WO1998004634A1 - Boitiers pour appareils electriques contenant de petits transformateurs - Google Patents

Boitiers pour appareils electriques contenant de petits transformateurs Download PDF

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Publication number
WO1998004634A1
WO1998004634A1 PCT/EP1997/004035 EP9704035W WO9804634A1 WO 1998004634 A1 WO1998004634 A1 WO 1998004634A1 EP 9704035 W EP9704035 W EP 9704035W WO 9804634 A1 WO9804634 A1 WO 9804634A1
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Prior art keywords
weight
component
graft
particle size
polymer
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PCT/EP1997/004035
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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
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Basf Aktiengesellschaft
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Publication of WO1998004634A1 publication Critical patent/WO1998004634A1/fr

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    • 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
    • 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
    • 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
    • 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
    • C08L51/04—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 rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • 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

Definitions

  • the invention relates to housings of small transformers containing electrical devices.
  • the invention relates to such housings which have high dimensional stability and aging resistance, in particular under thermal stress.
  • housings for small transformers such as for low-voltage power supplies for small electrical devices.
  • Polypropylene housings tend to shrink and warp. In addition, the heat resistance is low.
  • PPE / HIPS blends polyphenylene ether / high impact poly styrene
  • the blends have an insufficient resistance to stress cracking when exposed to household cleaners.
  • ABS / PC blends acrylonitrile-butadiene-styrene / polycarbonate
  • fire protection equipment in some cases has a negative effect on the color stability and the UV resistance behind glass.
  • Another object of the invention is to provide housings for small transformers containing electrical devices that avoid the disadvantages of the materials listed above.
  • thermoplastic molding composition different from ABS comprising, based on the sum of the amounts of components A, B, C and, if appropriate, D, which gives a total of 100% by weight,
  • component B 1-98% 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 mixtures thereof as component D. for the manufacture of housings for small transformers containing electrical devices.
  • UL94 UL Standard 94 Vertical Burning Test
  • a UL-VO rating of 1.6 mm and 0.8 mm wall thickness is usually required.
  • thermoplastic molding compositions described below meet these requirements.
  • thermoplastic molding compositions used according to the invention for producing the housings according to the invention are known per se.
  • DE-A-12 60 135, DE-C-19 11 882, DE-A-28 26 925, DE-A-31 49 358, DE-A-32 27 555 and DE-A-40 11 162 Molding compositions which can be used according to the invention are described.
  • c 1-98% by weight, preferably 50-95% by weight, in particular 60-90% by weight, of polycarbonates as component C, and
  • 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
  • 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. Polymers 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 O ⁇ 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 or d ⁇ value of the integral mass distribution is 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 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 is preferably alkyl acrylate rubbers of one or more Cj.g alkyl acrylates, preferably C. 4 8 -alkyl acrylates, preferably at least partially butyl, hexyl, octyl or 2-ethylhexyl acrylate, in particular n-butyl and 2-ethylhexyl acrylate.
  • the acrylate rubbers further contain 0.01-20% by weight, preferably 0.1-5% by weight, of cross-linking polyfunctional monomers (cross-linking monomers).
  • cross-linking monomers examples of these are monomers which contain 2 or more double bonds capable of copolymerization, which are preferably not conjugated in the 1,3 positions.
  • 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 methacrylate.
  • 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 from units of the general formulas I ⁇ SiO, RSiO 3 2 , R 3 SiO 1 2 and SiO 2 / , where the radical R represents a monovalent radical.
  • the amount of the individual siloxane units is such that for 100 units of the formula R 2 SiO 0 to 10 mol units of the formula RSiO 3/2 , 0 to 1.5 mol units R 3 SiO 1 2 and 0 to 3 mol Units of SiO 2 4 are present.
  • R can either be a monovalent saturated hydrocarbon radical with 1 to 18 C Atoms, the phenyl radical or the alkoxy radical or a group which can be attacked by free radicals such as the vinyl or the 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 prepared, 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 acid 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”).
  • core / shell structure a multi-stage polymer
  • core-shell morphology a rubber-elastic core (T. ⁇ 0 ° C) can be encased by a “hard” shell (polymers with T g > 0 ° C) or vice versa.
  • 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, as the graft base AI of this component A, particle sizes of 50- 350 nm, preferably from 50 to 300 nm and particularly preferably from 50 to 250 nm 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 being generally made from resin-forming monomers and having a glass transition temperature T_ above 30 ° C., preferably above 50 ° C.
  • the multi-stage structure serves among other things to achieve a (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 bases listed above. core materials AI. All polymers 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 (me_h) 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, for example, acrylonitrile,
  • (co) monomers styrene, vinyl, acrylic or meth acrylic compounds (eg, styrene optionally substituted with C j ⁇ alkyl, halo, halomethyl radicals;. vinylnaphthalene, vinyl carbazole, vinyl ethers with Vinylimidazole, 3- (4-) vinylpyridine, dimethylaminoethyl (meth) acrylate, p-dimethylaminostyrene, acrylonitrile, methacrylonitrile, acrylic acid, methacrylic acid, butyl acrylate, ethylhexyl acrylate and methyl methacrylate as well as fumaric acid, maleic acid, itaconic acid or their anhydrides or amides, nitrides, amides with 1 to 22 carbon atoms, preferably alcohols containing 1 to 10 carbon atoms) can be used.
  • vinyl, acrylic or meth acrylic compounds eg, styrene optionally substituted with C
  • 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 consists of at least one graft shell and the outermost graft shell thereof has a glass transition temperature of more than 30 ° C, a polymer formed from the monomers of the graft A2 would have a glass transition temperature of more than 80 ° 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 production processes for graft copolymers A are emulsion, solution, bulk or suspension polymerization.
  • the graft copolymers A are preferably prepared by 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 mitiators. Redox mitiators 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 A1 is first prepared by adding the acrylic acid ester (s) used according to one embodiment of the invention and the multifunctional crosslinking monomers, optionally together with the further comonomers, in aqueous emulsion in a manner known per se, at temperatures between 20 and 100 ° C., preferably between 50 and 80 ° C.
  • 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.
  • the weight ratio of water to monomers is from 2: 1 to 0.7: 1.
  • 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 are set, 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 used as further polymerization auxiliaries , are used in the polymerization.
  • a molecular weight regulator such as mercaptans, terpinols or dimeric ⁇ -methylstyrene
  • the particle size distribution of the latex should preferably be narrow. The quotient
  • a monomer mixture of styrene and acrylonitrile is then polymerized in a next step in the presence of the latex of the crosslinked acrylic ester polymer thus obtained, the weight ratio of styrene to acrylonitrile in the monomer mixture according to one embodiment of the invention 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 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 A1, 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 at The person skilled in the art is familiar with graft copolymerization and thus the degree of grafting of the finished graft copolymer A 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.
  • graft copolymers A In the production of the graft copolymers A by the emulsion process, in addition to the given process engineering advantages, reproducible particle size changes are also possible, for example by at least partially agglomeration of 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.
  • Component B is an amorphous or partially crystalline polymer.
  • Component B is preferably a copolymer of
  • b2 up to 60% by weight, preferably 30-40% by weight, of units of an ethylenically unsaturated monomer, preferably acrylonitrile or methacrylonitrile, in particular acrylonitrile as component B2.
  • the amorphous or partially crystalline polymers of component B of the molding composition used according to the invention for producing the housing according to the invention are preferably composed of at least one polymer from partially crystalline polyamides, partially aromatic copolyamides, polyolefins, ionomers, polyesters, polyether ketones, polyoxyalkylenes, polyarylene sulfides and polymers from vinyl aromatic monomers and / or selected ethylenically unsaturated monomers. Polymer mixtures can also be used.
  • component B of the molding composition used according to the invention for producing the housing according to the invention are partially crystalline, preferably linear polyamides such as polyamide-6, polyamide-6,6, polyamide-4,6, polyamide-6,12 and Semi-crystalline copolyamides based on these components are suitable.
  • polymers which are furthermore suitable as component B of the molding compositions used according to the invention for producing the housings according to the invention are partially crystalline polyolefins, preferably homo- and copolymers of olefins such as ethylene, propylene, butene-1, pentene-1, hexene-1 and heptene-1 , 3-methylbutene-1, 4-methylbutene-1, 4-methylpentene-1 and octene-1.
  • Suitable polyolefins are polyethylene, polypropylene, polybutene-1 or poly-4-methylpentene-1. In general, a distinction is made between polyethylene (PE) and high-density PE (HDPE), low-density PE (LDPE) and linear-low-density PE (LLDPE).
  • 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 other 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 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.
  • Component B 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 acrylonitrile 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.
  • 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 produced component B of the molding compositions used according to the invention is, for example, a mixture of a styrene / acrylonitrile copolymer and an ⁇ -methylstyrene / Acrylonitrile copolymer can act.
  • 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.
  • 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-hydroxypheny propane, 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'-dilydydroxydiphenylsulfane, 4,4'-dilrydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfite, 4,4'-D_hydroxydiphenylme_han, l, l-di- (4-hydroxyphenyl) ethane, 4,4-dihydroxydiphenyl or dihydroxydiphenylcycloalkanes, preferably dihydroxydiphenylcyclohexanes or dihydroxylcyclopentanes, in particular 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and mixtures of the aforementioned dihydroxy compounds.
  • 2,2-di (4-hydroxyphenyl) pentane 2,6-dihydroxynaphthalene
  • 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.
  • 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. This means that 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.
  • component C they are in amounts of 1 - 98% by weight, preferably from 50 to 95% by weight, in particular from 60 to 90% by weight, in each case based on the total molding composition.
  • Components A, B, C and optionally 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 thereupon and to work up the polymer mixture. However, components A, B and C are preferably mixed by extruding, kneading or rolling the components together, the components having, if necessary, been isolated beforehand from the solution or aqueous dispersion obtained in the polymerization.
  • 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 graft copolymers then being completely dried during the mixing.
  • the preferred thermoplastic molding compositions used according to the invention for producing the housings 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.
  • 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 for example aluminum flakes from Transmet Corp.
  • metal powder for example aluminum flakes from Transmet Corp.
  • metal fibers for example nickel-coated glass fibers and other additives which shield electromagnetic waves
  • metal flakes for example aluminum flakes from Transmet Corp.
  • metal fibers for example nickel-coated glass fibers and other additives which shield electromagnetic waves
  • Aluminum flakes K 102 from Transmet
  • EMI purposes glectro-biagnetic interference
  • the masses can also use additional carbon fibers, carbon black, in particular conductivity carbon black, or nickel-coated carbon fibers can be mixed.
  • the molding compositions used according to the invention for the production of the housings 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 for improving the thermostability, for increasing the light stability, for increasing the hydrolysis resistance and the chemical resistance, agents against heat decomposition and in particular the lubricants / lubricants, which are useful for the production of moldings or moldings.
  • These additional additives can be metered in at any stage of the production process, but preferably at an early point in time, in order to take advantage of the stabilizing effects (or other special effects) of the additive at an early stage.
  • Heat stabilizers or oxidation retardants 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 Irganox *, Tinuvin *, such as Tinuvin * 770 (HALS absorber, bis (2,2,6, 6-tetrameU_yl- 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-tetrameU_yl- 4-piperidyl) sebazate
  • Tinuvin * P UV absorber - (2H-benzotriazol-2-yl) -4-methylphenol
  • 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 for producing the housings 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.
  • the dry components can be mixed 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 housing and fastening parts according to the invention can be produced from the thermoplastic molding compositions used according to the known methods of thermoplastic processing.
  • production can be carried out by thermoforming, extrusion, injection molding, calendering, blow molding, pressing, pressing sintering, deep drawing or sintering, preferably by injection molding.
  • the molding compositions used according to the invention are used for the production of housings for electrical transformers containing small transformers.
  • Such electrical devices can be devices, for example, in which other electrical assemblies or mechanical assemblies are accommodated in addition to small transformers. Examples are computers and consumer electronics from the audio or video sector.
  • the housing for power supplies or chargers for battery imitators are used.
  • the housings essentially contain only one or more small transformers. Otherwise, the housings only contain smaller electronic assemblies, for example diodes or rectifiers.
  • small transformers are transformers which serve for low-voltage power supply and which are the usual mains voltage Reduce voltage to low voltage. Small transformers of this type are used, for example, for lighting (halogen spotlights), as well as for electrically operated toys, for example model trains or car racing tracks. Power supplies that are used separately from electrical devices and consist of a plug-in transformer that is plugged directly into a conventional socket and a connecting cable for the electrical device are widespread.
  • the housings can be installed in a stationary manner or can belong to a mobile (portable) device.
  • the housings can be part of a group of several housings.
  • the housings can have any shape, provided that this allows the inclusion of small transformers.
  • the housings especially on power supplies or chargers for accumulators, have only small gaps between the wall and the small transformer, so that they are in close thermal contact with the small transformer. Suitable designs are known to the person skilled in the art.
  • the invention also relates to the housing itself and power supplies, which consist essentially of a housing and at least one small transformer.
  • the molding compositions according to the invention have high color stability and aging resistance, in particular with continued thermal stress.
  • the housings are very heat-resistant and resistant to sustained heat. By adding the polycarbonate as component C, the heat resistance and impact resistance of the housing is very good. These housings also have a balanced ratio of toughness and rigidity and good dimensional stability, as well as excellent resistance to heat aging and high resistance to yellowing under thermal stress and exposure to UV radiation.
  • Housings made of molding compounds containing components A and B have excellent surface properties that can be obtained without further surface treatment.
  • the appearance of the finished surface of the housing can be modified by suitable modification of the rubber morphology, for example in order to achieve glossy or matt surface designs.
  • the housings When exposed to weather and UV radiation, the housings show a very slight graying or yellowing effect, so that the surface properties are retained.
  • Further advantageous properties of the housing are the high weather stability, good thermal resistance, high yellowing resistance under UV radiation and thermal stress, good stress crack resistance, especially 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.
  • the housings according to the invention made of the thermoplastic molding compositions used according to the invention do not show any significant loss of toughness or impact strength 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 already used to manufacture the housings according to the present invention Due to the high color stability, weather resistance and aging resistance, the molding compositions used according to the invention are very suitable for reuse.
  • the proportion of reused (recycled) molding compound can be high.
  • the relevant material properties such as flowability, Vicat softening temperature and impact resistance of the molding compounds and the housing according to the invention produced therefrom did not change significantly. Similar results were obtained when the weather resistance was examined.
  • 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.
  • the latex of the crosslinked butyl acrylate polymer obtained had a solids content of 40%.
  • the mean particle size (weight average) of the latex was found to be 410 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 19% by weight, based on the copolymer, and a viscosity number of 90 ml / g.
  • a polyphenylene ether / high impact polystyrene blend was used as the comparative polymer.
  • it is sold by General Electric under the trade name NoryI R SEI.
  • the graft rubber content was 29% by weight, based on the total weight of the finished polymer. Comparative Example 2
  • a vinyl chloride polymer which had been polymerized in suspension and had a k value of 61 was used as a further molding compound for comparison purposes.
  • the k value was determined as described in DIN 53 726.
  • the stated amounts of the corresponding polymers (A), (B) and (C) or the comparative compositions are mixed in a screw extruder at a temperature of 200 ° C. to 230 ° C.
  • Test specimens were produced from the molding compositions formed in accordance with the conditions specified in DIN standard 16777. All test specimens were colored with 2.0% by weight of TiO 2 .
  • the UV yellowing was investigated on the molding compositions given in the table below, assessed visually after irradiation with Xenotest 450 behind window glass for a period of 1000 hours.
  • the modulus of elasticity was determined in accordance with DIN 53 457.
  • VST / B Vicat temperature
  • the Izod impact strength was determined at 23 ° C according to ISO 180 / 1A.
  • Classification VI means a burning time of a maximum of 30 s, total burning time of a maximum of 250 s, no burning drip, the VO classification a burning time of max. 10 s, total burning time of max. 50 s, no burning dripping.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne l'utilisation d'une matière moulable thermoplastique pour produire des boîtiers pour appareils électriques contenant de petits transformateurs. Cette matière, différente de l'ABS, contient, par rapport à la somme des quantités des composants A, B, C et éventuellement D qui représente 100 % en poids, a) comme composant A, 1 à 98 % en poids, de préférence 1 à 20 % en poids, notamment 1 à 15 % 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 98 % en poids, de préférence 3 à 30 % en poids, notamment 5 à 25 % en poids d'au moins un polymère amorphe ou semi-cristallin, c) comme composant C, 1 à 98 % en poids, de préférence 50 à 95 % en poids, notamment 60 à 90 % 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.
PCT/EP1997/004035 1996-07-25 1997-07-24 Boitiers pour appareils electriques contenant de petits transformateurs WO1998004634A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE1996130120 DE19630120A1 (de) 1996-07-25 1996-07-25 Gehäuse von Kleintransformatoren enthaltenden Elektrogeräten
DE19630120.3 1996-07-25

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Publication Number Publication Date
WO1998004634A1 true WO1998004634A1 (fr) 1998-02-05

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WO (1) WO1998004634A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19846252A1 (de) * 1998-10-07 2000-04-13 Basf Ag Gehäuse von Kleintransformatoren enthaltenden Elektrogeräten
DE19846205A1 (de) * 1998-10-07 2000-04-13 Basf Ag Gehäuse für Geräte zur Informationsverarbeitung und -übermittlung
DE10319745A1 (de) 2003-04-30 2004-11-25 Ticona Gmbh Thermoplastische teilkristalline Formmasse mit reduziertem Oberflächenglanz und Produkte hieraus

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0320836A2 (fr) * 1987-12-17 1989-06-21 BASF Aktiengesellschaft Matières à mouler exemptes d'halogènes et résistant au feu, procédé pour leur préparation et leur utilisation
DE4242485A1 (de) * 1992-12-16 1994-06-23 Basf Ag Teilchenförmiges Pfropfpolymerisat und hieraus erhaltene thermoplastische Formmasse
DE4342048A1 (de) * 1993-12-09 1995-06-14 Basf Ag Dreistufige Pfropfcopolymerisate und solche enthaltende thermoplastische Formmassen mit hoher Zähigkeit
EP0676449A2 (fr) * 1994-04-04 1995-10-11 Mitsubishi Gas Chemical Company, Inc. Composition de résine thermoplastique pour extrusion de profile

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0320836A2 (fr) * 1987-12-17 1989-06-21 BASF Aktiengesellschaft Matières à mouler exemptes d'halogènes et résistant au feu, procédé pour leur préparation et leur utilisation
DE4242485A1 (de) * 1992-12-16 1994-06-23 Basf Ag Teilchenförmiges Pfropfpolymerisat und hieraus erhaltene thermoplastische Formmasse
DE4342048A1 (de) * 1993-12-09 1995-06-14 Basf Ag Dreistufige Pfropfcopolymerisate und solche enthaltende thermoplastische Formmassen mit hoher Zähigkeit
EP0676449A2 (fr) * 1994-04-04 1995-10-11 Mitsubishi Gas Chemical Company, Inc. Composition de résine thermoplastique pour extrusion de profile

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