EP2115056A1 - Matières à mouler pour des corps moulés en pmmi - Google Patents

Matières à mouler pour des corps moulés en pmmi

Info

Publication number
EP2115056A1
EP2115056A1 EP07822010A EP07822010A EP2115056A1 EP 2115056 A1 EP2115056 A1 EP 2115056A1 EP 07822010 A EP07822010 A EP 07822010A EP 07822010 A EP07822010 A EP 07822010A EP 2115056 A1 EP2115056 A1 EP 2115056A1
Authority
EP
European Patent Office
Prior art keywords
weight
molding composition
parts
composition according
ceramic beads
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Withdrawn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
EP07822010A
Other languages
German (de)
English (en)
Inventor
Klaus Schultes
Ursula Golchert
Stefan Nau
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.)
Evonik Roehm GmbH
Original Assignee
Evonik Roehm 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 Evonik Roehm GmbH filed Critical Evonik Roehm GmbH
Publication of EP2115056A1 publication Critical patent/EP2115056A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/16—Solid spheres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/24—Homopolymers or copolymers of amides or imides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]

Definitions

  • the invention relates to a molding compound for matted molded body and the corresponding moldings and their use.
  • PMMI polymethacrylimide
  • Extruded or co-extruded PMMI moldings are very versatile: Extruded or co-extruded sheets are used both for the exterior, in particular for automotive components, components, sporting goods surfaces and lamp covers, as well as indoors, especially in the furniture industry for lamp covers and interior fittings of automobiles.
  • WO 02/068519 describes a solid surface material of a matrix, such. As an acrylic resin, and dispersed therein ceramic beads, such as. B. W-410 Zeeospheres ®. The ceramic beads are provided with a functional coating that reacts with the resin of the matrix and covalently bonds the beads to the matrix.
  • the surface material of WO 02/068519 is characterized by a high flame resistance.
  • WO 03/054099 relates to an adhesive strip whose uppermost layer comprises a transparent resin and a matting agent, such as e.g. As ceramic beads includes.
  • WO 97/21536 discloses an extrusion process with which matting agents, such. B. ceramic beads, can bring in a thermoplastic polymer.
  • US 5,787,655 describes a non-slip film of a thermoplastic polymer into which inorganic beads, such as. B. ceramic beads are incorporated.
  • US 5,562,981 relates to the construction of a truck semi-trailer.
  • the sidewalls of the semi-trailer include fiber reinforced plastics, in which ceramic beads have been mixed to further strengthen the walls.
  • WO 2005/105377 discloses a composition of a thermoplastic having a processing temperature of at least 280 0 C, superabrasive particles and a filler, such as. B. ceramic beads. The composition is used for the production of abrasive utensils.
  • the aim of the present invention was to find a molding composition which can be used for the production of moldings with a fine-matte surface.
  • the molding composition should be producible and processable in the simplest possible way, in particular with relatively little energy expenditure.
  • the articles to be produced from the molding material should have the best possible optical and mechanical properties, the highest possible long-term stability and weathering resistance, and the most homogeneous possible matt surface with the lowest possible gloss.
  • the articles to be produced from the molding composition should preferably have a rough surface.
  • the molding composition has a volume melt index MVR, measured according to ISO 1133 at 260 0 C and 10 kg, in the range of 1, 0 cm 3 / 10 min to 20.0 cm 3 / 10 min, it is possible to make a molding compound that is not easily foreseeable, which is excellently suitable for the production of molded articles with a fine-matte finish.
  • the molding composition can be produced and processed in a comparably simple manner, in particular with relatively little energy expenditure, and also enables the realization of sophisticated part geometries.
  • the articles which can be produced from the molding compound are distinguished by a combination of advantageous properties:
  • the polymer matrix A) consists of at least one (meth) acrylimide (co) polymer.
  • the starting material used for the imidization is a polymer of alkyl esters of methacrylic acid, which is generally more than 50.0% by weight, preferably more than 80.0% by weight, particularly preferably 95.0% by weight. to 100.0 wt .-% of units of alkyl esters of methacrylic acid having 1 to 4 carbon atoms in the alkyl group. Preference is given to methyl methacrylate.
  • Preferred polymers are composed of at least 80.0% by weight, preferably more than 90.0% by weight, more preferably more than 95.0% by weight, of methyl methacrylate.
  • Suitable comonomers are all monomers which can be copolymerized with methyl methacrylate, in particular alkyl esters of acrylic acid having 1 to 4 carbon atoms in the alkyl radical, acrylonitrile or methacrylonitrile, acrylamide or methacrylamide, styrene or else maleic anhydride.
  • thermoplastically processable polymers of this type having a reduced viscosity in the range from 20 ml / g to 92 ml / g, preferably from 50 ml / g to 80 ml / g (measured according to ISO 8257, Part 2). They are used in the form of a powder or granules having an average particle size of about 0.03 mm to 3 mm.
  • methylamine is used in a subsequent process step (b) and the molar ratio of ammonia used to the methylamine used 1: 0.5 to 1: 3, preferably 1: 0.8 to 1: 2.7, more preferably 1: 0.9 to 1: 1, 1. Below this range, increased turbidity of the polymethacrylimide obtained can occur. With a molar excess of methylamine, based on the ammonia used, in turn, the proportion of carboxylic acid groups in the polymer increases in an undesired manner.
  • the process can be carried out continuously or batchwise.
  • the ammonia is added at the beginning of the reaction in process step (a) and the methylamine is added gradually or in one or more parts after the reaction of the ammonia in process step (b).
  • the imidating agent with a pressure pump be pressed uniformly or in periodic proportions in the reactor heated to the reaction temperature.
  • the gas phase accumulated in the reactor is depressurized, whereby the previously formed volatile reaction products are removed from the reaction mixture.
  • the imidization is conveniently carried out in a tubular reactor and the polymer and the imidating agent are introduced continuously into the tubular reactor.
  • the first part of the imidating agent, the ammonia is introduced and mixed with the molten polymer. Additional portions of the imidating agent may be introduced at one or more locations in the tubular reactor where the previously introduced imidating agent is partially or fully reacted.
  • the tube reactor used is preferably a single-screw or a multi-screw extruder.
  • pressure and degassing zones can alternate with one another in order to remove the reaction products formed up to that point from the reaction mixture which is gradually advanced further in the extruder, in each case before the addition of further imidating agent.
  • step (a) 1 mole of polymethyl methacrylate (the term "base mole” refers to the amount of the ester monomer underlying the polymerized ester units) in step (a) is reacted with 0.1 to 1 mole of ammonia.
  • base mole refers to the amount of the ester monomer underlying the polymerized ester units
  • step (b) the addition of methylamine in a molar ratio of 0.5 to 3, preferably from 0.8 to 2.7, more preferably from 0.9 to 1, 1 based on the total amount of ammonia used.
  • the molar ratio of ammonia used to methylamine used is 1: 0.5 to 1: 0.8.
  • the addition of the methylamine can be carried out in an analogous manner, preferably in one to five addition amounts. Here too It is advisable to use only up to 75% of the previously used amount when adding partial quantities.
  • the reaction with the imidating agent is stopped before the polymer is completely imidated.
  • the imidating agent in a total of z. B. 0.2 to 2.5, preferably from 0.5 to 1, 5, more preferably from 0.8 to 1, 2 mol per mole of the ester units are used.
  • the specified ratio of ammonia to methylamine This gives polymers which are composed of about 20 base mol% to 80 mol% of cyclic Methacrylimidäen and only extremely small amounts, less than 0.5 wt .-%, of methacrylic acid units.
  • the imidization process can largely in a conventional manner, for. As described in EP 441 148, executed.
  • the imidization best running at temperatures above the melting temperature or at least 20 0 C above the Vicat B softening temperature according to ISO 306 of the starting polymer from. Even better, a reaction temperature is selected which is at least 20 0 C above the softening temperature of the resulting imidized polymer. Since the Vicat softening temperature of the imidated polymer is usually the target of the process and the degree of imidization to be achieved is determined thereafter, it is also easily possible to determine the required minimum temperature.
  • a temperature range from 140 ° C to 300 0 C, in particular from 150 ° C to 260 ° C, more preferably from 180 0 C - 220 ° C. Excessive reaction temperatures sometimes result in a decrease in viscosity due to partial chain termination of the polymer.
  • the reaction temperature starting from a temperature close to the melting temperature of the starting polymer, gradually or gradually increased and only last exceed the softening temperature of the final product imid striv by at least 20 ° C.
  • self adjusting pressure can be at 50 bar to 500 bar worked.
  • the temperature of the reaction mixture can drop and must then be increased again to the required value. If imidating agent is supplied under reaction conditions, of course, a correspondingly high pressure must be used for this.
  • the reaction time depends on the reaction rate under the conditions used. It can be significantly shorter than the reaction time, which would be required for a complete imidization, but in any case should be sufficient to a partial, z. B. 20 - to ensure 80% preferably 30 - 60% imidation of the polymer. In general, 10 sec to 30 min, preferably 1 min to 7 min, are sufficient for each process stage. As a guideline 4 minutes - 6 minutes can apply.
  • the reaction can be carried out in one or both process stages in the presence of solvents or diluents, as known, for example, from US Pat. No. 2,146,209, DE 1 077 872, DE 1 088 231 or EP 234 726.
  • Suitable solvents are especially those which are liquid at room temperature and volatile at elevated temperature, optionally at low pressure and can be easily separated from the imidated polymer. They may be either for the starting polymer or for the imidated polymer or for both solvents, if appropriate only under reaction conditions, but this is not fundamentally necessary.
  • Suitable solvents and diluents include mineral oils, gasoline hydrocarbons, aromatics, alkanols, ethers, ketones, esters, halogenated hydrocarbons, as well as water.
  • the optionally used solvent or diluent can be separated off together with excess imidating agent and split-off alkanol from the imidized polymer.
  • This process stage is particularly advantageous when the method at least in the last stage in a tubular reactor, in particular an extruder is performed.
  • the substances to be separated from the polymer can be removed in liquid form or in vapor form before the end of the tubular reactor at one or more points where the polymer is still in the melt state.
  • the first portion of these substances can be removed under the full reaction pressure and the last residues from a relaxation zone in the vacuum.
  • This can be used per se known single or multi-stage degassing extruder.
  • the entire reaction mixture can be discharged from the tubular reactor, relaxed, cooled and crushed and only then separated from the secondary components.
  • the cooled and comminuted polymer can be washed with a suitable solvent or with water.
  • the resulting imidated product can be prepared in a conventional manner, for. B. thermoplastic, are processed. Due to the extremely low content of methacrylic acid groups in the polymer, it is characterized by a good miscibility and compatibility with other polymers. The weather resistance is also very good, since the water absorption in moisture is significantly reduced. In this case, the higher proportion of anhydride groups compared to the carboxyl groups seems to play only an insignificant role. This could be z. B. due to the fact that the anhydride groups are relatively well protected in the interior of the polymer molecule from hydrolytic action by moisture.
  • the process according to the invention makes it possible to obtain a polymethacrylalkylimide of high quality for practical use in two simple process steps.
  • Such units are formed in addition to methacrylic acid alkylimide units in the reaction of polymethyl methacrylate with primary amines.
  • the content of carboxylic acid or anhydride groups is generally below the above-mentioned limit.
  • lower imidation levels below 95% are desired so that the increased formation of the carboxylic acid or anhydride groups is a problem.
  • EP 456 267 (US Pat. No. 5,135,985) describes polymethacrylalkylimides having less than 2.5% by weight of methacrylic acid units which can be prepared by homogeneous mixing of polymethacrylalkylimides with different degrees of imidation. This method of preparation is also very complicated since it is always necessary to provide polymers with different degrees of imidation as raw materials for the preparation of a polymethacrylalkylimide.
  • EP 441 148 (US Pat. No. 5,110,877) describes a process for imidating a polymer of alkyl esters of methacrylic acid by reaction with an imidating agent in which a part of the imidating agent is added only after the previously added imidating agent has been at least partially or completely reacted .
  • Suitable imidating agents are ammonia or primary amines, such as. As methylamine called.
  • the process makes it possible to produce polymethacrylalkylimides having low contents of methacrylic acid units of 1.3% by weight and 1.7% by weight, respectively, with degrees of imidation of about 80%. In comparison, the content of methacrylic acid units in the non-inventive standard method with 4.9 wt .-% is given.
  • the miscibility of polymethacrylalkylimides with other thermoplastic polymers is improved when the methacrylic and / or methacrylic anhydride units are reacted by post-treating the polymer with an alkylating agent such as orthoformic acid esters to form methacrylic ester units.
  • an alkylating agent such as orthoformic acid esters to form methacrylic ester units.
  • polymethacrylalkylimides with less than 0.1 milliequivalents of acid groups per g (about 0.8 wt .-%) at Imid istsgraden be prepared by about 60 wt .-%.
  • the post alkylation is therefore very effective, it requires an additional and expensive process step.
  • a process for the preparation of an imidated polymer of alkyl esters of methacrylic acid having a content of carboxylic acid units of less than 0.5% by weight, based on the polymer, by imidization of a polymer of alkyl esters of methacrylic acid in two process steps (a) and (b) may be characterized in that in the first step
  • (B) methylamine is used as an imidating agent, wherein the molar ratio of the ammonia used to the methylamine used is 1: 0.5 to 1: 3.
  • the process is simple to carry out and provides Polymethacrylalkylimide with practical Imidleitersgraden, which have very good practical properties due to the low content of methacrylic acid units. Unexpectedly, it was because of the defined ratio of ammonia and methylamine in the process steps (a) and (b), side reactions that lead to the presence of methacrylic acid units in the final product, obviously fail.
  • the comparatively higher content of carboxylic anhydride groups of about 5% by weight to 15% by weight surprisingly does not have the same unfavorable effect as one would expect based on the state of the art.
  • the resulting polymers have high Vicat softening temperatures and are easy to process.
  • the starting material used for the imidization is a polymer of alkyl esters of methacrylic acid, which is generally more than 50% by weight, preferably more than 80% by weight, more preferably 95% by weight to 100% by weight. from units of alkyl esters of methacrylic acid having 1 to 4 carbon atoms in the alkyl radical. Preference is given to methyl methacrylate.
  • Preferred polymers are composed of at least 80% by weight, preferably more than 90% by weight, more preferably more than 95% by weight, of methyl methacrylate.
  • Suitable comonomers are all monomers which can be copolymerized with methyl methacrylate, in particular alkyl esters of acrylic acid having 1 to 4 carbon atoms in the alkyl radical, acrylonitrile or methacrylonitrile, acrylamide or methacrylamide, styrene or else maleic anhydride.
  • the molding composition of the invention further contains 0.5 wt .-% to 15.0 wt .-% ceramic beads.
  • Ceramics denote largely of inorganic, fine-grained raw materials with addition of water molded at room temperature and then dried objects, which are sintered in a subsequent firing above 900 0 C to hard, more durable items.
  • the term also includes materials based on metal oxides.
  • fiber-reinforced Keramikmatehalien include such.
  • B. from silicon-containing organic polymers (polycarbosilanes) can be prepared as a starting material, the group of ceramics used in the invention.
  • the ceramic beads are expediently not covalently bonded to the polymer matrix and can in principle by physical separation methods, such as. B. extraction method with suitable solvents, such. As tetrahydrofuran (THF) are separated from the polymer matrix.
  • B. extraction method with suitable solvents such as tetrahydrofuran (THF) are separated from the polymer matrix.
  • THF tetrahydrofuran
  • the ceramic beads preferably have a spherical shape, with small deviations from the perfect spherical shape can occur naturally.
  • the ceramic beads expediently have a diameter in the range of 1 to 200 .mu.m.
  • the average diameter (median value D 50 ) of the ceramic beads is preferably in the range of 1, 0 .mu.m to 15.0 .mu.m.
  • the D95 value is preferably less than or equal to 35 ⁇ m, more preferably less than or equal to 13 ⁇ m.
  • the maximum diameter of the beads is preferably less than or equal to 40 microns, more preferably less than or equal to 13 microns.
  • the particle size of the beads is preferably determined by sieve analysis.
  • the density of the ceramic beads is favorably in the range of 2.1 g / cm 3 to 2.5 g / cm 3 .
  • the concrete composition of the ceramic beads is of minor importance to the present invention.
  • Preferred beads contain, in each case based on their total weight,
  • the surface of the ceramic beads measured by BET nitrogen adsorption method, is preferably in the range of 0.8 m 2 / g to 2.5 m 2 / g.
  • the ceramic beads preferably have a compressive strength such that more than 90% of the beads can not be destroyed by applying a pressure of 410 MPa.
  • ceramic beads include the Zeeospheres ® by the company, 3M Germany, in particular the type W-210, W-410, G-200 and G-400th
  • the molding composition according to the invention can still conventional additives, auxiliaries and / or fillers, such as. B. thermal stabilizers, UV stabilizers, UV absorbers, antioxidants, in particular soluble or insoluble dyes or colorants.
  • UV stabilizers and radical scavengers UV stabilizers and radical scavengers
  • Optional UV protectants are z.
  • benzophenone whose substituents such as hydroxyl and / or alkoxy groups are usually in the 2- and / or 4-position. These include 2-hydroxy-4-n-octoxybenzophenone, 2,4-dihydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4, 4'-dimethoxybenzophenone, 2- Hydroxy-4-methoxybenzophenone.
  • substituted benzotriazoles are very suitable as UV protection additive, including especially 2- (2-hydroxy-5-methylphenyl) - benzotriazole, 2- [2-hydroxy-3,5-di- (alpha, alpha-dimethyl -benzyl) -phenyl] -benzotriazole, 2- (2-hydroxy-3,5-di-t-butylphenyl) -benzotriazole, 2- (2-hydroxy-3, 5-butyl-5-methylphenyl) -5-chlorobenzthazole , 2- (2-hydroxy-3,5-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5-di-t-amylphenyl) -benzotriazole, 2- (2-hydroxybenzoyl) 5-t-butylphenyl) benzotriazole, 2- (2-hydroxy-3-sec-butyl-5-t-butylphenyl) benzotriazole, and 2- (2-hydroxy-5-
  • UV protectants which can also be used are 2-cyano-3,3-diphenylacrylic acid ethyl ester, 2-ethoxy-2'-ethyl-oxalic acid bisanilide, 2-ethoxy-5-t-butyl-2'-ethyl-oxalic acid bisanilide and substituted phenyl benzoate.
  • the UV protectants can be present as low molecular weight compounds, as indicated above, in the polymethacrylate compositions to be stabilized. But it can also UV-absorbing groups in the matrix polymer molecules covalently after copolymerization with polymerizable UV absorption compounds, such as. As acrylic, methacrylic or allyl derivatives of benzophenone or Benzthazoldehvaten be bound.
  • the proportion of UV protection agents is generally 0.01% by weight to 1.0% by weight, especially 0.01% by weight to 0 , 5 wt .-%, in particular 0.02 wt .-% to 0.2 wt .-% based on the totality of all constituents of Polymethacrylatharzes invention.
  • radical scavengers / UV stabilizers are hindered amines, which are known under the name HALS (JHindered Amine Light Stabilizer) are called. They can be used for the inhibition of aging in paints and plastics, especially in polyolefin plastics (Kunstscher, 74 (1984) 10, pp. 620-623; paint + varnish, 96 vintage, 9/1990, pp. 689 to 693).
  • the stabilizing effect of the HALS compounds is due to the tetramethylpiperidine group contained therein. This class of compounds may be both unsubstituted and substituted with alkyl or acyl groups on the piperidine atom.
  • the sterically hindered amines do not absorb in the UV range. They catch formed radicals, which the UV absorbers can not do.
  • stabilizing HALS compounds which can also be used as mixtures are:
  • the radical scavengers / UV stabilizers are used in the molding compositions according to the invention in amounts of 0.01% by weight to 1.5% by weight, in particular in amounts of 0.02% by weight to 1.0% by weight. %, in particular in amounts of 0.02 wt .-% to 0.5 wt .-% based on the totality of all components.
  • Lubricants or mold release agents are of particular importance for the injection molding process, which can reduce or completely prevent possible adhesion of the molding compound to the injection mold.
  • As adjuvants can therefore lubricants, for. B. selected from the group of saturated fatty acids having less than C20, preferably C16 to C18 carbon atoms or the saturated fatty alcohols containing less than C20, preferably C16 to C18 carbon atoms. Preference is given to small amounts of at most 0.25 wt .-%, z. B. 0.05 wt .-% to 0.2 wt .-%, based on the molding composition. Suitable z. As stearic acid, palmitic acid, technical mixtures of stearic and palmitic acid. Further suitable z. As n-hexadecanol, n-octadecanol, and technical mixtures of n-hexadecanol and n-octadecanol.
  • a particularly preferred slip-release agent is stearyl alcohol.
  • the molding composition according to the invention can be prepared by dry blending the components, which may be in the form of powders, granules or preferably granules. Furthermore, it can also be prepared by melting and blending the polymer matrix and optionally the toughening modifier in the melt state or by melting dry premixes of individual components and adding the ceramic beads. This can be z. B. in single or twin-screw extruders. The resulting extrudate can then be granulated. Usual additives, auxiliaries and / or fillers can be added directly or added later by the end user as needed.
  • the molding composition of the invention is suitable as a starting material for the production of moldings with lecturmatter and preferably rough surface.
  • the transformation of the molding composition can be known per se, for. B. by processing over the elastoviskosen state, d. H. by kneading, rolling, calendering, extruding or injection molding, wherein extrusion and injection molding, in particular extrusion, are preferred in the present case.
  • the injection molding of the molding composition can be carried out in known manner at temperatures in the range of 240 0 C - 300 0 C (melt temperature) and a mold temperature of preferably 70 ° C to 150 0 C.
  • a mold temperature of preferably 70 ° C to 150 0 C.
  • the extrusion is preferably carried out at a temperature of 220 0 C to 260 0 C.
  • the roughness value R z according to DIN 4768 is expediently greater than or equal to 0.3 ⁇ m, preferably at least 0.7 ⁇ m, particularly preferably between 2.5 ⁇ m and 20.0 ⁇ m.
  • the degree of gloss (R 60 °) according to DIN 67530 (01/1982) is preferably at most 45, more preferably at most 38 ..
  • the Vicaterweichungstemperatur VET (ISO 306-B50) is preferably at least 90 0 C, particularly preferably at least 100 ° C, completely more preferably at least 110 ° C and is suitably between 110 0 C and 200 ° C, in particular between 125 ° C and 180 0 C.
  • the transmission according to DIN 5036 is preferably in the range of 40% to 93%, more preferably in the range of 55% to 93%, in particular in the range of 55% to 85%.
  • the intensity half-value angle according to DIN 5036 is preferably in the range of 1 ° to 55 °, more preferably in the range of 2 ° to 40 °, in particular in the range of 8 ° to 37 °.
  • the shaped body preferably has one or more, more preferably as many as possible, of the following properties: I. a breaking stress according to ISO 527 (5 mm / min) in the range of 80 to 110
  • the moldings according to the invention can be used, in particular, as parts of household appliances, communication devices, hobby or sports equipment, body parts or parts of body parts in automobile, ship or aircraft construction, as parts for lighting, signs or symbols, outlets or cosmetics sales stands, containers, home or office decorations , Furniture applications, shower doors and office doors, and as parts, in particular panels, used in the construction industry, as walls, in particular as noise barriers, as window frames, benches, lighting covers, diffusers and automotive glazing.
  • Typical automobile exterior parts are z. As spoilers, panels, roof modules or exterior mirror housing.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

L'invention concerne une matière à mouler contenant, par rapport au poids total de la matière à mouler, A) 83 à 99,5 % en poids d'une matrice polymère composée d'au moins un (co)polymère de (méth)acrylimide; et B) 0,5 à 15,0 % en poids de perles de céramique, la matière à mouler présentant un indice de fusion volumique (MVR), mesuré selon ISO 1133 à 260 °C et 10 kg, de 1,0 cm~ / 10 min à 20,0 cm~ / 10 min. La matière à mouler peut être employée pour la fabrication de corps moulés à surface dépolie de type velours, de préférence rugueuse. De tels corps moulés servent particulièrement de pièces d'appareils ménagers, d'appareils de communication, d'équipements de loisir et de sport, d'éléments de carrosserie ou de pièces d'éléments de carrosserie dans la construction automobile, navale ou aéronautique, de pièces d'éclairages, d'insignes ou de symboles, de points de vente ou de stands de vente de cosmétiques, de contenants, de décorations domestiques ou de bureau, de pièces de meubles, de portes de douche, de portes de bureau, et de pièces dans le bâtiment, par exemple de parois, de cadres de fenêtres, de bancs, de couvercles de lampes, de verre diffusant et de vitres de véhicules.
EP07822010A 2007-01-30 2007-10-30 Matières à mouler pour des corps moulés en pmmi Withdrawn EP2115056A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102007005428A DE102007005428A1 (de) 2007-01-30 2007-01-30 Formmassen für mattierte PMMI-Formkörper
PCT/EP2007/061656 WO2008092517A1 (fr) 2007-01-30 2007-10-30 Matières à mouler pour des corps moulés en pmmi

Publications (1)

Publication Number Publication Date
EP2115056A1 true EP2115056A1 (fr) 2009-11-11

Family

ID=38959668

Family Applications (1)

Application Number Title Priority Date Filing Date
EP07822010A Withdrawn EP2115056A1 (fr) 2007-01-30 2007-10-30 Matières à mouler pour des corps moulés en pmmi

Country Status (12)

Country Link
US (1) US20100098908A1 (fr)
EP (1) EP2115056A1 (fr)
JP (1) JP2010516518A (fr)
KR (1) KR20090115172A (fr)
CN (1) CN101611083A (fr)
BR (1) BRPI0721402A2 (fr)
CA (1) CA2676992A1 (fr)
DE (1) DE102007005428A1 (fr)
MX (1) MX2009008123A (fr)
RU (1) RU2009132410A (fr)
TW (1) TW200902623A (fr)
WO (1) WO2008092517A1 (fr)

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10345045A1 (de) * 2003-09-26 2005-04-14 Röhm GmbH & Co. KG Verfahren zur Oberflächenvergütung von Werkstoffen durch Aufbringen insbesondere transparenter Schichten auf Basis von Polymethacrylaten
MX2007008855A (es) * 2003-10-18 2008-03-13 Roehm Gmbh Masas de pieza moldeada de poli (met) acrilato resistentes a impactos con alta estabilidad termica.
DE102004022540A1 (de) 2004-05-05 2005-12-08 Röhm GmbH & Co. KG Formmasse für Formkörper mit hoher Witterungsbeständigkeit
DE102004045296A1 (de) * 2004-09-16 2006-03-23 Röhm GmbH & Co. KG Verwendung von Polyalkyl (meth) acrylat-Perlpolymerisaten und Formmasse zur Herstellung von extrudierten Formteilen mit mattierter Oberfläche
DE102004058083A1 (de) * 2004-12-01 2006-06-08 Röhm GmbH & Co. KG Gedeckt eingefärbte, infrarotreflektierende Kunststoffformmasse
DE102005055793A1 (de) * 2005-11-21 2007-05-24 Röhm Gmbh Transparente TPU (thermoplastische Polyurethane)/ PMMA (Polymethyl(meth)acrylat) Abmischungen mit verbesserter Kältesschlagzähigkeit
DE102006029613A1 (de) 2006-06-26 2007-12-27 Röhm Gmbh Transparenter Kunststoff-Verbund
DE102007026200A1 (de) * 2007-06-04 2008-12-11 Evonik Röhm Gmbh Zusammensetzung mit erhöhter Spannungsrissbeständigkeit
DE102007026201A1 (de) * 2007-06-04 2008-12-11 Evonik Röhm Gmbh Eingefärbte Zusammensetzung mit erhöhter Spannungsrissbeständigkeit
DE102007028601A1 (de) * 2007-06-19 2008-12-24 Evonik Röhm Gmbh Reaktivgemisch zur Beschichtung von Formkörpern mittels Reaktionsspritzguss sowie beschichteter Formkörper
DE102007029263A1 (de) * 2007-06-22 2008-12-24 Evonik Röhm Gmbh PMMA/PVDF-Folie mit besonders hoher Witterungsbeständigkeit und hoher UV-Schutzwirkung
DE102007051482A1 (de) 2007-10-25 2009-04-30 Evonik Röhm Gmbh Verfahren zur Herstellung von beschichteten Formkörpern
DE102008001231A1 (de) * 2008-04-17 2009-10-22 Evonik Röhm Gmbh Flammfeste PMMA-Formmasse
DE102008001695A1 (de) * 2008-05-09 2009-11-12 Evonik Röhm Gmbh Poly(meth)acrylimide mit verbesserten optischen und Farbeigenschaften, insbesondere bei thermischer Belastung
WO2019052360A1 (fr) * 2017-09-18 2019-03-21 Evonik Specialty Chemicals (Shanghai) Co., Ltd. Procédé de moulage par injection de composés polymères comprenant des particules de mousse de poly(méth)acrylimide
DE102018212447A1 (de) * 2018-07-25 2020-01-30 Eos Gmbh Electro Optical Systems Pulverförmiges Material geeignet für die Herstellung eines dreidimensionalen Objekts in einem generativen Schichtbauverfahren, dessen Verwendung und Herstellungsverfahren dafür

Family Cites Families (36)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2146209A (en) 1936-07-31 1939-02-07 Du Pont Preparation of resinous imides of substituted acrylic acids
DE1088231B (de) 1958-03-22 1960-09-01 Roehm & Haas Gmbh Verfahren zur Herstellung Stickstoff enthaltender Derivate der Polymethacrylsaeure
DE1077872B (de) 1958-03-22 1960-03-17 Roehm & Haas Gmbh Verfahren zur Herstellung Stickstoff enthaltender Derivate der Polymethacrylsaeure
DE2844687A1 (de) * 1978-10-13 1980-04-30 Hoechst Ag Formkoerper mit gleichmaessig matter oberflaeche
US4504565A (en) * 1984-04-17 1985-03-12 Markem Corporation Radiation imageable compositions containing hollow ceramic microspheres
US4727117A (en) 1985-08-27 1988-02-23 Rohm And Haas Company Imide polymers
JPH0629286B2 (ja) 1986-01-23 1994-04-20 三菱レイヨン株式会社 メタクリルイミド単位含有メタクリル樹脂
DE4002904A1 (de) 1990-02-01 1991-08-08 Roehm Gmbh Verfahren zum imidieren eines methacrylester-polymerisats
DE4015182A1 (de) 1990-05-11 1991-11-14 Roehm Gmbh Homogene polymermischung aus polymethacrylimid-polymeren
US5787655A (en) 1992-09-11 1998-08-04 Saylor, Jr.; Edward T. Slip-resistant cover system and method for making same
DE4402666A1 (de) 1994-01-29 1995-08-03 Roehm Gmbh Verfahren zum kurzzeitigen Behandeln einer Kunststoffschmelze mit einem flüssigen Behandlungsmittel und dabei hergestellter thermoplastischer Kunststoff
US5562981A (en) 1994-10-05 1996-10-08 Wabash National Corporation Trailer with fiberglass reinforced plastic side panels and method of making the same
DE19544479A1 (de) 1995-11-29 1997-06-05 Roehm Gmbh Verfahren zur Herstellung eines imidierten Polymerisats von Alkylestern
WO1997021536A1 (fr) 1995-12-08 1997-06-19 Minnesota Mining And Manufacturing Company Materiau en feuille renfermant des particules
US5731367A (en) * 1997-02-04 1998-03-24 Bayer Corporation Injection molded parts having improved surface gloss
DE10220470A1 (de) * 2002-04-30 2003-11-20 Roehm Gmbh ph-sensitives Polymer
TWI228137B (en) * 1999-06-17 2005-02-21 Rohm & Haas Capstock composition and process providing weatherability, reduced gloss, and high impact
JP2002080790A (ja) * 2000-09-08 2002-03-19 Nippon Paint Co Ltd 低光沢塗料組成物、塗膜形成方法および低光沢塗装物
US20020169236A1 (en) 2001-02-22 2002-11-14 Halterman David G. Decorative solid surfacing materials filled with ceramic microspheres
BR0106170A (pt) 2001-12-20 2003-09-23 3M Innovative Properties Co Fita antiderrapante fotoluminescente
DE10311437A1 (de) * 2003-03-15 2004-09-23 Degussa Ag Laser-Sinter-Pulver mit PMMI, PMMA und/oder PMMI-PMMA-Copolymeren, Verfahren zu dessen Herstellung und Formkörper, hergestellt aus diesem Laser-Sinterpulver
DE10320318A1 (de) * 2003-05-06 2004-12-02 Röhm GmbH & Co. KG Verfahren zur Herstellung von lichtstreuenden Formteilen mit hervorragenden optischen Eigenschaften
DE10349144A1 (de) * 2003-10-17 2005-05-12 Roehm Gmbh Polymermischung für mattierte Spritzgußteile
MX2007008855A (es) * 2003-10-18 2008-03-13 Roehm Gmbh Masas de pieza moldeada de poli (met) acrilato resistentes a impactos con alta estabilidad termica.
DE10354379A1 (de) * 2003-11-20 2005-06-23 Röhm GmbH & Co. KG Formmasse, enthaltend ein Mattierungsmittel
GB0408338D0 (en) 2004-04-14 2004-05-19 3M Innovative Properties Co Abrasive articles, compositions, and methods of making the same
DE102004022540A1 (de) * 2004-05-05 2005-12-08 Röhm GmbH & Co. KG Formmasse für Formkörper mit hoher Witterungsbeständigkeit
DE102004045296A1 (de) * 2004-09-16 2006-03-23 Röhm GmbH & Co. KG Verwendung von Polyalkyl (meth) acrylat-Perlpolymerisaten und Formmasse zur Herstellung von extrudierten Formteilen mit mattierter Oberfläche
DE102004058083A1 (de) * 2004-12-01 2006-06-08 Röhm GmbH & Co. KG Gedeckt eingefärbte, infrarotreflektierende Kunststoffformmasse
US7790079B2 (en) * 2005-04-18 2010-09-07 Evonik Rohm Gmbh Thermoplastic molding material and molding elements containing nanometric Inorganic particles for making said molding material and said molding elements, and uses thereof
DE102005021335A1 (de) * 2005-05-04 2006-11-09 Röhm Gmbh Verfahren zur Herstellung von Perlpolymerisaten mit einer mittleren Teilchengröße im Bereich von 1 µm bis 40 µm sowie Perlpolymerisat aufweisende Formmassen und Formkörper
DE102005055793A1 (de) * 2005-11-21 2007-05-24 Röhm Gmbh Transparente TPU (thermoplastische Polyurethane)/ PMMA (Polymethyl(meth)acrylat) Abmischungen mit verbesserter Kältesschlagzähigkeit
DE102006029613A1 (de) * 2006-06-26 2007-12-27 Röhm Gmbh Transparenter Kunststoff-Verbund
DE102007026201A1 (de) * 2007-06-04 2008-12-11 Evonik Röhm Gmbh Eingefärbte Zusammensetzung mit erhöhter Spannungsrissbeständigkeit
DE102007026200A1 (de) * 2007-06-04 2008-12-11 Evonik Röhm Gmbh Zusammensetzung mit erhöhter Spannungsrissbeständigkeit
DE102007028601A1 (de) * 2007-06-19 2008-12-24 Evonik Röhm Gmbh Reaktivgemisch zur Beschichtung von Formkörpern mittels Reaktionsspritzguss sowie beschichteter Formkörper

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2008092517A1 *

Also Published As

Publication number Publication date
BRPI0721402A2 (pt) 2014-03-04
US20100098908A1 (en) 2010-04-22
CA2676992A1 (fr) 2008-08-07
RU2009132410A (ru) 2011-03-10
KR20090115172A (ko) 2009-11-04
TW200902623A (en) 2009-01-16
CN101611083A (zh) 2009-12-23
DE102007005428A1 (de) 2008-07-31
JP2010516518A (ja) 2010-05-20
MX2009008123A (es) 2009-10-14
WO2008092517A1 (fr) 2008-08-07

Similar Documents

Publication Publication Date Title
EP2115056A1 (fr) Matières à mouler pour des corps moulés en pmmi
EP1675907B1 (fr) Melange polymere pour pieces moulees par injection depolies
EP2115062A1 (fr) Matières à mouler pour des corps moulés en polyacrylate dépolis
EP1742997B1 (fr) Matieres façonnables pour la production de corps façonnes presentant une resistance elevee aux intemperies
EP2150582B1 (fr) Composition présentant une meilleure résistance à la fissuration sous contrainte
EP2150581B1 (fr) Composition teintée présentant une meilleure résistance à la fissuration sous contrainte
EP1673409B1 (fr) Melange polymere et son utilisation pour des pieces moulees par injection
EP1844102B1 (fr) Matiere moulable poly(meth)acrylate resistante aux chocs a thermostabilite elevee
DE3037520C2 (fr)
EP2217658B1 (fr) Corps moulés à surface mate et structurée
EP1573150A1 (fr) Articles a base de matiere plastique de moulage pmma
WO2012004059A1 (fr) Matériau composite comportant un matériau cellulosique doté de polyméthacrylate de méthyle (pmma) en tant que matrice plastique à l'aide de différents éléments de couplage
DE4025219A1 (de) Thermoplastische polyoxymethylen-formmasse mit hoher zaehigkeit und ihre verwendung
DE4216341A1 (de) Lichtstreuende Polymethacrylat-Formkörper mit hohen Temperatur- und Wetterechtheitswerten
EP0946644B1 (fr) Copolymerisats de (methyl)methacrylate-anhydride d'acide maleique s'utilisant comme agents de modification polymeres pour des matieres plastiques et melanges et composites polymeres produits a l'aide desdits copolymerisats
DE69923327T3 (de) Acrylatisches material
EP0006562B1 (fr) Matières à mouler transparentes et résistant aux chocs et pièces moulées à partir de celles-ci
EP4263713B1 (fr) Mélanges contenant des siloxanes à fonction oxamide et des fibres organiques
EP0519947A1 (fr) Matieres moulables en polyolefine et leur utilisation
DE102022212610A1 (de) Thermoplastische harzzusammensetzung mit verbesserter schwärze und kratzfestigkeit und formteil, die diese umfasst

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20090721

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC MT NL PL PT RO SE SI SK TR

DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20120502