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
  • B32B27/06—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
  • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (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
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/40—Properties of the layers or laminate having particular optical properties
  • B32B2307/402—Coloured
  • B32B2307/4026—Coloured within the layer by addition of a colorant, e.g. pigments, dyes
• • 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
  • B32B2327/00—Polyvinylhalogenides
  • B32B2327/06—PVC, i.e. polyvinylchloride
• • 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
  • B32B2333/00—Polymers of unsaturated acids or derivatives thereof
  • B32B2333/04—Polymers of esters
  • B32B2333/12—Polymers of methacrylic acid esters, e.g. PMMA, i.e. polymethylmethacrylate
• • 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
  • B32B2355/00—Specific polymers obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of index codes B32B2323/00 - B32B2333/00
  • B32B2355/02—ABS polymers, i.e. acrylonitrile-butadiene-styrene polymers

Definitions

• the present invention relates to a method for protecting a structural plastic with an acrylic polymer.
• An intermediate ductile layer is disposed between the structural plastic and the protective layer.
• the invention also relates to the multilayer structure obtained from the process and to the uses of the multilayer structure.
• acrylic polymers are ideally suited to protect structural plastics.
• structural plastics also have a better gloss characteristic of acrylic polymers.
• the protective layer must adhere perfectly to the plastic to be protected in order to guarantee a good level of protection to the course of time.
• the plastic protected by the protective layer must also maintain its resistance to impact.
• the film comprises an acrylic surface layer (A), a layer (B3) made from a block copolymer and a possible acrylic layer (C).
• 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 ⁇ m, or even preferably at 100 ⁇ m, 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 an acrylic film. It also provides thicker protective structures.
• the European application EP 1174465 A1 describes a multilayer structure comprising a substrate covered with a surface layer composed of an acrylic copolymer, which is preferably a copolymer based on methyl 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. 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.
• US Pat. No. 6,239,226 B1 describes a block copolymer that can be used to form a layer on the surface of various types of plastics such as ABS, ASA, PVC, impact PS or impact-reinforced PMMA. There is no mention of the protective surface layer (I).
• the invention relates to a method for protecting a structural plastic consisting of superposing in order by coextrusion, hot compression or multiinjection:
• a protective layer (I) comprising a PMMA
• 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 9 of less than -5 0 C, and n polymer sequences A, connected to the polymer block B by covalent bonds, n designating 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, "a layer of the plastic structure (IV).
• the invention also relates to a multilayer structure obtained from the process.
• 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: polymeric 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 blocks A, linked to the polymer block B by covalent bonds, n designating an integer 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 total thickness of the layers (I) and (III) is greater than 310 ⁇ m, preferably greater than 350 ⁇ m.
• the total thickness of the layers (I), (II) and (III) is greater than 310 ⁇ m, preferably 350 ⁇ m.
• the structural plastic is PVC or ABS.
• 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 9 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 Tg greater than 0 0 C, for the preparation of an intermediate ductile layer
• the invention also relates to the use of the multilayer structure for the manufacture of objects and articles of everyday life such as: housings or casings for lawnmowers, chainsaws, jet skis, household appliances ; car roof boxes, body parts; number plates; exterior wall panels of caravans and mobile homes; exterior panels of refrigerators; shower enclosure panels; building doors; window moldings; - cladding panels.
• 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 (III) and layer 4 to the plastic structure (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
• 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.
• T 9 denotes the glass transition temperature of a polymer.
• the T 9 of a monomer will be referred to as the T 9 of the homopolymer obtained by radical polymerization of said monomer.
• the term (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 acrylate, 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 acrylate, propyl acrylate, butyl acrylate or butyl methacrylate.
• PMMA 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. PMMA can also be prepared by anionic polymerization.
• the protective layer (I) comprises a PMMA.
• the PMMA melt index (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 9 to 25 0 C.
• 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
• the polymer T g of less than -5 ° C is obtained from a monomer mixture comprising 50 to 100 parts of at least one (meth) acrylate, C 1 -C O, from 0 to 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 polymer of T g 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.
• the C1-C10 alkyl (meth) acrylate is preferably butyl, 2-ethylhexyl, octyl acrylate.
• the C 1 -C 4 alkyl (meth) acrylate is preferably methyl methacrylate.
• the monomer monoins . aturea copolymerizable may be a C ⁇ -Cio 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 Ran.
• hard-soft-hard particles having a rigid core, an elastomeric intermediate layer and a hard bark.
• US 2004/0030046 A1 describes examples of such particles.
• 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 that are formed when the st step. 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 9 below -5 ° 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 monomer (meth) acrylic having a T g greater than 0 0 C.
• 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 9 lower than -5 ° C.
• the T 9 of the monomer 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 9 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 9 lower than -5 ° C. 1 . for respectively
• the copolymerizable comonomer is a (meth) acrylic monomer different from the monomer
• the copolymerizable monomer is not a conjugated diene.
• 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 MA comprising by weight at least 60%, preferably at least 70%, preferably at least 80% of at least one (meth) acrylic having a T 9 greater than 0 ° C.
• the T 9 of the (meth) acrylic monomer of the polymer blocks A is greater than 25 ° C., still more preferably greater than 50 ° C.
• the (meth) acrylic monomer of the A polymer blocks is methyl methacrylate.
• the sequences A can be identical or different.
• the mixture M A comprises:
• the copolymerizable comonomer is a (meth) acrylic monomer different from the (meth) acrylic monomer of T 9 greater than 0 ° C. or a vinylaromatic monomer.
• the copolymerizable monomer is not a conjugated diene.
• 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).
• the sequence B has a T 9 lower than -5 ° C, preferably less than -15 ° C, even more preferably less than -25 ° C.
• the A sequences have a T g greater than 0 ° C., preferably greater than 0 ° C. 25 ° C, still more preferably greater than 50 ° C.
• Those skilled in the art can choose the monomers constituting sequences A and B to adjust their T 9 . 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 block copolymer is nanostructured, i.e. phases are formed whose size is less than 100 nm, preferably 10 to 50 nm.
• 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 polymer sequences that are contiguous, chemically different, that is to say derived from different monomers or derived from the same monomers but in different distributions.
• the copolymer can be linear, star or comb (brush copolymer).
• 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 of the NMP (Nitroxide-Mediated Polymerization) type,
• 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 metal, 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 monoaryloxydialkylaluminium or a bis (aryloxy) monoalkylaluminum such as for example isobutylbis (2,6-di-t-butyl-4-methylphenoxy) aluminum or diisobutyl (2, ⁇ -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. Activation. in question occurs by breaking 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 by a halogen atom such as F, Cl, Br or by a linear or branched alkyl radical having a number of carbon atoms ranging from 1 to 4 or alternatively 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 comprising 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;
• R5 and Re which may be 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 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;
• R 10 has the same meaning as R 5 and R 6 of formula (II), t is an integer from 1 to 4, u is an integer of 2 to 6 (the aromatic group is substituted); in which Rn has the same meaning as the radical Ri 0 of the formula (IV) and v is an integer between 2 and ⁇
• R 12 , R 13 and R ⁇ 4 which are 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 (V II ) wherein R 15 has the same meaning as R 3 of the formula (I), R 16 has the same meaning as R 5 or Re of the formula ( II);
• R 1 and R 8 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.
• a stable free radical a radical so persistent and nonreactive towards air and moisture in the ambient air that it can be handled and stored for a much longer time than the majority of radicals (see in this regard, 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:
• R 1 9, R 2 O / R 21 , R 22 , R 24 and R 24 denote linear or branched C 3 -C 20 alkyl groups, preferably C 1 -C 10 groups, such as methyl, ethyl, propyl or butyl groups; isopropyl, isobutyl, tert-butyl, neopentyl, substituted or unsubstituted, substituted or unsubstituted C 6 -C 3 aryls such as benzyl, aryl (phenyl) cyclic saturated C 1 -C 30 and wherein R 19 and R 22 groups may be part of a cyclic structure
• R 9 R 22 -CNC-optionally substituted can be selected from:
• x denotes an integer between 1 and 12.
• R a and R J3 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 L may for example have a molar mass of between 40 and 450 g / mol.
• 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 connected 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. They make it possible to obtain higher molecular weights than nitroxides such as TEMPO. Alkoxyamines of formula (XIII) having a nitroxide of formula (X) are therefore preferred: in which :
• Z is a multivalent group
• 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;
• R L 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 chosen from alkyl, cycloalkyl, alkoxyl, aryloxyl, aryl, aralkyloxyl, perfluoroalkyl and aralkyl radicals and may comprise 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 Rd are two identical or different alkyl groups, optionally connected in a manner to form a ring, comprising 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.
• 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 5 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 Ma.
• the initiation of the polymerization leading to the sequence B is carried out by the alkoxyamine ZT n .
• the initiation of the polymerization leading to the A sequences is achieved by the reactivation of the B sequence.
• 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). In the case where the radical initiator is introduced after the preparation of the B block, it will be chosen so that it has a temperature T ⁇ / 2, h i (that is to say the temperature for a half-life time of 1 h) which is 20 0 C lower than the reactivation temperature of the B block.
• the radical initiator can be an organic or inorganic initiator such as, for example, a persulfate.
• the azobisisobutyronitrile or Luperox ® 546 are two examples of suitable radical initiators.
• control of the polymerization is not perfect and that the monomer mixture (s) resulting in the A sequences also lead in part 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 50 parts of polymer A having the same composition as the A. This composition can be used also for the intermediate ductile layer.
• 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 block has been previously prepared by a mass process or in solution in a solvent comprises the following stages using an alkoxyamine ZT n : a) introducing water, at least one dispersing agent, the sequence B and the mixture M A , b) polymerizing the mixture M A by heating to a temperature sufficient to activate the sequence B, c) recovering the block copolymer BA n .
• the dispersing agent is a compound that 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.
• step b It is possible to introduce a radical initiator before and / or at the end of step b). If the radical initiator is introduced between step a) and step b), that is to say before reactivation of the sequence B, it is preferably chosen so that its temperature Ti / 2 / i h (that is to say the temperature to have a half-life time of 1 h) is 20 0 C lower than the reactivation temperature of the sequence B.
• the transfer agent may be the octyl mercaptan.
• the protective layer (I), the optional pigmented layer (II) and the intermediate ductile layer (III) may each comprise one or more additives chosen from: • thermal stabilizers;
• matting agents which may be mineral fillers such as for example talc, calcium carbonate, titanium dioxide, zinc oxide or magnesium 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 protective layer (I), the optional pigmented layer (II) and the intermediate ductile layer (III) may each comprise at least one anti-UV.
• the proportion of anti-UV is from 0 to 10 parts, advantageously from 0.2 to 10 parts, preferably from 0.5 to 5 parts, of anti-UV per 100 parts of polymer.
• a list of useful anti-UVs 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 anti-UV used include TINUVIN ® 770, Tinuvin ® 328, Tinuvin ® P or TINUVIN ® 234.
• the protective layer (I) and the intermediate ductile layer (III) may each comprise at least one pigment.
• the proportion of the pigment is from 0 to 20 parts, advantageously from 0.2 to 10 parts, 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.
• pigments that can be used mention may be made of titanium dioxide (white), clay (beige), particles metallized effect) or treated mica particles of the brand IRIODIN ® marketed by MERCK.
• ASA copolymer acrylic-styrene-acrylonitrile sold by GE PLASTICS particular under the trademark GELOY ®
• PE polyethylene
• PC polycarbonate
• plastics from the previous list it may be mixtures of two or more plastics from the previous list.
• it may be a PPO / PS or PC / ABS blend.
• the invention relates to a method for protecting a structural plastic.
• the method consists in protecting a structural plastic by superimposing in the order by coextrusion, by hot compression, by multiinjection: • 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 9 of less than -50 %; C, and
• Hot compression of the layers is a usable technique.
• the multiinjection technique consists of injecting into the same mold the melts constituting each of the layers. According to the technical era of multiinjection, the molten materials are injected simultaneously into the mold. According to 2 Technical Similarly, a movable insert is located in the mold. By this insert, a melt is injected into the mold, and then the movable 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 (for more details, see the book Principles of Polymer Processing of Z. Tadmor, Wiley edition, 1979). 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 technique of coextrusion is a technique known thermoplastic processing (see, e.g., Precis plastics, Patterns properties 1989 implementation and standardization 4th edition, Nathan, p. 126).
• US 5318737 discloses an example of coextrusion with a structural plastic. The method consists in protecting a structural plastic by coextruding in the order:
• the total thickness of the layers (I) and (III) is greater than 310 ⁇ m, preferably 350 ⁇ m.
• the total thickness of the layers (I), (II) and (III) is greater than 310 ⁇ m, preferably 350 ⁇ m.
• 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: 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 polymer blocks A, linked to the polymer block B by bonds covalentes, n denoting 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., • a layer of plastic of structure (IV), 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 ⁇ m, preferably greater than 350 ⁇ m.
• the total thickness of the layers (I), (II) and (III) is greater than 310 ⁇ m, preferably 350 ⁇ m.
• the layers (I) to (IV) are coextruded, hot-compressed or multi-injected.
• the protective layer (I) is transparent and without any pigment and the intermediate ductile layer (III) comprises at least one pigment.
• the pigmented layer (II) comprises at least one pigment dispersed in a thermoplastic polymer, which is preferably a PMMA.
• the proportion of pigment varies from 1 to 50 parts of pigment per 100 parts of thermoplastic polymer.
• the protective layer (I) has a thickness of between 10 and 1000 ⁇ m, preferably between 50 and 200 ⁇ m.
• the intermediate ductile layer (III) 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 multilayer structure in particular that obtained by one of the processes described above, 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 change of color (especially in dark shades such as blue or black) and / or a decrease in its 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.
• ABS is advantageously used as structural plastic in the manufacture of housings or casings, in particular household appliances, license plates, refrigerator outer panels or bodywork 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.
• the invention therefore also relates to a multilayer structure comprising in the following order:
• a layer of PVC or ABS the layers being arranged one above the other in the order (I), (II), (III), PVC or ABS indicated.
• the total thickness of the layers (I) and (III) is greater than 310 ⁇ m, preferably greater than 350 ⁇ m.
• the multilayer structure is a cladding panel.
• the multilayer structure is a bodywork part.
• Multilayer structures were obtained by coextrusion and then evaluated using a flexural test fast. Notched Izod shock was also measured on some samples.
• the multilayer structures were made on a three-layer 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 triblock copolymer layer 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 ° 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. During the test, the load applied to the 1 test piece. 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 one specimen during the stress is measured by an LVDT sensor on the hydraulic cylinder of 50 mm range.
• 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 dimensions of the specimen, in millimeters, are:
• the applied loading speed is 0.1 m / s.
• the face in contact with the striker is the ABS.
• the thin layer is stressed in tension.
• Triblock Copolymers Three triblock copolymers were prepared. 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 mass of 66960 g / mol, by weight of 128300 g / mol and a polymolecularity index of 1.9. All butyl acrylate is stripped under vacuum.
• a product composed of PMMA-b-poly (butyl acrylate) -PMMA is thus obtained.
• butyl acrylate In a 20 liter reactor stirred at 200 rpm, 14000 g of butyl acrylate were polymerized at 117 ° C. in the presence of 140 g of DIAMINS to a conversion level 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
• 2nd step preparation of the triblock copolymer 2
• 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. 20 g of deionized water, 509 g of a 5.3 wt.% Solution of PAMS and 0.37 g of NaOH were charged to a 20 liter reactor which had been degassed and purged with nitrogen. The mixture is brought to 70 ° C. with stirring at 200 rpm. 4230 g of the butyl polyacrylate solution are poured into the MMA prepared in step 1.
• the 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 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
• 14,000 g of butyl acrylate are polymerized at 117 ° C. in the presence of 140 g of DIAMINS to a conversion level 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 70 ° C in the presence of 13.7 g of AIBN in 30 g diluted 1 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
• 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).
• the reaction mixture is heated at 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 MMA is introduced.
• the reaction mixture was stirred at 100 c C for 1 hour.
• a mixture of 15 g of Luperox ® 531 and 100 g of MMA at one time is introduced a mixture of 15 g of Luperox ® 531 and 100 g of MMA at one time, and then the reactor temperature is raised to 12O 0 C for 2 hours.
• the reactor is cooled to 95 ° C. and a solution of 4.5 g of potassium persulfate in 150 ml of water is introduced in one go.
• the reaction mixture is maintained at 95 ° 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 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 (230 ° C., 3.8 kg) - thickness 3 mm

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