Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
  • C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
  • C08G81/028—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G containing polyamide sequences
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
  • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
  • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
  • C08L33/12—Homopolymers or copolymers of methyl methacrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
  • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
  • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L87/00—Compositions of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
  • C08L87/005—Block or graft polymers not provided for in groups C08L1/00 - C08L85/04

Definitions

• the present invention relates to a graft copolymer comprising a flexible polymer block (which can also be called a soft block) and at least one rigid polymer block (which may also be called a hard block), the rigid polymer block or blocks. carrying polyamide grafts (PA).
• PA polyamide grafts
• Such a graft copolymer is obtained by the reaction with an amine or acid-terminated polyamide of a copolymer comprising the flexible polymer block and the rigid polymer block or blocks, this or these rigid polymer blocks being functionalized.
• the graft copolymer is a hard-soft-hard type copolymer whose end blocks, in particular based on methyl methacrylate (MMA), carry the grafts of PA.
• thermomechanical properties and good chemical resistance, as well as, under particular conditions, good transparency are obtained which has good thermomechanical properties and good chemical resistance, as well as, under particular conditions, good transparency.
• Polymethylmethacrylate is a material that is valued for its excellent optical properties. However, it is limited in terms of thermomechanical behavior because its glass transition temperature (denoted T g ) is 105 ° C.
• EP 0 500 361 A2 describes the PMMA / PA alloys made using a graft copolymer obtained by melt reaction of a PMMA carrying glutaric anhydride functions and an amine-terminated polyamide as a compatibilizer of a mixture. PMMA and PA.
• the graft copolymer can be prepared in situ during the manufacture of the alloy.
• EP 0 438 239 A2 describes the use as a compatibilizing agent of a graft copolymer obtained by melt reaction of a PMMA bearing glutaric anhydride functions and a polyamide.
• EP 0 537 767 A1 describes a material obtained by the reaction of a PMMA carrying glutaric anhydride functions, a thermoplastic resin which may be a polyamide and a copolymer bearing epoxide functional groups.
• FR 2 868 785 A discloses a graft copolymer consisting of a PMMA trunk and polyamide grafts having a number-average molecular mass of between 1000 and 10,000 g / mol, and a material comprising this graft polymer, which material has both transparency and thermomechanical and chemical resistance.
• a first object of the present invention is a graft copolymer consisting of a trunk formed of a block copolymer of general formula:
• A is a rigid polymer block with a glass transition temperature greater than 0 ° C .
• B is a flexible polymer block of glass transition temperature below 0 ° C; and n is 1 or is a natural number greater than 1, the blocks A, when n is 2 or more, which may be the same or different, and polyamide graft (PA) carried by the rigid polymer block or blocks, the graft copolymer obtained being represented by the general formula:
• Ag is block A carrying at least one graft (PA); and m and p are natural whole numbers whose sum is equal to n, p being able to be equal to 0, however.
• identical A blocks is meant identical blocks of identical chemical nature since they are obtained from the same starting monomer composition.
• the composition and the molar mass of the blocks A indicated as identical may vary from one block A to the other.
• Another subject of the invention relates to the process for preparing the graft copolymer as defined above, characterized in that it consists in reacting with a polyamide terminated with a primary or acid amine function a copolymer of formula general B- (A) n , A, B and n being as defined above and the block or A bearing functionalities capable of reacting with primary amine or acid functions of the polyamide.
• Another subject of the invention relates to a material comprising the graft copolymer according to the invention.
• Yet another subject of the invention relates to the use of the graft copolymer according to the invention or of the material comprising it.
• the index "f" associated with the notation of a polymer block means that this block is functionalized, allowing it to react with the graft polyamide.
• FIGS. la. and Ib are TEM microscopy pictures of a functionalized triblock copolymer material P (MMAf-b-BA-b-MMAf) prior to polyamide grafting;
• FIGS. 2a to 2c are TEM micrographs of the grafted triblock copolymer material obtained in Example 2;
• Figures 3, 5 and 7 each show DMA conservation modulus curves for different samples of triblock copolymer material grafted with the invention and for the functionalized triblock copolymer before the grafting of the polyamide, FIG. 7 also containing the curve for a polyamide which has been used for the grafting;
• Figures 4a are TEM microscopy pictures of a functionalized triblock copolymer material P (MMAf-b-BA-b-MMAf) prior to polyamide grafting;
• FIGS. 2a to 2c are TEM micrographs of the grafted triblock copolymer material obtained in Example 2;
• Figures 3, 5 and 7 each show DMA conservation modul
• FIGS. 4d are TEM micrographs of grafted triblock copolymer materials Examples 2, 4 and 5 respectively and the material consisting of a PMMAf grafted with a polyamide;
• Figures 6a. at 6d are TEM micrographs of grafted triblock copolymer materials Examples 6, 5, 7 and 8, respectively.
• the trunk copolymer of formula B- (A) n is in particular a copolymer whose A blocks have a T g greater than 0 ° C., in particular greater than or equal to 50 ° C., advantageously greater than or equal to 80 ° C., and the block B has a T g lower than 0 ° C., in particular less than or equal to -1 0 ° C., advantageously less than or equal to -30 ° C.
• the monomers composing blocks A and B can be chosen from vinyl, vinylidene, diene, olefinic and alkylic monomers, the person skilled in the art knowing how to combine them to obtain the desired T g for each of them.
• vinyl monomers acrylic acid or its alkali or alkaline earth metal salts, such as sodium, potassium or calcium, (meth) acrylates, vinylaromatic monomers, vinyl esters, (meth) acrylonitrile, (meth) acrylamide and mono- and di- (C1-18 alkyl) - (meth) acrylamides, and monoesters and diesters of maleic anhydride and maleic acid.
• the (meth) acrylates are in particular those of the formulas respectively:
• R 0 is chosen from alkyl radicals comprising from 1 to 18 carbon atoms, linear or branched, primary, secondary or tertiary, cycloalkyl comprising from 5 to 18 carbon atoms, (alkoxy with 1 to 18 carbon atoms) - alkyl with 1 to 18 carbon atoms, (alkylthio with 1 to 18 carbon atoms) -alkyl with 1 to 18 carbon atoms, aryl and arylalkyl, these radicals being optionally substituted by at least one halogen atom (such as fluorine) and / or at least one hydroxyl group after protecting this hydroxyl group, the above alkyl groups being linear or branched; and (meth) acrylates of glycidyl, norbornyl, isobornyl.
• alkyl radicals comprising from 1 to 18 carbon atoms, linear or branched, primary, secondary or tertiary, cycloalkyl comprising from 5 to 18 carbon atom
• methacrylates examples include methyl, ethyl, 2,2,2-trifluoroethyl, n-propyl, isopropyl, n-butyl, sec-butyl and tertiary methacrylates.
• acrylates of the above formula mention may be made of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl and tert. -butyl hexyl, 2-ethylhexyl, isooctyl, 3,3,5-trimethylhexyl, nonyl, isodecyl, lauryl, octadecyl, cyclohexyl, phenyl, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, perfluorooctyl.
• the term "vinylaromatic monomer” means an ethylenically unsaturated aromatic monomer such as styrene, vinyltoluene, alpha-methylstyrene, methyl-4-styrene, methyl-3-styrene or methoxy-4-styrene. hydroxymethyl-2-styrene, ethyl-4-styrene, ethoxy-4-styrene, dimethyl-3,4-styrene, chloro-2-styrene, chloro-3-styrene, chloro 4-methyl-3-styrene, tert. 3-butyl-styrene, 2,4-dichloro-styrene, 2,6-dichloro-styrene and 1-vinyl-naphthalene.
• Vinyl esters include vinyl acetate, vinyl propionate, vinyl chloride and vinyl fluoride.
• vinylidene monomer vinylidene fluoride is mentioned.
• diene monomer is meant a diene chosen from linear or cyclic dienes, conjugated or non-conjugated, such as butadiene, 2,3-dimethyl-butadiene, isoprene, 1,3-pentadiene, 1, 4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,9-decadiene, 5-methylene-2-norbornene, 5-vinyl-2-norbornene, 2-alkyl-2, 5-norbonadienes, 5-ethylene-2-norbornene, 5-
• (2-propenyl -2-norbornene, 5- (5-hexenyl) -2-norbornene, 1,5-cyclooctadiene, bicyclo [2,2,2] octa-2,5-diene, cyclopendatiene, 4, 7, 8, 9-tetrahydroindene and 1-isopropylidene tetrahydroindene.
• Olefinic monomers include ethylene, butene, hexene and 1-octene.
• the fluorinated olefinic monomers can also be mentioned.
• n is 1 or is advantageously a natural number from 2 to 20.
• n at least 2
• all the blocks A are identical and / or all the blocks A g are identical.
• P O.
• triblock triblock copolymers ABA giving the graft copolymers A g -B-
• the blocks A are methacrylic functional blocks, predominantly comprising methyl methacrylate (MMA) units.
• the or each methacrylic block A may thus comprise from 70 to 99.5%, advantageously from 80 to 99.5%, and preferably from 85 to 99.5%, by weight, of MMA units.
• the or each block A thus comprises at least one unit carrying at least one function that has allowed the grafting and selected from acid, acid salt, anhydride or epoxide functions, advantageously from the acid and anhydride functions.
• the or each unit carrying at least one functional group chosen from acid, acid salt, anhydride and epoxide functions is especially chosen from:
• the units resulting from at least one monomer comprising a C C double bond, copolymerizable with the main monomer forming the block A concerned and bearing at least one functional group chosen from acid, acid salt, anhydride and epoxide functions; ; and the glutaric anhydride units of formula:
• R 3 and R 4 denote H or a methyl radical.
• the or each block A comprises at least one glutaric anhydride unit and / or at least one acrylic acid unit and / or at least one methacrylic acid unit.
• the or each block A can thus comprise, by weight, from 0.5 to 30%, advantageously from 0.5 to 20%, preferably from 0.5 to
• the pattern or patterns carrying at least one function acid, acid salt, anhydride or epoxide, advantageously at least one acid and / or anhydride function.
• a monomer carrying at least one acid function By way of example of a monomer carrying at least one acid function, mention may be made of 2-acrylamido-2-methylpropanesulphonic acid, vinylsulphonic acid, styrene sulphonic acid and l-allyloxy acid. 2-hydroxypropane sulfonic acid, alkyl allyl sulfosuccinic acid, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid.
• the acrylic acid is acrylic acid or methacrylic acid because these two monomers copolymerize very well with MMA.
• Methacrylic acid is particularly preferred. Indeed, when the copolymerization is conducted in an aqueous dispersed medium, the acrylic acid remains largely solubilized in water, which is not the case with methacrylic acid.
• the groups carrying an acid function are then as follows:
• the acid salt function can be obtained by known techniques.
• a monomer carrying at least one acid salt function is therefore of a monomer carrying at least one acid function by a neutralization reaction.
• a monomer carrying at least one acid salt function is derived from a monomer carrying at least one acid function from the preceding list.
• the cation of the acid salt can be for example Li + , Na + , K + , a quaternary ammonium salt.
• aliphatic glycidyl esters or aliphatic glycidyl ethers such as allyl glycidyl ether, vinyl glycidyl ether, maleate and glycidyl itaconate, and acrylate and glycidyl methacrylate
• alicyclic glycidyl esters or alicyclic glycidyl ethers such as 2-cyclohexene-1-glycidyl ether, cyclohexene-4,5-diglycidylcarboxylate, cyclohexene-4-glycidyl carboxylate, 5-norbornene 2-methyl-2-glycidyl carboxylate and endocis-bicyclo (2,2,1) -5-heptene-2,3-diglycidyl dicarboxylate.
• Glycidyl methacrylate is a preferred mono
• the comonomer (a) may be chosen for example from the following monomers:
• the or each block A may be based on MMA and include, by weight:
• the or each block A may be based on MMA and comprise, by weight: • from 80 to 99.5% of MMA;
• each MMA-based block A may comprise, by weight:
• the copolymerization can take place in bulk, in solution in a solvent, or in a dispersed medium (suspension, emulsion, miniemulsion).
• a methacrylic functional block A may also comprise glutaric anhydride groups represented by the formula:
• R 3 and R 4 denote H or a methyl radical.
• a methacrylic functional block A comprising glutaric anhydride groups is prepared from acrylic or methacrylic acid, the conversion of acid functions to glutaric anhydride functions is often incomplete.
• the methacrylic functional block therefore comprises both glutaric anhydride groups and acrylic or methacrylic acid groups (which have not reacted to give glutaric anhydride functions).
• This type of methacrylic functional block is very particularly preferred because the glutaric anhydride groups are very reactive, especially with the primary amine functions.
• the glutaric anhydride groups are introduced more easily into the methacrylic functional block than by the direct copolymerization of MMA with maleic anhydride or with another monomer carrying an anhydride group.
• the relative proportion of acid functions and glutaric anhydride functions depends on the content of initial acid functions and the conditions of the dehydration (temperature, reaction time, pressure, presence or absence of a catalyst, etc.).
• the overall content of the acid functions and glutaric anhydride functions is between 0.5 and 30%, advantageously between 0.5 and 20%, preferably between 0.5 and 15%.
• the relative proportion (by weight) of the glutaric anhydride functions with respect to the glutaric anhydride functions and the acid functions ie the weight percentage of glutaric anhydride functions / (glutaric anhydride functions + acid functions)) is as for it between 1 and 100%, preferably between 10 and 90%, more preferably between 50 and 90%.
• block B it advantageously comprises butyl acrylate units or mainly butyl acrylate units.
• the average molecular weight (M w) of the block copolymer B (A) n is generally between 10 000 and 500 000 g / mol.
• M w is between 50000 and 200000 g / mol because on the one hand the very small masses may affect the glass transition temperature (T g ) of the polymer while the very high masses affect its fluidity and make its transformation in the molten state difficult.
• T g glass transition temperature
• the person skilled in the art knows how to adjust the average molecular weight by weight, for example by introducing a transfer agent and / or using the parameter polymerization temperature.
• the polyamide this may be a homopolyamide or a copolyamide terminated by a primary amine function or an acid function.
• it is a primary amine function, which has a good reactivity with respect to acid, acid, anhydride or epoxide functions.
• the primary amine function is very reactive with respect to the acid or anhydride functions.
• the polyamide has a melting temperature of between 100 and 300 ° C., preferably between 140 and 250 ° C.
• homopolyamide is meant the condensation products of a lactam (or the corresponding amino acid) or a diacid with a diamine (or their salts). It does not take into account the chain limiter which can be a diacid, a monoacid, a diamine or a monoamine in the case of lactams and another diacid or another diamine in the case of polyamides resulting from the condensation of a diamine with a diacid.
• copolyamide is meant the precedents in which there is at least one monomer more than necessary, for example two lactams or a diamine and two acids or a diamine, a diacid and a lactam.
• the polyamide is chosen from PA 6, PA 6-6, PA 11, PA 12 and their copolymers.
• PA 6 because this polyamide provides a good resistance to the solvent by its crystallinity and a good thermomechanical resistance.
• the copolyamide results from the condensation of at least two alpha-omega aminocarboxylic acids or of at least two lactams having from 6 to 12 carbon atoms or a lactam and an aminocarboxylic acid which do not have the same number of carbon atoms.
• the copolyamide of this first type may also include units which are residues of diamines and dicarboxylic acids.
• dicarboxylic acid By way of example of a dicarboxylic acid, mention may be made of diacids such as isophthalic, terephthalic, adipic, azelaic, suberic, sebacic, nonanedioic and dodecanedioic acids.
• a diamine By way of example of a diamine, mention may be made of hexamethylenediamine, dodecamethylenediamine, metaxylylenediamine, bis-p-aminocyclohexylmethane and trimethylhexamethylenediamine.
• alpha-omega-aminocarboxylic acid mention may be made of aminocaproic acid, aminoundecanoic acid and aminododecanoic acid.
• lactam examples include caprolactam, oenantholactam and laurolactam.
• the copolyamide results from the condensation of at least one alpha-omega-aminocarboxylic acid (or a lactam), at least one diamine and at least one dicarboxylic acid.
• the alpha-omega-aminocarboxylic acid, the lactam and the dicarboxylic acid can be chosen from those mentioned above.
• the diamine may be a branched aliphatic diamine, linear or cyclic or arylic.
• hexamethylenediamine piperazine, isophorone diamine (IPD), methyl pentamethylenediamine (MPDM), bis (aminocyclohexyl) methane (BACM), bis (3-methyl-4-aminocyclohexyl) methane
• R 5 is hydrogen or a linear or branched alkyl group containing up to 20 carbon atoms
• Re is a group having up to 20 carbon atoms linear or branched alkyl or alkenyl
• a cycloaliphatic radical limiting may be by for example, laurylamine or oleylamine.
• the polyamide terminated with a primary amine or acid function has a number-average molecular weight (M n ) of between 1000 and 50000 g / mol, more preferably between 1000 and 40 000 g / mol, advantageously between 1000 and 30 000 g / mol, preferably between 1000 and 20000 g / mol.
• M n is therefore given in PMMA equivalents.
• the preferred monofunctional polymerization limiters are laurylamine and oleylamine.
• the polyamides can be manufactured according to methods known to man of the art, for example by polycondensation in an autoclave. The polycondensation is carried out at a temperature generally between 200 and 300 0 C, under vacuum or under an inert atmosphere, with stirring of the reaction mixture.
• the average chain length of the polyamide is determined by the initial molar ratio between the polycondensable monomer or the lactam and the chain limiter. For the calculation of the average chain length, there are usually a chain limiter molecule to a chain of f oligomer.
• the graft copolymer according to the invention may especially comprise the following characteristics: the number-average molecular mass of one or each A block is between 5000 and 100,000 g / mol, more preferably between 10,000 and 70,000 g / mol advantageously between 15,000 and 50,000 g / mol; the number-average molecular mass of block B is between 5000 and 100,000 g / mol, more preferably between 5000 and 60,000 g / mol, advantageously between 5,000 and 40,000 g / mol, preferably between 10,000 and 40 000 g / mol; and the number-average molecular mass of the polyamide grafts is between 1000 and 50 000 g / mol, more preferably between 1000 and 40 000 g / mol, advantageously between 1000 and 30 000 g / mol, preferably between 1000 and 20,000 g / mol.
• the weight ratio of the copolymer B- (A) n as defined above to the polyamide (PA) grafts is in particular from 10
• the graft copolymer according to the invention is obtained by the reaction of the copolymer B- (A) n (with the functionalized block or blocks A) and the polyamide terminated by a primary or acidic amine function. If the polyamide is terminated by a primary amine function, the A blocks are preferably carrying acid functions, acid salts, anhydride or epoxide. If the polyamide is terminated by an acid function, the A blocks are preferably carrying epoxide functions.
• a graft copolymer consisting of a trunk and polyamide grafts is formed (for more details on the graft copolymers, reference may be made to Kirk-Othmer, Encyclopaedia of Chemical Technology, 3 rd edition, Volume 6, page 798).
• the amounts of functional PMMA and polyamide that are introduced, as well as the conditions of the reaction a graft copolymer that is more or less rich in grafts can be obtained.
• block A g there is generally, in block A g , from 1 to 100, preferably from 1 to 50, polyamide grafts (PA).
• PA polyamide grafts
• the reaction can be carried out in solution in a solvent or in a molten state.
• the reaction is conducted in the molten state because it avoids the use of solvent which must then be eliminated once the reaction is complete.
• the molten state also makes it possible to accelerate the speed of the reaction.
• Any mixing tool suitable for thermoplastics may be used.
• a twin-screw extruder, in particular a corotating twin-screw, is entirely suitable because it makes it possible to carry out the mixing in the molten state, can operate continuously and ensures good homogenization of the starting copolymer and the polyamide.
• the reaction is conducted at a temperature between 180 and 32O 0 C, preferably between 180 and 28O 0 C.
• the average residence time of the melt in the extruder f may be between 1 second and 15 minutes, rather between 1 second and 10 minutes. If an extruder is used, granules are recovered at the outlet of the extruder. These granules can then be put into the desired form (film, injected part, molded part, plate, ...) using a thermoplastic transformation tool known to those skilled in the art, for example an extruder.
• reaction from 5 to 90%, preferably from 10 to 50%, advantageously from 20 to 40%, of polyamide terminated with a primary or acidic amine function are used for 10 to 95%, respectively, of 50 to 90%. preferably from 60 to 80% of starting copolymer.
• the reaction of 20 to 40% of polyamide terminated with a primary or acidic amine function and 60 to 80% of starting copolymer makes it possible to obtain a material having a good transparency, A being based on MMA.
• reaction conditions by example contact time, temperature
• B- (A) n and polyamide copolymer it may remain the starting copolymer and / or the unreacted polyamide.
• the reaction therefore leads to a material consisting of: the graft copolymer of the invention; unreacted copolymer B- (A) n , or the A blocks carrying functional groups capable of reacting with primary or acidic amine functions; of polyamide terminated by a primary amine or unreacted acid function.
• the material consists, by weight: from 10 to 98% graft copolymer of the invention; from 1 to 50% of said unreacted (functional) copolymer B- (A) n ; from 1 to 50% of polyamide terminated by a primary amine or unreacted acid function; the total making 100%.
• the material consists of, by weight: 20 to 80% graft copolymer of the invention; from 5 to 50% of said unreacted (functional) copolymer B- (A) n ; from 5 to 50% of polyamide terminated with a primary amine or unreacted acid function; the total making 100%.
• the presence of starting copolymer and / or unreacted polyamide is not necessarily detrimental to the final properties of the material, it may even improve some of its properties.
• the unreacted starting copolymer has a high affinity with the trunk of the graft copolymer, the unreacted polyamide has a high affinity with graft copolymer grafts.
• the Applicant has found that, in the case in particular where A is based on MMA, the graft copolymer, like the starting functionalized copolymer, is organized in nanodomains, that is to say in domains whose average size is less than 100 nm. This organization makes it possible to obtain a homogeneous material having all the properties described above.
• a core-shell shock modifier (more commonly known as core-shell) can be added to the material to improve its impact resistance.
• This impact modifier is in the form of fine particles having an elastomer core and at least one thermoplastic shell, the size of the particles being generally less than 1 ⁇ m and advantageously between 50 and 300 nm.
• the impact modifier is prepared using emulsion polymerization. From 0 to 60%, preferably from 0 to 30% by weight, of the core-shell impact modifier with respect to the material is added to the material.
• the heart can be constituted for example:
• the vinyl monomer may be styrene, alkylstyrene, acrylonitrile or alkyl (meth) acrylate.
• the heart can be made up of:
• Copolymers of an alkyl (meth) acrylate with at most 30 mol% of a monomer chosen from another alkyl (meth) acrylate and a vinyl monomer
• the alkyl (meth) acrylate is advantageously butyl acrylate.
• the vinyl monomer may be styrene, alkylstyrene, acrylonitrile, butadiene or isoprene.
• the heart may be advantageously crosslinked in whole or in part. It suffices to add at least difunctional monomers during the preparation of the core, these monomers may be chosen from poly (meth) acrylic esters of polyols such as butylene di (meth) acrylate and trimethylolpropane trimethacrylate. Other difunctional monomers are, for example, divinylbenzene, trivinylbenzene, vinyl acrylate and vinyl methacrylate.
• the core may also be cross-linked by grafting or as a comonomer during the polymerization, unsaturated functional monomers such as unsaturated carboxylic acid anhydrides, unsaturated carboxylic acids and unsaturated epoxides.
• the bark or bark consists of a homopolymer of styrene, an alkylstyrene or methyl methacrylate or copolymers comprising at least 70 mol% of one of these monomers and at least one comonomer chosen from other previous monomers, another alkyl (meth) acrylate, vinyl acetate and acrylonitrile.
• the bark may be functionalized by introducing, by grafting or as comonomer during the polymerization, unsaturated functional monomers such as unsaturated carboxylic acid anhydrides, unsaturated carboxylic acids and unsaturated epoxides. Mention may be made, for example, of maleic anhydride, (meth) acrylic acid and glycidyl methacrylate.
• impact modifiers include core-shell copolymers having polystyrene bark and core-bark copolymers having a PMMA bark. There are also core - shell copolymers with two barks, one made of polystyrene and the other outside PMMA. Examples of impact modifiers, as well as their method of preparation, are described in the following patents: US 4,180,494, US 3,808,180, US 4,096,202, US 4,260,693, US 3,287,443, US 3,657,391, US 4,299,928, US 3,985,704, US 5,773,520.
• the core represents, by weight, 70 to 90% of the impact modifier and the bark of 30 to 10%.
• the impact modifier can be soft / hard type.
• an impact modifier of the soft / hard type mention may be made of the one consisting of: (i) from 75 to 80 parts of a core comprising in moles at least 93% of butadiene, 5% of styrene and 0.5 to 1% of divinylbenzene and
• a soft / hard impact modifier is the one having a core made of polybutyl acrylate or a butyl acrylate / butadiene copolymer and a PMMA bark.
• the impact modifier can also be of the hard / soft / hard type, that is to say that it contains in the order a hard heart, a soft bark and a hard bark.
• the hard parts may consist of the above soft / hard shell polymers and the soft part may consist of the above soft core polymers.
• hard / soft / hard impact modifier is that consisting of:
• the shock modifier can also be hard (heart) / soft / medium hard.
• the outer shell "half hard” consists of two barks: one intermediate and one outer.
• the intermediate bark is a copolymer of methyl methacrylate, styrene and at least one monomer selected from alkyl acrylates, butadiene and isoprene.
• the outer bark is a PMMA homopolymer or copolymer.
• the impact modifier and the material according to the invention are mixed using a mixing tool suitable for thermoplastics, for example an extruder.
• additives can also be added to the material. It can be anti-UV additive (s), antioxidant (s), release agent (s), lubricating agents (s) ...
• anti-UV additives examples are those described in US Pat. No. 5,256,472.
• Benzotriazoles and benzophenones are advantageously used.
• Tinuvin® 213 or Tinuvin® 109 and preferably Tinuvin® 234 or Tinuvin P® or Tinuvin 770® from Ciba Specialty Chemicals can be used.
• the graft copolymer and the material containing it can be used in the form of films, extruded parts blown, injected parts. It can also be in the form of extruded plates that are used for sanitary applications (manufacture of bathtubs, washbasins, shower tubs ). In the sanitary field, the chemical resistance and the crack resistance of the material are two appreciated properties.
• the graft copolymer and the material containing it according to the invention can also be converted into organic panes, window frames, pipes, air ducts, seals, etc.
• it can be used to manufacture decorative panels in automobiles, trucks, trains and planes.
• it can be used as injected parts in the sports shoe, golf clubs ... It can also find applications in the fibers for example as fiber optic coatings, but also in parts medical use, in the field of electrical and electronic applications, and more generally as technical polymers without excluding applications in the packaging.
• the graft copolymer and the material containing it according to the invention can also serve as a compatibilizing agent for obtaining an alloy based on a polyamide and a polymer chosen from PMMA, PVDF and PVC. and acrylic polymers.
• a corotative extruder it is possible to use a corotative extruder to carry out the mixing.
• the polymer of the alloy is PMMA or PVDF.
• the polyamide may be a PA 6, PA 6-6, PA 11 or PA 12.
• the polyamide of the alloy is of the same nature as the polyamide terminated by a primary amine or acid function which serves to obtain the grafts.
• the grafts are made of polyamide 12.
• PMMA denotes a homo- or copolymer of MMA comprising more than 50% by weight of MMA.
• PVDF denotes a homo- or copolymer of vinylidene fluoride (VF 2 ) comprising more than 50% by weight of VF 2 .
• the VF 2 is copolymerized with at least one comonomer chosen from compounds containing a vinyl group capable of opening to polymerize and which contains, directly attached to this vinyl group, at least one fluorine atom, a fluoroalkyl group or a fluoroalkoxy group.
• the alloy comprises:
• a polyamide that may be chosen from PA 6, PA 6-6, PA 11 or PA 12; From 10 to 90% of a polymer chosen from PMMA, PVDF, PVC and acrylic polymers.
• the graft copolymer or the material containing it, according to the invention can also serve as a coextrusion binder in a polyamide-based multilayer structure and a polymer chosen from PMMA, PVDF, PVC and acrylic polymers.
• the multilayer structure is thus composed in the order of the following layers: a layer of polyamide; a layer c2 of the material according to the invention; a layer c3 of a polymer chosen from PMMA, PVDF, PVC and acrylic polymers; the layers adhering to each other.
• the multilayer structure may be for example in the form of a film, a plate, a tube or a hollow body.
• each layer c1, c2 and c3 may have a thickness of between 2 and 300 microns, advantageously between 5 and 200 microns, preferably between 10 and 100 microns.
• the layer c 2 of the material according to the invention has a thickness of between 2 and 300 ⁇ m, preferably between 2 and 300 ⁇ m. and 100 ⁇ m.
• the other cl and c3 layers have a thickness greater than 100 microns, rather between 0.1 and 100 mm.
• P (MMA f -b-BA-b-MMAf) triblock copolymer whose end blocks are PMMAf blocks and the central block is a block of polybutyl acrylate, the methacrylic acid and dimethylglutaric anhydride groups constituting reactive sites;
• P (MMA f -b-BA-b-MMAf) -g-PA graft triblock copolymers of the invention
• Mn number average molecular weight
• Ip polymolecularity index (ratio of the weight average molar mass to the number average molar mass)
• Tf melting temperature
• Grafted triblock copolymer materials were prepared by reactive extrusion of P (MMA f -b-BA-b-MMA f) and a PA terminal primary amine function on a micro-extruder DACA 3 g capacity to 25O 0 C for 6 minutes at a rotation speed of 200 rpm under a nitrogen atmosphere.
• the samples were subjected to thermal annealing at 235 ° C. for 1 hour under vacuum.
• the characteristics of the copolymer P are as follows: Mn and I p, determined by SEC with PMMA as a standard, are respectively 70,000 g / mol and 2.1; the molar percentage of BA is 34%, evaluated by 1 H NMR; the molar percentages of MMA, MAA and dimethylglutaric anhydride are respectively 58%, 6% and 2%, evaluated by FTIR in solution in chloroform.
• the morphology of the copolymer P (MMAf-b-BA-b-MMAf) was studied by MET; two complementary markings were tested, namely: the ruthenium marking in the liquid phase which makes it possible to densify the butyl acrylate which appears in black in FIG. ; and
• the copolymer P (MMAf-b-BA-b-MMAf) has a lamellar morphology corrugated and interconnected without order at great distance, which can be described as labyrinth lamellar phase.
• PAl it is a monoamine PA6 of Mn 2550 g / mol having a T f of 218 ° C.
• PA2 it is a monoamine PA6 of Mn 5320 g / mol having a T f of 219 ° C.
• PA3 it is a monoamine PA6 of Mn 16500 g / mol having a T f of 222 0 C.
• thermomechanical behavior of the samples obtained was followed by DMA.
• the rods were pressed at 25O 0 C in the form of rectangular bars, then subjected to a bending deformation of 20 microns amplitude at a frequency of 1 Hz, between -80 and 25O 0 C with a ramp of 3 ° C / min.
• the storage module (E ') is measured using the TA Instrument DMA 9980 apparatus.
• the conservation modules obtained are given in MPa units.
• the test consists of observing the resistance of a rod placed in chloroform for three days at ambient temperature (the ring represents 3% by weight relative to chloroform).
• the assessment of the resistance is qualitative and consists in seeing if the ring keeps its shape or disintegrates in contact with the solvent. If the ring disintegrates, the chemical resistance is very bad, whereas if the ring keeps its shape, the chemical resistance is very good.
• the morphology was studied by MET at the extruder outlet or after annealing (1 hour at 235 ° C. under vacuum). The samples were microtomed at room temperature and then labeled: - or with ruthenium: the domains formed by the blocks of poly (butyl acrylate), of poly (methyl methacrylate) and the polyamide grafts appear respectively in black, white and gray ;
• BzOH the domains formed by the polyamide (free or in the form of grafts), and the blocks of poly (methyl methacrylate) and of poly (butyl acrylate) appear in black, gray and white respectively.
• Figures 2a and 2b show the morphology of the material of Example 2 at the extruder outlet, observed by MET: ruthenium labeling ( Figure 2a) and PTA / BzOH labeling ( Figure 2b).
• the graft material is therefore stable and the residual homopolymers are incorporated into the graft copolymer structure.
• the rods of the extrudates annealed at 235 ° C. under vacuum for 1 hour could be dissolved in benzyl alcohol at 130 ° C., which shows that the P (MMA f -b-BA -b-MMA f ) has not undergone irreversible crosslinking.
• the module at ambient temperature (20 ° C.) is slightly greater than the reference.
• a module tray appears above the transition temperature of the poly (methyl methacrylate) block from 30% PA-I in the material.
• the plateau results from the crystallinity of PA-I in the mixtures. The grafting has therefore taken place.
• Example 4 behaves like the material of Example 2.
• the material of Example 5 has an interesting behavior since it does not flow significantly beyond the glass transition of blocks of poly (methyl methacrylate).
• the value of the module tray above the Tg of poly (methyl methacrylate) blocks is much higher than in the other mixtures of the same composition.
• the materials (extrudates) obtained are relatively transparent with the exception of the material of Example 8.
• the grafted triblock materials of the invention have fine and homogeneous morphologies, whatever the size of the PA chains used.
• the graft triblock copolymer content is high and the residual polymers P (MMAf-b-BA-b-MMAf) and PA are well incorporated into the structure.
• the morphology of the mixtures hardly changed during the annealing (1 h at 235 ° C. under vacuum). These results differ from those obtained in the absence of the PBA central block.
• the structuring of P (MMA f -b-BA-b-MMA f ) therefore plays an important role on the grafting process and on the stability of the mixtures obtained.
• thermomechanical properties and solvent resistance are observed in the case of mixtures extruded with PA6 of large mass (15000 g / mol). This translates into DMA by a higher modulus at room temperature, a stable material up to Tg PMMA blocks and a high modulus up to PA melting for blends with 70% PA content. mass.

Landscapes

• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
• Compositions Of Macromolecular Compounds (AREA)

Applications Claiming Priority (1)

Publications (1)

Family

ID=38436815

Family Applications (1)

Country Status (4)

Families Citing this family (6)

Family Cites Families (7)

• 2006
  • 2006-12-01 US US12/516,934 patent/US20100063223A1/en not_active Abandoned
  • 2006-12-01 WO PCT/FR2006/051271 patent/WO2008065259A1/fr active Application Filing
  • 2006-12-01 JP JP2009538738A patent/JP2010511088A/ja active Pending
  • 2006-12-01 EP EP06842082A patent/EP2094767A1/fr not_active Withdrawn

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events