EP0914383A1 - Plaques a grille pour obturer des orifices de ventilation - Google Patents

Plaques a grille pour obturer des orifices de ventilation

Info

Publication number
EP0914383A1
EP0914383A1 EP97934539A EP97934539A EP0914383A1 EP 0914383 A1 EP0914383 A1 EP 0914383A1 EP 97934539 A EP97934539 A EP 97934539A EP 97934539 A EP97934539 A EP 97934539A EP 0914383 A1 EP0914383 A1 EP 0914383A1
Authority
EP
European Patent Office
Prior art keywords
weight
component
graft
cover
particle size
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Withdrawn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
EP97934539A
Other languages
German (de)
English (en)
Inventor
Herbert Naarmann
Graham Edmund Mc Kee
Alfred Pirker
Hans-Josef Sterzel
Franz Brandstetter
Bernd-Steffen Von Bernstorff
Bernhard Rosenau
Ulrich Endemann
Burkhard Straube
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 SE
Original Assignee
BASF SE
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 SE filed Critical BASF SE
Publication of EP0914383A1 publication Critical patent/EP0914383A1/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Withdrawn legal-status Critical Current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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F04—POSITIVE - DISPLACEMENT MACHINES FOR LIQUIDS; PUMPS FOR LIQUIDS OR ELASTIC FLUIDS
    • F04D—NON-POSITIVE-DISPLACEMENT PUMPS
    • F04D29/00—Details, component parts, or accessories
    • F04D29/70—Suction grids; Strainers; Dust separation; Cleaning
    • F04D29/701—Suction grids; Strainers; Dust separation; Cleaning especially adapted for elastic fluid pumps
    • F04D29/703—Suction grids; Strainers; Dust separation; Cleaning especially adapted for elastic fluid pumps specially for fans, e.g. fan guards
    • 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
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
    • 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
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • 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
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • 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
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/12—Copolymers of styrene with unsaturated nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
    • C08L81/04—Polysulfides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24—HEATING; RANGES; VENTILATING
    • F24F—AIR-CONDITIONING; AIR-HUMIDIFICATION; VENTILATION; USE OF AIR CURRENTS FOR SCREENING
    • F24F13/00—Details common to, or for air-conditioning, air-humidification, ventilation or use of air currents for screening
    • F24F13/08—Air-flow control members, e.g. louvres, grilles, flaps or guide plates
    • F24F13/082—Grilles, registers or guards

Definitions

  • the invention relates to grilles for fan openings.
  • the invention relates to cover grilles with high resistance to weathering, resistance to yellowing, high surface quality and a low tendency to form weld lines.
  • ABS acrylonitrile / butadiene / styrene copolymer
  • HJPS High Impact PolyStyrene
  • the object of the present invention is to provide cover grilles for fan openings which have a high yellowing resistance and a high weather resistance.
  • Another object of the present invention is to provide cover grids for fan openings which have a low tendency to form weld lines and a high surface quality during manufacture.
  • Another object of the invention is to provide cover grilles for fan openings which avoid the disadvantages of the known cover grilles.
  • the object is achieved according to the invention by using a thermoplastic molding composition different from ABS, comprising, based on the sum of the amounts of components A and B, and possibly C and / or D, which gives a total of 100% by weight, a: 1 99% by weight of a particulate emulsion polymer with a glass transition temperature below 0 ° C. and an average particle size of 50-1000 nm, preferably 50-500 nm as component A,
  • b 1-99% by weight of at least one amorphous or partially crystalline polymer as component B,
  • thermoplastic molding compositions used according to the invention for the production of the cover grids according to the invention are known per se.
  • DE-OS 12 60 135, DE-PS 19 11 882, DE-OS 28 26 925, DE-OS 31 49 358, DE-OS 32 27 555 and DE-OS 40 11 162 molding compositions which can be used according to the invention are described.
  • the molding compositions other than ABS used to produce the cover grids according to the invention contain components A and B and optionally C and / or D, as defined below. They contain, based on the sum of the amounts of components A and B, and if appropriate C and / or D, which gives a total of 100% by weight,
  • b 1-99% by weight, preferably 40-85% by weight, in particular 50-75% by weight, of at least one amorphous or partially crystalline polymer as component B,
  • d 0 - 50% by weight of fibrous or particulate fillers or their mixtures as component D.
  • COMPONENT A Component A is a particulate emulsion polymer with a glass transition temperature below 0 ° C and an average particle size of 50-1000 nm.
  • Component A is preferably a graft copolymer
  • a22 up to 60% by weight, preferably 15-35% by weight, of units of an ethylenically unsaturated monomer, preferably acrylonitrile or methacrylonitrile, in particular acrylonitrile as component A22.
  • the graft pad A2 consists of at least one graft shell, the graft copolymer A overall having an average particle size of 50-1000 nm.
  • component AI consists of the monomers all: 80-99.99% by weight, preferably 95-99.9% by weight, one
  • al2 0.01-20% by weight, preferably 0.1-5.0% by weight, of at least one poly-crosslinking monomer, preferably diallyl phthalate and / or DCPA as component A12.
  • the average particle size of component A is 50-800 nm, preferably 50-600 nm.
  • the particle size distribution of component A is bimodal, 60-90% by weight having an average particle size of 50-200 nm and 10-40% by weight having an average particle size of 50-400 nm on the total weight of component A.
  • the sizes determined from the integral mass distribution are given as the average particle size or particle size distribution.
  • the mean particle sizes according to the invention are in all cases the weight average of the particle sizes, as determined by means of an analytical ultracentrifuge according to the method of W. Scholtan and H. Lange, Kolloid-Z. and Z.-Polymer 250 (1972), pages 782-796.
  • the ultracentrifuge measurement provides the integral mass distribution of the particle diameter of a sample. From this it can be seen what percentage by weight of the particles have a diameter equal to or smaller than a certain size.
  • the mean particle diameter which is also referred to as the C ⁇ Q value of the integral mass distribution, is defined as the particle diameter at which 50% by weight of the particles have a smaller diameter than the diameter which corresponds to the d ⁇ value . Likewise, 50% by weight of the particles then have a larger diameter than the d 50 value.
  • the d 10 and d Q values resulting from the integral mass distribution are used.
  • the d 10 or d ⁇ value of the integral mass distribution are defined in accordance with the d 50 value with the difference that they are based on 10 or 90% by weight of the particles. The quotient
  • Emulsion polymers A which can be used according to the invention as component A preferably have Q values less than 0.5, in particular less than 0.35.
  • the glass transition temperature of the emulsion polymer A and also of the other components used according to the invention is determined by means of DSC (differential scanning calorimetry) according to ASTM 3418 (mid point temperature).
  • emulsion polymer A such as epichlorohydrin rubbers, ethylene-vinyl acetate rubbers, polyethylene chlorosulfone rubbers, silicone rubbers, polyether rubbers, hydrogenated diene rubbers, polyalkylene rubber rubbers, polyalkylene rubber rubbers, polyalkylene rubber rubbers, according to one embodiment of the invention.
  • Acrylate rubber, ethylene-propylene (EP) rubber, ethylene-propylene-diene (EPDM) rubber, in particular acrylate rubber, are preferably used.
  • the diene basic building block content in the emulsion polymer A is kept so low that as few unreacted double bonds remain in the polymer. According to one embodiment, there are no basic diene building blocks in the emulsion polymer A.
  • the acrylate rubbers are preferably alkyl acrylate rubbers made from one or more C 1-6 alkyl acrylates, preferably C 4 . 8 -Al acrylates, preferably at least partially butyl, hexyl, octyl or 2-ethylhexyl acrylate, in particular n-butyl and 2-ethylhexyl acrylate, are used.
  • These alkyl acrylate rubbers can contain up to 30% by weight polymer monomers which form hard polymers, such as vinyl acetate, (meth) acrylonitrile, styrene, substituted styrene, methyl methacrylate or vinyl ether.
  • the acrylate rubbers further contain 0.01-20% by weight, preferably 0.1-5% by weight, of cross-linking polyfunctional monomers (crosslinking monomers).
  • cross-linking monomers examples include monomers that contain 2 or more double bonds capable of copolymerization, which are preferably not conjugated in the 1,3 positions. 4
  • Suitable crosslinking monomers are, for example, divinylbenzene, diallyl maleate, diallyl fumarate, diallyl phthalate, diethyl phthalate, triallyl cyanurate, triallyl isocyanurate, tricyclodecenyl acrylate, dihydrodicyclopentadienyl acrylate, triallyl phosphate, allyl acrylate.
  • Dicyclopentadienyl acrylate (DCPA) has proven to be a particularly favorable crosslinking monomer (cf. DE-C 12 60 135).
  • Suitable silicone rubbers can be, for example, crosslinked silicone rubbers composed of units of the general formulas R 2 SiO, RSiO 3/2 , R 3 SiO 1 2 and SiO 2 4 , the radical R representing a monovalent radical.
  • the amount of each Siloxane units are dimensioned such that for 100 units of the formula R 2 SiO 0 to 10 mol units of the formula RSi ⁇ 3/2 , 0 to 1.5 mol units R 3 SiO 1 2 and 0 to 3 mol units SiO 2 4 are available.
  • R can be either a monovalent saturated hydrocarbon radical having 1 to 18 carbon atoms, the phenyl radical or the alkoxy radical or a radical which is easily attackable by free radicals, such as the vinyl or mercaptopropyl radical. It is preferred that at least 80% of all R groups are methyl groups; combinations of methyl and ethyl or phenyl radicals are particularly preferred.
  • Preferred silicone rubbers contain built-in units of groups which can be attacked by free radicals, in particular vinyl, allyl, halogen, mercapto groups, preferably in amounts of 2-10 mol%, based on all radicals R. They can be, for example, as in EP-A-0 260 558 described.
  • an emulsion polymer A made from uncrosslinked polymer All of the monomers mentioned above can be used as monomers for the production of these polymers.
  • Preferred uncrosslinked emulsion polymers A are e.g. Homopolymers and copolymers of acrylic esters, especially n-butyl and ethyl hexyl acrylate, and homopolymers and copolymers of ethylene, propylene, butylene, isobutylene, and poly (organosiloxanes), all with the proviso that they are linear or may be branched.
  • the emulsion polymer A can also be a multi-stage polymer (so-called “core / shell structure", “core-shell morphology”).
  • a rubber-elastic core T g ⁇ 0 ° C
  • a hard shell polymers with T g > 0 ° C
  • component A is a graft copolymer.
  • the graft copolymers A of the molding compositions according to the invention have an average particle size d 50 of 50-1000 nm, preferably 50-600 nm and particularly preferably 50-400 nm. These particle sizes can be achieved if A1 of this component A is used as the graft base Particle sizes of 50-350 nm, preferably 50-300 nm and particularly preferably 50-250 nm are used.
  • the graft copolymer A is generally one or more stages, i.e. a polymer composed of a core and one or more shells.
  • the polymer consists of a basic stage (graft core) Al and one or - preferably - several stages A2 grafted thereon, the so-called graft stages or graft shells.
  • One or more graft shells can be applied to the rubber particles by simple grafting or multiple step-wise grafting, each graft sheath having a different composition.
  • polyfunctional crosslinking or reactive group-containing monomers can also be grafted on (see e.g. EP-A-0 230 282, DE-A-36 01 419, EP-A-0 269 861).
  • component A consists of a multi-stage graft copolymer, the graft stages generally being made from resin-forming monomers and having a glass transition temperature T g above 30 ° C., preferably above 50 ° C.
  • the multi-stage structure serves, inter alia, to achieve (partial) compatibility of the rubber particles A with the thermoplastic B.
  • Graft copolymers A are prepared, for example, by grafting at least one of the monomers A2 listed below onto at least one of the graft bases or graft core materials AI. All of the polymers which are described above under emulsion polymers A are suitable as graft bases AI of the molding compositions according to the invention.
  • the graft base AI is composed of 15-99% by weight of acrylate rubber, 0.1-5% by weight of crosslinking agent and 0-49.9% by weight of one of the further monomers or rubbers indicated.
  • Suitable monomers for forming the graft A2 can be selected, for example, from the monomers listed below and their mixtures:
  • Vinylaromatic monomers such as styrene and its substituted derivatives, such as ⁇ -methylstyrene, p-methylstyrene, 3,4-dimethylstyrene, p-tert-butylstyrene, o- and p-divinylbenzene and p-methyl- ⁇ -methylstyrene or C j - Cg-alkyl (meth) acrylates such as methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, s-butyl acrylate; styrene, ⁇ -methylstyrene, methyl methacrylate, in particular styrene and / or ⁇ -methylstyrene, and ethylenically unsaturated monomers, such as acrylic and methacrylic compounds, such as acrylonitrile, methacrylonit
  • (co) monomers styrene, vinyl, acrylic or methacrylic compounds (for example styrene, optionally substituted with C 2 alkyl radicals, halogen atoms, halogen methylene radicals; vinyl naphthalene, vinyl carbazole; Vinyl ether with C j .
  • component A comprises 50-90% by weight of the above-described graft base AI and 10-50% by weight of the above-described graft base A2, based on the total weight of component A.
  • crosslinked acrylic acid ester polymers with a glass transition temperature below 0 ° C. serve as the graft base.
  • the crosslinked acrylic ester polymers should preferably have a glass transition temperature below -20 ° C., in particular below -30 ° C.
  • the graft A2 is composed min- least one graft shell, and the outermost graft shell of which has a glass transition temperature greater than 30 ° C, where a polymer formed from the monomers of graft A2 would have a glass transition temperature of more than 80 C C.
  • the graft copolymers A can also be prepared by grafting pre-formed polymers onto suitable graft homopolymers. Examples of this are the reaction products of copolymers containing maleic anhydride or acid groups with base-containing rubbers. Suitable preparation processes for graft copolymers A are emulsion, solution, bulk or suspension polymerization.
  • the graft copolymers A are preferably prepared by free-radical emulsion polymerization, in particular in the presence of latices of component AI at temperatures from 20 ° C. to 90 ° C. using water-soluble or oil-soluble initiators such as peroxodisulfate or benzyl peroxide, or with the aid of redox initiators. Redox initiators are also suitable for polymerization below 20 ° C.
  • Suitable emulsion polymerization processes are described in DE-A-28 26 925, 31 49 358 and in DE-C-12 60 135.
  • the graft casings are preferably constructed in the emulsion polymerization process as described in DE-A-32 27 555, 31 49 357, 31 49 358, 34 14 118.
  • the defined particle sizes of 50-1000 nm according to the invention are preferably carried out after the processes that are described in DE-C-12 60 135 and DE-A-28 26 925, or Applied Polymer Science, Volume 9 (1965), page 2929.
  • the use of polymers with different particle sizes is known, for example, from DE-A-28 26 925 and US 5,196,480.
  • the graft base AI is first prepared by adding the acrylic acid ester (s) used according to one embodiment of the invention and the polyfunctional monomers which cause crosslinking, if appropriate together with the other comonomers, in an aqueous emulsion in a conventional manner at temperatures between 20 and 100 ° C, preferably between 50 and 80 ° C, polymerized.
  • the usual emulsifiers such as alkali salts of alkyl or alkylarylsulfonic acids, alkyl sulfates, fatty alcohol sulfonates, salts of higher fatty acids with 10 to 30 carbon atoms or resin soaps can be used.
  • the sodium salts of alkyl sulfonates or fatty acids having 10 to 18 carbon atoms are preferably used.
  • the emulsifiers are used in amounts of 0.5-5% by weight, in particular 1-2% by weight, based on the monomers used in the preparation of the graft base AI. In general, a weight ratio of water to monomers of 2: 1 to 0.7: 1 is used.
  • the usual persulfates, such as potassium persulfate, are used in particular as polymerization initiators. However, redox systems can also be used.
  • the initiators are generally used in amounts of 0.1-1% by weight, based on the monomers used in the preparation of the graft base AI.
  • buffer substances by means of which pH values of preferably 6-9, such as sodium bicarbonate and sodium pyrophosphate, and 0-3% by weight of a molecular weight regulator, such as mercaptans, terpinols or dimeric ⁇ -methylstyrene, can be added as further polymerization auxiliaries the polymerization can be used.
  • pH values of preferably 6-9 such as sodium bicarbonate and sodium pyrophosphate
  • a molecular weight regulator such as mercaptans, terpinols or dimeric ⁇ -methylstyrene
  • the exact polymerization conditions in particular the type, dosage and amount of the emulsifier, are determined in detail within the ranges given above such that the latex of the crosslinked acrylic ester polymer obtained ad 50 value in the range of about 50-1000 nm, preferably 50-150 nm, particularly preferably in the range of 80-100 nm.
  • the particle size distribution of the latex should preferably be narrow. The quotient
  • the weight ratio of styrene to acrylonitrile in the monomer mixture according to one embodiment of the invention should be in the range from 100: 0 to 40:60, preferably in the range from 65:35 to 85:15. It is advantageous to carry out this graft copolymerization of styrene and acrylonitrile on the crosslinked polyacrylic acid ester polymer used as the graft base again in an aqueous emulsion under the customary conditions described above.
  • the graft copolymerization can expediently take place in the same system as the emulsion polymerization for the preparation of the graft base AI, it being possible, if necessary, to add further emulsifier and initiator.
  • the monomer mixture of styrene and acrylonitrile to be grafted on according to one embodiment of the invention can be added to the reaction mixture all at once, batchwise in several stages or preferably continuously during the polymerization.
  • the graft copolymerization of the mixture of styrene and acrylonitrile in the presence of the crosslinking acrylic ester polymer is carried out in such a way that a degree of grafting of 1-99% by weight, preferably 20-45% by weight, in particular 35-45% by weight, based on the Total weight of component A, resulting in graft copolymer A. Since the graft yield in the graft copolymerization is not 100%, a somewhat larger amount of the monomer mixture of styrene and acrylonitrile must be used in the graft copolymerization than corresponds to the desired degree of grafting.
  • the control of the graft yield in the graft copolymerization and thus the degree of grafting of the finished graft copolymer A is known to the person skilled in the art and can be carried out, for example, by the metering rate of the monomers or by adding a regulator (Chauvel, Daniel, ACS Polymer Preprints 15 (1974), page 329 ff .).
  • the emulsion graft copolymerization generally gives rise to about 5 to 15% by weight, based on the graft copolymer, of free, non-grafted styrene / acrylonitrile copolymer.
  • the proportion of the graft copolymer A in the polymerization product obtained in the graft copolymerization is determined by the method given above.
  • reproducible changes in particle size are also possible, for example by at least partially agglomerating the particles into larger particles. This means that polymers with different particle sizes can also be present in the graft copolymers A.
  • Component A in particular, consisting of the graft base and graft shell (s) can be optimally adapted for the particular application, in particular with regard to the particle size.
  • the graft copolymers A generally contain 1-99% by weight, preferably 55-80 and particularly preferably 55-65% by weight of graft base AI and 1-99% by weight, preferably 20-45, particularly preferably 35-45% by weight .-% of the graft A2, each based on the entire graft copolymer.
  • Component B is an amorphous or partially crystalline polymer.
  • Component B is preferably a copolymer of
  • bl 40-100% by weight, preferably 60-70% by weight, of units of a vinyl aromatic monomer, preferably styrene, a substituted styrene or a (meth) acrylic acid ester or mixtures thereof, in particular styrene and / or ⁇ -methylstyrene as component Bl,
  • b2 up to 60% by weight, preferably 30-40% by weight, of units of an ethylenically unsaturated monomer, preferably of acrylonitrile or
  • Methacrylonitrile in particular acrylonitrile as component B2.
  • the viscosity number of component B is 50-90, preferably 60-80.
  • the amorphous or partially crystalline polymers of component B of the molding composition used according to the invention for producing the covering grids according to the invention are preferably composed of at least one polymer made from partially crystalline polyamides, partially aromatic copolyamides, polyolefins, ionomers, polyesters, polyether ketones, polyoxyalkylenes, polyarylene sulfides and polymers made from vinyl aromatic monomers and / or selected ethylenically unsaturated monomers. Polymer mixtures can also be used.
  • Partially crystalline, preferably linear, polyamides such as polyamide-6, polyamide-6,6, polyamide-4,6, polyamide-6,12 and partially crystalline copolyamides based on these components are suitable as component B of the molding composition used according to the invention for the production of the covering grids according to the invention .
  • partially crystalline polyamides can be used, the acid component of which consists wholly or partly of adipic acid and / or terephthalic acid and / or isophthalic acid and / or suberic acid and / or sebacic acid and / orginaic acid and / or dodecanedicarboxylic acid and / or a cyclohexanedicarboxylic acid, and the like
  • Diamine component wholly or partly in particular consists of m- and / or p-xylylenediamine and / or hexamethylenediamine and / or 2,2,4- and / or 2,4,4-trimethylhexamethylenediamine and / or isophoronediamine, and their compositions in principle are known from the prior art (cf. Encyclopedia of Polymers, Vol. 11, p. 315 ff.).
  • polymers which are further suitable as component B of the molding compositions used according to the invention for the production of the covering grids according to the invention are partially crystalline polyolefins, preferably homo- and copolymers of olefins such as ethylene, propylene, butene-1, pentene-1, hexene-1, heptene-1, 3 -Methylbutene-1, 4-methylbutene-1, 4-methylpentene-1 and octene-1. - 17 -
  • Suitable polyolefins are polyethylene, polypropylene, polybutene-1 or poly-4-methylene-1.
  • PE polyethylene
  • HDPE high-density PE
  • LDPE ow-density PE
  • LLDPE linear low-density PE
  • component B is an ionomer.
  • These are generally polyolefins, as described above, in particular polyethylene, which contain monomers co-condensed with acid groups, for example acrylic acid, methacrylic acid and optionally further copolymerizable monomers.
  • the acid groups are generally converted into ionic, optionally ionically crosslinked polyolefins with the aid of metal ions such as Na + , Ca 2+ , Mg 2+ and Al 3+ , but these can still be processed thermoplastically (see, for example, US Pat. No. 3,264,272; 3,404,134; 3,355,319 ; 4,321,337).
  • Component B according to the invention is also suitable for polyolefins containing free acid groups, which then generally have a rubber-like character and in some cases also contain further copolymerizable monomers, for example (meth) acrylates.
  • component B can also be polyester, preferably aromatic-aliphatic polyester.
  • polyester preferably aromatic-aliphatic polyester.
  • polyalkylene terephthalate e.g. based on ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol and 1,4-bis-hydroxymethyl-cyclohexane, as well as polyalkylene naphthalates.
  • Aromatic polyether ketones can also be used as component B, as described, for example, in documents GB 1 078 234, US 4,010,147, EP-A-0 135 938, EP-A-0 292 211, EA-0 275 035, EP A-0 270 998, EP-A-0 165 406, and in the publication by CK Sham et. al., Polymer 29/6, 1016-1020 (1988).
  • component B of the molding compositions used according to the invention for the production of the covering grids according to the invention can be polyoxyalkylenes, for example polyoxymethylene, and oxymethylene polymers.
  • suitable components B are the polyarylene sulfides, in particular the polyphenylene sulfide.
  • it is composed of 50-99% by weight of vinyl aromatic monomers and 1-50% by weight of at least one of the other specified monomers.
  • Component B is preferably an amorphous polymer, as described above as graft A2.
  • a copolymer of styrene and / or ⁇ -methylstyrene with acrylmtrile is used as component B.
  • the acrylonitrile content in these copolymers of component B is 0-60% by weight, preferably 30-40% by weight, based on the total weight of component B.
  • Component B also includes those formed in the graft copolymerization to produce component A. free, non-grafted styrene / acrylonitrile copolymers.
  • component B has already been formed in the graft copolymerization. In general, however, it will be necessary to mix the products obtained in the graft copolymerization with additional, separately prepared component B.
  • This additional, separately produced component B can preferably be a styrene / acrylonitrile copolymer, an ⁇ -methylstyrene / acrylonitrile copolymer or an ⁇ -methylstyrene / styrene / acrylonitrile terpolymer.
  • These copolymers can be used individually or as a mixture for component B, so that the additional, separately prepared component B used according to the invention
  • the molding compositions can be, for example, a mixture of a styrene / acrylonitrile copolymer and an ⁇ -methylstyrene / acrylonitrile copolymer.
  • component B of the molding compositions used according to the invention consists of a mixture of a styrene / acrylonitrile copolymer and an ⁇ -methylstyrene / acrylonitrile copolymer
  • the acrylonitrile content of the two copolymers should preferably not be more than 10% by weight. %, preferably not more than 5% by weight, based on the total weight of the copolymer, differ from one another.
  • Component B of the molding compositions used according to the invention can, however, also consist of only a single styrene / acrylonitrile copolymer if, in the graft copolymerizations for the production of component A and also in the production of the additional, separately produced component B, the same monomer mixture of styrene and acrylonitrile is assumed.
  • the additional, separately manufactured component B can be obtained by the conventional methods.
  • the copolymerization of the styrene and / or ⁇ -methylstyrene with the acrylonitrile can be carried out in bulk, solution, suspension or aqueous emulsion.
  • Component B preferably has a viscosity number of 40 to 100, preferably 50 to 90, in particular 60 to 80. The viscosity number is determined in accordance with DIN 53 726, 0.5 g of material being dissolved in 100 ml of dimethylformamide.
  • Components A and B and optionally C, D can be mixed in any desired manner by all known methods. If components A and B have been prepared, for example, by emulsion polymerization, it is possible to mix the polymer dispersions obtained with one another, to precipitate the polymers together and to work up the polymer mixture. However, components A and B are preferably mixed by extruding, kneading or rolling the components together, the components, if necessary, being obtained beforehand from the solution obtained in the polymerization or from aqueous solution. Dispersion have been isolated.
  • the products of the graft copolymerization (component A) obtained in aqueous dispersion can also only be partially dewatered and mixed as a moist crumb with component B, the complete drying of the graft copolymers then taking place during the mixing.
  • the molding compositions used according to the invention for the production of the cover grids according to the invention contain, in addition to components A and B, additional components C and / or D, and, if appropriate, further additives, as described below.
  • Suitable polycarbonates C are known per se. They preferably have a molecular weight (weight average M w , determined by means of gel permeation chromatography in tetrahydrofuran against polystyrene standards) in the range from 10,000 to 60,000 g / mol. They can be obtained, for example, in accordance with the processes of DE-B-1 300 266 by interfacial polycondensation or in accordance with the process of DE-A-1 495 730 by reacting diphenyl carbonate with bisphenols.
  • Preferred bisphenol is 2,2-di (4-hydroxyphenyOpropane, generally - as also hereinafter - referred to as bisphenol A.
  • aromatic dihydroxy compounds can also be used, in particular 2,2-di (4-hydroxyphenyl) pentane, 2,6-dihydroxynaphthalene, 4,4'-dihydroxydiphenylsulfane, 4,4'-dihydroxydiphenyl ether, 4,4 '-Dihydroxydiphenylsulfit, 4,4'-Dihydroxydiphenylmethan, l, l-Di- (4-hydroxyphenyI) ethane, 4,4-Dihydroxydiphenyl or Dihydroxydiphenylcycloalkane, preferably Dihydroxydiphenylcyclohexane or Dihydroxylcyclopentane, in particular l, l-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and mixtures of the aforementioned dihydroxy compounds.
  • 2,2-di (4-hydroxyphenyl) pentane 2,6-dihydroxynaphthalene
  • 4,4'-dihydroxydiphenylsulfane
  • Particularly preferred polycarbonates are those based on bisphenol A or bisphenol A together with up to 80 mol% of the aromatic dihydroxy compounds mentioned above.
  • Copolycarbonates according to US Pat. No. 3,737,409 can also be used; Of particular interest are copolycarbonates based on bisphenol A and di (3,5-dimemyl-dihydroxyphenyl) sulfone, which are characterized by a high heat resistance. It is also possible to use mixtures of different polycarbonates.
  • the average molecular weights (weight average M w , determined by means of gel permeation chromatography in tetrahydrofuran against polystyrene standards) of the polycarbonates C are in the range from 10,000 to 64,000 g / mol. They are preferably in the range from 15,000 to 63,000, in particular in the range from 15,000 to 60,000 g / mol.
  • the polycarbonates C have relative solution viscosities in the range from 1.1 to 1.3, measured in 0.5% strength by weight solution in dichloromethane at 25 ° C., preferably from 1.15 to 1.33.
  • the relative solution viscosities of the polycarbonates used preferably differ by no more than 0.05, in particular no more than 0.04.
  • the polycarbonates C can be used both as regrind and in granular form. They are present as component C in amounts of 0-50% by weight, preferably 10-40% by weight, based in each case on the entire molding composition.
  • the addition of polycarbonates leads, inter alia, to higher thermal stability and improved crack resistance of the molding compositions used according to the invention for the production of the cover grilles according to the invention.
  • the preferred thermoplastic molding compositions used according to the invention for the production of the cover grids according to the invention contain 0 to 50% by weight, preferably 0 to 40% by weight, in particular 0 to 30% by weight of fibrous or particulate fillers or mixtures thereof , each based on the entire molding compound. These are preferably commercially available products. Reinforcing agents such as carbon fibers and glass fibers are usually used in amounts of 5-50% by weight, based on the total molding composition.
  • the glass fibers used can be made of E, A or C glass and are preferably equipped with a size and an adhesion promoter. Their diameter is generally between 6 and 20 ⁇ m. Both continuous fibers (rovings) and chopped glass fibers (staples) with a length of 1-10 ⁇ m, preferably 3-6 ⁇ m, can be used.
  • fillers or reinforcing materials such as glass balls, mineral fibers, whiskers, aluminum oxide fibers, mica, quartz powder and wollastonite can be added.
  • metal flakes e.g. aluminum flakes from Transmet Corp.
  • metal powder e.g. aluminum powder
  • metal fibers e.g. nickel-coated glass fibers
  • metal-coated fillers e.g. nickel-coated glass fibers
  • other additives that shield electromagnetic waves are added to the molding compounds used in the manufacture of the cover grids according to the invention.
  • Aluminum flakes K 102 from Transmet
  • EMI purposes electro-magnetic interference
  • the compositions can be mixed with additional carbon fibers, carbon black, in particular conductivity carbon black, or nickel-coated carbon fibers.
  • the molding compositions used according to the invention for the production of the covering grids according to the invention can furthermore contain further additives which are typical and customary for polycarbonates, SAN polymers and graft copolymers or mixtures thereof.
  • additives are: dyes, pigments, colorants, antistatic agents, antioxidants, stabilizers to improve thermal stability, to increase light stability, to increase resistance to hydrolysis and chemicals, to prevent heat decomposition and in particular to lubricants / Lubricants that are useful for the production of moldings or moldings.
  • These further additives can be metered in at any stage of the production process, but preferably at an early stage in order to achieve the stabilization effects at an early stage (or other special effects) of the additive.
  • Heat stabilizers or oxidation retarders are usually metal halides (chlorides, bromides, iodides) which are derived from metals of group I of the periodic table of the elements (such as Li, Na, K, Cu).
  • Suitable stabilizers are the usual hindered phenols, but also vitamin E or compounds with an analog structure.
  • HALS stabilizers hindered amine light stabilizers
  • benzophenones hindered amine light stabilizers
  • resorcinols salicylates
  • benzotriazoles and other compounds are also suitable (for example Irangox *, Tinuvin *, such as Tinuvin 770 (HALS absorber, bis (2,2,6,6 -tetramethyl-4-piperidyl) sebazate) or Tinuvin * P (UV absorber - (2H-benzotriazol-2-yl) -4-methylphenol), topanol).
  • Tinuvin * such as Tinuvin 770 (HALS absorber, bis (2,2,6,6 -tetramethyl-4-piperidyl) sebazate) or Tinuvin * P (UV absorber - (2H-benzotriazol-2-yl) -4-methylphenol), topanol.
  • Suitable lubricants and mold release agents are stearic acids, stearyl alcohol, stearic acid esters or generally higher fatty acids, their derivatives and corresponding fatty acid mixtures with 12-30 carbon atoms.
  • the amounts of these additives are in the range of 0.05-1% by weight.
  • Silicone oils, oligomeric isobutylene or similar substances are also suitable as additives, the usual amounts being 0.05-5% by weight.
  • Pigments, dyes, color brighteners such as ultramarine blue, phthalocyanines, titanium dioxide, cadmium sulfides, derivatives of perylene tetracarboxylic acid can also be used.
  • Processing aids and stabilizers such as UV stabilizers, lubricants and antistatic agents are usually used in amounts of 0.01 - 5% by weight, based on the total molding compound.
  • thermoplastic molding compositions used according to the invention for the production of the cover grids according to the invention can be produced by methods known per se by mixing the components. It can be advantageous to premix individual components. Mixing the components in solution and removing the solvents is also possible.
  • Suitable organic solvents are, for example, chlorobenzene, mixtures of chlorobenzene and methylene chloride or mixtures of chlorobenzene or aromatic hydrocarbons, e.g. Toluene.
  • the solvent mixtures can be evaporated, for example, in evaporation extruders.
  • Mixing the e.g. dry components can be made by all known methods. However, the mixing is preferably carried out by extruding, kneading or rolling the components together, preferably at temperatures of 180-400 ° C., the components having, if necessary, been isolated beforehand from the solution obtained in the polymerization or from the aqueous dispersion.
  • the components can be metered in together or separately / one after the other.
  • the cover grids and fastening parts therefor according to the invention can be produced from the thermoplastic molding compositions used according to the known methods of thermoplastic processing.
  • the production can be carried out by thermoforming, extrusion, injection molding, calendering, blow molding, pressing, press sintering, deep drawing or sintering, preferably by injection molding.
  • the cover grilles according to the invention can be used both outdoors (outside of buildings) and indoors (inside buildings). They can be colored according to one embodiment of the invention, if necessary using pigments or dyes. The grilles can be used to cover fans.
  • the cover grilles according to the invention can also be used to cover cooling openings in electrical devices which are cooled, for example, by a fan.
  • the cover grilles for fan openings according to the invention are designed so that they allow good passage of air or other gases, but at the same time cover the opening to such an extent that intrusion of foreign objects is avoided or made impossible and the risk of injury to humans is minimized becomes.
  • the cover grilles for fan openings according to the invention can thus be used in small electrical devices, such as computers or electrical measuring and control devices. With the aid of the molding compositions used in accordance with the invention, fine structures can be formed without the formation of visible weld lines.
  • the cover grilles are used for ventilation openings in air conditioning technology, in particular for air conditioning rooms or vehicles.
  • the grilles can be used for ventilation, for example for supply air ducts or exhaust air ducts.
  • the cover grilles for fan openings are used for openings in which the gas exchange is brought about solely by a temperature gradient and not by technical aids. This can be the case, for example, with fan openings of electrical devices that do not have cooling fans.
  • the fan grilles can also be used to supply or remove gases other than air.
  • the gases must not enter into a chemical reaction with the cover grids according to the invention.
  • this risk is low.
  • the cover grilles for fan openings according to the invention can have any suitable shape. According to one embodiment of the invention, they have a round or polygonal outline.
  • the grids can be formed by parallel bars or ridges or, according to one embodiment of the invention, by crossing bars, wherein any suitable crossing angle can be set. Bars or burrs running in a star shape are also possible according to the invention.
  • the cover grilles according to the invention can also be constructed in the form of lamellae, as a result of which the air or gas flow is directed or derived in a specific direction.
  • the cross section of the bars or ridges or lamellae can be chosen as desired. Suitable geometries are known to the person skilled in the art.
  • Annular bars or ridges are also possible, which are connected by radial ridges.
  • the cover grilles for fan openings according to the invention have a high yellowing resistance and a high weather resistance. This is particularly important because when using the grille in cooling devices (such as fans) warm to hot air passes through the grille. In such applications, good heat resistance is therefore also important.
  • Cover grilles made of molding compositions which contain polycarbonates as component C are very heat-resistant and resistant to sustained heat. By adding the polycarbonate as component C, the heat resistance and impact resistance of the grille are further improved. These grilles also have a balanced ratio of toughness and rigidity and good dimensional stability, as well as excellent resistance to heat aging and ne high resistance to yellowing under thermal stress and exposure to UV radiation.
  • Cover grids made of molding compounds containing components A and B have excellent surface properties, which can be obtained without further surface treatment.
  • the appearance of the finished surfaces of the grille can be modified by suitable modification of the rubber morphology, for example in order to achieve glossy or matt surface designs.
  • the cover grids show very little graying or yellowing effect when exposed to weather and UV radiation, so that the surface properties are retained.
  • Further advantageous properties of the cover grilles are the high weather stability, good thermal resistance, high yellowing resistance under UV radiation and thermal stress, good stress crack resistance, in particular when exposed to chemicals, and good anti-electrostatic behavior. In addition, they have high color stability, for example due to their excellent resistance to yellowing and embrittlement.
  • cover grids according to the invention made of the thermoplastic molding compositions used according to the invention show no significant loss of toughness or impact strength, even at low temperatures or after prolonged exposure to heat, which loss is retained even when exposed to UV rays.
  • the tensile strength is also retained. They also show a balanced relationship between rigidity and toughness.
  • thermoplastic molding compositions which have already been used to produce the cover grids according to the present invention. Because of the high color stability, weather resistance and aging resistance, the molding compositions used according to the invention are very suitable for reuse.
  • the share of reused (recycled) molding compound When using, for example, 30% by weight of molding compound already used, which was mixed in the ground form with the molding compounds used according to the invention, the relevant material properties, such as flowability, Vicat softening temperature and impact resistance of the molding compounds and the covering grille according to the invention produced therefrom did not change significantly. Similar results were obtained when the weather resistance was examined.
  • the polymerization product obtained in the grafting table polymerization was then precipitated from the dispersion using a calcium chloride solution at 95 ° C., separated off, washed with water and dried in a warm air stream.
  • the degree of grafting of the graft copolymer was determined to be 27%.
  • the product was precipitated from the dispersion using calcium chloride solution at 95 ° C., washed with water and dried in a warm air stream.
  • the degree of grafting of the graft copolymer was 35%, and the average particle size of the latex particles was found to be 238 nm.
  • a monomer mixture of styrene and acrylonitrile was polymerized in solution under customary conditions.
  • the styrene / acrylonitrile copolymer obtained had an acrylonitrile content of 35% by weight, based on the copolymer, and a viscosity number of 80 ml / g.
  • a monomer mixture of styrene and acrylonitrile was polymerized in solution under customary conditions.
  • the styrene / acrylonitrile copolymer obtained had an acrylonitrile content of 35% by weight, based on the copolymer, and a viscosity number of 60 ml / g.
  • a monomer mixture of styrene and acrylonitrile was polymerized in solution under customary conditions.
  • the styrene / acrylonitrile copolymer obtained had an acrylonitrile content of 27% by weight, based on the copolymer, and a viscosity number of 80 ml / g.
  • the graft rubber content was 23% by weight, based on the total weight of the finished polymer.
  • Comparative Example 3 An ABS polymer as described in Comparative Example 1 was also used as the comparative polymer. However, it has 0.5% by weight of a HALS stabilizer (Tinuvin * 770) and 0.5% by weight of a UV absorber (Terluran * P from CIBA AG). Comparative Example 3
  • a HIPS polymer (High Impact PolyStyrene: impact-resistant polystyrene), which consisted of polystyrene with a proportion of 6.5% by weight of polybutadiene rubber, was used as a further molding compound for comparison purposes.
  • the damping maximum of the mechanical damping is -75 ° C.
  • the MVI 200/5 is 4 ml / 10 min.
  • the molding compositions used were colored with 2% by weight of TiO 2 , based on the total weight.
  • molding compositions III and comp. II in each case 0.5% by weight of a HALS stabilizer (Tinuvin 770: bis (2,2,6,6-tetrametryl) 4-piperidyl) sebazate) and a UV absorber (Tinuvin P: 2- (2H- Benzotriazole-2-4-methylphenol) used, both of which are available from CIBA.
  • HALS stabilizer Teuvin 770: bis (2,2,6,6-tetrametryl) 4-piperidyl) sebazate
  • a UV absorber Tinuvin P: 2- (2H- Benzotriazole-2-4-methylphenol
  • the molding compositions according to the invention have a significantly lower yellowness index after exposure to the weather than the comparative molding compositions. They are therefore less yellowed. At the same time, the penetration work is much higher, which can be attributed to a higher strength after weathering. In addition, the gloss is significantly higher than that of the comparative compositions, which indicates that the surface properties have been retained.
  • the weld line tests show that the molding compositions according to the invention have no visible weld line or in one case a slightly visible weld line. In any case, the comparison measures have a weld line that is at least slightly visible.
  • cover grilles for fan openings according to the invention have high yellowing resistance and high weather resistance, which lead to high surface quality even over a long period of time.
  • the molding compounds also have a slight tendency to form weld lines.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne l'utilisation d'une matière moulable thermoplastique pour produire des plaques à grille pour obturer des orifices de ventilation. Cette matière, différente de l'ABS, contient, par rapport à la somme des quantités des composants A et B, et éventuellement C et/ou D, représentant 100 % en poids, a) comme composant A, 1 à 99 % en poids, de préférence 15 à 60 % en poids, notamment 25 à 50 % en poids d'un polymère obtenu par émulsion, se présentant sous forme de particules et ayant une température de transition vitreuse inférieure à 0 °C et une taille moyenne de particules comprise entre 50 et 1000 nm, de préférence entre 50 et 500 nm, b) comme composant B, 1 à 99 % en poids, de préférence 40 à 85 % en poids, notamment 50 à 75 % en poids d'au moins un polymère amorphe ou semi-cristallin, c) comme composant C, 0 à 50 % en poids de polycarbonates et d) comme composant D, 0 à 50 % en poids de charges sous forme de fibres ou de particules, ou de mélange de ces charges.
EP97934539A 1996-07-25 1997-07-24 Plaques a grille pour obturer des orifices de ventilation Withdrawn EP0914383A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19630095 1996-07-25
DE19630095A DE19630095A1 (de) 1996-07-25 1996-07-25 Abdeckgitter für Lüfteröffnungen
PCT/EP1997/004032 WO1998004632A1 (fr) 1996-07-25 1997-07-24 Plaques a grille pour obturer des orifices de ventilation

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EP0914383A1 true EP0914383A1 (fr) 1999-05-12

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US (1) US6103813A (fr)
EP (1) EP0914383A1 (fr)
KR (1) KR20000029508A (fr)
DE (1) DE19630095A1 (fr)
WO (1) WO1998004632A1 (fr)

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US7004852B2 (en) * 2002-01-10 2006-02-28 Dogleg Right Corporation Customizable center-of-gravity golf club head
GB201012115D0 (en) * 2010-07-19 2010-09-01 Monodraught Ltd Ventillation arrangements
CN112920537B (zh) * 2021-02-01 2022-10-21 海信空调有限公司 一种hips复合材料的制备方法、hips复合材料、导流板及空调

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DE3742768A1 (de) * 1987-12-17 1989-06-29 Basf Ag Halogenfreie flammfeste formmassen, verfahren zur herstellung und ihre verwendung
DE4342048A1 (de) * 1993-12-09 1995-06-14 Basf Ag Dreistufige Pfropfcopolymerisate und solche enthaltende thermoplastische Formmassen mit hoher Zähigkeit
DE69504118T2 (de) * 1994-04-04 1998-12-24 Mitsubishi Gas Chemical Co., Inc., Tokio/Tokyo Thermoplastische Harzzusammensetzung für Profilextrusion

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US6103813A (en) 2000-08-15
WO1998004632A1 (fr) 1998-02-05
DE19630095A1 (de) 1998-01-29
KR20000029508A (ko) 2000-05-25

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