WO1993022353A1 - Polymeres et latex polymeres obtenus a partir d'esters vinyliques d'acides monocarboxyliques satures - Google Patents

Polymeres et latex polymeres obtenus a partir d'esters vinyliques d'acides monocarboxyliques satures Download PDF

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Publication number
WO1993022353A1
WO1993022353A1 PCT/EP1993/001133 EP9301133W WO9322353A1 WO 1993022353 A1 WO1993022353 A1 WO 1993022353A1 EP 9301133 W EP9301133 W EP 9301133W WO 9322353 A1 WO9322353 A1 WO 9322353A1
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Prior art keywords
polymers
vinylesters
monomer feed
polymer
monomer
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PCT/EP1993/001133
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English (en)
Inventor
Henricus Paulus Hubertus Scholten
Jan Vermeulen
David Pappie
Johannes Jacobus Keijsper
Roger Stewart Downing
Linda Louise Marie Guillaume Coppin
Bernadette Elisabeth Bongenaar-Schlenter
Jan Hofman
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Shell Internationale Research Maatschappij B.V.
Shell Canada Limited
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Publication of WO1993022353A1 publication Critical patent/WO1993022353A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
    • C07C53/126—Acids containing more than four carbon atoms
    • C07C53/128—Acids containing more than four carbon atoms the carboxylic group being bound to a carbon atom bound to at least two other carbon atoms, e.g. neo-acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F18/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
    • C08F18/02—Esters of monocarboxylic acids
    • C08F18/04—Vinyl esters
    • C08F18/10—Vinyl esters of monocarboxylic acids containing three or more carbon atoms

Definitions

  • This invention relates to polymers from vinylesters of satu ⁇ rated monocarboxylic acids, to latices containing such polymers, to the preparation of such polymers by means of emulsion, solution, or mass polymerization, to compositions comprising such latices and to solid polymeric products, for example redispersible latex powders formed by drying of such latices.
  • Vinylesters are used in many applications, ranging from the surface coating field, adhesives, textile impregnating, paper coating, cement mortars, etc. A group of compounds of particular
  • R-. , R», and R_ are alkyl groups of which at least one is a methyl group.
  • Particular interesting are vinylesters of a composi ⁇ tion of acids containing 9 carbon atoms, or of a composition of
  • VeoVa 15 acids containing 10 carbon atoms (sold by Shell under the trade ⁇ marks "VeoVa” 9, respectively “VeoVa” 10).
  • Another well-known example is vinyl pivalate (known as “VeoVa” 5).
  • a vinylester composition is known, previously sold as “VeoVa” 911, comprising a composition of vinylesters of
  • vinylesters impart on the resulting polymers excellent resistance to both saponification and exposure to ultra-violet light. Accordingly, these vinylester compositions and the polymers prepared therefrom have been subject of many patent applications. .25 Thus, they have been described in respect of emulsion polymers such as in general purpose, high quality and/or highly pigmented emul ⁇ sion paints, cement mortar modifiers, reactive latex primers; in respect of solution polymers such as solven -borne stoving paints, solven -borne air drying paints, and aqueous stoving paints suit ⁇ able for application by electrodeposition or spray; and in respect of mass polymers such as outdoor powder coatings, and aqueous or non-aqueous dispersion coatings.
  • emulsion polymers such as in general purpose, high quality and/or highly pigmented emul ⁇ sion paints, cement mortar modifiers, reactive latex primers
  • solution polymers such as solven -borne stoving paints, solven -borne
  • VeoVa 10 is known as a flexibilising comonomer
  • VeoVa 9 imparts rigidity to the polymer.
  • the second order (glass) transition temperature, Tg, of the homopolymers of these monomers reflect this difference, namely "VeoVa” 10 has a Tg of -3 °C, whereas that of "VeoVa” 9 is 60 ⁇ C.
  • water-borne coating systems generally contain a volatile organic diluent (coalescing agent) forming part of "the polymer particles dispersed in the aqueous phase.
  • a volatile organic diluent coalescing agent
  • a further example of a use of the aforementioned polymers of vinylesters of ⁇ . ⁇ -disubstituted monocarboxylic acid compositions is in the field of adhesives where a good balance between adhesive- ness, resistance against organic and alkaline/acidic solutions, and flexibility is required. In this field too, co onomers imparting enhanced flexibility are highly desirable.
  • R. and R naph each are branched or linear alkyl groups, and R, based on the weight of the composition of isomeric vinylesters, is
  • VEC's vinylester compositions
  • the invention provides for polymers, obtainable
  • the or each vinylester is a composition of vinylesters of isomeric saturated, monocarboxylic acids containing either 11, 12, 13, 14 or
  • R- and R- each are branched or linear alkyl groups
  • R based on the weight of the composition of isomeric vinylesters, is hydrogen in 1 to 25 %wt and a branched or linear alkyl group in 75 to 99 %wt
  • at least 80 %wt of the alkyl groups are linear alkyl groups, i.e., polymers obtainable by the polymeriza ⁇ tion of a monomer feed comprising one or more vinylesters selected from VEC 11, VEC 12, VEC 13, VEC 14 or VEC 15, and optionally one or more other copolymerizable monomers preferably in an amount of up to 90 %wt of the total monomer feed.
  • the polymers of the invention may be prepared by either emulsion, solution or mass polymerization of the monomer feed.
  • the one or more other copolymerizable monomers are suitably selected from monomers such as vinyl chloride, vinyl acetate, vinylidene chloride, vinyl propionate, acrylic acid (ester), methacrylic acid (ester) , alkali or alkaline earth metal vinyl sulphonates, lower olefins (ethene, propene, butene and/or pen- tene) , norbornadiene, other vinylesters, and styrene.
  • the one or more other copolymerizable monomers constitute 30 to 90 %wt of the total monomer feed, more preferably 50 to 80 %wt of the total monomer feed.
  • the optimum composition of the monomer feed used in each of the above polymer preparation processes is easily found by the following procedure. First a set of polymers is prepared from monomer feeds of a formulation similar to a proven monomer formula ⁇ tion. Then the resulting polymers are tested on their relevant properties (one or more of: storage stability of aqueous polymer suspensions; degree of conversion; hardness; flexibility; methyl- ethyl ketone resistance; water spot resistance; water absorption; etc.) . When schematically setting out the results in as many diagrams (for instance in three-component triangular diagrams) and then superimposing these diagrams, the overlapping area defines the monomer feed that meets the minimum requirements of the determined properties.
  • Polymer latices which are suitable for use as binders in paints and related products are usually made in batch or continuous (loop) reactors.
  • the presence of surfactant is an essential part of the emulsion polymerization process.
  • the polymerization is carried out in the presence of either a protective colloid, which improves the stability and flow-properties of the latex containing the polymer of the invention; a stabilising monomer; or a functional monomer.
  • Polymerization of the monomers occurs by a free-radical propagation reaction.
  • a polymer as defined above in accordance with the invention is prepared by emulsion polymerization wherein an aqueous emulsion comprising the monomer feed, one or more stabilizers, one or more buffering agents and one or more polymerization initiators is reacted at an elevated temperature.
  • Suitable monomer feeds resulting in polymers having a superior balance of properties contain one or more of the aforementioned VEC's, and optionally one or more of the monomers selected from: a further vinylester of a carboxylic acid; an alkyl ester of a polymerizable o,-.-ethylenically unsaturated carboxylic acid or their hydroxyethyl- or hydroxypropyl esters; a lower ole in; vinyl chloride; or a stabilising monomer selected from e.g. a, ⁇ -et yl- enically unsaturated carboxylic acids, (meth)acrylamide, diaceton acrylamide, sodium vinyl sulphonate, glycidylmethacrylate, or mixtures thereof.
  • polymers which are derivable from one or more of the aforementioned VEC's and vinyl acetate by emulsion polymerization in the presence of a colloid stabilizer such as hydroxyet yl cellulose (HEC), polyvinylalcohol (PVA) or polyvinyl- pyrrolidone (PVP).
  • a colloid stabilizer such as hydroxyet yl cellulose (HEC), polyvinylalcohol (PVA) or polyvinyl- pyrrolidone (PVP).
  • the polymers containing latices according to the present invention may be prepared under conditions which are known in the art and generally involve a temperature of from 75 to 85 ⁇ C when thermal initiation is used, or 40 to 70 "C when redox initiation is used.
  • Stabilizers suitably constitute about 1-8% by weight of the latex in total. It is preferred that the stabilizers used in the latex comprise at least one anionic surface active agent (stability during the polymerization process), or at least one surface active agent of the mixed anionic/non-ionic type (stability of the final latex). Optionally a non-ionic surface active agent is used too.
  • Suitable stabilizers, and the preferred amount to be used in, are for instance disclosed in European patent No. 295,727 and in Emulsifiers and detergents, international edition, volume 1 (by McCutcheon, The Manufacturing Confectioner Publishing Co., Glen Rock NY, USA 1990).
  • both an anionic surface active agent such as an alkylaryl sulphonate and a non-ionic surface active agent such as nonylphenol ethoxylate are used.
  • Suitable initiators forming free radicals tinder the reaction conditions for the aqueous emulsion polymerization, such as by thermal or chemical breakdown (redox) , may be found in European patent No. 295,727 too.
  • Initiators include organic water soluble peroxides, hydroperoxides, azo compounds and persulphates. Examples are hydrogen peroxide and sodium, ammonium or, especially, potas- sium persulphate. 0.1-1%, preferably 0.4-0.7% of initiator, based on weight of the reaction mixture, is suitably employed.
  • Suitable buffering agents to prevent the pH of the mixture falling below about 4 are for instance borax, acetic acid, or an alkali metal carbonate, bicarbonate, or acetate.
  • a premix is prepared in demineralized water from one or more surface active agents, a stabilising colloid, a part of one or more radical initiators, and a buffer.
  • the reactor is heated to a temperature in the specific range, e.g. 80 ⁇ C.
  • the reactor charge is heated up.
  • the temperature reaches 50-60 °C, 10% of the monomer feed is added.
  • ' Polymerization will start and the temperature will rise to 80 °C.
  • the further addition of monomers is started.
  • the addition is normally extended over a period of 2 to 5 hours during which the originally adjusted temperature is maintained.
  • the addition of the remaining amount of initiator in aqueous solution is started at the same time and is continued for a similar period as for the monomer addition.
  • a post polymerization period after termination of the addition of monomers of 1 to 3 hours is normally used at a temperature of e.g. 80 °C. After this post polymerization, the latex obtained is cooled and if necessary filtered.
  • the generally obtained latices have a total solids content in the range of from 30 to 60 %wt of the latex and preferably from 40 to 55 %wt and a weight average particle diameter in the range of from either 200-1000 nm (colloid stabilized) or 50-200 nm (colloid- free) depending on the type of surfactants, and when present, the type of colloid.
  • the present invention also relates to coating compositions comprising a latex and preferably at least one pigment.
  • these paints will commonly contain further constituents, examples being fillers, co-solvents, thicken ⁇ ers, dispersants, preservatives, fungicides, corrosion inhibitors, and anti-foaming agents.
  • Latices in accordance with the invention may find application as concrete additive, in paper or textile coatings, lacquers, paints, wood coatings, anti-corrosive paints, adhesives, polishes, sealants and textured putties. They are of particular interest for these applications due to their good film forming properties, their water resistance, their high pigment binding power, flexibility, the lack of tackiness of the films, their alkali resistance and resistance to ultra violet light.
  • a further aspect of the invention is provided by a powder product formed by drying a latex of the invention as defined above.
  • a powder product formed by drying a latex of the invention as defined above.
  • Such a powder could be reconstituted into a latex as required, or incorporated into a product such as a mortar.
  • Polymers in accordance with this embodiment may be applied in water-borne systems, but more commonly are applied in solvent-borne air-drying or thermosetting polymer systems.
  • solution- prepared polymers find use as adhesive, protective coating or textile coating (air-drying); and heat-cure top-coats for automo ⁇ tive or general industrial applications, electrodeposition, and coil coatings (thermosetting) .
  • the polymers may be prepared from the same copolymerizable monomers mentioned earlier.
  • the monomer feed will include monomers yielding polymers having reactive groups (e.g., ionic polymers), which polymers, optionally together with a curing agent or resin, are suitable used in thermosetting (coating) compositions.
  • Air-drying solvent-borne polymer compositions may for instance be prepared by copolymerising in a solvent and in the presence of one or more polymerization initiators a monomer feed comprising one or more of the aforementioned VEC's, a further vinylester of a carboxylic acid, and optionally one or more functional monomers.
  • the further vinylester is suitably vinyl acetate.
  • the optional functional monomers are suitably hydroxyalkyl esters of a polymer- izable ⁇ , -ethylenically unsaturated carboxylic acid, in particular hydroxyethyl acrylate and/or hydroxyethyl methacrylate.
  • the polymerization is generally carried out at a temperature of from 60 to 120 ⁇ C in a low boiling organic solvent.
  • the initia ⁇ tor suitably has a half-time at polymerization temperature of 30 to 120 minutes, and may be selected from commercially available initiators such as "Lucidol” B50 (trademark, benzoylperoxide) ,
  • Trigonox 121 (trademark, t-amylperoxy-2-ethylhexanoate) ⁇ , AIBN and the like.
  • the solvent-borne thermosetting polymer systems may be pre ⁇ pared by copolymerising in a solvent and in the presence of one or more polymerization initiators a monomer feed comprising one or more of the aforementioned VECs, one or more (hydroxy)alkyl esters of polymerizable o,3-ethylenically unsaturated carboxylic acids, the alkyl group of which contain from 1 to 8 carbon atoms; one or more polymerizable ⁇ ,?-ethylenically unsaturated carboxylic acids, and optionally styrene.
  • other functional monomers may be applied.
  • the reaction is suitably carried out at a temperature of 120 to 200 °C in a relatively high boiling solvent.
  • Suitable initiators have a half-time at the polymerization temperature of 120 to 200 minutes, and are for instance available under the trademarks "Trigonox" B (di-t-butylperoxide) and/or C (t-butylperoxybenzoate) .
  • the selection of the functional monomer depends on the cross- linking agent applied.
  • the functional monomers suitably are hydroxyl-functional monomers; for crosslinking with epoxides, the functional monomers are e.g., acid- functional monomers; and for crosslinking with polyacids glycidyl- functional monomers- are generally applied.
  • an acid or amine-functional monomer is added.
  • Other attractive curing or cross-linking resins for curable coating systems are for example those disclosed in European patent applications Nos. 244,897 and 281,213.
  • curable coating compositions according to the present invention can be applied by a variety of methods known in the art, for example by spraying,' dipping or brusb- or roller coating. Pigments, fillers, dispersing agents and other components known for coating formulations may be added to the curable binder system comprising the polymers according to the present invention. Polymers prepared by mass polymerization
  • a further embodiment of the present invention concerns poly- mers prepared by in situ (co)polymerising one or more of the aforementioned VEC's.
  • These polymers suitably may be used in for instance aqueous or non-aqueous dispersions for application in the coating industry. In addition, they may also be used in solution.
  • mass polymerization is carried out in a stainless steel batch reactor equipped with a stirrer, heating and temperature control, a metering pump for addition of the monomer feedstock and a drain valve for dumping the polymer. Since the (co)polymerization rates of the components of the monomer feedstock may be very different, it is often necessary to meter the monomers separately or in a separate rate to obtain random polymers.
  • Thermosetting mass-polymer systems may be prepared by copoly ⁇ merising in the presence of one or more polymerization initiators a monomer feed comprising one or more of the aforementioned VEC's, one or more (hydroxy) lkyl esters of polymerizable ⁇ , ?-ethylenical- ly unsaturated carboxylic acids, the alkyl group of which contain from 1 to 8 carbon atoms; one or more polymerizable ⁇ , -ethylen- ically unsaturated carboxylic acids, and optionally styrene.
  • other functional monomers may be applied.
  • the in situ reaction is suitably carried out at a temperature of 130 to 200 C C.
  • Suitable initiators and functional monomers are mentioned in the preceding part on solution polymerization.
  • the vinylesters listed in Table 1 were heated up to 115 "C in a glass distillation flask of 150 ml.
  • the initiator, dibenzoylper- oxide (dBP) was added, and after 15 minutes of reaction the reaction vessel was placed into an oven for another two hours of reaction at 90 C C.
  • the vinylester homopolymers were dissolved in n-pentane (15 %wt solution) , from which solution the homopoly ⁇ mers were precipitated by addition of acetone.
  • the glass transition temperature (Tg) of the homopolymers was measured in accordance with the method defined hereinafter.
  • a reaction vessel was heated up to about 80 °C.
  • an arylalkyl suphonate anionic surfactant (Humifen SF-90, a trademark, 10 %wt in water); 0.25 g 0.05 borax and 63.25 g (demineralized) water was added and the vessel was heated for 10 minutes.
  • polymers (a) to (f) were prepared using HEC or PVA as colloid, of which polymers (d) and (e) are comparative examples, and (f) exemplifies a slightly different adhesive-type formulation (*) .
  • the polymers were prepared by heating an initial reactor charge comprising 0.3 parts by weight (pbw) of anionic surfactant;
  • Example (g) is a conventional formulation
  • example (h) uses a redox initiator by which a high molecular weight is obtained
  • example (j) relates to a formulation wherein the vinyl acetate has been replaced by acrylic acid derivatives.
  • the redox initiator system comprises K_S_0_ and Na reputationS stress0, , and is applied conventionally as exemplified in the VeoVa Technical Manual VM 3.1.
  • Example 5 terpolymer of vinylester, vinyl acetate and ethene
  • a "pressure latex" was prepared in a 1-litre autoclave reactor equipped with a stirrer, thermometer, inlet tubes for initiator, monomers, nitrogen and ethene.
  • the reactor was charged with 30 g of the anionic surfactant, 0.5 g K-SpOg and 0.25 g borax in 250 g water.
  • a monomer feed was prepared by emulsifying 447.5 g vinyl acetate, 50 g VEC 11, 2.5 g acrylic acid (stabilizer) with 20 g of the anionic surfactant, 40 g of a non-ionic surfactant (a 1/1 mixture of the nonyl phenol ethoxylates "Ethylan" HA and "Ethylan” 44, "Ethylan” is a trade ⁇ mark) , 2 g IC j S ⁇ Og and 2 g borax in 150 g of water.
  • the initial reactor charge was heated to 80 °C.
  • a standard reactor was initially charged with 35.0 pbw VEC 11, 2.2 pbw styrene, 12.0 pbw of "ButylOxitol” (trademark) and 0.2 pbw of t-butylperoxybenzoate (tBPB) .
  • the reactor was heated, and simultaneously at constant rate a mixture consisting of 4.1 pbw acrylic acid (AA) , 6.5 pbw hydroxyethyl methacrylate (HEMA) , 10.8 pbw MMA, 9.0 pbw styrene, 15.0 pbw of ButylOxitol and 0.8 pbw of tBPB was added.
  • Two clear laquers were made by blending the aforementioned polymer in a weight ratio of 85/15 or 70/30 with a melamine solution ("Cymel” 301, a trademark) in ButylOxitol (solvent content of 38 % m/m), and catalyst (3 % para-toluenesulphonic acid in ButylOxitol).
  • the laquers were cured at 140 or 160 °C in 30 minutes.
  • the cured laquers showed excellent flow and excellent solvent resistance (more than 100 double rubs with MEK) .
  • the K ⁇ nig hardness varied from 142 to 154 seconds.
  • two pigmented paints were made, employing 70 g of pigment (titane dioxide, "Kronos” 2310, a trademark) per 100 g of the polymer/resin blend (solvent content of 30 % m/m) .
  • the prepared coatings had a K ⁇ nig hardness of from 123 to 144.
  • a paint for electrodeposition was made by blending the polymer and a melamine solution ("Cymel” 1116, a trademark) in a weight ratio of 70:30, which was subsequently neutralised with triethylamine and diluted with some demineralized water. Pigment was then added to part of this mixture (titane dioxide, 30 % m/m on total polymer), and thouroughly mixed therewith. Then, the remaining part of the polymer/melamine mixture was added, together with sufficient demineralized water to obtain a paint having a solids content of 10%. Paints were applied at different application voltages (ranging from 60 to 160 V) , subsequently followed by a stoving step at 175 ⁇ C for 30 minutes. The coatings so produced had a glossy appearance.
  • Example 8 thermosetting mass copolymer
  • a water-dispersible polymer using the mass polymerization technique was prepared by charging a standard reactor with 200 pbw VEC 11 and 150 pbw VeoVa 10 under a nitrogen blanket. The temperature was then raised to 170 ⁇ C, and a monomer feed comprising 280 pbw styrene, 170 pbw HEMA, 160 pbw butyl acrylate (BuA) , and 20 pbw of tBPB was added at a constant rate over 5 hours whilst maintaining the temperature at 170 °C. After the monomer addition was complete, the temperature was maintained for a further 40 minutes. The polymer was produced in a conversion of 93.2 % with Tg of 4.4 ⁇ C.
  • Ve 13 is the vinylester of a highly branched C._ carboxylic acid and Ve 11 is the vinylester of undecanoic acid.
  • VEHA is vinylester of 2-ethylhexanoic acid
  • the glass transition temperature (Tg) is measured by means of
  • DSC Differential Scanning Calorimetry
  • the water absorption of latex polymer and emulsion paint films was measured as described hereinafter.
  • a wet film of 2 mm thickness is applied on a polyethylene foil (the latex is kept on the foil by applying an automotive sealer on the edges of the foil).
  • the panels are covered with some water vapour transmitting material and then stored at 20 °C above the Tg for a week. The cover is removed after clear films are formed.
  • Three pieces of 2 x 2 cm are cut from the film after removal from the glass panel and weighed to the nearest 0.1 mg. These are stored in demineralized water at 23 °C and reweighed after 14 days (after removal of the excess of water by filter paper). The water absorp ⁇ tion is calculated from the observed weight increase. The result of the triplicate measurements are averaged.
  • the water spot resistance of latex polymer films was measured as follows. A wet latex film of 200 micron is applied on a glass panel and allowed to dry for a week at 20 ⁇ C above the T . When cooled to 23 *C a drop of water is brought on the film and the panel is placed on a dark underground. After 24 hours the whitening effect is visually judged. A rating between 10 (film is unaffected) and 0 (film is completely white) is given. In order to avoid evaporation of the water droplet, it can be covered overnight by a watch glass. The "storage stability" is measured at 40 °C. To obtain an indica ⁇ tion of polymer suspension storage stability, an accelerated test is carried out at 40 ⁇ C on a sample of about 100 ml.
  • Viscosity, pH and settlement of solids are noted after various periods of time e.g. 1, 2, 4 and 8 weeks. After 6 weeks the suspension is only allowed to show slight settlement of solids which solids can be easily redispersed, whereas no change in overall viscosity may occur.
  • MEK rubs is the number of double rubs given by hand to the cured coating with a cloth wetted with methyl ethyl ketone until the coating was wiped off. "MEK rubs" greater than 100 is an indication of a good cure and solvent resistance.
  • the conversion degree is determined by residual monomer measurement by GLC procedure (cf. VeoVa Technical Manual VM 2.1, pages 24 and 25) which measures residual monomers separately by using standard calibration of the analysis equipment for each monomer to be included in the comonomer starting mixture.
  • the analysis should be carried out shortly after preparation of polymer suspension and before adjustment, if any, of pH.
  • the hardness of the film is measured as K ⁇ nig hardness (DIN 53157), determined using an Erichson (trademark) apparatus.
  • film thickness as indicated throughout the present specification was determined with a Permascope ES (trademark) of Fisher.
  • the alkali resistance was determined by the following method.
  • the minimum film-forming temperature (MFT) was measured on an heatable panel having a non-porous surface, which panel showed a temperature gradient over the length of the surface varying approx ⁇ imately 20 ⁇ C.
  • a latex was applied to the panel to give a 60 micron wet film, and the film was allowed to dry with air flowing over the wet film.
  • the MFT was assessed visually as the temperature below which the film begins to crack, indicating incomplete coalescence of the film.
  • Film flexibility is either determined by a conical mandrel test (ASTM D 522) or by an impact resistance test (ASTM D2974-84) .

Abstract

L'invention se rapporte à des polymères pouvant être obtenus par polymérisation d'un ou plusieurs nouveaux esters vinyliques, et éventuellement d'un ou plusieurs autres monomères copolymérisables. L'invention se rapporte également à des latex contenant ces polymères, à la préparation de ces polymères en faisant appel à des procédés d'émulsion de solution et de polymérisation de masse, à des compositions comprenant de tels latex et à des produits polymères solides, par exemple des poudres latex redispersibles formées par séchage de ces latex.
PCT/EP1993/001133 1992-05-06 1993-05-04 Polymeres et latex polymeres obtenus a partir d'esters vinyliques d'acides monocarboxyliques satures WO1993022353A1 (fr)

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EP92201282.8 1992-05-06
EP92201281.0 1992-05-06
EP92201282 1992-05-06

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999042500A1 (fr) * 1998-02-23 1999-08-26 Exxon Chemical Patents Inc. Compositions polymeres derivees d'esters d'acide vinyl neo c9-c13 carboxylique
EP1033360A1 (fr) * 1999-02-26 2000-09-06 Oxeno Olefinchemie GmbH Procédé de préparation d'esters vinyliques à partir d'oligomers de butène
DE10004319A1 (de) * 2000-02-01 2001-08-09 Wacker Chemie Gmbh Vernetzbare Polymerzusammensetzung

Citations (2)

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Publication number Priority date Publication date Assignee Title
US3294727A (en) * 1962-01-25 1966-12-27 Shell Oil Co Emulsion polymerization of a terpolymer comprising a vinyl ester of an alpha-branched carboxylic acid
EP0462677A2 (fr) * 1990-06-20 1991-12-27 Shell Internationale Researchmaatschappij B.V. Dispersions de copolymères d'esters vinyliques d'acides carboxyliques ramifiés et d'acides à insaturation éthylénique et/ou leurs esters

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3294727A (en) * 1962-01-25 1966-12-27 Shell Oil Co Emulsion polymerization of a terpolymer comprising a vinyl ester of an alpha-branched carboxylic acid
EP0462677A2 (fr) * 1990-06-20 1991-12-27 Shell Internationale Researchmaatschappij B.V. Dispersions de copolymères d'esters vinyliques d'acides carboxyliques ramifiés et d'acides à insaturation éthylénique et/ou leurs esters

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999042500A1 (fr) * 1998-02-23 1999-08-26 Exxon Chemical Patents Inc. Compositions polymeres derivees d'esters d'acide vinyl neo c9-c13 carboxylique
EP1033360A1 (fr) * 1999-02-26 2000-09-06 Oxeno Olefinchemie GmbH Procédé de préparation d'esters vinyliques à partir d'oligomers de butène
JP2000248017A (ja) * 1999-02-26 2000-09-12 Oxeno Olefinchemie Gmbh ブテンオリゴマーからビニルエステルを製造する方法、コモノマーおよび可塑剤としてのその使用
US6281372B1 (en) 1999-02-26 2001-08-28 Oxeno Olefinchemie Gmbh Process for synthesis of vinyl esters from butene oligomers
JP4681095B2 (ja) * 1999-02-26 2011-05-11 エボニック オクセノ ゲゼルシャフト ミット ベシュレンクテル ハフツング ブテンオリゴマーからビニルエステルを製造する方法、コモノマーおよび可塑剤としてのその使用
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