EP2828334A1 - Verfahren zur herstellung von thermoplastischen formmassen mit hohem glasfaser-gehalt - Google Patents
Verfahren zur herstellung von thermoplastischen formmassen mit hohem glasfaser-gehaltInfo
- Publication number
- EP2828334A1 EP2828334A1 EP13711026.8A EP13711026A EP2828334A1 EP 2828334 A1 EP2828334 A1 EP 2828334A1 EP 13711026 A EP13711026 A EP 13711026A EP 2828334 A1 EP2828334 A1 EP 2828334A1
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- EP
- European Patent Office
- Prior art keywords
- component
- weight
- styrene
- thermoplastic molding
- molding composition
- 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.)
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/12—Copolymers of styrene with unsaturated nitriles
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—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 a halogen; Compositions of derivatives of such polymers
- C08L27/02—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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L35/00—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 a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L35/06—Copolymers with vinyl aromatic monomers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Definitions
- the present invention relates to a process for the preparation of thermoplastic molding compositions, in particular styrene copolymer compositions, a process for their preparation and their use.
- the preparation of styrenic copolymer compositions having various fillers is known, for example, US 3,951,906 discloses a composition having higher levels of glass fibers.
- US Pat. No. 3,951,906 describes compositions containing 40 to 60% by weight of styrene-acrylonitrile copolymer (SAN), 20 to 30% by weight of CaCO 3 and 20 to 30% by weight of glass fibers.
- JP-A 56 095953 deals with such fiber reinforced products.
- a vinyl monomer for example, a styrene, or (meth) acrylonitrile, in which a rubbery polymer (for example, a nitrile rubber) is dissolved or at least two copolymerizable vinyl monomers in which the rubber polymer is dissolved, is used. Thereafter, the components are polymerized in the presence of shredded strands of glass fibers.
- WO 201 1/023541 discloses styrene-acrylonitrile compositions with glass fibers.
- the document relates to processes for the preparation of thermoplastic molding compositions containing from 40 to 93.8% by weight of one or more styrene-acrylonitrile copolymers which do not contain maleic anhydride-derived units having a viscosity number VZ equal to or less than 70 ml / g (measured according to DIN 53727 at 25 ° C as 0.5% by weight solution in dimethylformamide), as component A, 0.1 to 20 wt .-% of one or more compatibilizer as component B, and 1 to 50 wt.
- KR 900004674 describes the preparation of glass fiber-containing SAN in the presence of maleic acid-containing styrene copolymer. However, the amount of glass fiber is limited to a maximum of 40 wt .-%.
- KR 900004674 also describes a glass fiber reinforced styrene-acrylonitrile resin composition containing from 60 to 95% by weight of the copolymer comprising 60-80% by weight of aromatic vinyl monomer and From 20 to 40% by weight of vinyl cyanide monomer, from 5 to 40% by weight of a glass fiber having a non-continuous phase, the surface of which has been treated with an aminosilane-based coupling reagent, and 0.1-10% by weight of styrene-maleic anhydride Copolymer containing 7 to 20 wt .-% maleic anhydride comprises.
- WO 2008/1 10539 describes fiber composites containing 15 to 95% by weight, based on the weight of the fiber composite, of a thermoplastic matrix M comprising 0 to 99% by weight, based on the weight of the thermoplastic matrix M, of a styrene Acrylonitrile copolymers and / or o methylstyrene-acrylonitrile copolymers as component A, and 1 to 100 wt .-%, based on the weight of the thermoplastic matrix M, of a styrene-acrylonitrile-maleic anhydride copolymer and / or an a- Methyl styrene-acrylonitrile-maleic anhydride copolymers as component B, and 0 to 50 wt .-%, of a rubbery elastomeric polymer as component C, and 0 to 50 wt .-%, based on the weight of the thermoplastic matrix M, plastic-compatible additives as Component D, wherein
- glass fiber-containing polymer compositions are available which either exhibit a good flow and impregnation quality but do not offer an optimum level of toughness, for example because of the low rubber content, the low molecular weight of the styrene-acrylonitrile copolymers or the short glass fiber length; or however those polymer compositions which have good adhesion between the fiber and the matrix and increased toughness, but due to limited flowability only permit incomplete fiber impregnation and have poor further processibility, in particular increased fiber abrasion with subsequent pneumatic conveying or metering.
- thermoplastic molding compositions with increased temperature-resistant and mechanical properties, which have particularly good flow properties over known molding compositions, in particular in a further processing into moldings, for example of window profiles.
- thermoplastic molding compositions in particular styrene copolymer compositions, with improved temperature-resistant and mechanical properties, which have good flow properties over known molding compositions.
- the object is achieved by the provision of a thermoplastic molding composition comprising:
- component B 0-40% by weight of a graft polymer as component B comprising:
- B1 a graft base composed of an alkyl acrylate, an allyl (meth) acrylate, a copolymerizable monomer and / or a diene monomer,
- B2 at least one graft shell composed of at least one vinylaromatic monomer and / or a copolymerizable monomer
- thermoplastic molding composition comprising:
- component B 0 - 15 wt .-% of a graft polymer as component B comprising:
- B1 a graft base composed of an alkyl acrylate, an allyl (meth) acrylate, a copolymerizable monomer and / or a diene monomer,
- B2 at least one graft shell composed of at least one vinylaromatic monomer and / or a copolymerizable monomer
- component E 0.1-4 wt .-% of stabilizer (s) as component E, wherein the sum of the components A, B, C, D and E (preferably) 100 wt .-% results.
- component A is a SAN copolymer
- component B is a graft copolymer with styrene and acrylonitrile and a polybutadiene or acrylate rubber
- component C is an S / AN / MSA copolymer.
- Another object of the invention is also a thermoplastic molding composition containing:
- component A 40-50 wt .-% of a styrene-acrylonitrile copolymer as component A,
- component C 0.5-8% by weight of a further copolymer as compatibilizer as component C,
- component E 0.1-4 wt .-% of stabilizer (s) as component E, wherein the sum of the components A, C, D and E 100 wt .-% results.
- component A is a SAN copolymer and component C is an S / AN / MSA copolymer.
- thermoplastic molding composition containing (or consisting of):
- the invention also relates to a thermoplastic molding composition, wherein the length of the glass fibers (component D) ⁇ 50 mm, often less than 20 mm, often less than 10 mm.
- the length of the glass fibers after extrusion is often in the range of 0.1 to 1 mm, often from 0.2 to 0.9 mm.
- the invention also relates to a thermoplastic molding composition, wherein the component A is a styrene-acrylonitrile copolymer having a styrene content of 65 to 76 wt .-% and an acrylonitrile content of 35 to 24 wt .-%.
- the invention also provides a thermoplastic molding composition, wherein the component C consists of one or more copolymers, wherein the component C comprises at least one styrene-acrylonitrile-maleic anhydride copolymer, wherein this 0.5 - 5 wt .-% of maleic anhydride derived units having.
- the invention also relates to a thermoplastic molding composition, which contains as component E from 0.05 to 5 wt .-% of at least two stabilizers. A combination of two (or three) stabilizers has been found to be advantageous.
- the invention also relates to a thermoplastic molding composition, which contains as additional component E a lubricant and a (medical) white oil.
- the invention also relates to a thermoplastic molding composition, wherein 20 to 60 wt .-% of component A is replaced by polyvinyl chloride (component A ') in the molding composition.
- the invention also relates to a process for the preparation of the thermoplastic molding composition, comprising: A) 40-55 wt .-% of a styrene-acrylonitrile copolymer and / or an o
- component B 0-40% by weight of a graft polymer as component B comprising:
- B1 a graft base composed of an alkyl acrylate, an allyl (meth) acrylate, a copolymerizable monomer and / or a diene monomer,
- B2 at least one graft shell composed of at least one vinylaromatic monomer and / or a copolymerizable monomer
- the invention also provides the use of the thermoplastic molding composition as described above for the production of window profiles, door profiles, sash profiles or frame profiles. Also subject matter is a window profile, door profile, sash or frame profile containing a thermoplastic molding composition as described above or a thermoplastic molding composition obtainable by the method described.
- the molding composition according to the invention is also characterized in that it has: a) a rigidity of more than 12 GPa, measured in the tensile test ISO 527, b) a linear thermal expansion coefficient ⁇ of ⁇ 50-K "1 10 " 6 mm / mc) has a heat transfer coefficient ⁇ which is at least 50% smaller than that of steel.
- the molding composition of the invention can be processed by thermoplastic processing at temperatures ⁇ 300 ° C and can be connected by heat, mirror welding or microwave welding with other thermoplastics.
- co-extrusion of the above-described SAN molding compound with other thermoplastics e.g. B. PVC possible.
- the combination of the o.g. SAN molding compounds with PVC are of particular importance for certain applications (window and door frames).
- component A in principle, all styrene-acrylonitrile copolymers known to the person skilled in the art and known in literature can be used.
- a styrene-acrylonitrile copolymer can also be understood as meaning a ring-alkylated styrene-acrylonitrile copolymer.
- component A is a SAN matrix.
- Component A is used in the molding compositions in amounts of 40-55, preferably 40-50, often 44-52 and in particular 45-50 wt .-%.
- Suitable monomers A1 for the copolymer are vinylaromatic monomers, preferably styrene and / or styrene derivatives, preferably ⁇ -methylstyrene, and ring-alkylated styrenes, such as, for example. p-methylstyrene and / or tert-butylstyrene.
- monomers A2 for the copolymer for example, the following compounds can be used: acrylonitrile, methacrylonitrile, methyl acrylate, ethyl acrylate, propyl acrylate, methyl methacrylate, ethyl methacrylate, phenylmaleimide, acrylamide, vinyl methyl ether.
- acrylonitrile is used.
- the preparation of the component A can be carried out by generally known methods, as described, for example, in DE-A 31 49 358, page 9, lines 18 to 32 and DE-A 32 27 555, page 9, lines 18 to 32 , for example by well-known copolymerization of A1, A2 and optionally further, copolymerizable monomers in bulk, solution, suspension or aqueous emulsion at conventional temperatures and pressures in known apparatus (reference Kunststoffsoff manual, Vieweg-Daumiller, Volume V (polystyrene), Carl Hanser Verlag, Kunststoff 1969, p. 124, Z. 12 ff.)
- Component B is used in amounts of 0-40, preferably of 0-30, often of 0-15% by weight, sometimes also of 10-30 and in particular of 12-24% by weight.
- Butadiene but also alkyl acrylates having usually 1 to 8 carbon atoms, more preferably 4 to 8 carbon atoms in the alkyl radical, in particular n-butyl acrylate and / or ethylhexyl acrylate are suitable as monomers for the preparation of the base step (graft core).
- the acrylic acid esters can be used individually or as a mixture in the preparation of the graft base B1.
- Suitable crosslinkers are allyl (meth) acrylate, in particular allyl methacrylate.
- up to 2 wt .-%, preferably up to 1 wt .-% and in particular up to 0.5 wt .-% of other copolymerizable monomers having at least two functional groups can be used.
- monomers containing two or more ethylenic double bonds capable of copolymerizing which are not conjugated in the 1,3-position are suitable.
- Suitable crosslinking monomers are, for example, divinylbenzene, diallyl maleate, diallyl fumarate and / or diallyl phthalate, tri-allyl cyanurate, allyl (meth) acrylate, preferably the acrylic acid ester of tricyclodecenyl alcohol and / or dicyclopentadienyl acrylate.
- Possible further copolymerizable monomers which can be used are, for example, the following compounds: alpha-methylstyrene, methacrylonitrile, methyl acrylate, ethyl acrylate, propyl acrylate, methyl methacrylate, ethyl methacrylate, phenylmaleimide, acrylamide, vinyl methyl ether.
- styrene and / or styrene derivatives preferably suitable as vinylaromatic monomers B21.
- p-methylstyrene and / or tert-butylstyrene are suitable.
- Examples of polar, copolymerizable unsaturated monomers for B2 are acrylonitrile and methacrylonitrile.
- Examples of possible further monomers, in particular copolymerizable monomers, in particular for B2, are the following compounds: acrylic acid, methacrylic acid, maleic anhydride, methacrylonitrile, methyl acrylate, ethyl acrylate, propyl acrylate, methyl methacrylate, ethyl methacrylate, phenyl maleinimide, acrylamide, vinyl methyl ether.
- these may be used alone as grafted shell B2 or, more preferably, as a copolymer in vinyl aromatic monomers B21.
- the customary auxiliaries and / or additives can be used, for example emulsifiers, such as alkali metal salts of alkyl or alkylarylsulfonic acids, alkyl sulfates, fatty alcohol sulfonates, salts of higher fatty acids having 10 to 30 carbon atoms or resin soaps, polymerization initiators such. conventional persulfates, for example potassium persulfate or known redox systems, polymerization auxiliaries, such as e.g. conventional buffering substances, by which pH values of preferably 6 to 9 are adjusted, e.g.
- emulsifiers such as alkali metal salts of alkyl or alkylarylsulfonic acids, alkyl sulfates, fatty alcohol sulfonates, salts of higher fatty acids having 10 to 30 carbon atoms or resin soaps
- polymerization initiators such.
- conventional persulfates for example potassium persulfate or known redox systems
- Sodium bicarbonate and / or sodium pyrophosphate and / or molecular weight regulators, for example mercaptans, terpinols and / or dimeric ⁇ -methylstyrene, wherein the molecular weight regulators are usually used in an amount of 0 to 3 wt .-%, based on the weight of the reaction mixture ,
- ASA acrylic ester-styrene-acrylonitrile
- the preparation of the ASA (acrylic ester-styrene-acrylonitrile) material according to the invention is generally known from the specialist literature and is described by way of example in DE-A 12 60 135, Pages 3 to 4, lines 13 to 23 and US 3,055,859, pages 2 to 4, lines 62 to 10, as well as for the grafting in two stages in DE-A 31 49 358, pages 6 to 8, lines 16 to 5 and DE A 32 27 555, pages 6 to 8, lines 16 to 5 described.
- the rubbery acrylic acid ester polymerizate serving as the graft base A21 may be e.g. are prepared by emulsion polymerization of A21 1, by polymerizing, for example, A21 1 and the at least bifunctional crosslinker, for example in aqueous emulsion, in a conventional manner at temperatures between 20 and 100 ° C, preferably between 50 and 80 ° C.
- a mixture of vinylaromatic monomers A221 with a polar, copolymerizable unsaturated monomer A222 and, if appropriate, A223 can be grafted onto this polyacrylate ester latex formed thereby, the graft copolymerization also preferably being carried out in aqueous emulsion.
- the rubber-elastic component B1 can also, as described in EP 534,212 B1, pages 4 to 5, lines 46 to 43, on a hard, optionally crosslinked with the monomers mentioned under A1 core consisting of the monomers mentioned for A1 is built up, grafted on.
- this is a hard core with a glass transition temperature Tg> 25 ° C, wherein the proportion of the core as already shown 5 to 50 wt .-%, based on the weight of A1.
- the rubbery elastic base B1 may consist of diene monomers, but preferably butadiene and isoprene, in particular butadiene, is used, optionally in combination with further monomers, such as styrene.
- the grafting according to DE-A 31 49 358, pages 6 to 8, lines 16 to 5 and DE-A 32 27 555, pages 6 to 8, lines 1 to 5 take place in two stages, wherein first the vinylaromatic monomer can be polymerized in the presence of the grafting base. In the second step, the graft copolymerization can then be carried out with a mixture comprising at least one vinylaromatic monomer and at least polar, copolymerizable monomer.
- the quantities of the various components used and contained in the ASA materials have already been described above.
- thermoplastic molding composition 0.5 to 30 wt .-%, often 0.5 to 15 wt .-% of at least one graft polymer as component B, consisting of: a) 10 - 90 wt .-% graft B1 from (part ) crosslinked polybutadiene or polyacrylate
- MMA methyl methacrylate
- thermoplastic molding composition up to 50% by weight of one or more components B may be added to the thermoplastic molding composition to improve the mechanical properties as an impact modifier.
- component B can at least partially replace component A in the thermoplastic molding composition (see experiments 2.3 and 2.4).
- the subject matter is also containing molding compositions (or consisting A) 20-25% by weight of a styrene-acrylonitrile copolymer and / or an o-methylstyrene-acrylonitrile copolymer as component A,
- Component C is often used in amounts of from 0.1 to 10, preferably from 1 to 10, and in particular from 2 to 5,% by weight.
- the component is preferably a copolymer.
- thermoplastic molding compositions which can be prepared by the process according to the invention contain one or more compatibilizers.
- compatibilizers suitable for styrene copolymer-glass fiber mixtures are known in principle to the person skilled in the art and are described in the literature.
- Compounds which can preferably be used as compatibilizers are (methyl) styrene-acrylonitrile-maleic anhydride copolymers. These often contain, based on the total component C, 0.5 to 5 wt .-% of maleic anhydride derived units. This maleic anhydride content is preferably from 1 to 3% by weight, in particular from 2.0 to 2.2% by weight.
- Component C is particularly preferably a styrene-acrylonitrile-maleic anhydride terpolymer.
- the proportion of acrylonitrile, based on the total terpolymer is preferably 10 to 30% by weight, more preferably 15 to 30% by weight, in particular 20 to 25% by weight. The remainder is styrene and MSA.
- the preferred maleic anhydride-containing (methyl) styrene-acrylonitrile copolymers generally have molecular weights Mw in the range from 30,000 to 500,000 g / mol, preferably from 50,000 to 250,000 g / mol, in particular from 70,000 to 200,000 g / mol, determined by GPC using tetrahydrofuran (THF) as eluent and polystyrene calibration.
- THF tetrahydrofuran
- the terpolymer described in the experimental part is used as component C.
- Component D Component D
- Component C is used in amounts of 40-55, preferably 42-55 and in particular 45-55 wt .-%.
- component D the producible thermoplastic molding compositions according to the invention contain glass fibers.
- the preparation of the glass fibers D is known to the person skilled in the art and described in the literature.
- glass fibers all technically available glass types can be used. A description of suitable glass fibers can be found, for. In Milewski, J.V., Katz, H.S. "Handbook of Reinforcements for Plastics", p. 233 et seq., Van Nostrand Reinholt Company Ine, 1987.
- the length of the glass fibers is ⁇ 50 mm. It may be, for example, short glass fibers or long glass fibers or continuous glass fibers.
- Preferred lengths of the glass fibers D are in the range of 0.1 mm to 50 mm, in particular 0.1 mm to 10 mm, often from 0.1 to 1.0 mm, also from 0.2 to 0.9 mm.
- the choice of the fiber length of the glass fibers used also depends on the type of incorporation into the plastic, which will be described later.
- the fiber length is not limited.
- the average length of the glass fibers is preferably in the range of 0.1 to 2 mm.
- by combining the glass fiber together with the components A and C increased rigidity of the molding material can be achieved, since the length of the fibers is greater than 150 ⁇ .
- the diameters of the glass fibers D are usually in the range of 0.1 to 300 ⁇ , preferably 1 to 100 ⁇ , more preferably 3 to 50 ⁇ , most preferably 5 to 30 ⁇ .
- the diameters mentioned relate to glass fiber strands or bundles, e.g. Rovings, on the diameter of the individual glass fibers (often referred to as "single filaments") of these strands or bundles.
- the glass fibers C can not only be used as single fibers, strands or bundles, in the form of, for example, mats, fabrics or nonwovens their use is basically possible.
- the glass fibers C may consist, for example, of A, E, C, E-CR, D, R, M or S glass (see DIN 1259: 2001 -09 [glass, part 1]).
- the glass fibers C can be provided with a size, for example a polyurethane size, a titanate size, or in particular a size of silane compounds, which ensures the compatibility of the fiber with the thermoplastic. improved plastic matrix M.
- Silane compounds suitable as size are, for example, those of the formula I.
- X is NH 2 -, HO- n is an integer from 2 to 10, preferably 3 or 4
- n is an integer from 1 to 5, preferably 1 or 2
- k is an integer from 1 to 3, preferably 1.
- Preferred silane compounds are aminopropyltrimethoxysilane, aminobutyltrimethoxysilane, aminopropyltriethoxysilane, aminobutyltriethoxysilane and the corresponding silanes which contain a glycidyl group as substituent X instead of NH 2 .
- the proportion of sizing is generally 0.05 to 5% by weight, based on the weight of glass fibers C.
- the component A is at least partially replaced by polyvinyl chloride.
- component A is a styrene-acrylonitrile copolymer having a styrene content of 65-76% by weight.
- component A may be a SAN polymer having an S / AN ratio of 67/33, a viscosity number of 80 dl / g (measured on 0.5% solution in DMF at 23 ° C).
- the component C comprises one or more (methyl) styrene-acrylonitrile copolymers which, based on the entire component C, comprises 0.5-5% by weight of units derived from maleic anhydride.
- Other components E
- the molding compound according to the invention contains 0.01-5% by weight of at least one further component E, in particular as auxiliary and / or additive.
- Component E is used in amounts of from 0.01 to 5, preferably from 0.025 to 2 and in particular from 0.05 to 1.5,% by weight. It may be a single component in the component or multiple components in the component.
- the mixtures according to the invention may preferably contain auxiliaries and / or additives in addition to (A) to (D). Particular preference is given according to the invention to mixtures containing up to 5% by weight of auxiliaries and / or additives.
- auxiliaries and / or additives for example, stabilizers, plasticizers, antistatic agents, light stabilizers, lubricants, blowing agents, other compatible thermoplastics, such as polyesters (eg polyethylene terephthalate, polybutylene terephthalate), polycarbonate, polyamide, polyoxymethylene, polystyrene, polyethylene, polypropylene, polyvinyl chloride , Fillers, surfactants, flame retardants, dyes and pigments.
- the stabilizers against oxidation, hydrolysis, light, heat or discoloration are preferably contained in amounts of 0.1 to 5 wt .-%. Often two different stabilizer types are included.
- the component E contains a light stabilizer, a lubricant and a (medical) white oil.
- the component E may consist of several substances, for example, to influence the appearance of the molding material.
- optical brighteners, radical scavengers that absorb the radicals generated by UV radiation in the molding composition, or light stabilizers may be included.
- Slip agents and also mold release agents which can generally be added in amounts of up to 1% by weight, are stearic acid, stearyl alcohol, stearic acid alkyl esters and amides and esters of pentaerythritol with long-chain fatty acids. It is also possible salts of calcium, zinc or aluminum of stearic acid and dialkyl ketones, z. B. distearyl ketone used. Particularly suitable according to the invention is calcium stearate.
- light stabilizers it is possible to use all conventional light stabilizers, for example compounds based on benzophenone, benzotriazole, cinnamic acid, organic phosphites and phosphonites, and sterically hindered amines.
- Suitable lubricants are, for example, hydrocarbons such as oils, paraffins, PE waxes, PP waxes, fatty alcohols having 6 to 20 carbon atoms, ketones, carboxylic acids such as fatty acids, montanic acid or oxidized PE wax, carboxylic acid amides and carboxylic acid esters, for example with the alcohols, ethanol , Fatty alcohols, glycerol, ethanediol, pentaerythritol and long-chain carboxylic acids as acid component into consideration.
- hydrocarbons such as oils, paraffins, PE waxes, PP waxes, fatty alcohols having 6 to 20 carbon atoms, ketones, carboxylic acids such as fatty acids, montanic acid or oxidized PE wax, carboxylic acid amides and carboxylic acid esters, for example with the alcohols, ethanol , Fatty alcohols, glycerol, ethanediol, pentaerythrito
- antioxidants such as phenolic antioxidants, eg., alkylated monophenols, esters and / or amides of b- (3,5-di-tertiary-butyl-4-hydroxyphenyl-propionic acid and / or benzotriazoles can be used.) Possible antioxidants are mentioned in EP-A 698637 and EP-A 669367.
- Tinuvin 770 is a Lower molecular weight di-carboxylic acid ester with the systematic name: decanedioicacid bis (2,2,6,6-tetramethyl-4-piperidinyl) ester, suitable in combination is eg Cyasorb UV-3853 (see Hostavin N845N) , a mixture of low molecular weight fatty acid esters m a heterocyclic alcohol (C12-21 and C18-unsaturated-2,
- Chimassorb 944 HALS-HS-944
- oligomeric HALS stabilizers having the empirical formula (CasHeeNe), with different chain lengths (poly [[6-f (1,1,3,3-tetramethylbutyl) amino] -s-triazine-2,4-diyl] - [(2,2,6,6-tetramethyl-4-piperidyl) imino] - hexamethylene - [(2,2,6,6-etramethyl-4-piperidyl) imino] ).
- the mixtures according to the invention can, for example, be pelletized or granulated or according to generally known processes, for example by extrusion, injection molding or calendering to cable sheathing, films, hoses, fibers, profiles, shoe shells, shoe soles, technical molded parts, utility articles, moldings of all kinds, coatings, bellows, Animal ear tags and / or blow moldings are processed.
- thermoplastic molding composition is prepared by a melt blending of the components A, B, C and D and E.
- the present invention describes a process for the preparation of styrene polymers with a glass fiber content of more than 40 wt .-%, characterized in that the glass fibers less than 5 mm, preferably less than 2 mm and more preferably less than 0.5 mm in length have, the amount of glass fiber at more than 40 wt .-% - based on 100 wt .-% total molding composition - and an amount of more than 1 wt .-%, preferably more than 2 wt .-% and particularly preferred contains more than 3% by weight of a styrene-acrylonitrile-MSA-based copolymer.
- the components A, C, D, E and optionally B are compounded.
- compounding plastic processing
- admixing additives fillers, additives, etc.
- the component E can be used for this purpose.
- the components A, B, C and D can be used simultaneously or sequentially.
- One after the other in the sense of the present invention means that, for example, first two components are mixed and then the other components are added.
- the compounding takes place mainly in extruders (mainly co-rotating twin-screw extruder, but also counter-rotating twin-screw extruder and co-kneader) and includes the process operations conveying, melting, dispersing, mixing, degassing and pressure build-up.
- extruders mainly co-rotating twin-screw extruder, but also counter-rotating twin-screw extruder and co-kneader
- Another object of the invention is the use of the thermoplastic molding composition according to the invention for the production of window profiles, door profiles, sash profiles or frame profiles.
- Preferred thermoplastic molding compositions and preferred processes are listed above. The invention is further described by the following examples and the claims.
- Example 1 The compounding of the SAN copolymer molding compositions was carried out on a compound extruder at different glass fiber concentrations.
- Component D glass fibers:
- Component A S / AN ratio 67/33, Viscosity number: 80 dl / g
- Graft rubber consisting of:
- Graft rubber consisting of: 60 wt .-% of a graft of 98 wt .-% butyl acrylate and 2 wt .-% of a
- Component D Glass Fiber (eg Cratex 183F-1 1P)
- Components E Additives, in particular stabilizers (eg Tinuvin 770 or a combination of two stabilizers (with Tinuvin 770)).
- stabilizers eg Tinuvin 770 or a combination of two stabilizers (with Tinuvin 770)
- the molding composition was prepared analogously to Example 2, but with 15% by weight of rigid PVC (and correspondingly less SAN, component A).
- the molding composition was prepared in analogy to Example 2 but with
- grafted rubber component B K-1 (polybutadiene-based)
- Example 5 The molding composition was prepared in analogy to Example 2 but with
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- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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EP13711026.8A EP2828334A1 (de) | 2012-03-21 | 2013-03-19 | Verfahren zur herstellung von thermoplastischen formmassen mit hohem glasfaser-gehalt |
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EP12160487 | 2012-03-21 | ||
PCT/EP2013/055644 WO2013139769A1 (de) | 2012-03-21 | 2013-03-19 | Verfahren zur herstellung von thermoplastischen formmassen mit hohem glasfaser-gehalt |
EP13711026.8A EP2828334A1 (de) | 2012-03-21 | 2013-03-19 | Verfahren zur herstellung von thermoplastischen formmassen mit hohem glasfaser-gehalt |
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EP2828334A1 true EP2828334A1 (de) | 2015-01-28 |
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EP13711026.8A Ceased EP2828334A1 (de) | 2012-03-21 | 2013-03-19 | Verfahren zur herstellung von thermoplastischen formmassen mit hohem glasfaser-gehalt |
Country Status (5)
Country | Link |
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US (1) | US9732210B2 (de) |
EP (1) | EP2828334A1 (de) |
KR (1) | KR101978538B1 (de) |
CN (1) | CN104220515B (de) |
WO (1) | WO2013139769A1 (de) |
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KR102514321B1 (ko) * | 2017-07-05 | 2023-03-24 | 이네오스 스티롤루션 그룹 게엠베하 | 개선된 uv 내성을 갖는 열가소성 스티렌 코폴리머 수지 조성물 |
KR102514316B1 (ko) * | 2017-07-05 | 2023-03-24 | 이네오스 스티롤루션 그룹 게엠베하 | 개선된 uv 내성을 갖는 열가소성 수지 조성물 |
Family Cites Families (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL99388C (de) | 1956-09-28 | |||
DE1260135B (de) | 1965-01-05 | 1968-02-01 | Basf Ag | Schlagfeste thermoplastische Formmassen |
US3951906A (en) | 1972-08-31 | 1976-04-20 | Uniroyal Inc. | Reinforced styrene-acrylonitrile polymers |
JPS5695953A (en) | 1979-12-28 | 1981-08-03 | Mitsubishi Monsanto Chem Co | Glass fiber reinforced thermoplastic resin composition |
DE3149358A1 (de) | 1981-12-12 | 1983-06-16 | Basf Ag, 6700 Ludwigshafen | Thermoplastische formmasse |
DE3227555A1 (de) | 1982-07-23 | 1984-01-26 | Basf Ag, 6700 Ludwigshafen | Thermoplastische formmasse |
KR900004674B1 (ko) | 1987-02-07 | 1990-07-02 | 주식회사 럭키 | 유리섬유보강 스티렌-아크릴로 니트릴 수지조성물 |
DE4131728A1 (de) | 1991-09-24 | 1993-03-25 | Basf Ag | Teilchenfoermiges pfropfcopolymerisat mit kern/schale-aufbau |
EP0669367A1 (de) | 1994-02-24 | 1995-08-30 | Ciba-Geigy Ag | Phenolische Stabilisatormischungen |
EP0698637A3 (de) | 1994-08-22 | 1996-07-10 | Ciba Geigy Ag | Mit ausgewählten 5-substituierten Benzotriazol-UV-Absorbern stabilisierte Polyurethane |
US20050215677A1 (en) * | 2002-06-13 | 2005-09-29 | Gaggar Satish K | Thermoplastic compositions and process for making thereof |
DE10233170A1 (de) * | 2002-07-22 | 2004-02-12 | Bayer Ag | Polymerblends auf Basis Polyamid |
DE102005040620A1 (de) * | 2004-10-11 | 2006-04-13 | Bayer Materialscience Ag | Glasfaserverstärkte Polymer-Zusammensetzungen |
DE102005027485A1 (de) * | 2005-06-14 | 2006-12-28 | Basf Ag | Verstärkte thermoplastische Formmassen |
WO2008110539A1 (de) | 2007-03-13 | 2008-09-18 | Basf Se | Faserverbundwerkstoff |
EP2251377B1 (de) | 2009-05-11 | 2011-07-20 | Basf Se | Verstärkte Styrolcopolymere |
WO2011023541A1 (de) | 2009-08-31 | 2011-03-03 | Basf Se | Verfahren zur herstellung von glasfaserverstärkten san-copolymeren mit verbesserter schlagzähigkeit und leichter verarbeitbarkeit |
JP5695953B2 (ja) | 2011-03-31 | 2015-04-08 | 住友大阪セメント株式会社 | 電気防食工法における短絡防止方法 |
-
2013
- 2013-03-19 KR KR1020147029300A patent/KR101978538B1/ko active IP Right Grant
- 2013-03-19 US US14/386,216 patent/US9732210B2/en active Active
- 2013-03-19 WO PCT/EP2013/055644 patent/WO2013139769A1/de active Application Filing
- 2013-03-19 CN CN201380015052.XA patent/CN104220515B/zh active Active
- 2013-03-19 EP EP13711026.8A patent/EP2828334A1/de not_active Ceased
Non-Patent Citations (2)
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None * |
See also references of WO2013139769A1 * |
Also Published As
Publication number | Publication date |
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WO2013139769A1 (de) | 2013-09-26 |
US9732210B2 (en) | 2017-08-15 |
CN104220515B (zh) | 2017-12-22 |
US20150087765A1 (en) | 2015-03-26 |
CN104220515A (zh) | 2014-12-17 |
KR20140145165A (ko) | 2014-12-22 |
KR101978538B1 (ko) | 2019-05-14 |
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