Copolymerization of ethylene with vinyl acetate. I. Effect of polymerization temperature on degree of branching

The degree of branching of a series of ethylene–vinyl acetate copolymers was found to be strongly dependent upon polymerization temperature. The copolymers were prepared by free-radical polymerization and had low molecular weights and molar ratios of ethylene: vinyl acetate greater than 3:1. Nuclear magnetic resonance and infrared studies showed that copolymers prepared at 150°C were highly branched and had little crystallinity. Branches were mainly alkyl groups on the polymethylene backbone segments. There was no evidence of δ-acetoxyalkyl branches. Long branches originating by intermolecular H abstraction from the acetylmethyl groups were also expected but could not be detected. These results were consistent with an intramolecular “backbiting” mechanism similar to that found in ethylene homopolymerizations. There was little or no participation by the vinyl acetate moiety in the branching scheme. Copolymers prepared at about 90°C had very few long or short branches and were more crystalline. Copolymers prepared between these temperatures had intermediate degrees of branching and crystallinity.     

Die kristallinität von äthylen-vinylacetat-copolymeren

Copolymers of ethylene and vinyl acetate of different composition were investigated by differential thermal and x-ray analysis in the temperature range of ?80 to 140°C. Compounds with more than 60 weight-% of vinyl acetate are amorphous. In the partially crystalline copolymers with lower contents of vinyl acetate the glass transition temperature is independent of composition and lies below that in amorphous copolymers. The melting points of the partially crystalline compounds increase with ethylene contents and can be described with the aid of a modified FLORY equation. The increase of the degree of crystallinity with ethylene content is demonstrated. The influence of thermal pre-treatment on the melting behaviour is discussed.     

Permeation of Phenol through Ethylene Copolymer Hollow Fibers

Abstract

Hollow fibers were spun from low-density polyethylene, an ethylene/propylene copolymer, ethylene/vinyl acetate copolymers, and ethylene/ethyl acrylate copolymers. The phenol permeation rates through these hollow fibers by reactive dialysis were measured over a range of temperatures, allowing the calculation of the apparent activation energies for transport. The permeation rates for phenol transport were found to be dependent upon the degree of crystallinity in the hollow fiber and the increased solubility of phenol in the hollow fiber due to the presence of the polar ethyl acrylate and vinyl acetate groups in the amorphous phase.     

氯醋树脂中残留单体脱吸工艺的改进

介绍了氯醋树脂中残留单体对氯醋树脂质量的影响,采用热水加热浆料、负压汽提等技术后,减少了氯醋树脂中残留单体的含量,提高了氯醋树脂的质量.     

Synthesis and evaluation of alkyl fumarate–vinyl acetate copolymers in combination with alkyl acrylates as flow improvers for Borholla crude oil

A number of alkyl fumarate–vinyl acetate copolymers were prepared and evaluated as flow improvers for high waxy Borholla crude oil. Alkyl fumarate–vinyl acetate copolymers having 19·2 as the average carbon number of the alkyl group in combination with polybehenyl acrylate were found to show optimum activity. Alkyl fumarate–vinyl acetate copolymers reduce the pour point, plastic viscosity and yield stress considerably and polybehenyl acrylate prevents the crude oil from attaining the gel structure on prolonged storage.     

Procedure for calculating the crystallinity of ethylene–vinyl acetate copolymers and low-density polyethylene as a function of temperature

A method is described for determining the x-ray crystallinity of ethylene–vinyl acetate copolymers at differing temperatures. An equation is derived for the symmetrical curves of crystallinity versus temperature thus obtained, from which the crystallinity at any temperature can be calculated. In order to determine the constants of the equation for a particular polymer, it is only necessary to determine the melting point and per cent crystallinity of the resin at a known temperature. The equation can also be applied to conventional polyethylenes, but not to linear polyethylenes. It is suggested that this is due to the former resins having a broad crystallite size distribution compared with the narrow distribution present in high-density polyethylene.     

The rheological properties of vinyl chloride–vinyl acetate copolymers

Copolymers of vinyl chloride–vinyl acetate have been prepared with different vinyl acetate contents and molecular weights and under different polymerization conditions. A rheological study of these copolymers indicates that they behave in some ways like externally plasticized PVC. For instance, as the vinyl acetate content increases, the melt viscosity decreases, the flow activation energy decreases, and the copolymer becomes more Newtonian. However, the critical shear rate for melt fracture increases, resembling the addition of elastic polymers to PVC. An increase in copolymer molecular weight has a similar effect on the rheological behavior as in PVC, except that the flow activation energy is observed to increase rather than decrease. Decreasing the polymerization temperature affects the flow properties of the copolymer, probably due to changes in degree of branching and crystallinity. A copolymer made by the delayed addition of vinyl chloride, having a more random structure than one made by the conventional batch method, exhibited quite different flow behavior. It had a lower melt viscosity, higher critical shear rate, and lower flow activation energy.     

Crystalline properties of poly(ε‐caprolactone)‐block‐poly(vinyl acetate) block copolymers: influence of synthesis route

Poly(ε‐caprolactone)‐block‐poly(vinyl acetate) (PCL‐b‐PVAc) block copolymers were synthesized using two approaches: a ‘coupling’ approach using click chemistry reaction and a ‘macroinitiator’ route. Different copolymers, varying by their block lengths, were prepared with both methods. PCL is a semi‐crystalline polymer, and consequently PCL blocks of PCL‐b‐PVAc are able to crystallize. The purpose of this work was to analyse the influence of the method of copolymer synthesis on the crystallinity of the PCL blocks. The results indicate a significant decrease of the crystallinity of the PCL blocks in copolymers obtained using the coupling method, compared to PCL homopolymers, in contrast to copolymers obtained through the macroinitiator approach for which the crystallinity of PCL is much less affected. This influence of the synthesis method is explained by the presence, in the copolymers obtained using the click reaction, of a rigid triazol cycle binding the two blocks, limiting their mobility and decreasing the tendency of PCL to crystallize. © 2013 Society of Chemical Industry     

Ataktisches polypropylen als pfropfgrundlage für die monomeren vinylacetat und vinylchlorid. Herstellung undeigenschaften der pfropfprodukte

The possibility of the application of atactic polypropylene is investigated as graft base for the preparation of graft copolymers of vinyl acetate and vinyl chloride respectively graft copolymers from vinyl acetate onto polypropylene as graft base for the preparation of graft copolymers of vinyl chloride in relation to the composition of the original mixture. After compounding of the graft products with polyvinyl chloride or ABS/polyvinyl-chloride mixtures selected mechanical properties are presented in relation to the quantity and composition of the incorporated graft copolymers.     

Improved adhesion of EVAs with different vinyl acetate contents treated with sulphuric acid

Four ethylene vinyl acetate copolymers (EVAs) containing 9, 12, 18 and 20 wt% vinyl acetate (VA) were treated with concentrated sulphuric acid to improve their adhesion to polychloroprene (PCP) adhesive. The tensile strength and Young's modulus of EVAs decreased as the VA content increased, due to the reduction in crystallinity of the polyethylene blocks in the copolymer. The modifications produced in the EVAs by treatment with sulphuric acid were followed using contact angle measurements (water, 25 °C), ATR-IR spectroscopy and scanning electron microscopy (SEM). Adhesive-bond strength was obtained by T-peel tests on treated EVA/polychloroprene adhesive joints. The vinyl acetate content in the EVA affected the extent, but not the nature, of the surface modification produced by treatment with sulphuric acid. The treatment produced both sulfonation and oxidation on the EVA surfaces. The higher the vinyl acetate content in the EVA, the more significant the modifications produced. Increased T-peel strengths of EVA/polychloroprene adhesive + 5 wt% polyisocyanate joints were obtained and a mixed failure (adhesion failure + cohesive failure in the adhesive) was produced. It was found that, to be effective, the treatment of EVAs must be carried out with 96 wt% sulphuric acid.     

Miscibility of poly(vinyl acetate) and vinyl acetate-ethylene copolymers with styrene-acrylic acid and acrylate-acrylic acid copolymers

Poly(vinyl acetate) and vinyl acetate-ethylene (VAE) copolymers compose one of the more important polymeric materials, widely employed in coating and adhesive applications. A new class of miscible polymer blends involving poly(vinyl acetate) and VAE with styrene-acrylic acid and acrylate-acrylic acid copolymers has been found. Experimental windows of miscibility as a function of the ethylene content for VAE copolymers and the acrylic acid content of the acrylate-acrylic acid copolymers are observed (acrylate = methyl acrylate, ethyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate). Employing well-established analog heat of mixing measurements, predicted windows of miscibility were compared with experimental results. Fair qualitative agreement was observed and supported the hypothesis that specific rejection arguments can be employed to explain the observed miscibility. Failure to quantitatively predict miscibility based on the analog heat of mixing measurements may be due to the higher association tendencies of the model compounds relative to acrylic acid units in the high molecular weight polymers. No miscible combinations were found for methyl methacrylate-acrylic acid copolymers or acrylate-methacrylic acid copolymers in admixture with poly(vinyl acetate) or the VAE copolymers, thus indicating the sensitivity of phase behavior to minor structural changes. VAE (30 wt % ethylene) copolymers were also noted to be miscible with several polymers previously noted to be miscible with poly(vinyl acetate), namely, poly(vinylidene fluoride), poly(ethylene oxide), and nitrocellulose. © 1995 John Wiley & Sons, Inc.     

Thermal characteristics of poly(ethylene terephthalate) fiber grafted with poly(vinyl acetate) and poly(vinyl alcohol)

Poly(ethylene terephthalate) (PET) fibers were grafted with poly(vinyl acetate) (PVAc) and poly(vinyl alcohol) (PVA). The effects of graft copolymers PVAc and PVA on morphological properties of PET were evaluated by differential thermal analysis, differential scanning calorimetry, and thermogravimetric analysis. Melting temperature, heat of fusion, and mass fractional crystallinity of PET was not affected by graft PVAc and PVA. No individual glass transition and melting points corresponding to the graft PVAc and PVA were observed, indicating thereby that graft copolymer mainly exists in the form of free chains inside the PET matrix. Poly(vinyl alcohol) graft copolymer degraded at much lower temperatures than poly(vinyl alcohol) in powder form. Thermal stability of PET fiber was not affected by graft PVAc, where as PET–g–PVA showed an additional degradation point at 360°C.     

The conversion of ethylene–vinyl acetate copolymers with aluminum alcoholates

If ethylene–vinyl acetate copolymers are converted with aluminum alcoholates, crosslinked products will form. This reaction was studied on the basis of the viscosity variation and the amount of acetic acid ester formed. The constants of the reaction velocity for the conversion with various aluminum alcoholates were determined and a reaction mechanism is discussed.     

Kinetic features of the nonisothermal oxidative degradation of ethylene vinyl acetate copolymers

Thermogravimetric analysis was used for a comparative investigation of the thermooxidative decomposition of ethylene vinyl acetate (EVA) copolymers with different vinyl acetate (VA) group contents. There were two stages of mass loss in this process. It was revealed that the apparent activation energies were correlated with the content of VA groups in the EVA copolymers. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1958–1961, 2004     

Synthesis of vinyl phenyl acetate and an evaluation of vinyl chloride/vinyl phenyl acetate copolymers

The synthesis of vinyl phenyl acetate, by an ester interchange reaction between phenyl acetic acid and vinyl acetate and utilizing a catalyst, is described. Copolymerization with vinyl chloride, in a suspension system and using a peroxide catalyst, is described on a laboratory and pilot plant scale. Monomer/copolymer compositions, for an initial charge consisting of vinyl chloride/vinyl phenyl acetate (80/20 by weight) are presented over a range of conversions, as an indication of reactivity ratios. Discs, molded from unstabilized copolymers, show very good clarity and color stability, which improve with increased comonomer loading. Some retention of unpolymerized vinyl phenyl acetate monomer occurred, and some increase in softening points resulted following two reprecipitations from acetone into excess methanol. Compound from a 96/4 vinyl chloride/vinyl phenyl acetate copolymer has better color stability than does an equivalent vinyl chloride/vinylidene chloride copolymer compound. The enhanced color and heat stability of the copolymers is attributed to the aromatic character of the comonomer vinyl phenyl acetate.     

New vinyl ester monomers for emulsion polymers

New vinyl ester monomers are now available for the preparation of emulsion copolymers with improved hydrolytic stability and water resistance. These improved properties are the result of uniform copolymerization of hydrophobic monomers having approximately the same reactivity as vinyl acetate. Latex coatings with excellent gloss, water spot resistance, blocking and other desirable performance properties can now be obtained with vinyl acetate copolymers.     

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     

Dynamic–mechanical properties of modified poly(ethylene‐co‐vinyl acetate)

To study the relationship among relaxation peaks observed in dynamic mechanical experiments and the structure of poly(ethylene‐co‐vinyl acetate) (EVA), EVA copolymers with different substitution in the carbonyl group were synthesized. EVA was hydrolyzed to obtain poly (ethylene‐co‐vinyl alcohol) and was subsequently reacted with formic, hexanoic, and octanoic acids. The copolymers synthesized were characterized by infrared spectroscopy. Analysis of the DMA spectra of the copolymers showed that their relaxation behavior depends on the vinyl acetate concentration. The α‐ and β‐transitions were observed in EVA copolymers with 8 and 18 wt % of functional groups, and the relationship among relaxation process with the structure of polymer was investigated. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1371–1376, 2005     

两亲性聚乙烯醇-b-聚苯乙烯嵌段共聚物的合成及表征

采用原子转移自由基聚合(ATRP)法合成了具有两亲性的聚乙烯醇-b-聚苯乙烯嵌段共聚物P(VA-b-St)。首先利用调聚反应制备了带三氯甲基端基的聚醋酸乙烯大分子引发剂。以联二吡啶作配体、氯化亚铜为催化剂,引发苯乙烯单体聚合,得到结构明确的P(VAc-b-St)嵌段共聚物,而后通过皂化反应将其水解,从而得到两亲性嵌段共聚物P(VA-b- St);产物采用FT-IR、1H NMR、GPC等方法进行结构表征。P(VA-b-St)在不同浓度溶剂中的自组装行为用TEM进行了观察,结果表明:P(VA-b-St)可在DMF溶剂中形成球状囊泡结构,其尺寸达到纳米级。     

Terpolymers. III. Isochronal viscoelastic parameters for terpolymers of vinyl stearate,vinyl acetate,and vinyl chloride

Isochronal viscoelastic parameters were collected for many of the copolymers, terpolymers, and diluent mixtures whose mechanical properties at ambient temperatures were reported in the preceding paper. In the polymeric systems, vinyl stearate, acting as the primary internal plasticizer, was introduced into terpolymers by displacing vinyl acetate from base copolymers of vinyl acetate and vinyl chloride, across the range of composition. In the diluent mixtures, poly(vinyl chloride) was plasticized by di-2-ethylhexyl phthalate across the range of compositions. For direct comparison with the mixtures, vinyl chloride was plasticized by copolymerization with vinyl stearate across the same range of compositions. Moduli for the co- and terpolymers reached the low values characteristic of soft materials at room temperature only through a short range of vinyl stearate composition. At higher internal plasticizer compositions, side-chain crystallization stiffened the samples and raised their moduli. In contrast, moduli for the mixtures decreased steadily with increase in diluent at ambient temperature. The effective use temperature ranges were narrow for the co- and terpolymers but broad for the mixtures. Curve broadening was similar for both types of systems, but reached a maximum at about 40 weight-% plasticizer for the diluent mixtures. The slopes of the glassy modulus with decreasing temperature at 50°C below T_g for the vinyl stearate copolymers were relatively large. However, moduli close to that of poly(vinyl chloride) were reached only near the temperature range associated with the γ-transition. Consequently, this behavior was attributed to motions of the side chains in the glassy matrix. Room temperature moduli, which could be obtained before the onset of melting, were correlated with the fractional side-chain crystallinity for polymers having a high vinyl stearate content. From this relation, the modulus for the hexagonal crystal form of the side-chain crystallites of poly(vinyl stearate) was estimated to be 1.2×10¹⁰ dynes/cm². Moduli for the glassy amorphous phase of this same polymer appeared to have one sixth of this value at 40°C below the glass transition. The glass transition temperature occurred about 10° below the inflection temperature at 10⁹ dynes/cm², as an average for all of the systems studied.