduced because of a propensity for the two monomers to form a styrene–maleic anhydride copolymer. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2456–2468, 2000     

Kinetic Investigations of Reactions with Maleic Anhydride Copolymers and Model Compounds

Alternating copolymers that contain maleic anhydride (MAn) as a component occur in two different stereochemical configurations which are differentiated by their reactivity. Model compounds, 2, 3-dialkylsuccinic acids and their anhydrides, were investigated and it was demonstrated that there is a distinct difference between threo and erythro configurations in their chemical and physical behavior. Both configurations also occur in the alternating copolymers. Beside the model compounds, the alternating copolymers ethylene-MAn, propylene-MAn, and styrene-MAn were investigated in their reactions with amines, alcohols, and water (hydrolysis). The cis configurations showed the higher reaction rates. Reactions of the anhydride moieties with equimolar amounts of aniline, ethanol, and water demonstrated that reactions follow second-order rate laws. With excess reactant, the reaction follows a pseudo-first-order rate law. The rate constants depend on the degree of polymerization and on the comonomer. Increasing steric hindrance and molecular weight lead to a decrease of the reaction rate. Catalysis of the hydrolysis reaction by tertiary amines results in similar rate constants for the configurations of the substituted succinic acid anhydrides. The reasons are discussed.     

Syntheses of monomethoxy polyethyleneglycol vinyl ether macromonomers and their radical copolymerization with maleic anhydride

In order to develop new biocompatible materials, monomethoxy polyethyleneglycol vinyl ethers (Me(EG)_n VE, n = 1–39) were synthesized from the corresponding monomethoxy polyethyleneglycol with acetylene. Successful purification of the macromonomers was performed by some adsorption procedures such as charcoal and ion-exchange resin treatments. The Me(EG)_n VE macromonomers were easily copolymerized with maleic anhydride (MAn) to give alternating copolymers. The copolymerization rates significantly depended on the ethyleneglycol chain length of the Me(EG)_n VE, resulting in relatively lower polymerization rate of higher MW macromonomer. The use of nonelectron donor solvent such as carbon tetrachloride led to higher yields and higher MW of copolymers.     

The Copolymerization of Alkenes with Maleic Anhydride

The investigations presented deal with the experimental results of the copolymerization of maleic anhydride (MAn) with alkenes. The course of the reaction is explained by the overall rate of the copolymerization (v _Br), which correlates with the solution viscosity of the copolymer, and the dependence of the v _Br maximum on the mole ratio of the monomers at constant total monomer concentration. The use of solvents with increasing donor power leads to increased complexing of the free MAn molecules and of the MAn radical chain ends. The results demonstrate that, for low 1-alkenes, the addition of the MAn chain radical is the rate-determining step of the copolymerization. As the substituents on the olefinic double bond become larger or the double bond shifts to the 1,2-position, the addition of MAn to the hydrocarbon radical becomes more and more the rate-determining step. On the other hand, an increase of the CT complexation of the MAn polymer radical by use of donor solvents decreases the alkene addition rate.     

A Novel,Facile Method for the Preparation of Uniform,Reactive Maleic Anhydride/Vinyl Acetate Copolymer Micro‐ and Nanospheres

Summary: A novel, stabilizer‐free dispersion polymerization with alkyl esters as reaction media gives uniform alternating microspheres of maleic anhydride (MAn)/vinyl acetate (VAc) copolymer. The diameter of the copolymer microspheres could be precisely controlled from 80 to 750 nm by changing the monomer concentration or feed ratio. Moreover, this new type of copolymer microspheres with reactive anhydride groups on the surface has good solubility in common nontoxic solvents such as water and ethanol.

SEM image of the powder surface of copolymer microspheres formed at [MAn] = [VAc] = 1.5 M .