EP1276778A1 - Matieres a mouler et procede de fabrication de corps moules - Google Patents

Matieres a mouler et procede de fabrication de corps moules

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Publication number
EP1276778A1
EP1276778A1 EP01925521A EP01925521A EP1276778A1 EP 1276778 A1 EP1276778 A1 EP 1276778A1 EP 01925521 A EP01925521 A EP 01925521A EP 01925521 A EP01925521 A EP 01925521A EP 1276778 A1 EP1276778 A1 EP 1276778A1
Authority
EP
European Patent Office
Prior art keywords
radicals
olefinically unsaturated
substituted
unsaturated monomer
arylalkyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP01925521A
Other languages
German (de)
English (en)
Inventor
Wolfgang Bremser
Peter Steiner
Beate Podlaski-Pyzik
Frank Strickmann
Ute Stockbrink
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Coatings GmbH
Original Assignee
BASF Coatings GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF Coatings GmbH filed Critical BASF Coatings GmbH
Publication of EP1276778A1 publication Critical patent/EP1276778A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C08F12/00—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 aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/32—Monomers containing only one unsaturated aliphatic radical containing two or more rings

Definitions

  • the present invention relates to the novel use of a copolymer and its aqueous dispersion for the production of molding compositions and foils. Furthermore, the present invention relates to new aqueous molding compositions and their use for the production of molding compositions and moldings. Last but not least, the present invention relates to a new process for the production of moldings.
  • Processes for the production of moldings by curing liquid molding compositions in a mold and removing the mold after curing are known per se. Examples of such processes are the production of metal castings such as bells by solidifying a molten metal in a suitable solid form, the injection molding of plastic moldings using melted thermoplastic materials, the RIM process (reaction injection molding), in which at least two starting products which are reactive with one another of polyurethanes are injected into a mold and cured therein, processes in which molding compositions based on olefinically unsaturated monomers, such as methyl methacrylate, are thermally cured in a mold, or processes in which molding compositions based on styrene and with UN radiation and / or thermally curable polymers such as polyesters can be used.
  • the disadvantage of these processes is the high energy expenditure which is necessary for melting the metals and the thermoplastics. In addition, there is the high expenditure on equipment, which is necessary due to the high process temperature fittings and / or pressures.
  • a disadvantage of the other processes is that highly reactive organic starting products are used, the handling of which is problematic in terms of safety and ecology. In all cases, the materials used in the molds must meet high requirements Temperature and pressure resistance as well as chemical resistance so that they are not damaged or destroyed by the molding compounds.
  • radicals R 1 , R 2 , R 3 and R 4 are each independently of the other
  • Arylcycloalkyl radicals in particular substituted or unsubstituted aryl radicals
  • the new molding compositions should allow molds made of cheap and / or not particularly thermostable and / or chemical-stable materials such as To use plastics, rubber, wood, paper, textile or leather, so that, among other things, prints of objects can be made from such materials
  • radicals R 1 , R, R 1 and R 4 are each independently of one another for hydrogen atoms or substituted or unsubstituted alkyl
  • Aryl residues stand, found in an aqueous medium for the production of molding compositions and moldings.
  • radicals R, R, R and R are each independently of one another hydrogen atoms or substituted or unsubstituted alkyl, cycloalkyl, alkylcycloalkyl, cycloalkylalkyl, aryl, alkylaryl,
  • Cycloalkylaryl, arylalkyl or arylcycloalkyl radicals with the proviso that at least two of the variables R 1 , R 2 , R 3 and R 4 are substituted or unsubstituted aryl, arylalkyl or arylcycloalkyl radicals, in particular substituted or unsubstituted aryl radicals; and
  • (B) contains at least one aminoplast resin
  • molding composition according to the invention is referred to below as "molding composition according to the invention.
  • radicals R 1 , R 2 , R 3 and R 4 each independently represent hydrogen atoms or substituted or unsubstituted alkyl, cycloalkyl, alkylcycloalkyl, cycloalkylalkyl, aryl, alkylaryl, cycloalkylaryl, arylalkyl or arylcycloalkyl radicals with the proviso that at least two of the variables R 1 , R 2 , R 3 and R 4 are substituted or unsubstituted aryl, arylalkyl or Arylcycloalkyl radicals, in particular substituted or unsubstituted aryl radicals;
  • thermally curable materials such as, for example, thermally curable coating materials based on aminoplast resins, usually have to be cured at temperatures above 100 ° C. in order to provide fully cured, thermosetting coatings within a short process time.
  • film body according to the invention includes moldings which are obtained by pouring molding compounds into molds or by embedding objects in molding compounds. The latter are also referred to as impressions.
  • the first essential constituent of the molding composition according to the invention is at least one copolymer (A).
  • the copolymer (A) is by radical (co) polymerization of at least one olefinically unsaturated Monomers (a) and at least one olefinically unsaturated monomer (b) which is different from the monomer (a).
  • a wide variety of olefinically unsaturated monomers are suitable as monomers (a).
  • suitable ammoplastic resin-reactive functional groups are thio, hydroxyl, amino, N-methylolamino, N-alkoxymethylamino, imino, carbamate and / or allophanate groups, especially hydroxyl groups.
  • Suitable monomers (a) are the monomers (al) such as
  • Derive alkylene glycol which is esterified with the acid or which can be obtained by reacting the alpha, beta-olefinically unsaturated carboxylic acid with an alkylene oxide such as ethylene oxide or propylene oxide, in particular hydroxyalkyl esters of acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid or itaconic acid, in which the hydroxyalkyl group contains up to 20 carbon atoms, such as 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 3-hydroxybutyl, 4-hydroxybutyl acrylate, methacrylate, ethacrylate, crotonate, maleate, fumarate or itaconate; or hydroxycycloalkyl esters such as 1,4-bis (hydroxymethyl) cyclohexane, octahydro-4,7-methano-1H-indene dimethanol or methyl propanediol monoacrylate, monomethacryl
  • olefinically unsaturated alcohols such as allyl alcohol
  • Polyols such as trimethylolpropane mono- or diallyl ether or pentaerythritol mono-, di- or triallyl ether;
  • (Meth) acrylic acid amides such as (meth) acrylic acid amide, N-methyl-, N-
  • the monomers (al) can be used as the sole monomers. According to the invention, however, it is advantageous to use further olefinically unsaturated monomers (a) in order to advantageously vary the property profile of the copolymers (A) to be used according to the invention and to adapt it to the particular intended use of the molding composition.
  • (al) essentially acid group-free (meth) acrylic esters such as (meth) acrylic or alkyl cycloalkyl esters with up to 20 carbon atoms in the alkyl radical, in particular methyl, ethyl, propyl, n-butyl, sec-butyl, tert. Butyl, hexyl, ethylhexyl, stearyl and lauryl acrylate or methacrylate; Cycloaliphatic (meth) acrylic esters, especially cyclohexyl, isobornyl, dicyclopentadienyl, octahydro
  • (Meth) acrylic acid derivatives can be used in minor amounts of higher functional (meth) acrylic acid alkyl or cycloalkyl esters such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, butylene glycol, pentane-1, 5-diol, hexane, 1,6-diol, octahydro 4,7-methano-1H-indene-dimethanol or cyclohexane-1,2-, 1,3- or -1,4-diol-di (meth) acrylate; Trimethylolpropane di- or tri (meth) acrylate; or Contain pentaerythritol di-, tri- or tetra (meth) acrylate.
  • higher functional (meth) acrylic acid alkyl or cycloalkyl esters such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, butylene glycol,
  • (a3) monomers which carry at least one acid group, which can be converted into the corresponding acid anion group, per molecule, such as acrylic acid,
  • (a4) Vinyl esters of monocarboxylic acids with 5 to 18 carbon atoms in the molecule which are branched in the alpha position.
  • the branched monocarboxylic acids can be obtained by reacting formic acid or carbon monoxide and water with olefins in the presence of a liquid, strongly acidic catalyst; the olefins can be cracked products of paraffinic hydrocarbons, such as mineral oil fractions, and can contain both branched and straight-chain acyclic and / or cycloaliphatic olefins.
  • a mixture of carboxylic acids is formed in which the carboxyl groups are predominantly located on a quaternary carbon atom.
  • Other olefinic starting materials are e.g. Propylene trimer, propylene tetramer and diisobutylene.
  • the vinyl esters (a4) can also be prepared from the acids in a manner known per se, e.g. by allowing the acid to react with acetylene. Because of the good availability, vinyl esters of saturated aliphatic monocarboxylic acids having 9 to 11 carbon atoms which are branched on the alpha carbon atom are particularly preferred, but in particular
  • (a6) (Meth) acrylic acid amides such as (meth) acrylic acid amide, N-methyl, N, N-dimethyl, N-ethyl, N, N-diethyl, N-propyl, N, N-dipropyl, N -Butyl-, N, N-dibutyl-, N-cyclohexyl-, and / or N, N-cyclohexyl-methyl- (meth) acrylic acid amide.
  • Vinylaromatic hydrocarbons such as styrene, alpha-alkylstyrenes, in particular alpha-methylstyrene and / or vinyltoluene, N, N-diethylaminostyrene (all isomers) and / or N, N-diethylamino-alpha-methylstyrene (all isomers).
  • Nitriles such as acrylonitrile and / or methacrylonitrile.
  • (alO) vinyl compounds in particular vinyl and / or vinylidene dihalides such as vinyl chloride, vinyl fluoride, vinylidene dichloride or
  • N-vinylamides such as vinyl-N-methylformamide, N-vinylcaprolactam, 1 -vinylimidazole or N-vinylpyrrolidone
  • Vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether and / or vinyl cyclohexyl ether
  • vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate and / or the vinyl ester of 2-methyl-2-ethylheptanoic acid.
  • (al l) allyl compounds in particular allyl ethers and esters such as allyl methyl, ethyl, propyl or butyl ether or allyl acetate, propionate or butyrate.
  • (al2) polysiloxane macromonomers which have a number average molecular weight Mn of 1,000 to 40,000 and an average of 0.5 to 2.5 ethylenically unsaturated
  • Polysiloxane macromonomers that have a number average molecular weight
  • compounds of the general formula I are used as monomers (b).
  • the radicals R 1 , R 2 , R ? and R 4 each independently of one another for hydrogen atoms or substituted or unsubstituted alkyl, cycloalkyl, alkylcycloalkyl, cycloalkylalkyl, aryl, alkylaryl, cycloalkylaryl, arylalkyl or arylcycloalkyl radicals, with the proviso that at least two of the variables R 1 , R 2 , R 3 and R 4 are substituted or unsubstituted aryl, arylalkyl or arylcycloalkyl radicals, in particular substituted or unsubstituted aryl radicals.
  • alkyl radicals examples include methyl, ethyl, propyl, isopropyl, n-butyl, iso-butyl, tert-butyl, amyl, hexyl or 2-ethylhexyl.
  • Suitable cycloalkyl radicals are cyclobutyl, cyclopentyl or cyclohexyl.
  • alkylcycloalkyl radicals examples include methylenecyclohexane, ethylenecyclohexane or propane-1,3-diylcyclohexane.
  • Suitable cycloalkylalkyl radicals are 2-, 3- or 4-methyl-, ethyl-, propyl- or butylcyclohex-1-yl.
  • Suitable aryl radicals are phenyl, naphthyl or biphenylyl, preferably phenyl and naphthyl and in particular phenyl.
  • alkylaryl radicals examples include benzyl or ethylene or propane-1,3-diyl-benzene.
  • Suitable cycloalkylaryl radicals are 2-, 3-, or 4-phenylcyclohex-l-yl.
  • Suitable arylalkyl radicals are 2-, 3- or 4-methyl-, ethyl, propyl or butylphen-1-y 1.
  • suitable arylcycloalkyl radicals are 2-, 3- or 4-cyclohexylphen-l-yl.
  • radicals R, R, R and R 4 described above can be substituted.
  • electron-withdrawing or electron-donating atoms or organic residues can be used.
  • Suitable substitutes are halogen atoms, in particular chlorine and fluorine, nitrile groups, nitro groups, partially or completely halogenated, in particular chlorinated and / or fluorinated, alkyl, cycloalkyl, alkylcycloalkyl, cycloalkylalkyl, aryl, alkylaryl, cycloalkylaryl, arylalkyl and Arylcycloalkyl radicals, including those exemplified above, in particular tert-butyl; Aryloxy, alkyloxy and cycloalkyloxy radicals, in particular phenoxy, naphthoxy, methoxy, ethoxy, propoxy, butyloxy or cyclohexyloxy; Arylthio, alkylthio and cycloalkylthio radicals, in particular phenylthio, naphthylthio, methylthio, ethylthio, propylthio, butylthio
  • Examples of monomers (b) used with particular preference in accordance with the invention are diphenylethylene, dinaphthaleneethylene, eis or trans-stilbene, vinylidene bis (4-N, N-dimethylaminobenzene), vinylidene bis (4-aminobenzene) or vinylidene bis (4- nitrobenzene).
  • the monomers (b) can be used individually or as a mixture of at least two monomers (b).
  • diphenyl ethylene is of very particular advantage and is therefore used with particular preference in accordance with the invention.
  • the monomers (a) and (b) to be used according to the invention are reacted with one another to give the copolymer (A) in the presence of at least one radical initiator.
  • initiators which can be used are: dialkyl peroxides, such as di-tert-butyl peroxide or dicumyl peroxide; Hydroperoxides, such as CumuUiydroperoxid or tert-butyl hydroperoxide; Peresters, such as tert-butyl perbenzoate, tert-butyl perpivalate, tert-butyl per-3,5,5-trimethyl hexanoate or tert-butyl per-2-ethyl hexanoate; Potassium, sodium or ammonium peroxodisulfate; Azodinitriles such as azobisisobutyronitrile; C-C cleavage initiators such as benzpinacol silyl ether; or a combination of a non
  • Comparatively large amounts of free-radical initiator are preferably added, the proportion of the initiator in the reaction mixture, based in each case on the total amount of the monomers (a) and the initiator, particularly preferably 0.5 to 50% by weight, very particularly preferably 1 to 20 % By weight and in particular 2 to 15% by weight.
  • the weight ratio of initiator to monomers (b) is preferably 4: 1 to 1: 4, particularly preferably 3: 1 to 1: 3 and in particular 2: 1 to 1: 2. Further advantages result if the initiator within the specified limits Excess is used.
  • the radical copolymerization is preferably carried out in the abovementioned ones
  • Reactor length the conditions of Taylor flow are met, even if the kinematic viscosity of the reaction medium changes greatly due to the copolymerization, in particular increases.
  • the copolymerization is carried out in an aqueous medium.
  • the aqueous medium essentially contains water.
  • the aqueous medium can contain minor amounts of the additives (C) and / or other dissolved solid, liquid or gaseous organic and / or inorganic, low and / or high molecular weight substances, in particular surface-active substances, provided that these are not affect or even inhibit the copolymerization in a negative way.
  • the term “minor amount” is understood to mean an amount which does not cancel out the aqueous character of the aqueous medium.
  • the aqueous medium can also be pure water.
  • the copolymerization is preferably carried out in the presence of at least one base.
  • Low molecular weight bases such as sodium hydroxide solution, potassium hydroxide solution, ammonia, diethanolamine, triethanolamine, mono-, di- and triethylamine, and / or dimethylethanolamine, in particular ammonia and / or di- and / or triethanolamine, are particularly preferred.
  • the copolymerization is advantageously carried out at temperatures above room temperature and below the lowest decomposition temperature of the monomers used in each case, a temperature range from 10 to 150 ° C., very particularly preferably 70 to 120 ° C. and in particular 80 to 110 ° C. being chosen. If particularly volatile monomers (a) and / or (b) are used, the copolymerization can also be carried out under pressure, preferably under 1.5 to 3,000 bar, particularly preferably 5 to 1,500 and in particular 10 to 1,000 bar.
  • the copolymer (A) is not subject to any restrictions with regard to the molecular weight distribution.
  • the copolymerization is advantageously carried out in such a way that a molecular weight distribution Mw / Mn measured using gel permeation chromatography using polystyrene as the standard results in ⁇ 4, particularly preferably ⁇ 2 and in particular ⁇ 1.5 and in individual cases also ⁇ 1.3.
  • the molecular weights of the copolymers (A) can be controlled within wide limits by the choice of the ratio of monomer (a) to monomer (b) to free radical initiator.
  • the content of monomer (b) in particular determines the molecular weight in such a way that the greater the proportion of monomer (b), the lower the molecular weight obtained.
  • the copolymer (A) resulting from the copolymerization is obtained as a mixture with the aqueous medium, generally in the form of a dispersion (A).
  • Their solids content can vary very widely; it is preferably 5 to 60, preferably 10 to 55, particularly preferably 15 to 50, very particularly preferably 20 to 45 and in particular 25 to 40% by weight, in each case based on the dispersion (A).
  • the dispersion (A) can be used directly for the production of the molding compositions and moldings according to the invention. According to the invention, however, it is advantageous to use the dispersion (A) or the copolymer (A) contained therein as a macroinitiator for the further reaction with at least one further monomer (a) in a second stage (ii).
  • the further reaction in step (ii) is preferably carried out under the usual conditions for free-radical polymerization, it being possible for suitable additives (C) to be present.
  • Steps (i) of (ii) can be carried out separately, both spatially and temporally.
  • steps (i) to (ii) can also be carried out in succession in one reactor.
  • the monomer (b) is first reacted completely or partially with at least one monomer (a) depending on the desired application and the desired properties, after which at least one further monomer (a) is added and polymerized by free radicals.
  • at least two monomers (a) are used from the start, the monomer (b) first reacting with one of the at least two monomers (a) and then the resulting reaction product (A) above a certain molecular weight also with the further monomer (a) responds.
  • Copolymers (A) which are prepared in the multi-stage procedure described above provide particularly advantageous dispersions (A), molding compositions and moldings, which is why they are used with particular preference according to the invention.
  • the solids content of the dispersions (A) prepared in a multi-stage procedure can also vary very widely; it is preferably 10 to 70, preferably 15 to 65, particularly preferably 20 to 60, very particularly preferably 25 to 55 and in particular 30 to 50% by weight, in each case based on the dip version (A).
  • the content of the molding composition according to the invention in the copolymers (A) prepared in a single-stage or multi-stage procedure can likewise vary very widely and is guided by the requirements of the individual case.
  • the content is preferably 5 to 60, preferably 10 to 55, particularly preferably 15 to 50, very particularly preferably 20 to 45 and in particular 25 to 40% by weight, in each case based on the molding composition according to the invention.
  • the second essential component of the molding composition according to the invention is at least one aminoplast resin (B).
  • Any aminoplast resin suitable for thermally curable lacquers or a mixture of such aminoplast resins can be used here.
  • melamine resins, guanamine resins, benzoguanamine resins or urea resins, especially melamine resins can be used.
  • the amount of amino resins (B) in the molding compositions according to the invention can also vary very widely. It depends primarily on the number and reactivity of the functional groups of the copolymers (A) which are reactive in the aminoplast resin and are present in the molding composition according to the invention.
  • the content is preferably 1 to 40, more preferably 2 to 35, particularly preferably 3 to 30, very particularly preferably 4 to 25 and in particular 5 to 20% by weight, in each case based on the molding composition according to the invention.
  • the molding composition according to the invention can also contain at least one customary and known additive (C) in the customary and known effective amounts.
  • At least one coloring and / or effect pigment (C) is used as additive (C), which can be added to the dispersions (A) before, during or after, in particular after the preparation of the copolymers (A).
  • the pigments (C) can consist of inorganic or organic compounds.
  • the molding composition according to the invention therefore ensures a universal range of use on account of this large number of suitable pigments (C) and enables the realization of a large number of color tones and optical effects.
  • the effect pigments (C) which can be used are metal plate pigments such as commercially available aluminum bronzes, aluminum bronzes chromated according to DE-A-36 36 183, commercially available stainless steel bronzes and metallic and non-metallic effect pigments, such as pearlescent or interference pigments, for example.
  • metal plate pigments such as commercially available aluminum bronzes, aluminum bronzes chromated according to DE-A-36 36 183, commercially available stainless steel bronzes and metallic and non-metallic effect pigments, such as pearlescent or interference pigments, for example.
  • metal plate pigments such as commercially available aluminum bronzes, aluminum bronzes chromated according to DE-A-36 36 183, commercially available stainless steel bronzes and metallic and non-metallic effect pigments, such as pearlescent or interference pigments, for example.
  • suitable inorganic color pigments (C) are titanium dioxide, iron oxides and carbon black.
  • suitable organic color pigments are thioindigo pigments indanthrene blue, irgalith blue, heliogen blue, irgazin blue, palomar blue, cromophthal red, pigment laser red T3, hostaperm pink, irgazin orange, sicotrans yellow, sicotane yellow , Hostaperm Yellow, Paliotan Yellow, and Heliogen Green.
  • varnishes and printing inks are used on Römpp Lexikon, Georg Thieme Verlag, 1998, pages 180 and 181, "iron blue pigments” to “iron oxide black”, pages 451 to 453, “pigments” to “pigment volume concentration”, page 563, “thioindigo pigments” and page 567, “titanium dioxide pigments «Referred.
  • the molding composition according to the invention can, in addition to or instead of the pigments (C), also contain organic and inorganic fillers (C) with which, for example, the hardness and / or color of the moldings according to the invention can be varied.
  • suitable organic and inorganic fillers (C) are chalk, calcium sulfates, barium sulfate, silicates such as talc or kaolin, silicas, oxides such as aluminum hydroxide or magnesium hydroxide, nanoparticles or organic fillers such as textile fibers, cellulose fibers, polyethylene fibers, polyacrylonitrile powder, polyamide powder or wood flour.
  • suitable fillers (C) are known from German patent application DE 196 06 706 A1, column 8, lines 30 to 64. They are preferably used in the amounts specified therein.
  • the proportion of pigments (C), including the fillers (C), in the molding materials according to the invention can vary very widely and depends on the requirements of the individual case, in particular on the optical effect to be set and or the opacity of the pigments and / or fillers used in each case (C).
  • the content is preferably 0.5 to 80, preferably 0.8 to 75, particularly preferably 1.0 to 70, very particularly preferably 1.2 to 65 and in particular 1.3 to 60% by weight, in each case based on the Solids content of the molding composition according to the invention.
  • the molding composition according to the invention can in addition to the pigments and / or fillers (C) at least one additive (C) selected from the Group consisting of oligomeric and polymeric binders, reactive thinners curable thermally and / or with actinic radiation, other crosslinking agents for thermal curing, low and high-boiling organic solvents ("long solvents"), UV absorbers, light stabilizers, radical scavengers, thermolabile radical initiators, Catalysts for thermal crosslinking, deaerating agents, slip additives, polymerization inhibitors, defoamers, emulsifiers, wetting and diperging agents, adhesion promoters, flow control agents, film-forming aids, rheology-controlling additives (thickeners), flame retardants, siccatives, drying agents, skin-preventing agents, anti-wax agents, corrosion inhibitors.
  • additives selected from the Group consisting of oligomeric and polymeric binders, reactive thinners curable thermally and
  • the molding composition according to the invention has no special features, but is preferably carried out by mixing and homogenizing the dispersions (A) with the aminoplast resins (B) and, if appropriate, the additives (C) in suitable mixing units such as stirred kettles, agitator mills, Ultraturrax, in-line dissolvers , static mixers, gear rim dispersers, pressure relief nozzles and / or microfluidizers.
  • suitable mixing units such as stirred kettles, agitator mills, Ultraturrax, in-line dissolvers , static mixers, gear rim dispersers, pressure relief nozzles and / or microfluidizers.
  • the resulting molding compositions according to the invention are preferably poured into the molds immediately after their production, the handling of the molding compositions not requiring any special precautionary measures.
  • the molds can consist of any materials which are preferably not attacked by water or aqueous media.
  • suitable materials are thermostable substances such as metals, glass, ceramics, natural
  • suitable shapes or objects comprise practically all technical objects or objects of daily use, from a comparatively simple shape such as a sphere, cone, cylinder, cuboid or ribbon, to a very complex three-dimensional shape.
  • the production of the moldings according to the invention has no special features in terms of method, but instead takes place by pouring the molding compositions according to the invention into molds or by embedding objects in the molding compositions according to the invention.
  • a customary and known, water-resistant non-stick layer or a release layer for example made of wax, silicone or silicon-coated paper or plastic, can be located between the molds or objects and the molding compound.
  • the molding compositions according to the invention are allowed to cure in direct or indirect contact with the molds or articles.
  • Hardening can be accelerated by increased temperature, reduced air humidity and / or actinic radiation such as near infrared, visible light, UV radiation or electron radiation.
  • the curing preferably takes place at room temperature without the additional measures.
  • the duration of curing can vary very widely and can last from 20 s to several days.
  • the moldings according to the invention are separated from the molds or objects without problems.
  • the moldings according to the invention can release the water they contain.
  • the moldings can shrink by the volume of the water dispensed, but surprisingly no stress cracks or other deformations occur, so that the moldings according to the invention represent a possibly scaled-down, but still true-to-size image of the molds or the objects.
  • the first and second feed were metered in within one hour.
  • the third feed was metered in within 1.25 hours.
  • the resulting reaction mixture was kept at 90 ° C. for four hours and then cooled to below 40 ° C. and filtered through a 100 ⁇ m GAF bag.
  • the resulting dispersion had a solids content of 32 to 34% by weight (1 hour, 130 ° C.) and a free monomer content of less than 0.2% by weight (determined by gas chromatography).
  • the dispersion (A) was used for the production of a block copolymer (A).
  • the resulting reaction mixture was stirred at 90 ° C for two hours.
  • the resulting dispersion was then cooled below 40 ° C. and filtered through a 50 ⁇ m GAF bag.
  • the dispersion (A) had a solids content of 41 to 42% by weight (1 hour, 130 ° C.) and a free monomer content of less than 0.2% by weight (determined by gas chromatography).
  • the dispersion (A) from preparation example 2, a melamine resin and a commercially available defoamer and, in example 3, a pigment were mixed and homogenized with vigorous stirring.
  • the table gives one Overview of the components used and their quantities.
  • the molding compositions according to the invention from Examples 1 to 3 were poured into customary, known, hanging, dimensionally stable laboratory gloves made of rubber and allowed to cure for 2 days in Examples 1 and 3 and for 3 minutes in Example 2. After curing, the gloves were cut open and the hand-shaped moldings removed. These were detailed images of the original inner volume of the laboratory gloves, which shrank slightly over time without cracking or other deformations. Because of their flat base, the "hands" could be used for decoration.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne l'utilisation, pour la fabrication de matières à mouler et de corps moulés, d'un copolymère (A), pouvant être obtenu par polymérisation radicalaire, dans un milieu aqueux, a) d'au moins un monomère oléfiniquement insaturé et b) d'au moins un monomère insaturé oléfinique différent dudit monomère oléfiniquement insaturé (a), de formule générale (I) R<1>R<2>C=CR<3>R<4>, dans laquelle R<1>, R<2>, R<3> et R<4> représentent, indépendamment les uns des autres, des atomes d'hydrogène ou des radicaux alkyle, cycloalkyle, alkylcycloalkyle, cycloalkylalkyle, aryle, alkylaryle, cycloalkylaryle, arylalkyle ou arylcycloalkyle substitués ou non substitués, sous réserve qu'au moins deux des variables R<1>, R<2>, R<3> et R<4> représentent des radicaux aryle, arylalkyle ou arylcycloalkyle substitués ou non substitués, en particulier des radicaux aryle substitués ou non substitués.
EP01925521A 2000-04-12 2001-04-03 Matieres a mouler et procede de fabrication de corps moules Withdrawn EP1276778A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10018078 2000-04-12
DE10018078A DE10018078A1 (de) 2000-04-12 2000-04-12 Formmassen und Verfahren zur Herstellung von Formkörpern
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DE10018078A1 (de) 2001-11-08

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