Reinforced thermoplastic molding compounds
Abstract
Moldable compound containing 10 to 100% by weight of a composition I consisting of A) 40 to 95% by weight in relation to the weight of composition I, of a copolymer, containing 55 to 90% by weight, in relation to weight of component A, of alpha-methylstyrene, 10 to 50% by weight, in relation to the weight of component A, of acrylonitrile, as well as 0 to 5% by weight, in relation to the weight of component A, of other monomers, such as component A; B) 2.5 to 75% by weight, in relation to the weight of the composition I, of a polymer B, consisting of 60 to 90% by weight, in relation to the weight of component B, of a vinyl aromatic monomer 8.01 at 39.8% by weight, in relation to the weight of component B, of acrylonitrile, 0.2 to 1.99% by weight, in relation to the weight of component B, of maleic acid anhydride, as component B, and C ) 2.5 to 60% by weight, in relation to the weight of the composition I, of glass fibers, as component C, wherein the sum of components A, B and C is 100% by weight.

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11 claims: 4 independent, 7 dependent
- 1ES 2 316 092 T3 REIVINDICACIONES 1. Compuesto moldeable que contiene 10 a 100% en peso de una composición I que consiste en A) 40 a 95% en peso en relación al peso de la composición I, de un copolímero, que contiene 55 a 90% en peso, en relación al peso del componente A, de α-metilestireno, 10 a 50% en peso, en relación al peso del componente A, de acrilnitrilo, así como 0 a 5% en peso, en relación al peso del componente A, de otros monómeros, como componente A;B) 2,5 a 75% en peso, en relación al peso de la composición I, de un polímero B, que consisten en 60 a 90% en peso, en relación al peso del componente B, de un monómero vinilaromático 8,01 a 39,8% en peso, en relación al peso del componente B, de acrilnitrilo, 0,2 a 1,99% en peso, en relación al peso del componente B, de anhídrido de ácido maleico, como componente B, y C) 2,5 a 60% en peso, en relación al peso de la composición I, de fibras de vidrio, como componente C, en donde la suma de los componentes A, B y C es de 100% en peso.
- 2Compuesto moldeable acorde a la reivindicación 1, en el cual el polímero B contiene 0,2 a 1,9% en peso, en relación al peso del componente B, de anhídrido de ácido maleico.
- 3Compuesto moldeable acorde a una de las reivindicaciones anteriores, en el cual el polímero B consiste en 70 a 80% en peso de estireno, 20 a 30% en peso de acrilnitrilo y 0,5 a 1,5% en peso de anhídrido de ácido maleico, siempre en relación al peso del componente B.
- 4Compuesto moldeable acorde a una de las reivindicaciones anteriores, en el cual, el compuesto moldeable contiene, como componente D, 0,1 a 50% en peso, en relación al peso de la composición I contenida en el compuesto moldeable, de un producto de polimerización o un elastómero con elasticidad de caucho.
- 5Compuesto moldeable acorde a la reivindicación 4, en el cual el producto de polimerización o elastómero con elasticidad de caucho es un caucho injertado en base a butadieno, butadieno/estireno, EPDM o acrilatos.
- 6Compuesto moldeable acorde a una de las reivindicaciones anteriores, en el cual, el compuesto moldeable contiene, como componente E, 0,1 a 50% en peso, en relación al peso de la composición I contenida en el compuesto moldeable, de otros aditivos.
- 7Procedimiento para la fabricación de un compuesto moldeable, acorde a una de las reivindicaciones 1 a 7, que comprende la mezcla de 40 a 95% en peso de un copolímero que contiene 55 a 90% en peso de α-metilestireno y 10 a 50% en peso de acrilnitrilo, así como 0 a 5% en peso de otros monómeros como componente A, 2,5 a 75% en peso de un polímero B, que consiste en 60 a 90% en peso de un monómero vinilaromático, 8,01 a 39,8% en peso de acrilnitrilo y 0,2 a 1,99% en peso de anhídrido de ácido maleico, y 2,5 a 60% en peso de fibras de vidrio, como componente C.
- 8Procedimiento acorde a la reivindicación 7, que comprende la extrusión de una masa que contiene 40 a 95% en peso de un copolímero que contiene 55 a 90% en peso de α-metilestireno y 10 a 50% en peso de acrilnitrilo, así como 0 a 5% en peso de otros monómeros como componente A, 2,5 a 75% en peso de un polímero B, que consiste en 60 a 90% en peso de un monómero vinilaromático,8,01 a 39,8% en peso de acrilnitrilo;0,2 a 1,99% en peso de anhídrido de ácido maleico, y 2,5 a 60% en peso de fibras de vidrio, como componente C, a una temperatura en el área de los 200 a 320°C.
- 9Procedimiento acorde a una de las reivindicaciones 7 y 8, que comprende, adicionalmente, el procesamiento del compuesto moldeable hasta obtener un cuerpo moldeado.
- 10Cuerpo moldeado que se puede obtener mediante el procedimiento acorde a la reivindicación 9.
- 11Aplicación de un compuesto moldeable acorde a una de las reivindicaciones 1 a 6, o un compuesto moldeable que se puede obtener mediante un procedimiento acorde a la reivindicación 7 u 8 para la fabricación de un cuerpo moldeado, asimismo, el cuerpo moldeado es un juguete o una parte de un juguete, un accesorio de un coche, un avión o un barco o una parte de un accesorio de un coche, un avión o un barco, un empaque o una parte de un empaque, un recipiente o una parte de un recipiente, un artefacto doméstico o una parte de un artefacto doméstico, un equipo ES 2 316 092 T3 médico o una parte de un equipo médico, un componente de un artículo cosmético, una parte de un dispositivo eléctrico o electrónico o un dispositivo utilizado en la construcción de viviendas o una parte de él.
Independent claims11
218 paragraphs in 13 sections, as filed
ES 2 316 092 T3
DESCRIPTION
Reinforced thermoplastic castable compounds.
The present invention comprises moldable compounds containing a composition I, consisting of a copolymer containing α-methylstyrene and acrylonitrile, as well as, optionally, other monomers as component A, a polymer B, consisting of a vinyl aromatic monomer, acrylonitrile and anhydride of maleic acid as component B, as well as glass fibers as component C, process for the manufacture of such moldable compounds, as well as the application of these molding compounds for the manufacture of a molded body.
Reinforced thermoplastic molding compounds based on styrene copolymers are known in the state of the art.
In the case of amorphous materials, it is possible to use filling or reinforcing materials to modify the properties. But so far only a few examples are known in which the addition of filler material to styrene copolymers was attempted.
DE 41 14 248 A1 presents thermoplastic moldable compounds of 40 to 95% by weight of a copolymer A of 90 to 50% by weight of styrene, α-methylstyrene, a nucleus-substituted styrene derivative or mixtures of these monomers, and 10 to 50% by weight of acrylonitrile, up to 50% by weight of a polymerization product as component B, 1 to 50% by weight of a reinforcing material based on an inorganic glass as component C, as well as 0.1 to 50% by weight of a terpolymer D based on styrene-methylmethacryl-maleic acid anhydride and, optionally, other comonomers with, respectively, 1 to 15% by weight of styrene and maleic acid anhydride and a styrene-maleic anhydride ratio of 5: 1 to 1: 5.
EP 0 303 919 A2 also presents reinforced thermoplastic moldable compounds consisting of three components A, B and C. The moldable composition contains, in turn, as component A, 40 to 94% by weight of a copolymer, consisting of 90 to 50% by weight of styrene, α-methylstyrene, a derivative of styrene with an alkyl substituted nucleus, or mixtures of these monomers and 10 to 50% by weight of (meth) acrylonitrile and / or methyl (meth) acrylate. As component B, the mouldable compound contains 20 to 0.5% by weight of a terpolymerization product, composed of 90 to 50% by weight of at least one monomer from the styrene group, α-methylstyrene, the core styrene substituted alkyl or mixtures of these monomers, 5 to 40% by weight of (meth) acrylonitrile and / or methyl (meth) acrylate and 2 to 30% by weight of another monomer, likewise, the terpolymerization product B necessarily contains, as another monomer, tert-butyl (meth) acrylate.
The castable compounds also contain 5 to 50% by weight of a reinforcing material as component C.
DE 1 949 487 presents thermoplastic moldable compounds based on copolymerization products of maleic anhydride, styrene and acrylonitrile and copolymerization products of styrene or α-methylstyrene and acrylonitrile or methacrylonitrile. Although the castable compounds according to DT 1 949 487 have a shape with high heat resistance, they are too brittle for many applications.
DE 35 15 867 A1 presents reinforced thermoplastic moldable compounds consisting of component A 5 to 95% by weight of at least one copolymer, composed of 90 to 50% by weight of styrene, α-methylstyrene, a derivative of styrene with alkyl substituted nucleus, or mixtures of these monomers, and 10 to 50% by weight of (meth) -acrylonitrile, as well as in component B 95 to 5% by weight of at least, a styrene as a monomer constituent element containing a terpolymerization product, and contains, as component C, 5 to 50% by weight of a reinforcing material. According to DE 35 15 867 A1, the mouldable compound has, as the terpolymerization product B, such a product that it consists of 90 to 59% by weight of a monomer from the styrene group, α-methylstyrene, of styrenes with core alkyl or mixtures of these monomers, 8 to 48% by weight of (meth) acrylonitrile and 2 to 30% by weight of a monomer from the group of acrylic acid, methacrylic acid, maleic acid anhydride or mixtures of these monomers. The mouldable composite contains, as reinforcing material C, known glass fibers.
The terpolymers B used according to the examples in DE 35 15 867 A1 have a maleic anhydride content of 5% or more.
In particular, the molding compounds according to DE 35 15 867 A1 have a shape with too low heat resistance for most applications.
Accordingly, a task of the present invention is to offer reinforced moldable compounds based on styrene copolymers with a high heat resistance and high fluidity shape.
Another task of the present invention is to offer reinforced moldable compounds based on styrene copolymers with a high heat resistance shape, high flowability and, at the same time, good impact resistance.
This task is solved, according to the invention, thanks to a mouldable compound containing 10 to 100% by weight of a composition I, which consists of
ES 2 316 092 T3
A) 40 to 95% by weight, in relation to the weight of composition I, a copolymer containing at 90% by weight, in relation to the weight of component A, of α-methylstyrene, at 50% by weight, in relation to the weight of component A, of acrylonitrile, as well as 5% by weight, relative to the weight of component A, of other monomers, as component A;
B) 2.5 to 75% by weight, relative to the weight of composition I, of a polymer B, composed of 90% by weight, relative to the weight of component B, of a vinyl aromatic monomer,
8.01 to 39.8% by weight, based on the weight of component B, of acrylonitrile, 0.2 to 1.99% by weight, based on the weight of component B, of maleic acid anhydride as component B; Y
C) 2.5 to 60% by weight, relative to the weight of composition I, glass fibers as component C, where the sum of components A, B and C is 100% by weight.
The terpolymer B contained in the molding compounds according to the invention B contains 0.2 to 1.99% by weight of maleic acid anhydride.
The finding was surprising that the mouldable compounds according to the invention have a favorable combination of a shape with high heat resistance, impact resistance and flowability. For this reason, the molding compounds according to the invention are characterized, for example, by a high elongation at break and a high impact resistance.
In addition to composition I, the molding compounds according to the invention can contain other components.
The mouldable compounds according to the invention are characterized in that they consist of 10 to 100% by weight, in particular 10 to 99.999% by weight of a composition I, consisting of components A, B and C.
The mouldable compounds according to the invention preferably contain 20 to 80% by weight of composition I, in particular 30 to 70% by weight, for example 35 to 65% by weight, particularly preferably 40 to 60% by weight.
Composition I contains, in turn, as component A, from 40 to 95% by weight, preferably from 45 to 92.5% by weight, preferably, above all, from 50 to 90% by weight, always relative to weight of composition I, of at least one copolymer containing 55 to 90% by weight, relative to the weight of component A, of α-methylstyrene and 10 to 50% by weight, relative to the weight of component A, of acrylonitrile, as well as 0 to 5% by weight, relative to the weight of component A, of other monomers.
According to the invention, copolymers A are composed of 55 to 90% by weight, relative to the weight of component A, of α-methylstyrene and 10 to 50% by weight, relative to the weight of component A, of acrylonitrile, thus as 0 to 5% by weight, relative to the weight of component A, of other monomers.
Copolymer A consists of, for example, 60 to 80% by weight, especially 65 to 75% by weight of α-methylstyrene and 20 to 40% by weight, especially 25 to 35% by weight of acrylonitrile, as well as 0 to 4.5% by weight, preferably 0.01 to 4% by weight, preferably 0.1 to 3.5% by weight, particularly preferably 0.2 to 3% by weight of other monomers, always in In relation to the weight of component A, likewise, the sum of the monomers is 100% by weight.
Suitable according to the invention are, as other monomers, for example vinylaromatic compounds such as styrene or alkyl-substituted styrene derivatives, or alkylalkyl acrylates, for example those with Ci to C alkyl radicals<sub>8</sub>, as well as Ci to C alkylnitrile<sub>8</sub>, preferably Ci to C alkylnitrile<sub>4</sub>, or mixtures of these compounds.
In the context of the present invention, composition I particularly preferably contains a copolymer A composed of 70% by weight of α-methylstyrene and 30% by weight of acrylonitrile, always relative to the weight of component A.
Copolymers A are known or can be obtained by known methods. For example, they can be obtained by radical polymerization, especially through emulsion, suspension, solution or mass polymerization. Said copolymers are also frequently obtained as graft copolymerization by-products to obtain component D, especially when large amounts of monomers are grafted onto small amounts of rubber.
The copolymers A preferably have viscosity figures in the area of 40 to 160. This corresponds to the molecular weights M<sub>w</sub> means (weight average value) in the area of 40,000 to 500,000 g / mol.
ES 2 316 092 T3
Composition I contained in the molding compounds according to the invention also contains a component B. As component B, composition I contains 2.5 to 75% by weight, relative to the weight of composition I, of a polymer B, composed of to 90% by weight, relative to the weight of component B, of a vinyl aromatic monomer,
8.01 to 39.8% by weight, relative to the weight of component B, acrylonitrile,
0.2 to 1.99% by weight, relative to the weight of component B, of maleic acid anhydride.
According to the invention, in turn, the sum of the components of polymer B is 100% by weight, in turn, polymer B preferably consists of 65 to 85% by weight of a vinyl aromatic monomer, especially of 70 to 80% by weight, always relative to the weight of component B. The proportion of acrylonitrile in polymer B is preferably 15 to 35% by weight, especially 20 to 30% by weight, always relative to weight of component B.
Suitable vinylaromatic monomers are compounds of the general structure
<img file="ES2316092T3_D0001.tif" />
In it, R<sup>3</sup> may mean hydrogen or a Ci to C8 alkyl radical, preferably a Ci to C3 alkyl, especially methyl, independently of R<sup>3</sup>, R<sup>2</sup> represents a C1 to C alkyl radical<sub>8</sub>, preferring a C alkyl<sub>1</sub> to C<sub>3</sub>. Above all it is preferred that R<sup>2</sup> be a methyl.
The variable n represents an integer from 0 to 3. Preferably, n is either 0 or 1.
Suitable vinylaromatic monomers are, for example, styrene or alkyl substituted styrene derivatives such as α-methylstyrene, styrene being especially preferred.
Polymer B consists of 0.2 to 1.99% by weight, based on the weight of component B, of maleic acid anhydride. The proportion of maleic acid anhydride is preferably 0.2 to 1.9% by weight, especially 0.3 to 1.8% by weight, for example 0.5 to 1.5% by weight, especially preferably 0.9 to 1.1% by weight, always based on the weight of component B.
In this area, particularly good mechanical properties are obtained with regard to tensile strength.
Accordingly, the present invention also comprises the moldable compound described above, in which polymer B comprises 0.2 to 1.9% by weight, relative to the weight of component B, of maleic acid anhydride.
According to another embodiment, the present invention comprises moldable compounds such as those described above, in which polymer B consists of 70 to 80% by weight of styrene, 20 to 30% by weight of acrylonitrile and 0.5 to 1, 5% by weight of maleic acid anhydride, always in relation to the weight of component B, likewise, the sum of the monomers is 100% by weight.
Polymer B can be prepared in a known manner. A suitable method is to dissolve the monomer components of the polymer, for example styrene, maleic acid anhydride or acrylonitrile, in a suitable solvent, for example methyl ethyl ketone (MEK). One or, eventually, multiple chemical triggers are added to this solution. Suitable triggers are known to the specialist. For example, peroxides are suitable. Subsequently, the mixture is polymerized for several hours at elevated temperature.
Subsequently, the solvent and unreacted monomers are removed in a known manner.
The ratio of vinyl aromatic monomer to acrylonitrile monomer in polymer B is preferably between 80:20 and 50:50. Preferably, the amount of vinyl aromatic monomer is selected to correspond to the amount of vinyl aromatic monomer in a graft copolymer D, optionally contained in the molding compounds according to the invention.
ES 2 316 092 T3
In addition to components A and B, composition I, which contains the molding compounds according to the invention, contains as component C, from 2.5 to 60% by weight, relative to the weight of composition I, of glass fibers. Composition I preferably contains 4 to 55% by weight, especially 5 to 50% by weight, for example 6 to 45% by weight of glass fibers, always relative to the weight of composition I.
For better compatibility with the matrix material, the glass fibers can be equipped with a lubricant, preferably a polyurethane lubricant, or with an adhesive agent. In general, the glass fibers used have a diameter in the area of 6 to 20 pm.
The incorporation of the glass fibers can be carried out both in the form of short glass fibers as well as in the form of endless fibers (rovings). The average length of the glass fibers is preferably in the area of 0.5 to 50 mm, particularly preferably in the area of 0.08 to 25 mm.
Glass fibers can also be applied in the form of glass silk fabrics, mats or rovings.
In addition to composition I, the molding compounds according to the invention may contain, according to another embodiment of the present invention, a polymerization product or elastomer with rubber elasticity as another component D. The molding compounds according to the The invention may contain from 0.1 to 50% by weight, relative to the weight of the composition I contained in the molding compound, of a polymerization product or elastomer with rubber elasticity.
Accordingly, the present invention also comprises the molding compound as described above, in which the molding compound contains, as component D, 0.1 to 50% by weight, relative to the weight of the composition I contained in the mouldable compound of a polymerization product or an elastic rubber elastomer.
Preferred molding compounds according to the invention contain component D in amounts of 0.1 to 50, in particular 0.2 to 45% by weight, and more preferably 0.3 to 40% by weight or 0.4 to 30% by weight, always in relation to the weight of composition I contained in the molding compound. Especially preferred moldable compounds contain from 0.5 to 25% by weight, based on the weight of composition I contained in the moldable compound, of component D.
As component D it is also possible to use mixtures of two or more different polymerization products or elastomers with rubber elasticity.
In principle, all polymerization products or elastomers with rubber elasticity, known to the specialist for such applications, are suitable according to the invention. For example, grafted rubbers based on butadiene, butadiene / styrene, EPDM or acrylates are suitable.
Accordingly, the present invention comprises, according to another embodiment, moldable compounds as described above, likewise, the polymerization product or elastomer with rubber elasticity is a grafted rubber based on butadiene, butadiene / styrene, EPDM or acrylates. .
As polymerization products or elastomers with rubber elasticity D, in the framework of the present invention, in principle all polymerization products with elasticity of rubber with Tg <0 ° C, especially those containing, as rubber ,
- a diene rubber based on dienes, such as butadiene or isoprene,
- an alkylacrylate rubber based on alkyl acryl esters, such as n-butylacrylate and 2-ethylhexylacrylate,
- an EPDM rubber based on ethylene, propylene and a diene,
- a silicone rubber based on polyorganosiloxanes, or mixtures of these rubbers or rubber monomers.
Preferably, the rubber elastic polymerization product or elastomer D is a graft polymerization product composed of a base and a graft level.
The preferred graft polymerization products D contain, relative to D, d1) 30 to 95, preferably 40 to 90, and especially preferably 40 to 85% by weight of a base with rubber elasticity, relative to d1) d11) 50 to 100, preferably 60 to 100, and especially preferably 70 to 100% by weight of an (alkyl) ester (C<sub>1</sub>-C<sub>10</sub>) of acrylic acid,
ES 2 316 092 T3 d12) 0 to 10, preferably 0 to 5, and especially preferably 0 to 2% by weight of a polyfunctional crosslinked monomer, d13) 0 to 40, preferably 0 to 30, and, especially preferably 0 to 2% by weight of one or more other unsaturated monoethylenic monomers, or by d11 *) 50 to 100, preferably 60 to 100, and especially preferably 70 to 100% by weight of a diene with conjugated double bonds, d12 *) 0 to 50, preferably 0 to 40, and, especially preferably 0 to 35% by weight of one or more other unsaturated monoethylenic monomers, or by d11 **) 50 to 100, preferably 60 to 100, and especially preferably 65 to 100% by weight of a mixture of ethylene, propylene and a diene, d12 **) 0 to 50, preferably 0 to 40, and especially preferably 0 to 35% by weight of one or more other unsaturated monoethylenic monomers, and d2) 5 to 70, preferably 10 to 60, and especially preferably, fifteen at 60% by weight of a graft level, relative to d2), d21) 50 to 100, preferably 60 to 100, and especially preferably 65 to 100% by weight of a styrene compound of the formula general
<img file="ES2316092T3_D0002.tif" />
Where R<sup>2</sup>, R<sup>3</sup> are, independently of each other, H or Ci or C alkyl<sub>8</sub>, and n is 0, 1, 2 or 3, d22) 0 to 40, preferably 0 to 38, and especially preferably 0 to 35% by weight of an acrylonitrile or methacrylonitrile or their mixtures, d23) 0 to 40 preferably 0 to 30, and especially preferably 0 to 20% by weight of one or more other unsaturated monoethylenic monomers,
The graft covering can also be predominantly methylmethacrylate. It is also possible to use products with multiple graft coatings.
As (alkyl) ester (C<sub>1</sub>-C<sub>10</sub>) of acrylic acid, component d11), especially ethylacrylate, 2-ethylhexylacrylate and n-butylacrylate are suitable. 2-Ethylhexylacrylate and n-butylacrylate are preferred, especially preferably n-butylacrylate. It is also possible to use mixtures of different alkyl acrylates that differ in their alkyl radical.
The cross-linked monomers d12) are bi- or polyfunctional comonomers with at least two olefin double bonds, for example, butadiene and isoprene, divinyl ester of dicarboxylic acids, such as succinic acid and adipinic acid, diallyl- and divinylether of bifunctional alcohols, such as ethylene glycol and butane-1,4-diol, diesters of acrylic acid and methacrylic acid with the bifunctional alcohols mentioned, 1,4-divinylbenzole and triallylcyanurate. Especially preferred are the acrylic acid ester of tricyclodecenyl alcohol (see E-OS 12 60 135), known under the name oihydrodicyclopentadienyl acrylate, as well as the allylester of acrylic acid and methacrylic acid.
Depending on the type of molding compounds to be obtained, especially according to the desired characteristics of the molding compounds, the crosslinked monomers d12) may or may not be contained in the molding compound.
If the crosslinked monomers are present in the molding compounds, they amount to amounts of 0.01 to 10, preferably 0.3 to 8, and particularly preferably 1 to 5% by weight, relative to to d1).
ES 2 316 092 T3
In the case of the other unsaturated monoethylenic monomers d13), which may be contained in the graft nucleus d1) at the expense of monomers d11) and d 12), these are, for example:
vinylaromatic monomers such as styrene, derived from styrene of the above general formula 1;
- acrylonitrile, methacrylonitrile;
- C1 to C4 alkyl esters of methacrylic acid such as methylmethacrylate, in addition, also glycidyl esters, glycidylacrylates and glycidylmethacylates,
- N-substitution maleinimides, such as N-methyl-maleinimide, N-phenyl-maleinimide and N-cyclohexylmaleinimide;
- acrylic acid, methacrylic acid, in addition, dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid, as well as their anhydrides such as maleic acid anhydride;
- nitrogen functional monomers such as dimethylaminoethylacrylate, diethylaminoethylacrylate, vinylimidazole, vinylpyrrolidone, vinylcaprolactam, vinylcarbazole, vinyllaniline, acrylamide and methacrylamide;
- aromatic and araliphatic esters of acrylic acid and methacrylic acid such as phenylacrylate, phenylmethacrylate, benzylacrylate, benzylmethacrylate, 2-phenylethylacrylate, 2-phenylethylmethacrylate, 2-phenoxyethylacrylate and 2-phenoxyethylmelacrylate;
- unsaturated ethers such as vinylmethyl ether, as well as mixtures of these monomers.
The preferred monomers d13) are styrene, acrylonitrile, methylmethacrylate, glycidylacrylate and glycidylmethacrylate, acrylamide and methacrylamide.
Instead of the base monomers d11) to d13), the base d1) can also consist of the monomers d11 *) and d12 *).
As dienes with conjugated double bonds, d11 *), butadiene, isoprene, norborene, and their halogen-substituted derivatives, for example chloroprene, can be used. Butadiene and isoprene, especially butadiene, are preferred.
As another unsaturated monoethylenic monomer, d12 *), the already mentioned monomers, d13) can be used together.
The preferred monomers d12) are styrene, acrylonitrile, methylmethacrylate, glycidylacrylate and glycidylmethacrylate, acrylamide and methacrylamide.
The graft core d1) can also be constituted as a mixture of the monomers d11) to d13), and d11 *) to d12 *).
Instead of the base monomers d11) to d13), or d11 *) to d12 *), the base d1) can also consist of the monomers d11 *) and d12 *). As diene, in the monomer mixture d11 **), used in the mixture with ethylene and propylene, ethylidene-norbornenes and dicyclopentadiene are especially suitable.
As other unsaturated monoethylenic monomers d12 **), the monomers mentioned for d13) can be used together.
The graft core can also be made up of a mixture of monomers d11) to d13) and d11 **) to d12 **), or of a mixture of monomers d11 *) to d12 *) and d11 **) a d12 **), or by a mixture of monomers d11) to d13), d11 *) to d12 *) and d11 **) to d12 **).
If the graft core contains monomers d11) to d13), after mixing with a hard phase of styrene and acrylonitrile (SAN), the so-called ASA (acrylonitrile-styrene-acrylester) molding compounds are produced. If the graft core contains the monomers d11 *) to d12 *), after mixing with a hard phase of styrene and acrylonitrile (SAN), so-called moldable compounds of the ABS type (acrylonitrile-butadiene-styrene) originate. If the graft core contains the monomers d11 **) to d12 **), after mixing with a hard phase of styrene and acrylonitrile (SAN), the so-called AES-type castable compounds (acrylonitrile-EPDM-styrene) originate. In a preferred embodiment, therefore, the polymerization product or elastomer with rubber elasticity D is ASA-graft polymerization product, or ABS graft polymerization product, or graft polymerization product AES, or ASA, ABS and AES graft polymerization product mix types.
ES 2 316 092 T3
The monomers d21) are, in particular, styrene compounds of the general formula
<img file="ES2316092T3_D0003.tif" />
where R<sup>2</sup>, R<sup>3</sup> are, independently of each other, H or Ci or C alkyl<sub>8</sub>, and n is 0, 1, 2, or 3.
The monomer d21) used is preferably styrene, α-methylstyrene as well as styrene with a C1-C8 alkylated nucleus, such as p-methylstyrene or tert-butylstyrene. Styrene is especially preferred. Mixtures of the styrene mentioned may also be used, especially styrene and α-methylstyrene.
Instead of styrene compounds, or mixtures with them, C1 to C8 alkyl esters of acrylic acid and / or methacrylic acid can be used, especially those derived from methanol, ethanol, n- and iso-propanol, sec. , tert.- and iso-butanol, pentanol, hexanol, heptanol, octanol, 2-ethylhexanol and n-butanol. Methylmethacrylate is especially preferred.
Monomer d23) is an unsaturated monoethylenic monomer. Suitable compounds as monomers d23) are, for example:
- N-substitution maleinimides, such as N-methyl-maleinimide, N-phenyl-maleinimide and N-cyclohexylmaleinimide;
- acrylic acid, methacrylic acid, in addition, dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid, as well as their anhydrides such as maleic acid anhydride;
- nitrogen functional monomers such as dimethylaminoethylacrylate, diethylaminoethylacrylate, vinylimidazole, vinylpyrrolidone, vinylcaprolactam, vinylcarbazole, vinyllaniline, acrylamide and methacrylamide;
- aromatic and araliphatic esters of acrylic acid and methacrylic acid such as phenylacrylate, phenylmethacrylate, benzylacrylate, benzylmethacrylate, 2-phenylethylacrylate, 2-phenylethylmethacrylate, 2-phenoxyethylacrylate and 2-phenoxyethylmelacrylate;
- unsaturated ethers such as vinylmethyl ether, as well as mixtures of these monomers.
Accordingly, the graft cover d2) may contain, at the expense of monomers d12), other monomers d22), or d23) or their mixtures. Preferably, the graft cover d2) consists of polymerization products, selected from the group consisting of polystyrene, copolymers of styrene and acrylonitrile, copolymers of α-methylstyrene and acrylonitrile and copolymers of styrene and methylmethactylate.
Obtaining the graft level d2) can be carried out under the same conditions as the obtaining of the base d1), likewise, the graft level d2) can be prepared in one or more process steps. In turn, the monomers d21), d22) and d23) can be added one by one or mixed with each other. The ratio of the monomers in the mixture can be temporally constant or a gradient. Combinations of these procedure modes are also possible.
For example, only styrene can be polymerized first, and then a mixture of styrene and acrylonitrile, until the base d1) is obtained.
The raw composition is not modified by the aforementioned conditions of the process.
Furthermore, "soft" and "hard" multi-level graft polymerization products, for example of the constitution d1) -d2) -d1) -d2) or d2) -d1) -d2), are also suitable on everything, the largest particles.
If ungrafted polymers of monomers d2) are obtained during grafting, these amounts, which are generally below 10% by weight of d2), are assigned to the mass of component D.
The preparation of the graft polymerization products D can be carried out differently, especially in emulsion, in microemulsion, in miniemulsion, in suspension, in microsuspension, in minisuspension, than the polymerization by precipitation, in bulk or in solution. , continuously or discontinuously.
In the case of emulsion polymerization and its variants (microemulsion, mini-emulsion), the monomers are emulsified in water, for which emulsifiers are also used. Suitable emulsifiers for stabilizing the emulsion are saponaceous auxiliaries which surround the monomer droplets and thus protect them from confluence.
ES 2 316 092 T3
Suitable emulsifiers are the emulsifiers known to the specialist, anionic, cationic and neutral (non-ionogenic). Anionic emulsifiers are, for example, alkali metal salts of higher fatty acids with 10 to 30 C atoms such as palmitic acids, stearic acid and oleic acid, alkali metal salts of sulfonic acid with, for example, 10 to 16 C atoms, especially, sodium salts of alkyl sulfonate acids or alkylaryl sulfonate acids, alkali metal salts of phthalic acid half esters, and alkali metal salts of resin acids, such as abietic acid: Cationic emulsifiers are, for example, long chain salts, especially unsaturated amines with 12-18 carbon atoms, or the long chain quaternary ammonium compounds of olefin or paraffin residues (i.e. quaternized amine salts) . Neutral emulsifiers are, for example, ethoxylated fatty alcohols, ethoxylated fatty acids or phenols and ethoxylated fatty acid esters of polyhydric alcohols, such as pentaerythritol or sorbitol.
For emulsion polymerization, triggers with poor dissolution in monomer but good dissolution in water are preferably used. Therefore, preferably, peroxosulfates such as potassium, sodium or ammonium peroxodisulfate, or also redox systems are used, especially those based on hydroperoxides such as cumol hydroperoxide, dicumyl peroxide, benzoyl peroxide or lauride peroxide.
In the case of the application of redox systems, water-soluble metal compounds are also used, the metal cations of which can easily change the degree of oxidation, for example iron sulfate hydrate.
Usually, complexing agents are also used, such as sodium pyrophosphate or ethylene diamine tetraascetic acid, which prevent the separation of metal compounds of low solubility during polymerization. As reducing agent in redox systems, organic compounds such as dextrose, glucose and / or sulfoxylates are generally used.
As additional substances during the polymerization, depressants such as Na<sub>2</sub>HPO<sub>4</sub>/ NaH<sub>2</sub>PO<sub>4</sub> or Na citrate / citronic acid, to regulate an essentially constant pH value. In addition, molecular weight regulators can be used, for example, mercaptans such as t-dodecyl mercaptan, or ethylhexyl thioglycollate. These other additional substances can also be added, like emulsifiers and triggers, or redox systems, continuously or discontinuously, at the beginning and / or during preparation of the emulsion and / or during polymerization.
The precise polymerization conditions, especially the type, quantity and dosage of the emulsifier and the other polymerization auxiliary substances are preferably selected in such a way that the latex obtained from the grafted polymerization product has an average particle size, defined by the d50 value of the particle size distribution, from 50 to 1000, preferably from 100 to 600 and especially preferably from 150 to 450 nm.
The particle size distribution can be, for example, monomodal or bimodal. A bimodal particle size distribution by (partial) agglomeration of the polymer particles is preferred. For this, one can proceed, for example, as follows: The monomers d1), which constitute the nucleus, are polymerized until a conversion of usually at least 90, preferably greater than 95%, is obtained, in relation to the monomers used. Rubber latex in general has a mean particle size d50 of at most 200 nm and a narrow particle size distribution (almost monodisperse system).
On the second level the rubber latex is agglomerated. This generally occurs by adding a dispersion of an acrylester polymerization product (see DE-A 24 27 960). Preferably, dispersions of copolymerization products of (alkyl) esters (C<sub>1</sub> -C<sub>4</sub>) of acrylic acid, preferably ethyl acrylate, with 0.1 to 20% by weight of monomers forming polar polymerization products, for example acrylic acid, methacrylic acid, acrylamide or methacrylamide, N-methylolmethacrylamide or N-vinylpyrrolidone . A copolymerization product of 96% ethyl acrylate and 4% methacrylamide is especially preferred. The concentration of the acrylester polymerization products in the dispersion used for agglomeration should generally be between 3 and 40, preferably between 5 and 20% by weight.
Under the conditions mentioned only a part of the rubber particles agglomerates, so that a bimodal distribution is obtained. In turn, in general, according to a first mode of execution, after agglomeration, more than 50, preferably between 75 and 95% of the particles (distribution by figures) are found in the non-agglomerated state.
According to a second mode of execution, the agglomeration is carried out in such a way that, after agglomeration, the polymer particles present a polymodal particle size distribution, in which, in each particle size range of width 50 nm is less than 40% by weight, preferably less than 37.5% by weight, especially preferably less than 35% by weight, and especially preferably less than 32.5% by weight, especially less than 30% by weight of the particles. Mean particle diameter, in turn, refers to weight unless otherwise stated. This is in particular the d50 value of the integral mass distribution, which is determined using an ultracentrifuge. The particle size distribution is also preferably determined by an ultracentrifuge, as will be detailed below. In the case of determining the particle size distribution, in general, the integral is applied through mass or weight, depending on the size of the particles. If a certain range of particle size is selected, with a width of 50 nm, then, according to this mode of execution, the increase in weight or mass in the integral is less than 40% by weight, preferably,
ES 2 316 092 T3 less than 37.5% by weight, especially preferably less than 35% by weight, and especially preferably less than 32.5% by weight, especially less than 30% by weight. Usually, the particle sizes in an agglomerated latex are in the area up to 1000 nm. Therefore, in general, the 50 nm range is within this particle size area of up to 1000 nm. According to this second mode of execution, for a freely positioned particle size window with a width of 50 nm, the present requirement must be fulfilled.
Preferably, in this embodiment in a particulate emulsion polymerization product, the ratio D<sub>w</sub>/ D<sub>n</sub> of the mean of the weight d50 to the mean of the figures d50 of the particle size is <5, particularly preferably <4, especially <3. Preferably, the integral of the weight, applied against the size of the particles, is a monotonic upward function. This means that during the function from 0 to 100% by weight there is no plateau, but rather a constantly rising curve.
In this second embodiment, the particle size of the binder latex of the acrylester polymerization product is preferably approximately in the area of the particle size of the latex to be agglomerated. In this second embodiment, the ratio of the mean particle size of the acrylester latex to the mean size of the substrate latex particles is preferably 0.2 to 2, particularly preferably 0.5 to 1.5.
In this embodiment, the agglomeration is preferably carried out at a temperature of 20 to 120 ° C, particularly preferably 30 to 100 ° C. The addition of agglomerated latex is preferably carried out in such a way that 1 to 1/100 of the total amount of agglomerated latex to be added are added per minute. This agglomeration time is preferably between 1 minute and 2 hours, particularly preferably between 10 and 60 minutes.
In this second embodiment, the amount of agglomerated latex, relative to the latex to be agglomerated, is preferably 0.1 to 20, preferably 0.5 to 10, especially 1 to 5% by weight. , in relation to solid substances.
In general, the emulsion polymerization reaction is carried out under slow or moderate stirring.
Microemulsion polymerization differs from normal emulsion polymerization, above all, because an emulsion is prepared from the monomers, water, and emulsifiers, causing high shear forces to act. For this, homogenizers known to the specialist are used, for example laboratory solvents from VMA-Getzmann, Reichshof, Germany, Ultra-Turax, Janke und Kunkel, Staufen, Germany, equipment with a rotor-stator system, for example For example, Dispax, from Janke und Kunkel, Staufen, Germany. Usually, these equipments are used with a number of revolutions of 1000 to 25,000 min<sup>-1</sup>preferably 2,000 to 25,000 min<sup>-1</sup>.
Mini-emulsion polymerization differs, above all, from normal emulsion polymerization and microemulsion polymerization, mainly because the size of the particles in general is between 30-500 nm (that is, it is between the typical size of particles from emulsion and microemulsion polymerization), and the particles are usually stabilized against confluence, by a combination of ionic emulsifiers and co-emulsifiers. In the case of the minimemulsion, the mixture of monomers, water and co-emulsifiers is exposed to high shear forces, whereby the components are intimately mixed. Subsequently, the polymerization takes place. High shear forces can be generated, for example, by ultrasound or by microfluidizing equipment. As co-emulsifiers, those compounds are selected that cause the droplets that form before initiating polymerization to be very small but not thermodynamically stable (see Gilbert, “Emulsion Polymerization, A Mechanistic Approach”). ), Academic Press, London, San Diego 1995, pages 12-14). Long-chain alkanes, such as hexadecane, or long-chain alcohols such as hexadecanol (cetyl alcohol) or dodecanol are usually used as co-emulsifiers.
In the case of suspension polymerization and its variants (microsuspension, minisuspension) the monomers are suspended in water, for which protective colloids are also used. Suitable protective colloids are cellulose derivatives such as carboxymethylcellulose and hydroxymethylcellulose, poly-N-vinylpyrrolidone, polyvinyl alcohol and polyethyleneoxide, anionic polymers such as polyacrylic acids and their copolymers and cationics such as poly-N-vinylimidazole. The amount of these protective colloids is preferably 0.1 to 5% by weight of the total mass of the emulsion. Preferably, one or more polyvinyl alcohols are used as protective colloid, especially those with a degree of hydrolysis of less than 96% by mol.
Additionally, it is possible to use, in addition to the protective colloid, colloidal silicic acid in a concentration of generally 0.2 to 5% by weight, relative to the amount of the dispersion.
For suspension polymerization, triggers with a half-life of one hour are preferred, if the temperature is between 40 to 150 ° C, and with a poor dissolution in the monomer but a good dissolution in water. Therefore, organic peroxides, organic hydroperoxides, azo compounds and / or compounds with single CC bonds are used as IR triggers. In the same way, monomers that spontaneously polymerize at an elevated temperature are used as polymerization triggers. Mixtures of the mentioned RI triggers can also be used. In the case of peroxides, those with properties
ES 2 316 092 T3 hydrophobic. Dilauric peroxide and dibenzoyl peroxide are especially preferred. Preferred azo compounds are 2,2'-azobis (2-methylbutyronitrile) and 2,2'-azobis (isobutyronitrile). As compounds with labile CC bonds, 3,4-dimethyl-3,4-diphenylhexane and 2,3-dimethyl-2,3-diphenylbutane are preferably used.
During the polymerization reaction, in general, only slow or moderate stirring is carried out.
Microsuspension polymerization differs from normal suspension polymerization, primarily because, under the influence of high shear forces, a fine suspension is prepared. The details have already been described in microemulsion polymerization.
Mini-suspension polymerization differs from normal suspension polymerization and microsuspension polymerization, primarily because the particle size is generally between those of suspension polymerization and microsuspension polymerization.
In the case of precipitation polymerization, the monomers used are soluble in the continuous phase (for example, in solvents or a mixture of solvents), the polymers obtained, however, are not soluble or are limited soluble and therefore separate during polymerization. Also in-substance polymerizations, in which the polymer obtained is insoluble in the monomer and therefore separates, are possible. Depending on the reaction medium, the triggers described in emulsion or suspension polymerizations are possible. It can also be thermally started.
In the case of bulk polymerization, the monomers are polymerized without the addition of a reactive medium, using the mentioned triggers monomer solvents, that is, the monomers are the reactive medium. It can also be thermally started.
Solution polymerization differs from bulk polymerization primarily because an organic solvent such as cyclohexane, ethylbenzole, or dimethylsulfoxide is also used to dilute the monomers. The above triggers can also be used, or it can be thermally initiated.
The process for obtaining grafted polymerization products can also be carried out by a combined process in which at least two of the polymerization processes described are combined with each other. Among them, it is worth mentioning, especially, mass / solution, solution / precipitation, mass / suspension and mass / emulsion, in which one begins with the first mentioned and ends with the last one mentioned.
The molding compounds according to the invention may contain, as a further component E, in addition to composition I, additional substances such as processing aids or mixtures of different additives.
The proportion of component E is generally up to 50% by weight, for example 0.1 to 50% by weight, preferably 0.1 to 40% by weight, especially 0.5 to 35% by weight , always in relation to the weight of composition I contained in the molding compound.
Accordingly, the present invention also comprises, according to another embodiment, molding compounds, as described above, whereby the molding compounds contain, as component E, 0.1 to 50% by weight, relative to the weight of composition I contained in the mouldable compound, other additives.
Other additives within the meaning of the present invention are, for example, oxidation stabilizers and retarders, means against dissolution of heat and decomposition by ultraviolet light, slip and mold release agents, dyeing agents such as colorants and pigments, and softeners.
Pigments and colorant are generally present in up to 6% by weight, preferably 0.5 to 5% by weight and especially 0.5 to 3% by weight.
Pigments for coloring thermoplastics are known, see, for example, R. Gachter and H. Müller, Taschenbuch der Kunststoffadditive (Pocket book of additives for plastics), Carl Hanser Publishing House, 1983, pages 494 to 510. As First preferred group of pigments we must mention the white pigments such as zinc oxide, zinc sulfide, basic lead carbonate, lithopon, antimony white and titanium dioxide. Of the two most common crystal modifications (rutile type and anatas type) of titanium dioxide, the rutile form in particular is used to tint the molding compounds according to the invention white.
The black pigments that can be used according to the invention are iron oxide black, spinel black, manganese black (mixture of manganese dioxide, sicilium dioxide and iron oxide), cobalt black and antimony black. as well as, especially preferably, carbon black, which is generally used in the form of furnace black or gas black (see G. Benzing, Pigmente für Anstrichmittel (Pigments for colorants), Editorial Expert (1988), pages 78 et seq.).
Of course, inorganic color pigments, such as chromium oxide green, or organic color pigments, such as azo pigments and phthalocyanine, can be used according to the invention and to adjust certain shades. Such pigments are commercially available.
ES 2 316 092 T3
The oxidation retardants and heat stabilizers that can be added to the thermoplastic compounds according to the invention are, for example, metal halides of group I of the periodic system, for example sodium, potassium, lithium halides. In addition, zinc fluoride and zinc chloride can be used. In addition, hindered phenols, hydroquinones, substituted representatives of this group, secondary aromatic amines, optionally, combined with acids with phosphoric content, or their salts, and mixtures of these compounds can be used, preferably in concentrations of up to 1% by weight. , in relation to the weight of composition I.
Examples of UV stabilizers are different resorcins, salicylates, benzotriazoles and substituted benzophenones, which, in general, can be used in amounts up to 2% by weight.
The slip and release agents, which are added, in general, in amounts of up to 1% of the thermoplastic compound, are stearic acid, stearylalcohol, stearic acid alkylester and stearic acid amides, as well as esters of pentaerythrite with chain fatty acids. long. Calcium, zinc or aluminum salts of stearic acid can also be used, as well as diallyl ketones, for example distearyl ketone. According to the invention, for example calcium stearate is suitable.
As other additional substances nucleating elements are used, such as talc.
The molding compounds according to the invention can be prepared by mixing the components in a known manner.
The components are advantageously implemented finely ground, provided they are not liquid. Products with an average particle size less than 100 µm, preferably less than 50 µm, are especially suitable. The components can be mixed at the same time, together or one after the other.
The mouldable compounds according to the invention can, in principle, be obtained according to a known process, for example by extrusion. The molding compounds according to the invention can be obtained, for example, by mixing the starting components in conventional mixing devices such as worm extruders, preferably twin worm extruders, Brabender mills or Banbury mills, as well as kneaders, and then extruders. After extrusion, the extrudate is preferably cooled and ground. The order of mixing the components may vary. For example, two or more components can be premixed. But within the framework of the present invention, it is also possible to mix all the components together.
To obtain a mixture that is as homogeneous as possible, it is advantageous to intensively intermix the components. This generally requires average mixing times of 0.2 to 30 minutes at temperatures of 200 to 320 ° C, preferably 225 to 310 ° C. After extrusion, the extrudate can be cooled and ground.
Advantageously, the mixing of the components is carried out on an extruder and, preferably, the mixing is carried out in molten form.
Accordingly, the present invention also comprises a process for the manufacture of a mouldable compound, as described above, comprising the mixture of 40 to 95% by weight of a copolymer containing 55 to 90% by weight of α-methylstyrene and 10 to 50% by weight of acrylonitrile, as well as 0 to 5% by weight of other monomers as component A, 2.5 to 75% by weight of a polymer B, consisting of 60 to 90% by weight of a vinyl aromatic monomer , 8.01 to 39.8% by weight of acrylonitrile and 0.2 to 1.99% by weight of maleic acid anhydride, and 2.5 to 60% by weight of glass fibers as component C.
Furthermore, the present invention comprises this process, the extrusion of a mouldable compound, which comprises 40 to 95% by weight of a copolymer containing 55 to 90% by weight of α-methylstyrene and 10 to 50% by weight of acrylonitrile, thus as 0 to 5% by weight of other monomers as component A, 2.5 to 75% by weight of a polymer B, consisting of 60 to 90% by weight of a vinyl aromatic monomer, 8.01 to 39.8% in weight of acrylonitrile and 0.2 to 1.99% by weight of maleic acid anhydride, and 2.5 to 60% by weight of glass fibers as component C, at a temperature in the area of 200 to 320 ° C.
The present invention further comprises a mouldable compound obtainable through the process described above.
The term "mouldable compound", as used within the framework of the present invention, refers to a mass according to one of the aforementioned compositions, which can be deformed by at least one suitable step. Accordingly, deformation molded bodies can be obtained from the molding compounds according to the invention. Castable compounds can also be made into foils, films, and foams. For this reason, the castables have advantageous mechanical properties for such applications.
The molding compounds can be shaped by a modeling step, for example, by injection molding, extrusion, pressing, pelletizing, obtaining shaped bodies such as, for example, granules, spheres, pellets, tablets.
ES 2 316 092 T3
Accordingly, the present invention also comprises a process as described above, further comprising the processing of the mouldable compound to obtain a molded body.
The present invention also comprises, according to another embodiment, a molded body that can be obtained through the process described above.
Other shaped articles can be obtained from the shaped body according to the invention. For example, it is possible to melt a granulate according to the invention and, if necessary, process it by adding at least one suitable additional substance, until another shaped body is obtained. As a suitable additional substance there may be mentioned, for example, the components mentioned above.
Accordingly, the present invention also comprises a shaped body containing at least 10% by weight, preferably at least 20% by weight, preferably, above all, at least 50% by weight and particularly preferably at least 90% by weight, for example 90, 91, 92, 93, 94, 95, 96, 97, 98, 99 or 100% by weight of the molding compound according to the invention.
A particularly preferred shaped body according to the invention is a granulate which contains 100% by weight of the moldable composition according to the invention. Preferably, the granulate particles have a size in the area of 1 to 6 mm, preferably between 1.5 and 5 mm. and especially preferably between 2 to 4 mm. The geometry of the shaped body is in principle not subject to any limitation and can, depending on the specific construction, be configured, for example, in a cylindrical, lenticular or spherical shape, or also have other shapes.
The molding compounds and the shaped body according to the invention are characterized by good thermal stability and, at the same time, good mechanical properties.
Furthermore, the present invention comprises the application of a moldable compound, as described above, for the manufacture of a molded body, likewise, the molded body is a toy or a part of a toy, an accessory of a car, an airplane or a boat or a part of an accessory of a car, an airplane or a boat, a package or a part of a package, a container or a part of a container, a household appliance or a part of a household appliance, a medical equipment or a part of a medical equipment, a component of a cosmetic article, a part of an electrical or electronic device or a device used in the construction of houses or a part of it.
Examples of specific applications are, for example, clips, fasteners, quick connections, elastic elements, speaker grilles, ventilation bodies for toilet tanks, rollers, levers, guides for, for example, sliding roofs for vehicles, components of transmission, regulating drives, coffee machine units, sprinkler systems, switches, spherical buckets for joints, pendulum supports for vehicles, check valves, vehicle wiper nozzles, vehicle internals, Bowden transmissions inner tubes, vehicle sun visor mounts, push buttons, seat belt winding mechanisms, grinding mechanisms, outsert chassis; seat backs, gas meters (measuring chamber housing and functional parts), window or door hardware, computer parts, printer parts, decorative items.
The following examples illustrate the present invention.
Examples
Measurement procedure
Determination of molar mass
The viscosity figure of the copolymers is determined according to DIN 53 727, in a solutions of 0.5% by weight in DMF.
Obtaining and evaluating the castable compounds
The granules were processed at a compound temperature of 260 ° C and a tool temperature of 60 ° C.
The formal heat resistance of the samples was determined by the Vicat softening temperature. The Vicat softening temperature was determined, according to DIN 53 460, with a force of 49.05 N and a temperature increase of 50 K per hour, in small standard bars.
The impact resistance of the products was determined in ISO bars, according to ISO 179 1eU.
The flowability was determined according to ISO 1133, at 240 ° C and with a load of 5 kg.
The stiffness of materials is characterized by the E modulus determined in the tensile test according to ISO 527. In this test, the elongation at break is also determined.
ES 2 316 092 T3
Components used
Component A1
Copolymer of 70% by weight of α-methylstyrene, and 30% by weight of acrylonitrile, characterized by a viscosity of 66 ml / g (measured at 25 ° C in a solution in 0.5% by weight of DMF)
AV component
Styrene-acrylonitrile copolymer with 75% by weight of styrene and 25% by weight of acrylonitrile, characterized by a viscosity of 66 ml / g (measured at 25 ° C in a solution in 0.5% by weight of DMF)
Component B1
S-AN-MA terpolymer (74/25/1% by weight) with a VZ of 80 ml / g
Component B2
S-AN-MA terpolymer (74/25/1% by weight) with a VZ of 65 ml / g
Component B3
S-AN-MA terpolymer (73.2 / 24.9 / 1.9% by weight) with a VZ of 66 ml / g
Component BV1
S-AN-MA terpolymer (70.6 / 23.7 / 5.7% by weight) with a VZ of 80 ml / g
Component C
Glass fibers with an aminosilane lubricant, a fiber diameter of 10 pm, staple fibers with a length of 4.5 mm.
Component D1
Rubber grafted with 70% by weight of polybutadiene in the core and 30% by weight of a graft cover of 75% by weight of styrene and 25.0% by weight of acrylonitrile mean particle size, approximately 370 nm
Component E1
Calcium stearate (Ceasit AV 40, from Barlocher)
Obtaining the castable compounds
The components were mixed in a twin-shaft extruder at a dough temperature of 240 to 290 ° C. The fluid was led to a water bath, and granulated.
The composition of the molding compounds and the results of the measurements are detailed in table 1.
ES 2 316 092 T3
TABLE 1
<td>Castable compound</td><td>SAW</td><td> 2</td><td> 3</td><td>V4</td><td>V5</td><td> 6</td><td> 7</td><td>V8</td><td> 9</td>
<td>Component [% by weight]</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>
<td>To the</td><td> 85</td><td> 80</td><td> 80</td><td> -</td><td> 80</td><td> 75</td><td> 74,8</td><td> -</td><td> 75</td>
<td>av</td><td> -</td><td> -</td><td> -</td><td> 80</td><td> -</td><td> -</td><td> -</td><td> 75</td><td> -</td>
<td>B1</td><td> -</td><td> 5</td><td> -</td><td> 5</td><td> -</td><td> 5</td><td> 5</td><td> 5</td><td> -</td>
<td>B2</td><td> -</td><td> -</td><td> 5</td><td> -</td><td> -</td><td> -</td><td> -</td><td> -</td><td> -</td>
<td>B3</td><td> -</td><td> -</td><td> -</td><td> -</td><td> -</td><td> -</td><td> -</td><td> -</td><td> 5</td>
<td>BV1</td><td> -</td><td> -</td><td> -</td><td></td><td> -</td><td> 5</td><td> -</td><td> -</td><td> -</td>
<td>C</td><td> 15</td><td> 15</td><td> 15</td><td> 15</td><td> 15</td><td> 15</td><td> 15</td><td> 15</td><td> 15</td>
<td>GAVE</td><td> -</td><td> -</td><td> -</td><td> -</td><td> -</td><td> 5</td><td> 5</td><td> 5</td><td> 5</td>
<td>The</td><td> -</td><td> -</td><td> -</td><td> -</td><td> -</td><td> -</td><td> 0,2</td><td> -</td><td> -</td>
<td>Castable compound</td><td> 1</td><td> 2</td><td> 3</td><td> 4</td><td> 5</td><td> 6</td><td> 7</td><td> 8</td><td> 9</td>
<td>Temperature of Vicat [° C]</td><td> 122</td><td> 121</td><td> 120</td><td> 112</td><td> 122</td><td> 120</td><td> 120</td><td> 108</td><td> 120</td>
<td>MVI [ml / 10 ']</td><td> 7,6</td><td> 6,2</td><td> 9,7</td><td> 10,7</td><td> 7,2</td><td> 4,6</td><td> 5,9</td><td> 9,6</td><td> 5,8</td>
<td>RT [kJ / m2]</td><td> 11,8</td><td> 17,7</td><td> 16,9</td><td> 15,4</td><td> 12,0</td><td> 26,2</td><td> 28,4</td><td> 26,2</td><td> 27,6</td>
<td>Modulus E [MPa]</td><td> 7075</td><td> 6950</td><td> 6940</td><td> 6970</td><td> 7005</td><td> 6545</td><td> 6450</td><td> 6480</td><td> 6480</td>
<td>Elongation at break. [%]</td><td> 1,6</td><td> 1,8</td><td> 1,7</td><td> 1,7</td><td> 1,5</td><td> 2,5</td><td> 2,6</td><td> 2,4</td><td> 2,6</td>
Contents13
3 sheets
Sheet 1 Sheet 2 Sheet 3
11 members in 7 offices
Priority claims5
| Document | Office | Kind | Date |
|---|---|---|---|
| 102005027485 | Germany | A | |
| 102005027485 | Germany | A | |
| 20051027485 | Germany | – | |
| 06777312102005027485 | – | – | – |
| DE20051027485 | – | – | – |
Members11
| Document | Office | Kind | |
|---|---|---|---|
| WO2006134096A1 | World Intellectual Property Organization (WIPO) | A1 | |
| DE102005027485A1 | Germany | A1 | |
| EP1893687A1 | European Patent Office (EPO) | A1 | |
| KR20080024127A | Republic of Korea | A | |
| US2008207821A1 | United States of America | A1 | |
| EP1893687B1 | European Patent Office (EPO) | B1 | |
| AT417892T | Austria | T | |
| ATE417892T1 | Austria | T1 | |
| DE502006002387D1 | Germany | D1 | |
| ES2316092T3This record | Spain | T3 | |
| US9018300B2 | United States of America | B2 |
Numbers
- Publication
- 2316092
- Publication, DOCDB
- 2316092
- Publication, EPODOC
- ES2316092T
- Application
- 6777312
- Application, DOCDB
- 06777312
- Application, EPODOC
- ES20060777312T
Titles2
- Spanish
- COMPUESTOS MOLDEABLES TERMOPLASTICOS REFORZADOS.
- English
- REINFORCED THERMOPLASTIC MOLDING COMPOUNDS.
Classification
- CPC, 6
- C08L25/04
- C08L25/00
- C08K7/14
- C08L25/18
- C08L35/06
- C08J5/08
- IPC, 2
- C08L25 00
- C08L25 04