Graft polymerization of vinyl acetate onto starch. Saponification to starch–g–poly(vinyl alcohol)

Graft polymerizations of vinyl acetate onto granular corn starch were initiated by cobalt-60 irradiation of starch-monomer-water mixtures, and ungrafted poly(vinylacetate) was separated from the graft copolymer by benzene extraction. Conversions of monomer to polymer were quantitative at a radiation dose of 1.0 Mrad. However, over half of the polymer was present as ungrafted poly-(vinyl acetate) (grafting efficiency less than 50%), and the graft copolymer contained only 34% grafted synthetic polymer (34% add-on). Lower irradiation doses produced lower conversions of monomer to polymer and gave graft copolymers with lower % add-on. Addition of minor amounts of acrylamide, methyl acrylate, and methacrylic acid as comonomers produced only small increases in % add-on and grafting efficiency. However, grafting efficiency was increased to 70% when a monomer mixture containing about 10% methyl methacrylate was used. Grafting efficiency could be increased to over 90% if the graft polymerization of vinyl acetate-methyl methacrylate was carried out near 0°C, although conversion of monomers to polymer was low and grafted polymer contained 40-50% poly(methyl methacrylate). Selected graft copolymers were treated with methanolic sodium hydroxide to convert starch–g–poly(vinyl acetate) to starch–g–poly(vinyl alcohol). The molecular weight of the poly(vinyl alcohol) moiety was about 30,000. The solubility of starch–g–poly(vinyl alcohol) in hot water was less than 50%; however, solubility could be increased by substituting either acid-modified or hypochlorite-oxidized starch for unmodified starch in the graft polymerization reaction. Vinyl acetate was also graft polymerized onto acid-modified starch which had been dispersed and partially solubilized by heating in water. A total irradiation dose of either 1.0 or 0.5 Mrad gave starch–g–poly(vinyl acetate) with about 35% add-on, and a grafting efficiency of about 40% was obtained. A film cast from a starch–g–poly(vinyl alcohol) copolymer in which homopolymer was not removed exhibited a higher ultimate tensile strength than a comparable physical mixture of starch and poly(vinyl alcohol).     

Preparation and properties of blends from poly(3‐hydroxybutyrate) with poly(vinyl acetate)‐modified starch

This research used the ceric ion to initiate the graft‐polymerization of vinyl acetate (VAc) to a soluble potato starch. Fourier transform infrared spectra confirmed the formation of starch graft copolymer. After 4 h of reaction at 50°C, total monomer conversion, grafting efficiency, and grafting ratio were measured as 91%, 12.5%, and 0.223, respectively. The synthesized PVAc‐modified starch was then blended with poly(3‐hydroxybutyrate) (PHB). Structures, thermal and mechanical properties of the prepared blends were examined. The results showed the PHB and PVAc‐modified starch were miscible in all compositions. In addition, thermal gravimetric analysis revealed that the addition of PVAc‐modified starch increased the thermal stability of the PHB component. Further evidence also showed that the addition of PVAc‐modified starch reduced the extent of decrease in molecular weight of PHB in a melt‐mixer. PHB/PVAc‐modified starch blends exhibit higher toughness than pure PHB because of increased compatibility and the leathery PVAc‐modified starch. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers     

Synthesis,characterization, and properties of poly(vinyl acetate)‐ and poly(vinyl alcohol)‐grafted chitosan

Graft copolymers of chitosan and vinyl acetate were synthesized by free radical technique using cerium (IV) as the initiator. Under controlled conditions, as much as 92% grafting with a grafting yield of 30–40% could be achieved. Chitosan‐g‐poly(vinyl alcohol) copolymers were derived by the alkaline hydrolysis of the chitosan‐g‐poly(vinyl acetate) precursor. Thermogravimetric, FTIR, and X‐ray diffraction analyses of chitosan and the copolymers confirmed the grafting reaction between chitosan and vinyl acetate and also the subsequent hydrolysis. Both the copolymers possessed very good film‐forming properties. Grafting resulted in a significant increase in mechanical strength of both the copolymers in the dry condition. Chitosan‐g‐poly(vinyl acetate) (CH‐PVAc) proved more hydrophobic than did pure chitosan, whereas chitosan‐g‐poly(vinyl alcohol) (CH‐PVOH) exhibited enhanced hydrophilicity as evident from their swelling characteristics and contact angle measurements. The enhanced swelling of CH‐PVOH was ascribed to the presence of the pendant poly(vinyl alcohol) group. At pH 1.98, the CH‐PVAc copolymer films showed greater stability than do pure chitosan films, which is highly beneficial for specific biomedical applications. Both the copolymers showed lower glass transition temperature than do pure chitosan. Grafting did not affect the overall thermal stability, and the differential thermogram substantiated the grafting. The investigations indicate that the synthetic–natural hybrid copolymers having desirable mechanical properties and tailored hydrophilic/hydrophobic characteristics are realizable. These polymers could be exploited for varied biomedical applications. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1852–1859, 2007     

Preparation and characterization of biodegradable polymer blends from poly(3‐hydroxybutyrate)/poly(vinyl acetate)‐modified corn starch

Biodegradable polymer blends prepared by blending poly(3‐hydroxybutyrate) (PHB) and corn starch do not form intact films due to their incompatibility and brittle behavior. For improving their compatibility and flexibility, poly(vinyl acetate) (PVAc) was grafted from the corn starch to prepare the PVAc‐modified corn starch (CSV). The resulting CSV consisted of 47.2 wt% starch‐g‐PVAc copolymer and 52.8 wt% PVAc homopolymer and its structure was verified by FT‐IR analysis. In comparison with 35°C of the neat PVAc, the glass transition temperature (T_g) of the grafted PVAc chains on starch‐g‐PVAc was higher at 44°C because of the hindered molecular mobility imposed from starch on the grafted PVAc. After blending PHB with the CSV, structure and thermal properties of the blends were investigated. Only a single T_g was found for all the PHB/CSV blends and increased with increasing the CSV content. The T_g‐composition dependence of the PHB/CSV blends was well‐fitted with the Gordon‐Taylor equation, indicating that the CSV was compatible with the PHB. In addition, the presence of the CSV could raise the thermal stability of the PHB component. It was also found that the presence of the PHB and PVAc components would not hinder the enzymatic degradation of the corn starch by α‐amylase. POLYM. ENG. SCI., 55:1321–1329, 2015. © 2015 Society of Plastics Engineers     

Grafting of vinyl acetate onto low density polyethylene—starch biodegradable films for printing and packaging applications

Starch‐based biodegradable low‐density polyethylene (LDPE) films were used for graft copolymerization of vinyl acetate with ceric ammonium nitrate (CAN) in aqueous acidic medium as redox initiator with nitric acid. The extent of grafting was examined by Fourier‐transform infrared (FTIR) spectroscopy, attenuated total reflectance (ATR) spectroscopy, X‐ray diffraction (XRD) and scanning electron microscopy (SEM). The objective behind the grafting of vinyl acetate onto the LDPE–starch biodegradable films is to make these suitable for printing and packaging applications without affecting the biodegradability of the original films. Copyright © 2004 Society of Chemical Industry     

Research on starch‐g‐polyvinyl acetate and epoxy resin‐modified corn starch adhesive

A new corn starch adhesive modified by starch‐g‐polyvinyl acetate (starch‐g‐PVAc) and epoxy resin is described in this study. Starch‐g‐PVAc is used as high cohesive energy component to improve the dry shear strength of the starch adhesive. Although the epoxy resin, which can easily crosslink with the oxidized starch, is used as water‐resistant component to improve the wet shear strength. Because there is no chemical reaction happening between polyvinyl acetate and epoxy resin, both the dry shear strength and the wet shear strength of the corn starch adhesive are notably increased. Considering all the related factors, the optimum of the modification is achieved when the dosage of starch‐g‐PVAc and epoxy resin is 70% of the oxidized starch latex with m(Ep): m(starch‐g‐PVAc) = 1:2. That is, the epoxy resin is 23% in mass fraction and starch‐g‐PVAc 47% in mass fraction. The dry shear strength is 4.50 MPa, and the wet shear strength is 2.51 MPa. The modified corn starch has a broad prospect in the application of plywood industry. POLYM. COMPOS., 2013. © 2012 Society of Plastics Engineers     

Synthesis of poly(vinyl acetate)‐graft‐polystyrene and application to preparation of porous membranes

Poly(vinyl acetate)–TEMPO (PVAc–TEMPO) macroinitiators were synthesized by bulk polymerization of vinyl acetate in the presence of benzoyl peroxide (BPO) followed by termination with 2,2,6,6‐tetramethyl‐1‐piperidinyloxy (TEMPO). Radicals were mainly transferred to the acetoxy methyl groups in PVAc during the polymerization. The PVAc–TEMPO macroinitiators had several TEMPO‐dormant sites and styrene bulk polymerization with the macroinitiators produced poly(vinyl acetate)‐graft‐polystyrene (PVAc‐g‐PS). All the TEMPO‐dormant sites of PVAc–TEMPO macroinitiators participated in the styrene polymerization with almost equal reactivity. Methanolysis of PVAc‐g‐PS broke the PS branches apart from the PVAc backbone chains. Hydrophobic or hydrophilic porous membranes with controlled pore size could be prepared by removing the PVAc domains or the PS domains from the graft copolymer. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1658–1667, 2001     

Preparation of narrowly distributed nanoparticles of poly(n‐butyl methacrylate‐co‐vinyl pyrrolidone) through microemulsion polymerization

Narrowly distributed nanoparticles of poly (n‐butyl methacrylate‐co‐vinyl pyrrolidone) were prepared through microemulsion polymerization with a nonionic surfactant of Tween‐80 as emulsifier (6 wt % of the latex) and n‐butanol as coemulsifier. The polymerizations were initiated with benzoylperoxide (BPO), potassium persulfate (KPS), KPS/ferric sulfate (FeSO₄), and BPO/FeSO₄, respectively, where the initiation in the case of BPO/FeSO₄ took place mainly at the interphase between the oil phase and the reaction media. Namely, this interfacial‐initiated microemulsion polymerization resulted in larger particles with relatively narrower particle size distribution as well as higher limiting monomer conversion but lower polymerization rate compared with the polymerization initiated with KPS/FeSO₄. In this article, the influences of initiation method, monomer ratio, and addition of water‐soluble components on microemulsion polymerization and latex particle size were studied to discuss the mechanism of interfacial‐initiated microemulsion polymerization. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2334–2340, 2004     

Atom transfer radical polymerization of methyl methacrylate initiated with a macroinitiator of poly(vinyl acetate)

Well‐defined poly(vinyl acetate‐b‐methyl methacrylate) block copolymers were successfully synthesized by the atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) in p‐xylene with CuBr as a catalyst, 2,2′‐bipyridine as a ligand, and trichloromethyl‐end‐grouped poly(vinyl acetate) (PVAc–CCl₃) as a macroinitiator that was prepared via the telomerization of vinyl acetate with chloroform as a telogen. The block copolymers were characterized with gel permeation chromatography, Fourier transform infrared, and ¹H‐NMR. The effects of the solvent and temperature on ATRP of MMA were studied. The control over a large range of molecular weights was investigated with a high [MMA]/[PVAc–CCl₃] ratio for potential industry applications. In addition, the mechanism of the polymerization was discussed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1089–1094, 2006     

Thermoresponsive and biocompatible poly(vinyl alcohol)‐graft‐poly(N,N‐diethylacrylamide) copolymer: Microwave‐assisted synthesis,characterization, and swelling behavior

Novel thermoresponsive poly(vinyl alcohol)‐graft‐poly(N,N‐diethylacrylamide) (PVA‐g‐PDEAAm) copolymers were prepared by microwave‐assisted graft copolymerization using a potassium persulfate/N,N,N′,N′‐tetramethylethylenediamine (KPS/TEMED) initiator system. The structures of PVA‐g‐PDEAAm copolymers were characterized by ¹H‐NMR, Fourier transform infrared spectroscopy, differential scanning calorimetry/thermogravimetric analysis, gel permeation chromatography, X‐ray diffraction, and scanning electron microscopy. The effects of various process parameters on grafting were systematically studied: microwave power, KPS, monomer and PVA concentrations, and ultraviolet irradiation. Under optimal conditions, the maximum grafting percent and graft efficiency were 101% and 93%, respectively. Furthermore, a lower critical temperature of copolymers was measured in the range 29–31 °C by ultraviolet spectroscopy. The swelling behavior of graft membranes was carried out at various temperatures, and the results showed that the swelling behavior of membranes was dependent on the temperature. In vitro cell culture studies using L929 fibroblast cells confirmed cell compatibility with the PVA‐g‐PDEAAm copolymer and its membrane, making them an attractive candidate for drug delivery systems. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45969.     

Preparation of high molecular weight poly(vinyl alcohol) with high yield by emulsion polymerization of vinyl acetate using 2,2′‐azobis(2‐amidinopropane) dihydrochloride

To prepare high molecular weight (HMW) poly(vinyl acetate) (PVAc) with high yield and high linearity as a precursor of HMW poly(vinyl alcohol) (PVA), vinyl acetate (VAc) was emulsion polymerized using, azo initiator, 2,2′‐azobis(2‐amidinopropane) dihydrochloride (AAPH). This was compared with the polymerization using potassium peroxodisulfate (KPS) as an initiator at various polymerization conditions. PVA, having a maximum number average degree of polymerization (P_n) of 3500 was obtained by the saponification of PVAc with P_n of 13,000–14,000, degree of branching (DB) for the acetyl group of about 3.4–3.5, and a maximum conversion of VAc into PVAc of 95%, which was polymerized by AAPH. These numerical values were superior compared with 14,500–15,000 of P_n of PVAc, obtained by KPS, and 3100 of maximum P_n of resulting PVA, DB of about 3.7–3.8, and maximum conversion of 90%. From the foregoing experimental results, we found that AAPH was a more efficient initiator than KPS in increasing both conversion of PVAc and molecular weight of PVA. In addition, PVAc microspheres, obtained by these emulsion polymerizations, can be converted to PVA / PVAc shell / core microspheres through a series of surface‐saponifications, maintaining their spherical morphology. Various surface morphologies, such as flat or wrinkled and swellable or nonswellable ones formed by the various molecular parameters and saponification conditions, were examined. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2356–2362, 2004     

PVAc Microspheres via Semicontinuous Emulsion Polymerization: Synthesis,Characterization, Kinetic,and Surface Morphology Studies

Poly (vinyl acetate) (PVAc) latexes are economically important products with many desirable features. They are used as adhesives for porous materials in various processing stages of industries. Synthesis parameters have an important role on the physico-chemical properties of PVAc latexes such as: viscosity, average molecular weight, degree of polymerization, and surface morphology. In this work, PVAc was prepared via semicontinous emulsion polymerization (delayed monomer and initiator addition process) in the presence of ammonium persulfate (APS) as conventional anionic initiator, poly (vinyl alcohol) (PVA) as stabilizer, and sodium lauryl sulfate (SLS) as anionic emulsifier. The surface morphology of PVAc microspheres was, examined using a scanning electron microscope (SEM) and atomic force microscope (AFM). It is evident from the SEM photographs that all the particles became microspheres and are uniform in shape. The use of AFM for imaging of polyvinyl acetate confirms a typical sphere polymer. The effect of changes in the different parameters such as concentration of emulsifier, initiator concentration, and presence or absence of buffer on the vinyl acetate (VAc) conversion, the steady state polymerization rate, the viscosity-average molecular weight, and the final latex viscosity of synthesized PVAc were investigated. The effects of anionic emulsifier on the synthesized PVAc are also compared with those obtained by the nonionic emulsifier. The comparison indicated that the VAc monomer conversion and the final latex viscosity of the anionic system were higher than for the nonionic system but the viscosity-average polymer molecular weight of the anionic system was lower than that of the nonionic system. The adhesive strength of the synthesized PVAc latex was examined and the load and deflection data were reported.     

Controlled grafting of poly(vinyl acetate) onto starch via RAFT polymerization

A structure‐exact starch‐based xanthate agent was prepared and used as chain transfer agent to mediate RAFT polymerization of vinyl acetate, which offered a convenient way to well control the structure and composition of starch‐g‐poly(vinyl acetate). The structures of the intermediate and the polymer were verified with FTIR and ¹H‐NMR. Gel permeation chromatography measurement results indicated that the polymerization was performed as expected. It was found that the relationship between number average molecular weight and monomer conversion was linear. The polydispersity index of grafted side‐chain ranged from 1.19 to 1.53 and most of them were around 1.2. There was one more degradation stage appeared on the thermogravimetric analysis profile of starch‐g‐poly(vinyl acetate) than that of starch. TEM observation exhibited that the product was able to self‐assemble into micelles in aqueous solution, which suggested the copolymer was amphiphilic. Both the thermal and amphiphilic properties demonstrated the starch‐g‐poly(vinyl acetate) was successfully synthesized as well. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Preparation and characterization of dual responsive sodium alginate‐g‐poly(vinyl alcohol) hydrogel

Poly(vinyl alcohol) (PVA) was chosen as a controllable gelator to prepare sodium alginate (SA)‐based physically cross‐linked dual‐responsive hydrogel by three steps. First, polyvinyl acetate (PVAc) was grafted onto SA via radical copolymerization. Then, the copolymer was subsequently converted into SA‐g‐poly(vinyl alcohol) (SAPVA) by alcoholysis reaction. PVA content of SAPVA was tailored by controlling the graft percentage of PVAc, i.e. through varying the amount of vinyl acetate during copolymerization. Finally, SAPVA hydrogels were formed by freezing‐thawing cycles. The structure of the graft copolymers was verified with FTIR spectroscopy. X‐ray diffraction analysis results revealed that the crystallinity of SAPVA hydrogels depended on the PVA content of SAPVA. The swelling test showed that SAPVA hydrogels were pH‐responsive, and the swelling was reversible. SAPVA hydrogels also behaved electric‐responsive. In addition, the pH‐sensitivity of SAPVA hydrogels was able to be controlled with the composition of the hydrogels. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis and Characterization of Starch-Poly(vinyl Acetate) Graft Copolymers and their Saponified Form

A redox initiation system based on potassium persulfate/acetone sodium bisulphite (KPS/ASBS) was developed to initiate the graft copolymerization of vinyl acetate (VAc) monomer onto corn starch in aqueous solution. The grafting reaction was studied with respect to grafting yield (GY), grafting efficiency (GE) and total conversion (TC) and results obtained were compared with those a well-established redox initiation system namely potassium persulfate/sodium bisulphite (KPS/SBS). The effect of reaction variables such as redox initiator concentration, liquor ratio, reaction time and temperature as well as VAc concentration were investigated. The GY, GE and TC increased significantly with increase of the redox initiation concentration up to 8/16 mmol/l irrespective of the initiation system used. Moreover, optimal grafting was obtained at 60 ^○C for KPS/ASBS redox system and 70 ^○C for KPS/SBS redox system. Saponification of poly (vinyl acetate)-starch graft copolymers were effected using NaOH in three different bath media (n-hexane, acetone or methanol) to convert starch-g-poly(vinyl acetate) to starch-g-poly(vinyl alcohol). Higher extent of solubility in hot water of the saponified form was achieved by using a bath containing n-hexane/sodium hydroxide; however, increasing the graft yield higher than 26.3% decreases the solubility. The structures and thermal stability of starch, grafted starch copolymer and saponified grafted starch copolymer were characterized by infrared spectroscopy and thermogravimetric analysis. Moreover, the rheological behavior as well as sizing performance of the saponified grafted starch copolymers were evaluated and compared with the native starch and commercial polyvinyl alcohol.     

Study of polymer–solvent interactions by gas chromatography. Copolymers of vinyl acetate and vinyl alcohol with hydrocarbons and alcohols

The specific retention volumes of nine hydrocarbons and 12 alcohols were measured at several temperatures within the range 120–150°C in columns whose stationary phases were poly(vinyl acetate) (PVAc) and four copolymers of vinyl acetate and vinyl alcohol with 94.8, 74.4, 60.9, and 43.4 mol % of vinyl acetate units (mol % VAc). No chromatographic retention for hydrocarbons was detected in columns loaded with poly(vinyl alcohol) (PVA) or a copolymer with 11.9 mol % VAc. The retention trends are discussed and the polymers solubility parameters (δ₂) were computed from the measured Flory–Huggins χ parameters. The copolymers δ₂ values increase almost linearly with decreasing mol % VAc; PVAc, however, has a distinct behavior. The limitations of the approach in the prediction of χ parameters are discussed.     

Improvement of film properties of vinyl acetate based emulsion polymers by using different types of maleic acid diesters

Two types of maleic acid diesters, dibutyl maleate (DBM) and dioctyl maleate (DOM) were used as comonomers in semicontinuous emulsion copolymerization of vinyl acetate (VAc) in order to improve the film properties of poly(vinyl acetate), PVAc emulsion polymer. The effects of the comonomer type and comonomer ratio on minimum film forming temperature (MFFT), glass transition temperature (T_g), polymer structure, molecular weights, water contact angle and water resistance of PVAc latex films were examined. It was found that MFFT and T_g of the PVAc emulsion polymer decreased by the presence of the maleic acid disters in copolymer composition. This decrease was more affected by the increasing content and alkyl chain length of the comonomers. The molecular weights of the emulsion polymers were also affected by the comonomers and their ratios. Moreover, hydrophobicity and water resistance of the PVAc latex films were increased by using DBM and DOM as comonomer.     

Competitive removal of nickel (II), cobalt (II), and zinc (II) ions from aqueous solutions by starch‐graft‐acrylic acid copolymers

Graft copolymerization of acrylic acid (AA) onto starch was carried out with ceric ammonium nitrate as initiator under nitrogen atmosphere. The grafting percentages (GP%) of starch‐graft‐acrylic acid (St‐g‐AA) copolymers were determined. The effect of GP% of St‐g‐AA copolymers on the competitive removal of Co²⁺, Ni²⁺, Zn²⁺ ions from aqueous solution was investigated at different pH (2, 4, 6). The concentrations of each ion in aqueous solution 5 mmol/L. Effects of various parameters such as treatment time, initial pH of the solution and grafting percentage of starch graft copolymers were investigated. Metal ion removal capacities of St‐g‐AA copolymers increased with GP% of the copolymers and pH. The results show that the removal of metal ions followed as given in the order Co²⁺ > Ni²⁺ > Zn²⁺. In this study, metal ion removal capacities were determined by atomic absorption spectrophotometer (AAS). © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Synthesis of a cellulose‐grafted polymeric support and its application in the reductions of some carbonyl compounds

The reduction of carbonyl compounds by borohydride supported on a cellulose–anion exchange resin is known. The synthesis of a graft copolymer of cellulose and poly(4‐vinyl pyridine) [CellO‐g‐poly(4‐VP)] has been carried out with ceric ions as a redox initiator. A postgrafting treatment of CellO‐g‐poly(4‐VP) with sodium borohydride has produced CellO‐g‐poly(4‐VP) borane, a polymer‐supported reducing agent. Optimum conditions pertaining to the maximum percentage of grafting have been evaluated as a function of the concentrations of the initiator, monomer, and nitric acid, amount of water, time, and temperature. The maximum percentage of grafting (585%) has been obtained with 0.927 mol/L of 4‐vinyl pyridine and 0.018 mol/L of ceric ammonium nitrate in 120 min at 45°C. The polymeric support, CellO‐g‐poly(4‐VP) borane, has been used for reduction reactions of different carbonyl compounds such as benzaldehyde, cyclohexanone, crotonaldehyde, acetone, and furfural. The graft copolymer has been characterized with IR and thermogravimetric analysis. The grafted cellulose has been found to be thermally stable. The reduced products have been characterized with IR and NMR spectral methods. The reagent has been reused for the reduction of a fresh carbonyl compound, and it has been observed that the polymeric reagent reduces the compounds successfully but with a little lower product yield. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Study on segmental interaction parameter between ethylene and vinyl acetate monomer units of EVA by inverse gas chromatography

A method of analysis of inverse gas chromatography (IGC) measurements on copolymers to calculate segmental interaction parameters was proposed. Poly(ethylene‐co‐vinyl acetate) (EVA), poly(vinyl acetate) (PVAc), and dotriacontane (C32) were studied at 120°C with eight different probes of varying polarities by IGC. The value of the segmental interaction parameter between ethylene units and vinyl acetate units in EVA was found to be 1.18, which is consistent with the literature values. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 693–698, 1999