Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
  • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
  • B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
  • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2250/00—Layers arrangement
  • B32B2250/24—All layers being polymeric
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/40—Properties of the layers or laminate having particular optical properties
  • B32B2307/406—Bright, glossy, shiny surface
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2419/00—Buildings or parts thereof
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2509/00—Household appliances
  • B32B2509/10—Refrigerators or refrigerating equipment
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2590/00—Signboards, advertising panels, road signs
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2605/00—Vehicles
  • B32B2605/08—Cars

Definitions

• the present invention relates to a structural plastic protected by an impact-reinforced acrylic polymer with an intermediate ductile layer disposed between the structural plastic and the protective layer.
• HIPS high impact polystyrene
• ABS resins acrylonitrile-butadiene-styrene
• PVC polyvinyl chloride
• the film comprises an acrylic surface layer (A), a layer (B3) made from a block copolymer and a possible acrylic layer
• the film is applied in two stages. In the st step, the film, which may be previously stored in roll form, is preformed to the required geometry, and in a 2 nd step, the thermoplastic melt is injected into a mold and the film is applied on the molten thermoplastic.
• an acrylic film has disadvantages. First of all, because of its rigidity, such a film is not handled (that is, stored in roll form, then unrolled) easily. Then, the dimensions of the film sold to a transformer are not necessarily adapted to those of the mold, which can cause significant rejects. Finally, there may be the problem of the adhesion of the film to the plastic to be protected. Indeed, the film is rigid when applied to the molten thermoplastic. In contact with the latter, it softens which facilitates the contact and adhesion but the softening may not be homogeneous and regular, especially in the presence of a mold with complicated geometry, resulting in inhomogeneous adhesion of the film.
• the thickness of the film (that is to say the set of layers (A) / (B3) / optionally (C)) is limited to 300 microns, preferably even to 100 microns. , to ensure easy handling of the film and good adhesion to the plastic by the "Film Insert Molding" technique used.
• the Applicant has found that it is possible to protect a structural plastic with a protective layer which adheres perfectly and which does not affect the impact resistance of the plastic structure.
• the process used is simpler and more economical than the process that uses acrylic film and allows for thicker structures.
• European application EP 1174465 A1 discloses a multilayer structure comprising a substrate coated with a surface layer composed of an acrylic copolymer, which is preferably a copolymer based on methyl methacrylate (MMA) and butyl methacrylate.
• MMA methyl methacrylate
• EP 1174465 A1 discloses a multilayer structure comprising a substrate coated with a surface layer composed of an acrylic copolymer, which is preferably a copolymer based on methyl methacrylate (MMA) and butyl methacrylate.
• European application EP 1548058 A1 describes a multilayer structure comprising a substrate covered with a surface layer composed of a core-shell type acrylic copolymer.
• US Pat. No. 4,350,742 describes a multilayer structure comprising a layer of polystyrene and a layer of an acrylic polymer. The adhesion between the layers is enhanced when the polystyrene contains as comonomer an ⁇ , ⁇ -unsaturated carboxylic acid.
• US Pat. No. 6,455,171 discloses a multilayer structure comprising an acrylic surface layer, an intermediate ductile layer based on a copolymer of an olefin and an acrylate or block copolymer composed of a conjugated diene and a a vinylaromatic monomer.
• the invention relates to a multilayer structure comprising in the order: "a protective layer (I) comprising a PMMA, • optionally a pigmented layer (II), • an intermediate ductile layer (III) comprising a block copolymer of formula BA n compound: a polymer block B comprising by weight at least 60% of at least one (meth) acrylic monomer having a T 9 lower than -5 0 C, and n polymer A sequences, connected to the polymer block B by covalent bonds, n denoting an integer of between 1 and 10, comprising by weight at least 60% of at least one (meth) acrylic monomer having a T 9 greater than 0 ° C.,
• the invention also relates to a method for protecting a structural plastic consisting of coextruding in the order:
• a protective layer (I) comprising a PMMA, optionally a pigmented layer (II),
• An intermediate ductile layer (III) comprising a block copolymer of the formula BA n composed of: a polymer block B comprising by weight at least 60% of at least one (meth) acrylic monomer having a T g of less than -5 ° C. , and
• the invention also relates to the use of a block copolymer of formula BA n composed of: a polymer block B comprising by weight at least 60% of at least one (meth) acrylic monomer having a T g less than -5 0 C, and n polymer sequences A, connected to the polymer block B by covalent bonds, n denoting an integer of between 1 and 10, comprising by weight at least 60% of at least one (meth) acrylic monomer having a T 9 greater than 0 ° C, for the preparation of a ductile interlayer (ID
• Figures 1 shows a multilayer structure 1 comprising three layers referenced 2, 3 and 4 arranged one on the other.
• Layer 2 corresponds to the protective layer (I), layer 3 to the intermediate ductile layer (II) and layer 4 to the structural plastic (IV).
• FIG. 2 represents a multilayer structure 5 comprising four layers referenced 2, 2 ', 3 and 4 arranged one on the other.
• Layer 2 corresponds to the protective layer (I), the layer 2 'to the pigmented layer, the layer 3 to the intermediate ductile layer (II) and the layer 4 to the structural plastic (IV).
• FIG. 3 represents a diagram of the device for measuring the resilience 6.
• the bar 7 is placed on supports 8 and 8 '.
• the striker 9 applies a force F to the bar 7.
• a device not shown continuously records the force and displacement.
• FIG. 4 represents an AFM atomic force microscopy diagram of the triblock copolymer 3, the preparation of which is detailed in the examples section. Detailed description of the invention definitions
• T 9 denotes the glass transition temperature of a polymer.
• T g of a monomer will be referred to as the T g of the homopolymer obtained by radical polymerization of said monomer.
• (meth) acrylate designates for simplicity an acrylate or a methacrylate.
• Monomer (meth) acrylic a monomer that can be:
• An acrylic monomer such as acrylic acid or its salts, C 1 -C 10 alkyl acrylates, cycloalkyl or aryl acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, of isobutyl, tert-butyl, 2-ethylhexyl, hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate, alkyl ether acrylates such as 2-methoxyethyl acrylate, alkoxy- or aryloxypolyalkyleneglycol acrylates such as methoxypolyethylene glycol acrylates or ethoxypolyethylene glycol acrylates, aminoalkyl acrylates such as 2- (dimethylamino) ethyl acrylate, silyl acrylates, glycidyl acrylate,
• a methacrylic monomer such as methacrylic acid or its salts, alkyl methacrylates, C 2 -C 0, cycloalkyl or aryl such as ethyl methacrylate, propyl, n-butyl, of isobutyl, tert-butyl, 2-ethylhexyl, hydroxyalkyl methacrylates such as 2-hydroxyethyl methacrylate, ether alkyl methacrylates such as 2-methoxyethyl methacrylate, alkoxy- or aryloxypolyalkyleneglycol methacrylates such as methacrylates methoxypolyethylene glycol or ethoxypolyethylene glycol, aminoalkyl methacrylates such as 2- (dimethylamino) ethyl methacrylate, silyl methacrylates, glycidyl methacrylate.
• a methacrylic monomer such as methacrylic acid or its salts,
• PMMA means a homo- or copolymer of MMA, comprising by weight at least 50% MMA.
• the copolymer is obtained from MMA and at least one comonomer copolymerizable with MMA.
• the copolymer comprises, by weight, from 70 to 99.5%, advantageously from 80 to 99.5%, preferably from 80 to 99% by MMA, respectively from 0.5 to 30%, advantageously from 0.5 to 20%, preferably 1 to 20% comonomer.
• the comonomer is a (meth) acrylic monomer or a vinylaromatic monomer such as for example styrene, substituted styrenes, alpha-methylstyrene, monochlorostyrene, tertbutyl styrene.
• the comonomer is an alkyl (meth) acrylate. It is preferably methyl acrylate, ethyl, propyl, butyl, butyl methacrylate.
• the acrylic polymer is prepared by radical polymerization according to the techniques known to those skilled in the art.
• the polymerization may take place in solution, in bulk, in emulsion or in suspension.
• the acrylic polymer can also be prepared by anionic polymerization.
• the protective layer (I) comprises a PMMA.
• the PMMA-index melt (measured at 230 ° C., under a load of 3.8 kg) is between 0.5 and 10 g / 10 min, advantageously between 1 and 5 g / 10 min.
• the protective layer (I) serves to protect the structural plastic against scratches, chemicals and against aging. It also improves the gloss of certain structural plastics.
• ABS has a gloss only of the order of 40-50 at an angle of 60 °.
• a gloss between 70 and 95, preferably between 85 and 90 can be obtained via the protective layer (I).
• the impact modifier may be an acrylic elastomer such as a styrene-butadiene-methyl methacrylate block copolymer. It can also be in the form of fine multilayer particles, called core-shell, having at least one elastomeric (or soft) layer, that is to say a layer formed of a polymer having a T g lower than -5 0 C. and at least one rigid layer (or hard), that is to say formed of a polymer having a T g greater than 25 0 C.
• an acrylic elastomer such as a styrene-butadiene-methyl methacrylate block copolymer. It can also be in the form of fine multilayer particles, called core-shell, having at least one elastomeric (or soft) layer, that is to say a layer formed of a polymer having a T g lower than -5 0 C. and at least one rigid layer (or hard), that is to say formed of a polymer having a T g
• the T g polymer of less than -5 ° C. is obtained from a monomer mixture comprising from 50 to 100 parts of at least one C 1 -C 10 alkyl (meth) acrylate, from 50 parts of a monounsaturated copolymerizable comonomer, from 0 to 5 parts of a copolymerizable crosslinking monomer and from 0 to 5 parts of a copolymerizable grafting monomer.
• the T g polymer greater than 25 ° C. is obtained from a monomer mixture comprising from 70 to 100 parts of at least one C 1 -C 4 alkyl (meth) acrylate, from 0 to 30 parts of a monounsaturated copolymerizable monomer, 0 to 5 parts of a copolymerizable crosslinking monomer and 0 to 5 parts of a copolymerizable grafting monomer.
• the polymer of T g greater than 25 0 C has a weight-average molecular weight expressed in PMMA equivalents of between 10,000 and 1000000, advantageously between 50000 and 500000 g / mol.
• alkyl-Ci 0 is preferably butyl acrylate, 2-ethylhexyl, octyl.
• the (meth) acrylate of C 1 -C 4 alkyl is preferably methyl methacrylate.
• the monounsaturated copolymerizable monomer may be a C 1 -C 10 alkyl (meth) acrylate, styrene, alpha-methyl styrene, butyl styrene, acrylonitrile. It is preferably styrene or ethyl acrylate.
• the grafting monomer may be allyl (meth) acrylate, diallyl maleate, crotyl (meth) acrylate.
• the crosslinking monomer may be diethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, divinyl benzene, trimethylolpropane triacrylate (TMPTA).
• TMPTA trimethylolpropane triacrylate
• the multilayer particles can be of different morphologies.
• "hard-soft" type particles having an elastomeric core (inner layer) and a rigid shell (outer layer) can be used.
• European application EP 1061100 A1 describes such particles.
• "soft-hard” type particles composed of a soft core (40% by weight) obtained by polymerizing 99 parts of butyl acrylate and 1 part of allyl methacrylate; and hard bark (60% by weight) obtained by polymerizing 95 parts of MMA, 5 parts of butyl acrylate in the presence of 0.002 parts of n-dodecyl mercaptan; particle size: 145-155 nm.
• “dur-nau-hard” type particles having a rigid core, an elastomeric intermediate layer and a rigid bark.
• US 2004/0030046 A1 describes examples of such particles.
• “hard-soft-hard” type particles composed of a hard core (23% by weight) obtained by polymerizing 92.7 parts of MMA, 10 parts of ethyl acrylate, 0.3 part of methacrylate allyl; and a soft interlayer (47% by weight) obtained by polymerizing 81.7 parts of butyl acrylate, 17 parts of styrene and 1.3 parts of allyl methacrylate; a hard bark (30% by weight) obtained by polymerizing 96 parts of MMA and 4 parts of ethyl acrylate; particle size: 157 nm.
• soft-hard-soft-hard type particles compound a soft core (4% by weight) obtained by polymerizing 19.1 parts of butyl acrylate, 4.5 parts of styrene, 0.5 parts of allyl methacrylate; and a hard layer (25% by weight) obtained by polymerizing 141 parts of MMA, 9 parts of ethyl acrylate and 0.6 part of allyl methacrylate; a soft layer (56% by weight) obtained by polymerizing 266.8 parts of butyl acrylate, 62.5 parts of styrene, 6.7 parts of allyl methacrylate; hard bark (15% by weight) obtained by polymerizing 84.6 parts of MMA and 5.4 parts of ethyl acrylate; particle size: 270 nm.
• the elastomeric layer may also be of the silicone type as taught in US 2005/0124761 A1.
• the size of the particles is generally less than 1 ⁇ m and advantageously between 50 and 300 nm.
• the multilayer particles are prepared by means of the aqueous emulsion polymerization in several stages. During the st step, forming nuclei around which will constitute the layers. The final particle size is determined by the number of nuclei which are formed during the step era. During each of the following steps, by polymerizing the appropriate mixture, a new layer is successively formed around the seeds or particles of the preceding step. At each stage, the polymerization is conducted in the presence of a radical initiator, a surfactant and optionally a transfer agent. For example, sodium, potassium or ammonium persulfate is used. The particles once formed are recovered by coagulation or spraying. An agent Anti-clumping can be added to prevent particles from clumping together.
• the proportion of impact modifier in PMMA varies from 0 to 60 parts, advantageously from 1 to 60 parts, preferably from 5 to 40 parts, more preferably from 10 to 25 parts, per 100 parts of PMMA.
• the impact modifiers used are for example: DURASTRENGTH ® D320 from Arkema; IRH 70 from MITSUBISHI (soft / hard bilayer with butadiene-butyl acrylate copolymer soft core and hard PMMA bark); KM-355 from ROHM and HAAS.
• this comprises a block copolymer of formula BA n composed of: a polymer block B comprising by weight at least 60% of at least one (meth) acrylic monomer having a T g of less than -5 0 C, and n polymer blocks a, connected to the polymer block B by covalent bonds, wherein n denotes an integer between 1 and 10, comprising by weight at least 60% of at least one monomer
• this is obtained from a mixture M B comprising by weight at least 60%, advantageously at least 70%, preferably at least 80% of at least one (meth) acrylic monomer having a T 0 lower than -5 ° C.
• (meth) acrylic is less than -15 ° C., more preferably less than -25 ° C.
• the (meth) acrylic monomer of the polymer block B is the
• butyl (meth) acrylate 2-ethylhexyl or octyl.
• the mixture M B comprises: from 60% to 100%, advantageously from 70% to 100%, preferably from 80% to 100% of at least one (meth) acrylic monomer having a T 3 of less than -5 ° C. for respectively
• the copolymerizable comonomer is a (meth) acrylic monomer different from the (meth) acrylic monomer of T g lower than -5 ° C. or a vinylaromatic monomer.
• the weight-average molecular weight of the B block is between 40,000 and 200,000 g / mol, advantageously between 50,000 and 150,000 g / mol (expressed in PMMA equivalents).
• sequences A these are obtained from a mixture M A comprising by weight at least 60%, advantageously at least 70%, preferably at least 80% of at least one (meth) acrylic monomer having a T g greater than 0 0 C.
• the (meth) acrylic monomer of the polymer blocks A is methyl methacrylate.
• the mixture M A comprises:
• the copolymerizable comonomer is a (meth) acrylic monomer different from the (meth) acrylic monomer of T g greater than 0 ° C. or a vinylaromatic monomer.
• the weight-average molecular weight of each of the A blocks is between 10,000 and 100,000 g / mol, advantageously between 30,000 and 60,000 g / mol (expressed in PMMA equivalents).
• Sequence B has a T g lower than -5 ° C., preferably less than -15 ° C., and even more preferentially lower than -25 ° C.
• Sequences A have a T g greater than 0 ° C., preferably greater than 0 ° C. 25 0 C, even more preferably greater than 50 0 C.
• Those skilled in the art can choose the monomers constituting sequences A and B to adjust their T 3 . In particular, he can use Fox's law (see: Bulletin of the American Physical Society 1, 3, page 123 (1956)).
• the sequence B and the sequences A will be chosen so that they are incompatible, that is to say as they have a Flory-Huggins% AB interaction parameter at room temperature. .
• the intermediate ductile layer (III) may also comprise a core-shell impact additive whose proportion varies from 0 to 60 parts, preferably from 0 to 30 parts, per 100 parts of block copolymer.
• the intermediate ductile layer has the function of reinforcing the impact resistance of the plastic structure / protective layer assembly. Indeed, when applying a protective layer based on PMMA which is a brittle material, on a structural plastic, the impact resistance of the assembly is lower than that of the structural plastic alone and is substantially equivalent to that of the protective layer. A crack initiated in the PMMA layer propagates unabated to the structural plastic and damages it. In the presence of the intermediate ductile layer, the impact resistance of the assembly is maintained or even improved compared to the structural plastic because, in this case, the crack is stopped by the intermediate ductile layer.
• a block copolymer consists of macromolecules having several contiguous polymer sequences, chemically different that is ie derived from different monomers or derived from the same monomers but in different distributions.
• the copolymer may be linear, star or comb (brush copolymer).
• the copolymer is a triblock copolymer of formula ABA.
• the block polymers can be prepared by so-called living polymerization. It may be a group transfer polymerization using a silylketene-Lewis acid coupling system as described in Japanese Application JP 62-292806. It may also be a controlled radical polymerization technique such as NMP (Nitroxide-Mediated Polymerization), ATRP (Atom Transfer Radical Polymerization) or RAFT (Reversible Addition-Fragmentation Chain Transfer). Information on these techniques can be found in the following publications: DA Shipp et al., "Water-borne block copolymer synthesis and a simple and effective one-pot synthesis of acrylate-methacrylate block copolymers by atom transfer radical polymerization," Am. Chem. .
• the living anionic polymerization can also be a living anionic polymerization.
• the living anionic polymerization is initiated by an organic compound of an alkali metal or alkaline earth such as for example n-butyl lithium, sec-butyllithium, 1,1-diphenylhexyl lithium or fluorenyllithium.
• Control of the polymerization can be improved by combining the initiator with an aluminum compound and optionally with a Lewis base such as an ether or an amine.
• the aluminum compound is preferably a monoaryloxydialkylaluminum or a bis (aryloxy) monoalkylaluminum such as for example isobutylbis (2,6-di-t-butyl-4-methylphenoxy) aluminum or diisobutyl (2,6-di- t-butyl-4-methylphenoxy) aluminum.
• the Lewis base is, for example, chosen from the following list: dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether, anisole; 1,2-dimethoxyethane, 1,2-diethoxyethane, 1,2-diisopropoxyethane, 1,2-dibutoxyethane, 1,2-diphenoxyethane, 1,2-dimethoxypropane, 1,2-diethoxypropane, 1,2-diisopropoxypropane, 1, 2-dibutoxypropane, 1,2-diphenoxypropane, 1,3-dimethoxypropane, 1,3-diethoxypropane, 1,3-diisopropoxypropane, 1,3-dibutoxypropane, 1,3-diphenoxypropane, 1,4-dimethoxybutane, 1,4 diethoxybutane, 1,4-diisopropoxybutane, 1,4-dibutoxybutane, 1,4-diphenoxybutane,
• the NMP type polymerization is used to prepare the block copolymer in the presence of an alkoxyamine of formula ZT n in which Z denotes a multivalent group and T denotes a nitroxide.
• Z denotes a multivalent group, that is to say a group capable of releasing several radical sites after activation. The activation in question occurs by breaking the covalent ZT bonds.
• Z may be chosen from the following groups (I) to (VIII):
• R 3 and R 4 are identical or different, represent an alkyl radical linear or branched with a number of carbon atoms ranging from 1 to 10, phenyl or thienyl radicals optionally substituted with a halogen atom such as F, Cl, Br or with a linear or branched alkyl radical having a number of carbon atoms ranging from 1 to 4, or else by nitro, alkoxy, aryloxy, carbonyl or carboxy radicals; a benzyl radical, a cycloalkyl radical having a number of carbon atoms ranging from 3 to 12, a radical containing one or more unsaturations; B represents a linear or branched alkylene radical having a number of carbon atoms ranging from 1 to 20; m is an integer from 1 to 10;
• R 5 and Re which are identical or different, represent aryl, pyridyl, furyl or thienyl radicals optionally substituted by a halogen atom such as F, Cl, Br, or by an alkyl radical, linear or branched, having a number of carbon atoms ranging from 1 to 4, or alternatively by nitro, alkoxy, aryloxy, carbonyl or carboxy radicals;
• D represents a linear or branched alkylene radical having a number of carbon atoms ranging from 1 to 6, a phenylene radical or a cycloalkylene radical; p being an integer from 1 to 10;
• R 7 , R 8 and R 9 which are identical or different, have the same meanings as R 3 and R 4 of the formula (I), q, r and s are integers ranging from 1 to 10;
• Rn has the same meaning as the radical Ri 0 of the formula (IV) and v is an integer between 2 and 6 wherein R 12 , R 13 and R 14 ; identical or different, represent a phenyl radical, optionally substituted with a halogen atom such as Cl, Br, or with a linear or branched alkyl radical having a number of carbon atoms ranging from 1 to 10; W is oxygen, sulfur, selenium, w is zero or 1;
• R 15 -CH-CO-CH 2 -CH-R 16 (VII) wherein R 5 has the same meaning as R 3 of the formula (I), Ri ⁇ has the same meaning as R5 or Re of formula (II) ;
• R 1 and R 6 which are identical or different, represent a hydrogen atom, a linear or branched alkyl radical having a number of carbon atoms ranging from 1 to 10, an aryl radical, optionally substituted with a halogen atom or a hetero atom.
• stable free radical denotes a radical that is so persistent and non-reactive with respect to air and moisture in the ambient air that it can be handled and stored for a much longer period than the majority free radicals (see Accounts of Chemical Research 1976, 9, 13-19).
• the stable free radical is thus distinguished from free radicals whose lifetime is ephemeral (from a few milliseconds to a few seconds) such as free radicals from conventional polymerization initiators such as peroxides, hydroperoxides or azo initiators.
• Free radicals initiating polymerization tend to accelerate polymerization whereas stable free radicals generally tend to slow it down. It can be said that a free radical is stable within the meaning of the present invention if it is not a polymerization initiator and if, under the usual conditions of the invention, the average lifetime of the radical is at least one minute.
• T is represented by the structure:
• Ri 9, R20, R21, R22, R24 and R 2 4 denote groups: linear or branched C 1 -C 2 0, preferably C1-C1 0 such as methyl, ethyl, propyl, butyl, isopropyl, isobutyl substituted or unsubstituted, substituted or unsubstituted, substituted or unsubstituted C 6 -C 30 aryls, such as C 1 -C 30 saturated benzyl, aryl (phenyl) cyclic, and wherein the groups R 19 and R 22 may be part of a ring structure R 19 CNC-R 2 2 optionally substituted which can be chosen from: in which x denotes an integer between 1 and 12.
• R a and Rb denoting identical or different alkyl groups having from 1 to 40 carbon atoms, optionally linked to each other so as to form a ring and optionally substituted with hydroxyl, alkoxy or amino groups,
• R L denoting a monovalent group of molar mass greater than 16 g / mol, preferably greater than 30 g / mol.
• the group R 1 may, for example, have a molar mass of between 40 and 450 g / mol. It is preferably a phosphorus group of general formula (XI):
• X and Y which may be the same or different, may be selected from alkyl, cycloalkyl, alkoxyl, aryloxyl, aryl, aralkyloxy, perfluoroalkyl, aralkyl and may include from 1 to 20 carbon atoms; X and / or Y may also be a halogen atom such as a chlorine, bromine or fluorine atom.
• R L is a phosphonate group of formula:
• R c and R d are two identical or different alkyl groups, optionally linked so as to form a ring, comprising from 1 to 40 carbon atoms, optionally substituted or not.
• the R L group may also comprise at least one aromatic ring such as the phenyl radical or the naphthyl radical, substituted for example by one or more alkyl radicals comprising from 1 to 10 carbon atoms.
• nitroxides of formula (X) are preferred because they make it possible to obtain good control of the radical polymerization of (meth) acrylic monomers as taught in WO 03/062293.
• Alkoxyamines of formula (XIII) having a nitroxide of formula (X) are therefore preferred:
• R a and R b denote identical or different alkyl groups having from 1 to 40 carbon atoms, optionally linked to each other so as to form a ring and optionally substituted with hydroxyl, alkoxy or amino groups;
• RL denotes a monovalent group of molar mass greater than 16 g / mol, preferably greater than 30 g / mol.
• the group R L may for example have a molar mass of between 40 and 450 g / mol. It is preferably a phosphorus group of general formula (XI):
• X and Y which may be identical or different, may be selected from alkyl, cycloalkyl, alkoxyl, aryloxy, aryl, aralkyloxy, perfluoroalkyl, aralkyl, and may comprise from 1 to 20 carbon carbon; X and / or Y may also be a halogen atom such as a chlorine, bromine or fluorine atom.
• R L is a phosphonate group of formula:
• R c and Ra are two identical or different alkyl groups, optionally linked so as to form a ring, comprising from 1 to 40 carbon atoms, optionally substituted or not.
• the group R L may also comprise at least one aromatic ring such as the phenyl radical or the radical naphthyl, substituted for example with one or more alkyl radicals having 1 to 10 carbon atoms.
• N-tert-butyl-1-phenyl-2-methylpropyl nitroxide N- (2-hydroxymethylpropyl) -1-phenyl-2-methylpropyl nitroxide; N-tert-butyl-1-dibenzylphosphono-2,2-dimethylpropyl nitroxide; N-tert-butyl-1-di (2,2,2-trifluoroethyl) phosphono-2,2-dimethylpropyl nitroxide; N-tert-butyl [(1-diethylphosphono) -2-methylpropyl] nitroxide; N- (1-methylethyl) -1-cyclohexyl-1- (diethylphosphono) nitroxide; N- (1-phenylbenzyl) - [(1-diethylphosphono)
• nitroxide of formula (XIV) is particularly preferred:
• N-tert-butyl-1-diethylphosphono-2,2-dimethylpropyl nitroxide commonly referred to as SG1 for simplicity.
• This nitroxide makes it possible to effectively control the polymerization of the (meth) acrylic monomers.
• the alkoxyamines can be prepared by recipes described for example in US590549 or in FR99.04405.
• Alkoxyamines that can be used in the context of the invention are represented below:
• the alkoxyamine DIAMS is the preferred alkoxyamine.
• a process for obtaining the BA n block copolymer comprises the following steps:
• the sequence B is prepared by heating the mixture M B in the presence of at least one alkoxyamine ZT n , the heating being carried out at a temperature sufficient to activate the alkoxyamine and polymerize the mixture M B until a conversion of at least 60%,
• sequences A are prepared by heating the sequence B obtained in step 1 in the presence of the mixture M A , the heating being carried out at a temperature sufficient to activate the sequence B and polymerize the mixture M A.
• the initiation of the polymerization leading to the sequence B is carried out with the alkoxyamine ZT n .
• the initiation of the polymerization leading to the A sequences is achieved by the reactivation of the B sequence.
• a nitroxide identical or different from that which is worn on the alkoxyamine.
• the molar proportion of the added nitroxide relative to the alkoxyamine ZT n is between 0 and 20%, preferably between 0 and 10%.
• the conversion to monomer (s) of the mixture M B in step 1 is between 60 and 100%.
• the conversion is between 60 and 95%, advantageously between 70 and 95%.
• all or part of the non-converted monomer (s) may be removed under vacuum, possibly by heating.
• the radical initiator may be introduced at each stage before or after the preparation of the corresponding sequence (s).
• the control of the polymerization is not perfect and that the mixture of monomer (s) leading to the A blocks also partly leads to a polymer A of the same composition as the A sequences.
• a composition comprising from 50 to 100 parts of AB n block copolymer and from 0 to 100 parts of polymer A having the same composition as the A blocks.
• This composition can also be used for the intermediate ductile layer.
• the radical initiator is introduced before the preparation of a sequence (for example, in the case of the sequence B, if it is added to the mixture M B and the alkoxyamine ZT n ), it will be chosen so that it does not interfere with the preparation of the sequence.
• the radical initiator is selected so that it has a temperature Ti / 2 , i h (i.e., the temperature to have a half-life time of 1 h) which is 0 C greater than the activation temperature of the alkoxyamine ZT n or of the sequence B.
• the radical initiator may be an organic or inorganic initiator such as a persulfate.
• the azobisisobutyronitrile or Luperox ® 546 are two examples of suitable radical initiators.
• Each of the steps of the process can be carried out according to a mass process, in solution in a solvent or in an aqueous dispersed medium (emulsion, suspension).
• the two stages can be carried out in an aqueous dispersed medium or only in step 2.
• the B-block will have been previously prepared at the stage 1 according to a mass method or in solution in a solvent.
• An example of a process for the preparation of the BA n block copolymer in an aqueous dispersed medium in which the B sequence has previously been prepared by a mass process or in solution in a solvent comprises the following steps: a) the water is introduced, at least a dispersing agent, the sequence B and the mixture M A , b) the mixture M A is polymerized by heating at a temperature sufficient to activate the sequence B, c) recovering the block copolymer BA n .
• the dispersing agent is a compound which stabilizes the emulsion or suspension. It may be for example a surfactant or a protective colloid.
• the block copolymer is recovered in the form of particles whose size depends on the operating conditions and the process used (emulsion, suspension).
• the copolymer is advantageously granulated, for example by means of an extruder.
• radical initiator it is possible to introduce a radical initiator before and / or at the end of step b). If the radical initiator is introduced before step b), it is preferably chosen so that it does not interfere with sequence B in the polymerization of the mixture M A. It is preferably chosen so that its temperature T1 / 2, 1 h (that is to say, the temperature to have a half-life time of 1 h) is 20 ° C higher than the temperature of reactivation of sequence B.
• the transfer agent may be the octyl mercaptan.
• the intermediate ductile layer (II) and the protective layer (I) may each comprise one or more additives chosen from:
• matting agents which may be mineral fillers such as for example talc, calcium carbonate, titanium dioxide, zinc oxide or organic fillers such as for example crosslinked beads based on styrene and / or MMA (examples of such beads are given in EP 1174465).
• the intermediate ductile layer (II) and the protective layer (III) may each comprise at least one anti-UV.
• the proportion of anti-UV in the intermediate ductile layer (II) or in the protective layer (III) is from 0 to 10 parts, advantageously from 0.2 to 10 parts, preferably from 0.5 to 5 parts, anti-UV for 100 parts of polymer.
• a list of useful UV-stabilizers can be found in the document "Plastics Additives and Modifiers Handbook, chap. 16, Environmental Protective Agents ", J. Edenbaum, Ed., Van Nostrand, pp. 208-271, incorporated by reference into the present application.
• the anti-UV is a compound of the family of HALS, triazines, benzotriazoles or benzophenones. Combinations of several anti-UV agents can be used to obtain better UV resistance. Examples of UV used include TINUVIN ® 770, Tinuvin ® 328, Tinuvin ® P or TINUVIN ® 234.
• the intermediate ductile layer (II) and the protective layer (III) may each comprise at least one pigment.
• the proportion of the pigment in the intermediate ductile layer (II) or in the protective layer (III) is from 0 to 20 parts, advantageously from 0.2 to 10 parts, of preferably from 0.5 to 5 parts, of pigment per 100 parts of polymer.
• a list of useful pigments can be found in the document "Plastics Additives and Modifiers Handbook, Section VIII, Colorants", J. Edenbaum, Ed., Van Nostrand, pp. 884-954, incorporated by reference into the present application. 'examples of suitable pigments include titanium dioxide (white), clay (beige), metal particles (metallic effect) or the particles of mica treated in the Iriodin trade mark ® marketed by MERCK.
• ASA copolymer acrylic-styrene-acrylonitrile sold by GE PLASTICS particular under the trademark GELOY ®
• polystyrene crystal or shock
• PE polyethylene
• PC polycarbonate
• Multilayer structure It can also be mixtures of two or more plastics from the above list.
• it may be a PPO / PS or PC / ABS blend.
• the multilayer structure comprises in the order: a protective layer (I) comprising a PMMA, optionally a pigmented layer (II), an intermediate ductile layer (III) comprising a block copolymer of formula BA n composed of: polymer block B comprising by weight at least 60% of at least one (meth) acrylic monomer having a T 9 lower than -5 ° C., and - n polymer A sequences, linked to the polymer block B by covalent bonds, n denotes an integer between 1 and 10, comprising by weight at least 60% of at least one (meth) acrylic monomer having a T g greater than 0 ° C.,
• the intermediate ductile layer (III) comprises at least one pigment and the protective layer (I) is transparent and without any pigment.
• a pigmented layer (II) can be placed between the protective layer (I) and the intermediate ductile layer (III).
• the pigmented layer (II) comprises at least one pigment dispersed in a thermoplastic resin which is preferably a PMMA. The proportion of pigment varies from 1 to 50 parts of pigment per 100 parts of acrylic polymer.
• the protective layer (I) has a thickness of between 10 and 500 ⁇ m, preferably between 50 and 200 ⁇ m.
• the intermediate ductile layer (II) has a thickness of between 100 and 1000 ⁇ m, preferably between 100 and 400 ⁇ m.
• the optional pigmented layer (II) has a thickness of between 10 and 80 ⁇ m, preferably between 10 and 50 ⁇ m.
• the set of layers (I), (II) and (III) may have a thickness greater than 310 microns.
• the multilayer structure can be obtained by hot compression of the layers (I) to (IV).
• a multi-injection technique consisting of injecting into the same mold the melts constituting the layers.
• the molten materials are injected simultaneously into the mold.
• a 2nd technique a movable insert is located in the mold. By this insert, a melt is injected into the mold, and then the moving insert is moved to inject another melt.
• the preferred technique is coextrusion which relies on the use of as many extruders as there are layers to extrude. This technique is more flexible than the previous ones and makes it possible to obtain multilayer structures even for complicated geometries, for example profiles. It also allows to have excellent mechanical homogeneity.
• the coextrusion technique is a known technique in thermoplastics processing (see, for example, Precis of Plastics, Structures-Properties, 1989, Implementation and Standardization 4th Edition, Nathan, 126). US 5318737 discloses an example of coextrusion with a structural plastic.
• the method consists in protecting a structural plastic by superimposing in the order by coextrusion, hot compression or multiinjection: • a protective layer (I) comprising a PMMA, • optionally a pigmented layer (II), • an intermediate ductile layer (III) comprising a block copolymer of the formula BA n composed of: a polymer block B comprising by weight at least 60% of at least one (meth) acrylic monomer having a T g lower than -5 ° C., and n sequences polymer A, linked to the polymer block B by covalent bonds, n denoting an integer of between 1 and 10, comprising by weight at least 60% of at least one (meth) acrylic monomer having a T g greater than 0 ° C. • a layer of the structural plastic (III).
• the method consists in protecting a structural plastic by coextruding in the order:
• the multilayer structure of the invention can be used for the manufacture of objects and articles of everyday life. It can be for example:
• PVC is advantageously used as structural plastic in the manufacture of parts which are intended for exterior applications such as building doors, gutters, window moldings or cladding.
• the degradation of PVC under the effect of UV rays causes a color change (especially in dark shades such as blue or black) and / or decreased resistance to impact.
• PVC panels generally contain as a UV stabilizer titanium dioxide which also acts as a white pigment.
• the proportion of titanium dioxide is generally of the order of 3%, which makes it difficult to obtain dark shades. Panels can only be dyed in light or pastel shades.
• the invention solves the problem of coloring and / or UV protection of PVC outer facade panels while preserving the impact resistance of PVC.
• the invention therefore also relates to an exterior facade panel comprising in order:
• a protective layer (I) comprising a PMMA, optionally a pigmented layer (II),
• An intermediate ductile layer (III) comprising a block copolymer of formula BA n composed of: a polymer block B comprising by weight at least 60% of at least one (meth) acrylic monomer having a T g of less than -50 %; C, and n polymer sequences A, linked to the polymer block B by covalent bonds, n denoting an integer of between 1 and 10, comprising by weight at least 60% of at least one (meth) acrylic monomer having a T g greater than 0 0 C,
• a layer of PVC the layers being arranged one above the other in the order (I) to (IV) indicated.
• the total thickness of the layers (I) and (III) is greater than 310 microns.
• ABS is advantageously used as structural plastic in the manufacture of housings or casings, in particular household appliances, license plates, refrigerator outer panels or carosseriè parts.
• ABS has a gloss in the range of 40-50 at an angle of 60 °. Thanks to the invention, it is possible to obtain a gloss between 70 and 95, preferably between 85 and 90 at an angle of 60 ° while maintaining the impact resistance of ABS and protecting the ABS.
• Multilayer structures were obtained by coextrusion and then evaluated using a rapid bending test. Notched Izod shock was also measured on some samples.
• the multilayer structures were made on a trilayer co-extrusion line AMUT brand.
• a lamella layer distribution block was used for coextrusion and a 650 mm wide coat rack. Calibration of the structure was carried out on a vertical grille consisting of three independently thermoregulated rolls.
• the ABS is extruded at a temperature between 245 and 255 0 C using a 70 mm diameter machine, length equal to 32D provided with a degassing well.
• the extruder used for the layer of the triblock copolymer has a diameter of 30 mm and a length of 24D.
• the temperature is regulated at approximately 250 ° C.
• the surface PMMA is extruded with an extruder with a diameter of 30 mm and a length of 25 ° C. at a temperature of approximately 250 ° C. as well.
• Resilience expressed in kJ / m 2 , is measured on ABS specimens protected or not by an acrylic protective layer. Resilience is measured using a fast bending test. The specimen is flexed in the middle of the span at a constant speed.
• the load applied to the specimen is measured.
• the bending test is carried out at constant speed on the MTS-831 servo-hydraulic equipment.
• the force is measured by means of a piezoelectric cell embedded in the nose of the striker 569.4 N.
• the displacement of the specimen during the stress is measured by an LVDT sensor on the hydraulic cylinder of 50 mm range.
• Joule is representative of the energy supplied to the system when loading.
• the flexural strength, denoted Re is the breaking energy relative to the central cross section of the bar expressed in kJ / m 2 .
• Bars corresponding to the dimensions below are manufactured using a Charlyrobot CRA digital milling machine from multilayer structures. 6 bars per plate are cut.
• the specimen dimensions are:
• the applied loading speed is 0.1 m / s.
• the face in contact with the firing pin is ABS.
• the thin layer is stressed in tension.
• the copolymer 1 was prepared by mass polymerization while the triblock copolymers 2 and 3 were prepared in suspension in water.
• the triblock copolymer 1 is prepared by bulk polymerization. 6000 g of butyl acrylate, 35 g of the DIAMS alkoxyamine and 1 g of SG1 nitroxide are introduced into a metal reactor equipped with mechanical stirring and a jacket. The temperature of the mixture is raised to 115 ° C. After 225 minutes, the conversion is 60% and the butyl polyacrylate has a number average weight of 66960 g / mol, by weight of 128300 g / mol and a polymolecularity index of 1.9.
• the viscous mixture temperature is 90 0 C.
• a product composed of PMMA-b-poly (butyl acrylate) -PMMA is thus obtained.
• Triblock copolymer 2 l st step preparing a solution comprising polybutyl acrylate living in MMA.
• butyl acrylate In a 20 liter reactor stirred at 200 rpm, 14000 g of butyl acrylate are polymerized at 117 ° C. in the presence of 140 g of DIAMINS to a conversion rate of 70%, measured by dry extract.
• Butyl polyacrylate has the following molecular weights in PMMA equivalent: average mass at the peak: 97220 g / mol average mass by number: 67810 g / mol average mass by weight: 106990 g / mol average mass in z: 148020 g / mol polymolecularity 1.6
• the copolymer is prepared in suspension in water.
• the polymer resulting from the polymerization of 2-acrylamido-2-methylpropanesulphonic acid neutralized with NaOH sodium hydroxide is used as dispersing agent.
• the dispersing agent is prepared according to Example 1 of US Pat. No. 5,733,992; it has a Brookfield viscosity of 4 Pa.s at 25 ° C.
• the dispersing agent is designated by PAMS in the following examples.
• the reaction mixture is brought to 100 ° C. for a period of 2 hours at the end of which a mixture of 3.7 g of octyl mercaptan diluted in 11.2 g of MMA is introduced.
• the reaction mixture is stirred at 100 ° C. for 1 hour.
• a solution of 1.35 g of Luperox ® 26R in 11.2 g of MMA mounting the reactor temperature to 105 0 C and held for 1 hour.
• the suspension is then cooled, filtered using a wringer, plumped with 7000 g of water, and then dewatered again. This is done 3 times.
• the triblock copolymer 2 is in the form of beads composed of PMMA-b-poly (butyl acrylate) -b-PMMA, with a mean diameter of 334 ⁇ m.
• Triblock Copolymer 3 Step 1 Preparation of a solution comprising living butyl polyacrylate and deactivated butyl polyacrylate in MMA
• butyl acrylate In a 20 liter reactor stirred at 200 rpm, 14000 g of butyl acrylate are polymerized at 117 ° C. in the presence of 140 g of DIAMINS to a conversion rate of 70%, measured by dry extract.
• Butyl polyacrylate has the following molecular weights in PMMA equivalent: average mass at the peak: 97220 g / mol average mass by number: 67810 g / mol average mass by weight: 106990 g / mol average mass in z: 148020 g / mol polymolecularity 1.6
• 4240 g of the above mixture is heated (that is to say comprising polybutyl acrylate and butyl acrylate) at 7O 0 C in the presence of 13.7 g AIBN 1 diluted in 30 g of butyl acrylate.
• An exotherm of approximately 25 ° C. is observed, that is to say that the temperature in the reactor increases to 95 ° C., then the reaction medium is maintained at 70 ° C. for 6 hours and then cooled to 30 ° C. 0 C, and diluted with MMA to obtain a solution comprising 45% by weight of butyl polyacrylate.
• This butyl polyacrylate corresponds to living butyl polyacrylate, that is to say reactivatable, and deactivated butyl polyacrylate.
• step 2 preparation of the triblock copolymer 3 7000 g of deionized water, 509 g of a 5.3% solution of PAMS and 0.37 g of sodium hydroxide are charged into a 20-liter reactor which has been degassed before and is purged with nitrogen. This solution is brought to 70 ° C. with stirring at 200 rpm. When the temperature reaches 70 ° C., a solution of 4218 g of the solution prepared in the previous step 1 is poured.
• the reaction mixture is brought to 100 ° C. for a period of 2 hours at the end of which a mixture of 3.7 g of octyl mercaptan diluted in 11.2 g of MMA is introduced.
• the reaction mixture is stirred at 100 0 C for 1 hour, then continuous way of introducing a mixture of 6.75 g of Luperox ® 26R and 247 g of MMA for 1 hour, then 1.35 g of Luperox ® 26R in 11.25 g of MMA, and the temperature of the reactor is raised to 105 0 C for 1 hour.
• the suspension is then cooled, filtered using a wringer, plumped with 7000 g of water and then dewatered again. This is done 3 times.
• the triblock copolymer 3 is in the form of beads composed of a mixture of PMMA-b-poly (butyl acrylate) -PMMA and poly (butyl acrylate), with a mean diameter of 168 ⁇ m.
• Figure 4 shows an AFM image of the product obtained. We notice that it has a nanostructuration (phase microseparation) with phases (see the points that appear in clear) whose size is less than 100 nm (the scale of the plate is 5 microns).
• reaction mixture is brought to 100 ° C. for a period of 2 hours, after which a mixture of 3.7 g of octyl mercaptan diluted in 11.2 g of
• the suspension is then cooled, filtered using a wringer, plumped with 7000 g of water and then dewatered again. This is done 3 times.
• the copolymer triblock 2 is in the form of beads whose average size is 209 microns. The triblock copolymer is then granulated.
• ABS alone has a resilience of 50.6 kJ / m 2 (ex.l). It drops when the ABS is covered by ALTUGLAS ® VO44 or DRT (ex.2 and 3).
• the structure of the ex. 10 has a high UV resistance thanks to TINUVIN ® P.
• ABS MAGNUM 3904 marketed by DOW, having a melt index of 1, 5 g / 10 min (23 O 0 C, 3, 8 kg) - thickness 3 mm

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• 2005
  • 2005-11-17 CN CNA2005800467802A patent/CN101102894A/zh active Pending
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