EP1123351A1 - Corps moule a utiliser dans les domaines du jardin et des soins aux animaux - Google Patents

Corps moule a utiliser dans les domaines du jardin et des soins aux animaux

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Publication number
EP1123351A1
EP1123351A1 EP99948964A EP99948964A EP1123351A1 EP 1123351 A1 EP1123351 A1 EP 1123351A1 EP 99948964 A EP99948964 A EP 99948964A EP 99948964 A EP99948964 A EP 99948964A EP 1123351 A1 EP1123351 A1 EP 1123351A1
Authority
EP
European Patent Office
Prior art keywords
weight
component
garden
phase
graft
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Withdrawn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
EP99948964A
Other languages
German (de)
English (en)
Inventor
Norbert Güntherberg
Heiner GÖRRISSEN
Graham Edmund Mc Kee
Norbert Niessner
Martin Weber
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
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP1123351A1 publication Critical patent/EP1123351A1/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Withdrawn legal-status Critical Current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
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Ethylene-propylene or ethylene-propylene-diene copolymers
    • 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
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • 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
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates

Definitions

  • the invention relates to moldings for the garden and animal husbandry sector: In particular, the invention relates to moldings of this type with good properties
  • Wood has a poor stability against weather influences and is susceptible to mold, rotting, small animal bites and insect damage. A high maintenance effort is necessary.
  • Sheet steel has a high density and thus a high weight, is susceptible to corrosion and can only be processed with great effort.
  • ABS (acrylonitrile / butadiene / styrene) polymers do not always show sufficient results
  • ASA Acrylnitri Styrol / Acrylat molding compounds show good stress cracking behavior, but the scratch resistance, color depth and the toughness / stiffness ratio are not sufficient for all applications. Even adding small amounts of polycarbonate to produce a blend does not lead to a sufficient improvement.
  • the object of the present invention is therefore to provide moldings for the garden and To provide animal husbandry areas that are stable and resistant to chemicals and do not yellow. They should also be scratch-resistant and have good dimensional stability.
  • the UV and heat aging resistance should be high, so that the surface gloss is retained. Further requirements are good recyclability and poor fire behavior as well as good dimensional stability under thermal stress during manufacture and use.
  • thermoplastic molding composition different from ABS comprising, based on the sum of the amounts of components A, B, C and optionally D, which gives a total of 100% by weight
  • b 1 to 48% by weight of at least one amorphous or partially crystalline
  • d 0 to 47% by weight of conventional additives and / or fibrous or particulate
  • Specified glass transition temperatures of phases refer to a polymer with the composition corresponding to this phase.
  • the moldings described for gardening and animal husbandry are scratch-resistant, stable and resistant to chemicals. They also have very good yellowing resistance and depth of color.
  • thermoplastic molding compositions used 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 Components and molding compositions which can be used according to the invention are described.
  • the molding compositions other than ABS used to produce the moldings according to the invention for gardening and animal husbandry contain components A and B and C and optionally D, as defined below. They contain, based on the sum of the amounts of components A, B, C and optionally D, which gives a total of 100% by weight,
  • b 1 to 48% by weight, preferably 5 to 40% by weight, in particular 5 to 35% by weight, of at least one amorphous or partially crystalline polymer as component B,
  • c 51 to 98% by weight, preferably 55 to 90% by weight, in particular 60 to 85% by weight, of polycarbonates as component C, and
  • d 0 to 47% by weight, preferably 0 to 37% by weight, in particular 0 to 30% by weight, of additives or mixtures thereof as component D.
  • additives or mixtures thereof as component D.
  • Component A is at least one single-phase or multi-phase particulate emulsion polymer with a glass transition temperature below 0 ° C. in at least one phase and an average particle size of 50 to 1000 nm.
  • Component A is preferably a multi-phase polymer
  • a2 1 to 99% by weight, preferably 20 to 85% by weight, in particular 35 to 60% by weight, of a second phase A2 from the monomers, based on A2,
  • a21 40 to 100% by weight, preferably 65 to 85% by weight, units of a vinylaromatic monomer, preferably styrene, a substituted styrene or a (meth) acrylic acid ester or mixtures thereof, in particular styrene and / or ⁇ -methyl s tyrols as component A21 and
  • a22 0 to 60% by weight, preferably 15 to 35% by weight, units of an ethylenically unsaturated monomer, preferably acrylonitrile or methacrylonitrile, in particular acrylonitrile as component A22.
  • a3 0 to 50% by weight of a third phase with a glass transition temperature of more than 0 ° C as component A3, the total amount of components AI, A2 and A3 giving 100 wt .-%.
  • the phases can be linked together in the manner of a graft copolymerization.
  • the first phase AI can form the graft base and the second phase A2 a graft pad.
  • Several phases can be provided, corresponding to a graft copolymer with one graft base and several graft pads.
  • the graft pad need not necessarily be in the form of a sheath around the graft core.
  • Different geometries are possible, for example part of the first phase AI can be covered with the second phase A2, interpenetrating networks can form etc.
  • the first phase AI particularly preferably has a glass transition temperature below -10 ° C., in particular below - 15 ° C.
  • the third phase preferably has a glass transition temperature of more than 60 ° C. This third phase can be, for example, 1 to 50% by weight, in particular 5 to 40% by weight, based on the
  • Component A are present.
  • first phase it can also be understood to mean “graft base”, corresponding to “graft base” instead of “second phase”.
  • the third phase can preferably be constructed from more than 50% by weight of styrene, in particular from more than 80% by weight of syrene, based on the total number of monomers of the third phase.
  • component AI consists of the monomers
  • the average particle size of component A is 50 to 1000 nm, preferably 50 to 800 nm
  • the particle size distribution of component A is bimodal, 1 to 99, preferably 20 to 95, in particular 45 to 90% by weight an average particle size of 50 to 200 nm and 1 to 99, preferably 5 to 80, in particular 10 to 55% by weight an average
  • the sizes determined from the integral mass distribution are given as the average particle size or particle size distribution.
  • the average 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, were determined.
  • the ultracentrifuge measurement provides the integral mass distribution of the particle diameter of a sample. From this it can be seen how many percent by weight of the particles have a diameter equal to or smaller than a certain size
  • the dso 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 dso value. 50% by weight then also has
  • the dio and d9o values resulting from the integral mass distribution are used, the dio and dw values of the integrals Mass distribution is defined according to the dso value with the difference that they are based on 10 or 90% by weight of the particles quotient
  • the glass transition temperature of the emulsion polymer A and of the other components used according to the invention is determined by means of DSC (differential scanning calorimetry) in accordance with ASTM 3418 (mid-point temperature).
  • customary rubbers can be used as emulsion polymer A.
  • Acrylate rubber, ethylene propylene (EP) rubber, ethylene propylene diene (EPDM) rubber, in particular acrylate rubber, are preferably used.
  • the molding compositions are preferably free of butadiene rubbers.
  • 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 from one or more Gs-alkyl acrylates, preferably C 1 -s-alkyl acrylates, preferably at least partially butyl, hexyl, octyl or 2-ethylhexyl acrylate, in particular n-butyl and 2-ethylhexyl acrylate, is used.
  • This alkyl acrylate rubber can contain up to 30% by weight of copolymerizable monomers, such as vinyl acetate, (meth) acrylonitrile, styrene, substituted styrene, methyl methacrylate or vinyl ether, in copolymerized form
  • the acrylate rubbers further contain 0.01 to 20% by weight, preferably 0.1 to 5% by weight, of crosslinking, polyfunctional monomers (crosslinking monomers).
  • crosslinking monomers examples of these are monomers which have 2 or more double bonds capable of copolymerization included, which are preferably not conjugated in the 1,3 positions
  • Suitable crosslinking monomers are, for example, ethylene glycol diacrylate or - methacrylate, butanediol diacrylate or hexanediol diacrylate or methacrylate, divinylbenzene, di allyl maleate, diallyl fumarate, diallyl isocyanurate, diethyl phthalate, triallyl cyanurate, triallyl, tricyclodecenyl acrylate, dihydrodicyclopentadienyl acrylate, Triallylphos- phosphate, allyl acrylate, allyl methacrylate and dicyclopentadienyl acrylate (DCPA ) (see DE-C-12 60 135)
  • Suitable silicone rubbers can be, for example, crosslinked silicone rubbers composed of units of the general formulas PvzSiO, RSiO- ⁇ , R3S-O1 ⁇ and SiO ⁇ , where the radical R represents a monovalent radical.
  • the amounts of the individual siloxane units are such that 0 to 10 mol units of the formula RSiO- ⁇ , 0 to 1.5 mol units 3S.O1 ⁇ and 0 to 3 mol units SiO per 100 units of the formula R-SiO -v 4 are present, R can either be 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.
  • radicals R are methyl radicals, particularly preferred are combinations of methyl and ethyl or phenyl radicals
  • 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 to 10 mol%, based on all radicals R. They can be prepared, for example, as in EP-A-0 260 558.
  • 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 ethylhexyl acrylate, and homopolymers and copolymers of ethylene, propylene, butylene, isobutylene and poly (organosiloxanes), all with the proviso that they are linear or branched allowed to.
  • 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 g ⁇ 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 dso of 50 to 1000 nm, preferably from 50 to 800 nm.
  • 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) AI and one or more stages A2 (graft layer) grafted thereon, the so-called graft stages or graft shells.
  • each graft sheath having a different composition.
  • polyfunctional crosslinking or reactive group-containing monomers can also be grafted on (see, for example, 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 g above 30 ° C., preferably above 50 ° C.
  • the outer graft shell 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 grafting materials A1 listed above. 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 from 15 to
  • Suitable monomers for forming the graft A2 can be selected, for example, from the monomers listed below and their mixtures:
  • Nmyl aromatic monomers such as styrene and its substituted derivatives, such as ⁇ -methylstyrene, p-methylstyrene, 3,4-dimethylstyrene, p-tert-butylstyrene, p-methyl- ⁇ -methylstyrene or C 8 -C 8 alkyl (meth) acrylates such as methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, i-butyl acrylate; are preferred
  • (co) monomers styrene, vinyl, acrylic or methacrylic compounds (for example styrene, optionally substituted with C 1 -C 2 alkyl radicals, halogen atoms, halogen methylene radicals, vinyl naphthalene, vinyl carbazole, vinyl ether with C 1 -C 1) 2 -ether esters, vinylimidazole, 3- (4-) vinylpyridine, dimethylaminoethyl (meth) acrylate, p-dimethylaminostyrene, acrylonitrile, methacrylonitrile, acrylic acid, methacrylic acid,
  • component A comprises 50 to 100% by weight, preferably 50 to 90% by weight of the first phase described above (graft base) Al and 0 to 50% by weight, preferably 10 to 50% by weight of the second described above Phase (graft) A2, based on the total weight of component A
  • the third phase comes in particular from styrene
  • crosslinked acrylic acid ester polymers with a glass transition temperature below 0 ° C. serve as the graft base AI.
  • the crosslinked acrylic acid 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 or more graft shells, the outermost graft shell of which has a glass transition temperature of more than 30 ° C, a polymer formed from the monomers of the graft A2 having 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 preparation processes for graft copolymers A are emulsion, solution, bulk or suspension polymerization.
  • 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 less soluble ones Initiators such as peroxodisulfate or benzoyl peroxide, or with the help of redox initiators, redox initiators are also suitable for polymerization below 20 ° C
  • the graft shells are preferably built up in the emulsion polymerization process, as described in DE-A-32 27 555, 31 49 357, 31 49 358, 34 14 118.
  • the particle sizes of 50 to 1000 nm according to the invention are preferably set according to Methods 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 usual emulsifiers such as alkali metal salts of alkyl or alkylarylsulphonic acid alkyl sulphates, fatty alcohol sulphonates, salts of higher fatty acids with 10 to 30 carbon atoms or resin soaps can be used.
  • the emulsifiers are used in amounts of 0.5 to 5
  • % By weight, in particular from 1 to 2% by weight, based on the monomers used in the preparation of the graft base AI, is generally used with a weight ratio of water to monomers of 2 1 to 0.7 1.
  • the polymerization initiators used are in particular the Usable persulfates, such as potassium persulfate. However, redox systems can also be used.
  • the initiators are generally used in amounts of 0.1 to 1% by weight, based on the monomers used in the preparation of the graft base AI.
  • the customary polymerization auxiliaries can be conventional Buffer substances, by means of which pH values of preferably 6 to 9, such as sodium bicarbonate and sodium pyrophosphate, and 0 to 3% by weight of a molecular weight regulator, such as mercaptans, terpinols or dimeric ⁇ -methylstyrene, are used in the polymerization
  • 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 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.
  • Acrylonitrile 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 to 99% by weight, preferably 20 to 85% by weight, in particular 35 to 60% by weight, based on the total weight of component A results in the graft copolymer A.
  • 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 a few% by weight, based on the graft copolymer, of free, un-grafted
  • the proportion of the graft copolymer A in the polymerization product obtained in the graft copolymerization is determined by the method given above.
  • bimodal particle size distributions of component A have proven to be particularly advantageous. These can be generated by mixing separately produced particles of different sizes, which can also be different in their composition and shell structure (core / shell, core / shell / shell etc.), or a bimodal one can be produced
  • 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 to 99% by weight, preferably 15 to 80 and particularly preferably 40 to 65% by weight of the first phase (graft base) Al and 1 to 99% by weight, preferably 20 to 85, particularly preferably 35 to 60% by weight of the second phase (graft layer) A2, in each case based on the entire graft copolymer.
  • Component B is an amorphous or partially crystalline polymer.
  • Component B is preferably a copolymer of
  • bl 40 to 100% by weight, preferably 60 to 85% by weight, units of a vinyl aromatic monomer, preferably styrene, of a substituted one Styrene or a (meth) acrylic acid ester or mixtures thereof, in particular styrene and / or ⁇ -methylstyrene as component B1,
  • b2 0 to 60% by weight, preferably 15 to 40% by weight, of units of an ethylenically unsaturated monomer, preferably acrylonitrile or methacrylonitrile, in particular acrylonitrile as component B2
  • the viscosity number of component B is 50 to 120, preferably 55 to 100
  • the amorphous or partially crystalline polymers of component B of the molding composition used according to the invention for producing the shaped articles for gardening and animal husbandry are made from at least one polymer made from partially crystalline polyamides, partially aromatic copolyamides, polyolefins, ionomers, polyesters, polyether ketones, polyoxyalkylenes, polyarylene sulfides and preferably polymers selected from vinyl aromatic monomers and / or ethylenically unsaturated monomers. Polymer mixtures can also be used
  • component crystalline, preferably linear polyamides such as polyamide-6, polyamide-6,6, polyamide-4,6, polyamide-6,12 and partially crystalline copolyamides are also used as component B of the molding compound used for the production of the shaped articles according to the invention for the garden and animal husbandry area Suitable on the basis of these components.
  • Partially crystalline polyamides can also be used, the acid component of which consists wholly or partly of adipic acid and / or terephthalic acid and / or isophthalic acid and / or cork acid and / or sebacic acid and / orginaic acid and / or dodecanedicarboxylic acid and / or a cyclohexanedicarboxylic acid , and their diamine component wholly or partly in particular from m- and / or p-xylylenediamine and / or hex-imethylenediainine and / or 2,2,4- and / or 2,4,4-trimethylhexamethylenediamine and / or isophoronediamine, and the compositions of which are known in principle from the prior art (see Encyclopedia of Polymers, Vol 11, p 315 ff)
  • Shaped bodies for the molding compositions used in the garden and animal husbandry area according to the invention are also suitable polymers 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 Suitable polyolefins are polyethylene, polypropylene, polybutene-1 or poly-4-methylpentene-l. In general, a distinction is made with polyethylene (PE) high-density PE (HDPE) , Low-density PE (LDPE) and linear low-density PE (LLDPE)
  • PE polyethylene
  • HDPE High-density PE
  • LDPE Low-density PE
  • LLDPE linear low-density PE
  • component B is an ionomer.
  • ionomer are generally polyolefins as described above, in particular polyethylene, which contain monomers copolymerized with acid groups, for example acrylic acid, methacrylic acid and, if appropriate, further copolymerizable monomers Acid groups are generally identified with the help of
  • Metal ions such as Na + , Ca + , Mg + and Al + are converted into ionic, optionally ionically crosslinked polyolefins, which, however, can still be processed thermoplastically
  • component B can also be polyester, preferably aromatic-aliphatic polyester.
  • polyester preferably aromatic-aliphatic polyester.
  • polyalkylene terephthalates for example based on ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol and 1,4-bis- hydroxymethyl-cyclohexane
  • Aromatic polyether ketones can also be used as component B, as described, for example, in documents GB 1,078,234, US Pat. No.
  • the molding compositions used according to the invention for the production of the moldings according to the invention for gardening and animal husbandry can be used polyoxyalkylenes, for example polyoxymethylene, and oxymethylene polymers
  • suitable components B are the polyarylene sulfides, in particular the polyphenylene sulfide
  • An amorphous copolymer of styrene and / or ⁇ -methylstyrene with acrylonitrile is preferably used as component B.
  • the acrylonitrile content in these copolymers of component B is 0 to 60% by weight, preferably 15 to 40% by weight, based on the total weight of the Component B
  • Component B also includes the free, non-grafted styrene / acrylonitrile copolymers formed in the graft copolymerization for the production of component A.
  • component B may be possible that in the graft copolymerization A sufficient proportion of component B has been formed. In general, however, it will be necessary to mix the products obtained in the graft copolymerization with additional, component B prepared separately
  • This additional, separately prepared component B can preferably be a styrene / acrylonitrile copolymer, an ⁇ -methylstyrene / acrylonitrile copolymer or an ⁇ -methylstyrene / styrene / acrylonitrile polymer.
  • These copolymers can be used individually or as a mixture for component B, so that the additional, separately prepared component B of the invention can, for example, be a mixture of a styrene / acrylonitrile copolymer and an ⁇ -methylstyrene / acrylonitrile copolymer according to the molding compositions used.
  • 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 should preferably
  • the acrylonitrile content of the two copolymers does not differ by more than 10% by weight, preferably not more than 5% by weight, based on the total weight of the copolymer.
  • Component B of the molding compositions used according to the invention can, however, also consist of only a single styrene / acrylonitrile copolymer if the graft copolymers used to prepare the
  • Component A as well as in the production of the additional, separately produced component B is based on the same monomer mixture of styrene and acrylonitrile.
  • the additional, separately manufactured component B can according to the conventional
  • 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 120, preferably 50 to 120, in particular 55 to 100. 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 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 and B 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.
  • graft products obtained in aqueous dispersion Copolymerization can also only be partially dewatered and mixed with component B as a moist crumb, the complete drying of the graft copolymers then taking place during the mixing
  • 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 are, for example, according to the methods of DE-B-1 300 266 by
  • Interfacial polycondensation or according to the process of DE-A-1 495 730 obtainable by reacting diphenyl carbonate with bisphenols.
  • Preferred bisphenol is 2,2-di (4-hydroxyphenyl) 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'-dihydroxydiphenylsulfane, 4,4'-dihydroxydiphenyl ether, 4,4 '-Dihydroxy-diphenylsulfite, 4,4'-dihydroxydiphenylmethane, l, l-di- (4-hydroxyphenyl) ethane, 4,4-dihydroxydiphenyl or dihydroxydiphenylcycloalkanes, preferably dihydroxydiphenylcyclohexanes or dihydroxylcyclopentanes, in particular l, l-bis (4- hydroxyphenyl) -3,3,5-trimethylcyclohexane and mixtures of the aforementioned dihydroxy compounds
  • Particularly preferred polycarbonates are those based on bisphenol A or
  • Copolycarbonates according to US Pat. No. 3,737,409 can also be used, copolycarbonates based on bisphenol A and are of particular interest
  • the average molecular weights (weight average M w , determined by means of gel permeation chromatography in tetrahydrofuran against polystyrene standards)
  • 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 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, preferably the relative solution viscosities of the polycarbonates used differ by no more than 0.05, especially not 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 51 to 98% by weight, preferably 55 to 90% by weight, in particular 60 to 85% by weight, based in each case on the total Molding compound, before
  • 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 molding materials according to the invention for the garden and animal husbandry sector
  • Component D contains the preferred thermoplastic molding compositions used according to the invention for the production of the molded articles according to the invention for the garden and animal husbandry sector from 0 to 50% by weight, preferably from 0 to 37% by weight, in particular from 0 to 30% by weight, of fibrous or particulate fillers and other additives or their mixtures, in each case based on the total molding composition.
  • These are preferably commercially available products
  • Reinforcing agents such as carbon fibers and glass fibers are usually used in amounts of 5 to 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 H-ift mediator.Your diameter is generally between 6 and 20 ⁇ m. Both continuous fibers (rovings) and commercially available chopped glass fibers (staple ) are 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 Co ⁇
  • metal powder e.g. aluminum flakes from Transmet Co ⁇
  • metal fibers e.g. nickel-coated glass fibers and other additives that shield electromagnetic waves
  • metal flakes e.g. aluminum flakes from Transmet Co ⁇
  • metal fibers e.g. nickel-coated glass fibers
  • metal-coated fillers e.g. nickel-coated glass fibers and other additives that shield electromagnetic waves
  • metal flakes e.g. aluminum flakes from Transmet Co ⁇
  • metal powder e.g. aluminum flakes from Transmet Co ⁇
  • metal-coated fillers e.g. nickel-coated glass fibers
  • other additives that shield electromagnetic waves can be added to the molding materials used according to the invention for the production of the shaped body according to the invention.
  • aluminum flakes K 102 from Transmet
  • EMI electro-magnetic interference
  • the masses can also be mixed with additional carbon fibers, carbon black, in particular conductivity black,
  • the molding compositions used according to the invention for the production of the molding materials according to the invention for the garden and animal husbandry area may also contain further additives D which are typical and customary for polycarbonates, SAN polymers and graft copolymers or mixtures thereof.
  • additives D are dyes, pigments, colorants, Antistatic agents, antioxidants, stabilizers to improve the thermal stability, to increase the light stability, to increase the hydrolysis resistance and the chemical resistance, buffer substances, flame retardants, drip inhibitors, transesterification inhibitors, agents against heat decomposition and in particular those Lubricants / lubricants and waxes which are expedient for the production of moldings or moldings.
  • Heat stabilizers or oxidation retarders are usually metal halides (chlorides, bromides, iodides) which are derived from metals from 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-tetramethyl-4-piperidyl) sebazate) or Tinuvin P (UV absorber - (2H-benzotriazol-2-yl) -4-methylphenol), Topanol ® )
  • Tinuvin 770 HALS absorber, bis (2.2 , 6,6-tetramethyl-4-piperidyl) sebazate
  • Tinuvin P UV absorber - (2H-benzotriazol-2-yl) -4-methylphenol
  • Topanol ® these are usually used in amounts of up to 2% by weight -% (based on the total mixture) used
  • Suitable lubricants and mold release agents are stearic acids, stearyl alcohol, stearic acid esters or generally higher fatty acids, their derivatives and corresponding ones
  • Fatty acid mixtures with 12 to 30 carbon atoms The amounts of these additives are in the range from 0.05 to 1% by weight.
  • Silicones, oligomeric isobutylene or similar substances are also suitable as additives; the usual amounts are 0.05 to 5% by weight of pigments, dyes,
  • Color brighteners such as ultramarine blue, phthalocyanine, titanium dioxide, cadmium sulfides, derivatives of perylene tetracarboxylic acid can also be used
  • halogen-free or halogen-containing flame retardants can also be used in customary amounts, for example up to 20% by weight.
  • halogen-free flame retardants are described in EP-A-01 49 813 DE-A-34 36 815, wherein poly (tetrabromobisphenol A (glycidil / ether) with a molecular weight of 40,000 is particularly preferred
  • Processing aids and stabilizers such as UV stabilizers, lubricants and antistatic agents are usually used in amounts of 0.01 to 5% by weight, based on the total molding composition
  • thermoplastic molding materials used for the production of the moldings according to the invention for gardening and animal husbandry 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 solvent is also an option possible
  • Suitable organic solvents are, for example, chlorobenzene, mixtures of chlorobenzene and methylene chloride or mixtures of chlorobenzene or aromatic hydrocarbons, for example toluene
  • the solvent mixtures can be evaporated, for example, in evaporation extruders
  • the mixing of, for example, dry components can be carried out by all known methods. However, the mixing is preferably carried out by extruding, kneading or rolling the components together, preferably at temperatures of 180 to 400 ° C., the components if necessary beforehand from the solution obtained in the polymerization or have been isolated from the aqueous dispersion
  • the components can be metered in together or separately / one after the other
  • the mold body according to the invention for the garden and animal husbandry area can be according to an embodiment of the invention according to the known methods of Thermoplastic processing can be produced from the thermoplastic molding compositions used in accordance with the invention.
  • production can be carried out by thermoforming, extrusion, injection molding, calendering, hollow-body blowing, pressing, press sintering, deep-drawing or sintering, preferably by injection molding.
  • thermoforming, extrusion, injection molding, calendering, hollow-body blowing, pressing, press sintering, deep-drawing or sintering preferably by injection molding.
  • plates and foils are used as an intermediate stage generated or used
  • the shaped elements for the garden and animal husbandry area can be garden buildings, garden tools, garden furniture and garden equipment.
  • garden buildings are, for example, garden houses, tool sheds, carports,
  • Examples of garden tools or housings thereof are lawn mowers, quick composters, shredders, rainwater collection systems and weather stations.
  • Examples of garden equipment include garden lamps, candelabras, lighting systems, party lights, decorative elements, decorative grilles, flower boxes and planters, hose cars and irrigation systems, as well as irrigation systems , for example garden gnomes, nesting boxes, etc.
  • For garden furniture for example, benches, tables, chairs, loungers, parasols, etc. are considered.
  • Body parts from the animal husbandry area are, for example, pasture fences, for example for paddocks, small animal cages and small animal transport containers, play equipment for small animals, for example cat trees, chicken houses and other houses, rabbits Buildings that are suitable for animal husbandry
  • the invention also relates to semifinished products from the molding compositions and to plates, profiles, foils, etc
  • hollow profiles suitable for garden buildings can also be foamed using suitable foam systems (e.g. PUR) by adding a foaming system into the cavity of the component later or already during profile extrusion and foaming there.
  • suitable foam systems e.g. PUR
  • Such profile / plate systems are suitable, for example, for the garden houses mentioned above , Fences,
  • Ca ⁇ orts, trellis elements and garden furniture Such profiles can also be closed, for example, in the open spaces formed by mineral glass, acrylic glass, PC plates and other partially or fully transparent materials.
  • the molding compositions according to the invention can be stiff, scratch-resistant, weather-resistant, resistant to mold and bacteria and resistant to biting can also be used for transport and holding cages for small animals. They are easy to clean, since animal excrements adhere poorly and cleaning agents generally do not lead to corrosion
  • the molding compositions according to the invention can also be used for parts of solar systems, for example in the field of photovoltaics and hot water preparation
  • the moldings according to the invention for gardening and animal husbandry or their housings are resistant to yellowing and very stable. They have a balanced ratio of toughness and bending stiffness
  • the moldings for the garden and animal husbandry area are very heat resistant and resistant to persistent heat.
  • the addition of the polycarbonate as component C further improves the heat resistance and impact resistance of the molded articles for the garden and animal husbandry area
  • These molded parts for gardening and animal husbandry also have good dimensional stability, excellent resistance to heat aging and high resistance to yellowing under thermal stress and exposure to UV radiation
  • the molded bodies for the garden and animal husbandry sector have excellent surface properties, which can also be obtained without further surface treatment.
  • the appearance of the finished surfaces of the molded bodies for the garden and animal husbandry area can be modified by suitable modification of the rubber morphology, for example with glossy or matt surface designs to achieve
  • the moldings for the garden and animal husbandry 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 moldings for the gardening and keeping area are the high weather stability, good thermal
  • thermoplastic molding compositions used according to the invention show no 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.
  • the molding compositions or molding bodies according to the invention also show the Garden and animal husbandry areas have high resistance to scratching, high resistance to swelling and low permeability to liquids and gases, as well as good fire resistance
  • thermoplastic molding compositions already used for the production of the molded articles according to the invention for the garden and animal husbandry area according to the present invention Because of the high color stability, weathering resistance and aging resistance, the molding materials used according to the invention are very suitable for reuse reused (recycled) molding compound should be high when using, for example, 30% by weight of molding compound already used, which is in ground form
  • the relevant material properties such as flowability, Vicat softening temperature and impact strength of the molding compositions and the molding bodies according to the invention produced therefrom for the garden and animal husbandry area were not significantly similar. Results were obtained when the weather resistance was examined
  • Tricyclodecenyl acrylate added After the monomer addition had ended, the mixture was left to react for an hour.
  • the latex of the crosslinked butyl acrylate polymer obtained had a solids content of 40% by weight.
  • the mean particle size (weight average) was found to be 76 nm.
  • the polymerization product was precipitated from the dispersion using calcium chloride solution at 95 ° C., washed with water and dried in a warm air stream.
  • the Pfropfgra 'd of the graft copolymer was 35%.
  • Latex was after the addition of 50 parts of water and 0.1 part of potassium persulfate in the course of 3 hours on the one hand a mixture of 49 parts of butyl acrylate and 1 part of tricyclodecenyl acrylate and on the other hand a solution of 0.5 part of the sodium salt of a C 2 - to cis-paraffin sulfonic acid in Let 25 parts of water run in at 60 ° C. After the end of the feed, polymerization was continued for 2 hours.
  • 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 18% by weight, based on the copolymer, and a viscosity number of 70 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. Comparative Example 1
  • the graft rubber content was 30% by weight, based on the total weight of the finished polymer.
  • PC polycarbonate
  • composition of the molding compositions is shown in the table below:
  • the scratch resistance is determined using a CSEM Automatic Scratch Tester model AMI (manufacturer Center Suisse d ⁇ lectronique et de Microtechnique SA).
  • the scratch tester has a diamond tip with a 120 ° tip angle and 0.2 mm radius. This diamond tip is used to injection-molded test specimens from the material to be tested Scratches of 5 mm in length, unless otherwise stated, the contact pressure of the diamond is 2.6 N. After an hour of waiting, the scratches created are scanned in the transverse direction and displayed as a high / low profile. The scratch depth can then be read off
  • the resistance to stress cracking is determined using the bending strip method in accordance with ISO 4599.
  • the test specimens used are injection molded. They have the dimensions 80 x 15 x 2 mm. Unless otherwise stated, the test specimen was bent with a bending radius of 50 mm. The test specimens were clamped in a template. bent and wetted with the test medium for 24 hours. The impact energy at break is then determined with a pendulum. The test medium was used in bl isopropanol. In b2, a common household cleaner (Ajax Ultra Classic® from Colgate Palmolive Germany, a surfactant household cleaner) was used
  • injection-molded shoulder bars (tensile bars according to ISO 3167 with a thickness of 4 mm) are stored in the medium to be tested for 96 hours, then they are superficially dried, and the change in weight and, if necessary, the change in tensile modulus (determined according to ISO 527) are in Comparison to the initial value determined.
  • Table ⁇ , column cl shows the change in weight in methanol, in C2 in super gasoline and in C3 the change in tensile modulus in super gasoline.
  • foils are pressed from the material to be tested (thickness about 120 to 250 ⁇ m), the permeability of which to the specified gases or liquids is determined at 23 ° C. The values are given in (cm 3 100 ⁇ m) / (m 2 d bar) for gases or in (g 100 ⁇ m) / (m 2 d) for water. (Table HI)
  • Molding compositions which can be used advantageously should meet the following conditions: scratch depth of less than 6 ⁇ m, change in impact energy compared to the initial value of less than 10%, swelling in methanol of less than 1% or
  • the maximum service temperature was 110 ° C for molding compound and ⁇ il5 ° C for molding compound.
  • the molding compositions with a polycarbonate content of more than 50% by weight had an excellent combination of properties. This advantageous property spectrum makes them particularly suitable for use in molded articles for the garden and animal husbandry sector.

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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

Utilisation d'une matière moulable thermoplastique, différente de l'acylnitrile/butadiène/styrol (ABS), qui comprend, par rapport à la somme des quantités des constituants A, B, C et éventuellement D représentant au total 100 % en poids, (a) de 1 à 48 % en poids d'au moins un polymérisat par émulsion particulaire à une ou plusieurs phases présentant une température de transition vitreuse inférieure à 0 °C pour une phase au moins et une taille moyenne des particules de 50 à 100 nm, de préférence de 50 à 800 nm en tant que constituant A, (b) de 1 à 48 % en poids d'au moins un polymérisat amorphe ou partiellement cristallin en tant que constituant B, (c) de 51 à 98 % en poids de polycarbonate en tant que constituant C et (d) de 0 à 47 % en poids d'additifs courants et/ou de charges particulaires ou fibreuses ou de leurs mélanges en tant que constituant D, pour la fabrication de corps moulés et de demi-produits pour les domaines du jardin et des soins aux animaux.
EP99948964A 1998-10-07 1999-10-06 Corps moule a utiliser dans les domaines du jardin et des soins aux animaux Withdrawn EP1123351A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19846244 1998-10-07
DE19846244A DE19846244A1 (de) 1998-10-07 1998-10-07 Formkörper für den Garten- und Tierhaltungsbereich
PCT/EP1999/007491 WO2000020510A1 (fr) 1998-10-07 1999-10-06 Corps moule a utiliser dans les domaines du jardin et des soins aux animaux

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EP1201827A1 (fr) * 2000-10-23 2002-05-02 Borealis Technology Oy Poteau pour barrière de sécurité routière
WO2004036661A2 (fr) 2002-10-15 2004-04-29 Solvay Advanced Polymers, Llc Compositions polymeres de polycondensation anti-jaunissement et articles associees
US20070106022A1 (en) * 2003-10-10 2007-05-10 Basf Aktiengesellschaft Thermoplastic molding compositions
US8182855B2 (en) * 2004-11-22 2012-05-22 T.F.H. Publications, Inc. Fish food containing fermented soyfood
US7332188B2 (en) * 2004-11-22 2008-02-19 T.F.H. Publications, Inc. Animal chew containing fermented soyfood
CN100366675C (zh) * 2005-12-30 2008-02-06 上海林达塑胶化工有限公司 Abs(丙烯腈-丁二烯-苯乙烯共聚物)塑料加工用消泡除湿干燥母料的制备方法
AT10711U1 (de) 2008-02-01 2009-08-15 Rinner Michael Ing Solarwanne
US20110297106A1 (en) * 2010-06-07 2011-12-08 Kaplan Andrea J Leash, collar, and harness with interchangeable accessories

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DE4234296A1 (de) * 1992-10-12 1994-04-14 Basf Ag Thermoplastische Formmasse
DE19630061A1 (de) * 1996-07-25 1998-01-29 Basf Ag Gehäuse für Gartengeräte
DE19630062A1 (de) * 1996-07-25 1998-01-29 Basf Ag Formteile für Garten- und Gerätehäuser

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