Showing papers on "Methyl acrylate published in 1971"

Effects of complexing agents in radical copolymerization

Abstract: Radical copolymerization of methyl methacrylate (MMA, M1) with various monomers has been studied in presence of modifiers, i.e., complexing agents (CA): ZnCl2, AlCl3, AlBr3, Al(C2H5)2Cl, forming coordinate complexes with ester group of the monomer and of the propagating radical. The comonomers of the first group form complexes of similar structure and stability as MMA, methyl acrylate, or butyl acrylate. The comonomers of the second group do not form complexes with the modifiers (vinylidene chloride, 2,6-dichlorostyrene, p-chlorostyrene, styrene). For all systems studied the copolymer composition follows the Mayo-Lewis equation. In the first group of the systems the effective reactivity ratios (r1, r2) approach unity with increase of the CA molar content (r1 = r2 ≃ 1 at [(CA)/MMA] + [MA] ≥ 0,3) In the second group of the systems the values of r1 either increase to a limit value (at [CA]/[MMA] ≥ 0.3), pass through maximum, or decrease to a limiting value with the CA molar content. The values of r2 decrease in all systems. The character of variation of r1 and r2 has been explained in terms of effects of the CA's on reactivity of MMA and PMMA radical. The equations for the copolymer compositions in these systems have been derived.

Free‐radical homopolymerization and copolymerization of vinylferrocene

Abstract: The benzene solution homopolymerization of vinylferrocene, initiated by azobisisobutyronitrile, gave a series of benzene-soluble homopolymers. Thus, free-radical copolymerization studies were performed with styrene, methyl acrylate, methyl methacrylate, acrylonitrile, vinyl acetate, and isoprene in benzene. With the exception of vinyl acetate and isoprene, which did not give copolymers with vinylferrocene under these conditions, smooth production of copolymers occurred. The relative reactivity ratios, r1 and r2, were obtained for vinylferrocene–styrene copolymerizations by using the curve-fitting method for the differential form of the copolymer equation, by the Fineman-Ross technique, and by computer fitting of the integrated form of the copolymer equations applied to higher conversion copolymerizations. In styrene (M2) copolymerizations, the curve-fitting and Fineman-Ross methods both gave r1 = 0.08, r2 = 2.50, while the integration method gave r1 = 0.097, r2 = 2.91. Application of the integration method to methyl acrylate and methyl methacrylate (M2) gave values of r1 = 0.82, r2 = 0.63; r1 = 0.52, r2 = 1.22, respectively. The curve-fitting method gave r1 = 0.15, r2 = 0.16 for acrylonitrile (M2) copolymerizations. From styrene copolymerizations, vinylferrocene exhibited values of Q = 0.145 and e = 0.47.

The Codimerizations of Styrene with Vinyl Compounds Catalyzed by Olefin-palladium(II) Chloride Complexes

Abstract: The codimerization of styrene with vinyl compounds catalyzed by di-μ-chloro-dichlorobis(styrene)dipalladium(II), (Pd(C6H5CH=CH2)Cl2)2, was investigated in a homogeneous system under mild conditions. The reaction of styrene and methyl acrylate carried out at 50°C for 6 hr yielded 220% codimers, 169% dimers of methyl acrylate, and 18% dimers of styrene, on the basis of the palladium(II) used. The codimerizations of styrene with vinyl acetate and with methyl vinyl ketone gave 50% codimer and 125% codimers respectively. When nitroethylene and n-butyl vinyl ether were used as the vinyl compound, no codimers were formed. The codimerization of styrene-d3 with ethylene was also carried out. The reaction mechanism involving the five-coordinate hydridopalladiumolefin intermediate was proposed and discussed in the terms of the distribution of deuterium in the codimer of styrene-d3 and ethylene, the functional group effects of vinyl compounds, and solvent effects on the codimerization.

Thermische, nichtkatalysierte Cycloadditionen der Acrylverbindungen an Cycloheptatrien

Abstract: The cycloaddition reactions of cycloheptatriene with acrylonitrile and methyl acrylate have been investigated in some detail. The exo (1) and endo (2) adducts resulting from the [2+2+2]-cycloaddition of acrylic components to the 2,5-positions of cycloheptatriene have been separated and the structures have been elucidated by NMR. The by-products are 7-endo-substitued derivatives of bicyclo[4,2,1]nona-2,4-diene (3), resulting from the formal [6+2]-cycloaddition to the 1,6-positions of cycloheptatriene. The mechanism of their formation is discussed. Irradiation (λ = 253,7 nm) of 3 in various solvents gave an almost quantitativ yield of [2+2]-cyclodimers of the 14 type. No intramolecular photocyclization of 3 to cyclobutenes 13a and/or 13b was observed.

1,3-Dipolar character of six-membered aromatic rings. Part I. 1-Methyl-3-oxidopyridinium

Abstract: The title compound reacts as a 1,3-dipole across the 2- and 6-positions with the dipolarophiles N-phenylmaleimide, acrylonitrile, methyl acrylate and methyl methacrylate. The stereochemistry of the adducts is deduced from n.m.r. spectra. The title compound and maleic anhydride yield a salt.

Oil spill recovery

Abstract: An article of manufacture for use in the removal and recovery of oil slicks or spills floating on the surfaces of bodies of water consisting essentially of a foam of an ethylene-alkyl acrylate copolymer having a melt index of at least 800, preferably an ethylene copolymer containing from about 10 up to about 45 weight percent methyl acrylate having a melt index in the range of from about 1,000 up to about 2,000 and a process for using such foams in the selective removal of oil from water surfaces and the recovery of the absorbed oils from said foams is disclosed.

Stereoregularity of radically polymerized poly(alkyl acrylates) and poly(trimethylsilyl acrylates) and the preparation of syndiotactic poly(methyl acrylate)

Abstract: Nuclear magnetic resonance (NMR) spectroscopy was used to determine the stereoregularity of radically polymerized poly(ethyl acrylates), poly(trimethylsilyl acrylates), and poly(isopropyl acrylate-α,β-d2). The ethyl acrylate polymers consisted of a random configuration having about 50% of isotactic diads, and their stereoregularities were independent of the polymerization temperature (40 to −78°C). Poly(trimethylsilyl acrylates) and poly(isopropyl acrylate-α,β-d2) prepared at low temperatures had a syndiotactic configuration. Syndiotactic poly(methyl acrylate) was derived from syndiotactic poly(trimethylsilyl acrylate). For poly(methyl acrylate), an approximate estimation of the stereoregularity by infrared spectroscopy was proposed.

Transport of noble gases in poly(methyl acrylate)

Abstract: The permeability, diffusivity, and solubility of He, Ne, Ar, and Kr were determined in poly(methyl acrylate) (PMA), in a temperature range encompassing the glass transition temperature, Tg. Activation energies for diffusion, ED, were higher above Tg than below Tg for all four penetrants in PMA and in the structural isomer of PMA, poly(vinyl acetate) (PVA). For all penetrants studied, the Tg, the magnitude of the enthalpy of mixing (ΔHm), as well as the ED were all larger for PVA than for PMA. These differences were attributed to the stronger dipole-dipole interactions possible in PVA where the dipolar carbonyl group is separated from the chain backbone by an oxygen atom. The carbonyl group in PMA is immediately adjacent and presumably sterically hindered by the chain backbone which suggests that PMA might be a stiffer molecule than PVA. Entropy considerations suggest that molecularly stiff polymers should be associated with small values of v Δα, ΔED, ΔED, ΔHp, and (β), where v is the specific vol...

The thermal degradation of poly(methyl acrylate) V. Relative rates of crosslinking and chain scission

Abstract: By using the treatment of CHARLESBY and PINNER the relative rates of scission and crosslinking during the thermal degradation of poly(methyl acrylate) at 210 and 243°C have been determined. It is shown that the relative frequency of crosslinking to scission increases as the degree of branching in the sample increases. Die relativen Geschwindigkeiten von Spaltung und Vernetzung beim thermischen Abbau von Polymethylacrylat bei 210 und 243°C wurden nach der Methode von CHARLESBY und PINNER bestimmt. Die relative Haufigkeit der Vernetzung gegenuber der Spaltung nimmt zu, wenn der Anteil an Verzweigungen in den eingestzten Proben ansteigt.

Film formation from polymer dispersions

Abstract: The coalescence of a poly(vinylidene chloride/methyl acrylate/acrylic acid) latex was found to occur only above the Tg. The various theories of film formation from polymer dispersions attribute latex coalescence to three types of forces: the pressure due to the polymer–air interface, the pressure due to a polymer–water interface, and the pressure due to capillary action. Analysis of the forces indicates that none are sufficient to cause coalescence below Tg while any, or all, may cause coalescence above Tg.

Cyclocopolymerization of Diallyl Phthalate with Vinyl Acetate and Methyl Acrylate

Abstract: フタル酸ジアリル (M1) と酢酸ビニルおよびアクリル酸メチル (M2) との共重合を過酸化ベンゾイルを開始剤として種々の条件下で行なった。共重合速度あるいはコポリマーの極限粘度は仕込みモノマー中の M1 含量の増加とともに著しく減少し, その様子はコモノマーが共役モノマーか非共役モノマーかにより差異が見られた。これは生長ラジカルによる DAP のアリル水素の引き抜き易さ, さらにはアリルラジカルの再開始能の違いなどに起因するものと推察された。M1 の分子内環化反応を考慮した共重合組成式を用いて各速度定数比を求め, 次の値を得た。これらの結果について考察した。

Heat vulcanizable polysiloxane compositions containing asbestos

Abstract: A heat vulcanizable silicone rubber composition comprising 5 to 94.47 percent by weight of an organopolysiloxane polymer, 5 to 75 percent by weight of an asbestos filter, and 0.25 to 10 percent by weight of an acrylic ester. The composition also includes a silica filler, a peroxide curing catalyst and a process aid. The preferred acrylic ester are methyl acrylate and trimethylolpropanethimethacrylate.

Process for the production of ion exchangers with tertiary amino groups

Abstract: 1,222,929 Ion exchange resins CHEMIEKOMBINAT BITTERFIELD VEB 25 Sept, 1969, No 47258/69 Heading C3P Weakly basic anion exchangers with tertiary amino groups are prepared by a process wherein an ion exchanger containing primary and/or secondary amino groups is pre-swollen in dilute formic acid and then treated with concentrated formic acid and with an aldehyde or ketone at an initial temperature of at least 0‹ C, the temperature being increased stepwise during the course of the reaction to reflux temperature The resin may be prepared by copolymerizing styrene or methylstyrene with divinyl benzene, chloromethylating and aminating, or by copolymerizing an acrylic acid derivative with divinyl benzene and aminating Specified aldehydes and ketones are formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde and acetophenone, which may be used in aqueous or alcoholic solutions Many suitable amines are listed and examples describe the reaction of formic acid and formaldehyde with preswollen exchangers derived from chloromethylated (1) styrene/divinylbenzene copolymer; and (2) styrene/acrylonitrile/divinylbenzene copolymer and ethylene diamine; chloromethylated (3) styrene/divinylbenzene copolymer and diethylene triamine; (4) ethyl acrylate/divinylbenzene copolymer and diethylenetriamine; and (5) methyl acrylate/divinyl benzene copolymer and triethylene tetramine

Mixed Monolayers of Poly(methyl acrylate) and Its Saponified Polymer

Abstract: A film balance study of the mixed monolayers with various ratios of poly(methyl acrylate) and its saponified polymer or of the monolayers themselves was carried out on distilled water, and the mixed monolayers were compared with individual monolayers of the saponified polymers. These mixed monolayers expanded more than individual saponified polymers at the same degree of saponification, giving larger limiting areas. Their limiting areas deviated from the linearity between the limiting area and the degree of saponification, in contrast to the fact that the limiting areas of individual monolayers decreased linearly with an increase in the degree of saponification. This fact can be considered to be due to interactions between the side chains of the ploymers.

Crystal structure of methyl acrylate

Abstract: Methyl acrylate, CH2CHCOOCH3, has been crystallized, and x-ray data have been collected at −120°C. The crystals are orthorhombic, space group Pnma, with four molecules in the unit cell. The structure has been determined by using symbolic addition procedures, and refined to a final residual R factor of 0.10. The molecule is planar, and the intramolecular bond distances and angles are in good agreement with values obtained for the liquid monomer by electron diffraction techniques. Considerations of crystal geometry indicate that the packing hardly permits dimerization or polymerization of the molecules in regions of crystal perfection.

Diels–Alder reaction of unsymmetrical dienes with methyl acrylate

Abstract: The Diels–Alder reactions of 1-(p-substituted phenyl)buta-1,3-dienes with methyl acrylate are shown to give 2-arylcyclohex-3-enecarboxylates, irrespective of the nature of the aryl-substituent, but the steric course of the reaction is affected by the substituent. Similar results were obtained with 1-aryl-2,3-dimethylbuta-1,3-dienes.

The graft photopolymerization of acrylates and methacrylates on wool in dimethyl sulfoxide

Abstract: Irradiation of wool by short-wavelength ultraviolet light in the presence of acrylate or methacrylate esters in dimethyl sulfoxide causes intermediate grafts (2%–10%) of polymer on the surface of the wool. The amount of grafting and homopolymerization and the evenness and regularity of photografted polymer are dependent upon the monomer used. With methyl acrylate, the reaction time, monomer concentration, and introduction of water as cosolvent affect the degree of fiber grafting and the amount and molecular weight of accompanying homopolymer. Polymers grafted onto wool by this technique change the tensile properties and the water desorption characteristics of the wool.

Polymerization and Copolymerization of Allyl Allyl Sulfonate

Abstract: Allyl allyl sulfonate (AAS) has been polymerized under the influence of azobisisobutyronitrile to low molecular weight polymers containing cyclic structures. This is in contrast to the behavior of allyl ethane sulfonate (AES) and of propyl allyl sulfonate (PAS) which did not polymerize under the same conditions. AAS has been copolymerized with styrene, methyl acrylate, and vinyl acetate. The following copolymerization reactivity factors have been found: rAAS 0.01 ± 0.01 rstyrene 13 ± 1 rAAS 0-37 ± 0.09 rmethyl acrylate 5.3 ± 0-7 rAAS 1.54 ± 0.08 rvinyl acetate 0.5 ± 0.15 The results indicate that AAS has a higher reactivity than AES or PAS.

The michael reaction in non-alkaline media. v. effect of structure on the rate and mechanism of addition of 1,1-dinitrocarbanions to methyl acrylate,

Abstract: : The kinetics of the addition of a series of substituted 1,1-dinitromethide ions to methyl acrylate were studied in 50% dioxane and in water. The requirement for acid catalysis in these Michael additions was defined as a lowering of the free energy of the transition state for the reversal of the initially formed carbanion RC(NO2)2CH2CHCO2CH3. This can be accomplished by a substituent R which is able to delocalize negative charge by a resonance interaction. For borderline cases, the rate of protonation of the carbanion RC(NO2)2CH2CHCO2CH3 may be a deciding factor in effecting a change from an acid catalyzed to an uncatalyzed reaction. A comparison of the specific rate and activation parameters for fluorodinitromethide ion with alkyl, chloro and hydrogen dinitromethide ions shows that the 2000-fold increase in rate for R = F is due to a 5 kcal./mo1 decrease in Delta H*. This enhanced nucleophilicity is attributed to a destabilization of an sp2-hybridized carbon by an alpha-fluorine substituent. (Author)

Graft polymers containing epoxide groups

Abstract: 1,220,786. Grafted epoxy resins. FARBENFABRIKEN BAYER AG.. 28 May, 1969 [12 June, 1968], No. 26889/69. Heading C3G. A graft polymer is prepared in the presence of free radicals from at least one ethylenically unsaturated-monomer and a graft base which is an optionally modified epoxidic compound with more than one epoxy group and at least one alcoholic hydroxyl group per molecule, at least 5% of the alcoholic hydroxyl groups being esterified by at least one monoisocyanate, said epoxidic compound being derived from a polyhydric phenol, a polyhydric alcohol, aniline, 4,4 1 - bis - (N - methylamino) - diphenylmethane or an olefinically unsaturated compound. The epoxide compound may be modified with a polyamine, cyclic carboxylic acid anhydride, carboxylic acid, polyalcohol, phenol-urea or melamine-aldehyde resin, or a diisocyanate as well as the monoisocyanate. In the examples an epoxy resin derived from bisphenol-A and epichlorohydrin is (i) modified with methoxymethyl isocyanate and grafted with vinyl acetate; (ii) modified with methoxymethyl isocyanate or methyl isocyanate and grafted with methyl methacrylate and acrylic acid; (iii) simultaneously modified with methoxymethyl isocyanate and grafted with (a) methyl acrylate and allyl glycidyl ether, (b) ethyl acrylate and N - methylolmethacrylamide methyl ether, (c) n-butyl acrylate and 2-hydroxypropyl methacrylate or (d) ethyl acrylate, acrylamide and styrene; (iv) modified with methoxymethyl isocyanate and grafted with (a) methyl methacrylate, acrylonitrile and acrylic acid (b) methyl methacrylate, methyl acrylate and acrylic acid (c) methyl methacrylate and methacrylic acid ethyl ester isocyanate (d) styrene, methyl methacrylate and acrylic acid (e) methyl methacrylate and acrylic acid, with further addition of methoxymethyl isocyanate and methyl methacrylate during grafting; (v) modified with methoxymethyl isocyanate and grafted with (a) ethyl acrylate and acrylic acid or (b) styrene, acrylonitrile and acrylic acid; (vi) modified with cyclohexyl isocyanate and grafted with (a) methyl methacrylate and acrylic acid (b) methyl methacrylate, n-butylacrylate and acrylic acid (c) methyl methacrylate, vinylacetate and acrylic acid (d) styrene and maleic anhydride or (e) methyl methacrylate, glycidyl methacrylate and, optionally, methacrylic acid ethyl ester isocyanate; (vii) modified with stearyl isocyanate and grafted with methyl methacrylate, and acrylic acid; (viii) modified with methoxymethyl isocyanate and grafted with ethyl methacrylate, or methyl methacrylate, and acrylic acid; in addition, an epoxy resin derived from bisphenol-A, epichlorohydrin and the glycidyl ethers of o- and p-tert.butyl phenols is modified with methoxymethyl isocyanate and grafted with methyl methacrylate and acrylic acid and a bisphenol-A/epichlorohydrin resin is modified with hexamethylene diamine prior to being reacted with methoxymethyl isocyanate and grafted with methyl methacrylate and glycidyl methacrylate. The graft polymers are cross-linked alone or with an agent such as hexahydrophthalic acid anhydride and, optionally, ungrafted epoxidic compound.

Primer coating composition

Abstract: Subject disclosure relates to a novel and improved one package primer coating composition which readily adheres to the metal surface to be protected and to the subsequently applied acrylic lacquer topcoat. The ingredients of the improved one package primer composition include strontium or zinc chromate, a magnesium silicous extender, a methyl methacrylate ethyl acrylate copolymer, a methyl methacrylate methyl acrylate copolymer and the solvent, toluene.

Syntheses and reactions of functional polymers. LVI. Syntheses and properties of poly-(N-2-oxazolidonyl-methacrylamide) and poly-5-(3-phenyl-2-oxazolidonyl)-methyl acrylate

Abstract: N-2-Oxazolidonyl-methacrylamide was synthesized by the reaction of N-amino-2-oxazolidone with methacrylic chloride. N-2-Oxazolidonyl-methacrylamide(M1) was polymerized and copolymerized with some vinyl compounds such as styrene(M2), methacrylic acid, N-vinyl-2-oxazolidone and N-vinyl-2-pyrrolidone by free radical initiator. The monomer reactivity ratios, r1 (= 0.38) and r2 (= 1.15) were determined by the method of FINEMAN and ROSS, and the ALFREY-PRICE Q (= 1.99) and e (= 0.11) values were estimated. These polymers were soluble in dimethylformamide and formic acid, but insoluble in common solvents such as water, methanol and acetone. These polymers adsorbed phenol effectively, and the bonding characters in the complexes of polymers and phenol were investigated. In addition, 5-(3-phenyl-2-oxazolidonyl)methyl acrylate was synthesized by the reaction of 3-phenyl-5-chloromethyl-2-oxazolidone with acrylic acid and polymerized by radical initiator. N-2-Oxazolidonyl-methacrylamid (M1) wurde durch Umsetzung von N-Amino-2-oxazolidon mit Methacrylsaurechlorid dargestellt und mittels eines radikalisch zerfallenden Initiators polymerisiert, auserdem mit Styrol (M2), Methacrylsaure, N-Vinyl-2-oxazolidon und N-Vinyl-2-pyrrolidon copolymerisiert. Die relativen Reaktivitatskonstanten r1 (= 0.38) und r2 (= 1.15) wurden mit Hilfe der FINEMAN-ROSSschen Gleichung bestimmt sowie die Q- (= 1.99) und e- (= 0.11) Werte nach ALFREY und PRICE berechnet. Diese Polymeren sind loslich in Dimethylformamid und Dimethylsulfoxid, aber unloslich in den ublichen Losungsmitteln wie Wasser, Methylalkohol und Aceton. Diese Polymeren adsorbieren Phenol. Der Charakter der Bindung in den Komplexen aus Polymeren und Phenol wurde untersucht. Schlieslich wurde 5-(3-Phenyl-2-oxazolidonyl)-methylacrylat durch Umsetzung von 3-Phenyl-5-chloromethyl-2-oxazolidon mit Acrylsaure dargestellt und mittels eines radikalisch zerfallenden Initiators polymerisiert.

Photopolymerization of Methyl Acrylate in Dimethyl Sulfoxide

Abstract: Methyl acrylate in dimethyl sulfoxide was polymerized by 2537 A ultraviolet light. The photo reaction exhibited zero-order kinetics for a given initial concentration and produced short chain polymers (M[Mbar]W ∼ 20,000). Low sulfur values of isolated polymers indicated no appreciable solvent incorporation during the polymerization.

Graft copolymers of olefinic nitriles and olefinic esters on diene rubbers

Abstract: Impact resistant polymers having low permeability to gases and vapors are prepared by polymerizing an olefinic nitrile such as acrylonitrile with an olefinic ester such as methyl acrylate in an aqueous medium in the presence of a diene rubber.

Hydroxy-terminated copolymers of butadiene and acrylates

Abstract: 1. THE HYDROXY-TERMINATED COPOLYMERS OF BUTADIENE AND FERROCENYL METHYL ACRYLATE PREPARED BY REACTING FERROCENYL METHYL ACRYLATE AND A SUITABLE POLYMERIZATION INITIATOR IN AN INERT ORGANIC SLVENT WITH BUTADIENE AT A REACTION TEMPERATURE AND FOR A REACTION TIME PERIOD SUFFICIENT FOR SAID REACTION TO TAKE PLACE ABOUT WHICH SOLVENT REMOVAL IS EFFECTED AND SAID COPOLYMERS ARE DRIED AT A SUITABLE DRYING TEMPERATURE WHILE UNDER REDUCED PRESSURE; SAID INITIATOR BEING SELECTED FROM AZO-BIS-(2-METHYL-5-HYDROGENVALERONITRILE), AND AZO-BIS(HYDROXYETHYL-2-METHYL PROPIONATE), TRILE), AND AZO-BIS(HYDROXYETHYL-2-METHYL PROPIONATE), SAID INERT ORGANIC SOLENT BEING SELECTD FROM TOLUENE, DIOXANE, AND DIMETHYL FORMAMIDE, SAID REACTION TEMPERATURE BEING IN THE RANGE OF ABOUT 60*C. TO ABOUT 80*C, SAID REACTION TIME BEING FROM ABOUT 24 HOURS TO ABOUT 120 HOURS, SAID DRYING IS ACCOMPLISHED AT A SUITABLE TEMPERATURE IN THE RANGE OF ABOUT 70*C. TO ABOUT 75*C. AND SAID REDUCED PRESSURE IS IN THE RANGE OF ABOUT 1 MILLIMETER, SAID COPOLYMERS BEING CHARACTERIZED BY A MOLECULAR WEIGHT IN THE RANGE FROM ABOUT 1000 TO ABOUT 10,000, HYDROXY-END GROUP CONTENT OF ABOUT 0.1 WEIGHT PERCENT TO ABOUT 2.5 WEIGHT PERCENT, AND AN IRON CONTENT OF ABOUT 0.74 PERCENT WEIGHT PERCENT TO ABOUT 12.0 WEIGHT PERCENT.