EP1144505A3 - Antistatic acrylic polymer compositions - Google Patents

Antistatic acrylic polymer compositions

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Publication number
EP1144505A3
EP1144505A3 EP00960806A EP00960806A EP1144505A3 EP 1144505 A3 EP1144505 A3 EP 1144505A3 EP 00960806 A EP00960806 A EP 00960806A EP 00960806 A EP00960806 A EP 00960806A EP 1144505 A3 EP1144505 A3 EP 1144505A3
Authority
EP
European Patent Office
Prior art keywords
copolymers
acid
parts
ethylene
acrylate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP00960806A
Other languages
German (de)
French (fr)
Other versions
EP1144505A2 (en
Inventor
Christophe Lacroix
Gilles Meunier
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Arkema SA
Original Assignee
Atofina SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from FR9911744A external-priority patent/FR2798666A1/en
Application filed by Atofina SA filed Critical Atofina SA
Publication of EP1144505A2 publication Critical patent/EP1144505A2/en
Publication of EP1144505A3 publication Critical patent/EP1144505A3/en
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/14—Copolymers of styrene with unsaturated esters
    • 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
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; 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
    • C08L2201/00—Properties
    • C08L2201/04—Antistatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • 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
    • C08L77/12—Polyester-amides

Definitions

  • the present invention relates to compositions of antistatic acrylic polymers and more specifically a composition comprising an acrylic polymer (A), a copolymer (B) containing polyamide blocks and polyether blocks essentially comprising ethylene oxide units ((C2H4— O) - and a polymer (C) chosen from acrylic impact modifiers and / or functional polymers.
  • Acrylic polymer (A) antistatic properties.
  • the formation and retention of static electricity charges on the surface of most plastics is known.
  • the presence of static electricity on thermoplastic films leads for example these films to stick to each other making their separation difficult.
  • the presence of static electricity on packaging films can cause the accumulation of dust on the objects to be packaged and thus hinder their use.
  • Acrylic resins such as for example PMMA are used to make various objects and in particular transparent objects. Static electricity causes the accumulation of dust on the surface of these objects which is troublesome for transparency.
  • antistatic agents such as ionic surfactants of the ethoxylated amine or sulfonate type which are added to polymers.
  • the antistatic properties of the polymers depend on the ambient humidity and they are not permanent since these agents migrate to the surface of the polymers and disappear.
  • antistatic agents copolymers with polyamide blocks and hydrophilic polyether blocks these agents have the advantage of not migrating and therefore of giving permanent antistatic properties and more independent of ambient humidity.
  • the aim of the present invention is to make commercially available acrylic resins permanently antistatic, ie (i) resins essentially consisting only of acrylic polymer or (ii) resins consisting of a mixture of polymer acrylic and a shock modifier.
  • Another object of the invention is also to improve the impact resistance, in particular multiaxial shock. With regard to transparent PMMA, the aim is also not to alter the transparency.
  • Japanese patent application JP 60 023 435 A published on February 6, 1985 describes antistatic compositions comprising 5 to 80% of polyetheresteramide and 95 to 20% of a thermoplastic resin chosen among others from polystyrene, ABS and PMMA, this resin being functionalized with acrylic acid or maleic anhydride.
  • a thermoplastic resin chosen among others from polystyrene, ABS and PMMA, this resin being functionalized with acrylic acid or maleic anhydride.
  • examples show compositions consisting of 60 to 70 parts of carboxylated PMMA and 40 to 30 parts of polyetheresteramide (per 100 parts).
  • Others show compositions consisting of 30 to 45 parts of carboxylated PMMA, 40 to 25 parts of PMMA and 30 parts of polyetheresteramide (per 100 parts).
  • Japanese patent application JP 03 237 149 A published on October 23, 1991 describes antistatic compositions consisting of 40 to 99% of an acrylic resin, 1 to 60% of polyetheresteramide and 0.2 to 15% of a grafted polymer having maleic anhydride or epoxide functions and a part soluble in acrylic resin.
  • the grafted polymer is complicated to prepare.
  • Japanese patent applications JP 08 253640 A published on October 1, 1996 and JP 04 146 947 A published on May 20, 1992 describe anti-static and transparent compositions made of acrylic resin, polyetheresteramide and salts. It is not desirable to add salts to such compositions because then during the use of the compositions they can migrate.
  • JP 05 295 213 A published on November 9, 1993 and JP 05 287 157 A published on November 2, 1993 describe anti-static and transparent compositions made up of acrylic resin, polyetheresteramide and optionally an electrolyte or sulphonic acid .
  • Japanese patent applications JP 05 078 543 A and JP 04 146 947 A describe anti-static and transparent compositions made of acrylic resin and polyetheresteramide. The mechanical properties of the base resin are greatly altered.
  • the present invention therefore relates to an antistatic composition with improved impact resistance comprising per 100 parts by weight:
  • C being a polymer chosen from acrylic impact modifiers, copolymers (C1) of low mass of styrene and of an acid anhydride unsaturated carboxylic, copolymers (C2) of ethylene and an unsaturated carboxylic acid anhydride, copolymers (C3) of ethylene and an unsaturated epoxide or their mixtures.
  • the invention is particularly useful for impact modified PMMA, ie a mixture of (A) and an acrylic impact modifier (C). It suffices to add thereto (B) to make this composition antistatic without it being necessary to add thereto one or more of the copolymers (C1) to
  • an acrylic polymer (A) mention may be made of homopolymers of an alkyl (meth) acrylate.
  • Alkyl (meth) acrylates are described in KIRK-OTHMER, Encyclopedia of chemical technology, 4th edition in Vol 1 pages 292-293 and in Vol 16 pages 475-478. Mention may also be made of copolymers of at least two of these (meth) acrylates and copolymers of at least one (meth) acrylate with at least one monomer chosen from acrylonitrile, butadiene, styrene, isoprene provided that the proportion of (meth) acrylate is at least 50 mol%, the invention is particularly useful for PMMA.
  • acrylic polymers are either made up of the monomers and possibly of the comonomers mentioned above and do not contain an impact modifier or they additionally contain an acrylic impact modifier.
  • the acrylic impact modifiers are, for example, random or block copolymers of at least one monomer chosen from styrene, butadiene, isoprene and at least one monomer chosen from acrylonitrile and alkyl (meth) acrylates. , they can be of core-shell type.
  • These acrylic impact modifiers can be mixed with the acrylic polymer (A) once prepared or be introduced during the polymerization of (A) or prepared simultaneously during the polymerization of (A).
  • the MFI (melt flow index) of (A) can be between 2 and 15 g / 10 min measured at 230 ° C under a load of 3.8 kg.
  • the amount of acrylic impact modifier can for example be from 0 to 30 parts per 100 to 70 parts of (A) and advantageously from 5 to 20 parts per 95 to 20 parts of (A).
  • polymers (B) containing polyamide blocks and polyether blocks result from the copolycondensation of polyamide blocks with reactive ends with polyether blocks with reactive ends, such as, inter alia:
  • polyetherdiols Polyamide sequences at the ends of dicarboxylic chains with polyoxyalkylene sequences at the ends of diamine chains obtained by cyanoethylation and hydrogenation of polyoxyalkylene alpha-omega dihydroxylated aliphatic sequences called polyetherdiols.
  • copolymers (B) are advantageously of this type.
  • polyamide sequences with dicarboxylic chain ends originate, for example, from the condensation of alpha-omega aminocarboxylic acids, lactams or dicarboxylic acids and diamines in the presence of a chain-limiting dicarboxylic acid.
  • the number-average molar mass Mn of the polyamide blocks is between 300 and 15,000 and preferably between 600 and 5,000.
  • the mass Mn of the polyether blocks is between 100 and 6,000 and preferably between 200 and 3,000.
  • polymers containing polyamide blocks and polyether blocks can also comprise units distributed randomly. These polymers can be prepared by the simultaneous reaction of polyether and precursors of polyamide blocks.
  • polyetherdiol, a lactam (or an alpha-omega amino acid) and a chain-limiting diacid can be reacted in the presence of a little water.
  • a polymer is obtained which essentially has polyether blocks, polyamide blocks of very variable length, but also the various reactants which have reacted randomly which are distributed statistically along the polymer chain.
  • polymers containing polyamide blocks and polyether blocks whether they originate from the copolycondensation of polyamide and polyether blocks prepared beforehand or from a reaction in one step, exhibit, for example, shore D hardnesses which may be between 20 and 75 and advantageously between 30 and 70 and an intrinsic viscosity between 0.8 and 2.5 measured in metacresol at 250 ° C for an initial concentration of 0.8 g / 100 ml.
  • the MFIs can be between 5 and 50 (235 ° C under a load of 1 kg)
  • polyetherdiol blocks are either used as such and copolycondensed with polyamide blocks with carboxylic ends, or they are aminated to be transformed into polyether diamines and condensed with polyamide blocks with carboxylic ends. They can also be mixed with polyamide precursors and a chain limiter to make polymers with polyamide blocks and polyether blocks having randomly distributed units.
  • the polyamide sequences with dicarboxylic chain ends originate, for example, from the condensation of alpha-omega aminocarboxylic acids, lactams or dicarboxylic acids and diamines in the presence of a chain-limiting dicarboxylic acid.
  • alpha omega aminocarboxylic acids mention may be made of aminoundecanoic acid, by way of example of lactam one can cite caprolactam and lauryllactam, as an example of a dicarboxylic acid, adipic acid, decanedioic acid and dodecanedioic acid may be mentioned, as an example of diamine, hexamethylene diamine may be mentioned.
  • the polyamide blocks are made of polyamide12 or of polyamide 6. The melting point of these polyamide blocks which is also that of the copolymer (B) is generally 10 to 15 ° C. below that of PA 12 or PA 6.
  • the polyamide sequences result from the condensation of one or more alpha omega aminocarboxylic acids and / or of one or more lactams having from 6 to 12 carbon atoms in the presence of a dicarboxylic acid having 4 to 12 carbon atoms and are of low mass, that is to say Mn from 400 to 1000.
  • alpha omega aminocarboxylic acid mention may be made of aminoundecanoic acid and aminododecanoic acid.
  • dicarboxylic acid By way of example of dicarboxylic acid, mention may be made of adipic acid, sebacic acid, isophthalic acid, butanedioic acid, 1,4 cyclohexyldicarboxylic acid, terephthalic acid, sodium salt or lithium sulphoisophthalic acid, dimerized fatty acids (these dimerized fatty acids have a dimer content of at least 98% and are preferably hydrogenated) and dodecanedioic acid HOOC- (CH 2 ) 10-COOH.
  • a lactam mention may be made of caprolactam and lauryllactam.
  • Caprolactam should be avoided unless the polyamide is purified from the monomeric caprolactam which remains dissolved therein.
  • Polyamide sequences obtained by condensation of lauryllactam in the presence of adipic acid or dodecanedioic acid and of mass Mn 750 have a melting temperature of 127-130 ° C.
  • the polyamide sequences result 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 can be an aliphatic diamine having from 6 to 12 atoms, it can be arylic and / or cyclic saturated.
  • Examples include hexamethylenediamine, piperazine, 1-aminoethylpiperazine, bisaminopropylpiperazine, tetramethylene diamine, octamethylene diamine, decamethylene diamine, dodecamethylene diamine, 1.5 diaminohexane, 2, 2,4-trimethyl-1, 6-diamino-hexane, polyols diamine, isophorone diamine (IPD), methyl pentamethylenediamine (MPDM), bis (aminocyclohexyl) methane (BACM), bis (3-methyl- 4 aminocyclohexyl) methane (BMACM).
  • IPD isophorone diamine
  • MPDM methyl pentamethylenediamine
  • ALM bis (aminocyclohexyl) methane
  • BMACM bis (3-methyl- 4 aminocyclohexyl) methane
  • the various constituents of the polyamide block and their proportion are chosen to obtain a melting temperature below 150 ° C. and advantageously between 90 and 135 ° C.
  • Copolyamides with low melting temperature are described in US Patents 4,483,975, DE 3,730,504, US 5,459,230, the same proportions of the constituents are used for the polyamide blocks of (B).
  • (B) can also be the copolymers described in US 5,489,667.
  • the polyether blocks can represent 5 to 85% by weight of (B).
  • the polyether blocks can contain other units than the ethylene oxide units, such as for example propylene oxide or polytetrahydrofuran (which leads to polytetramethylene glycol sequences).
  • PEG blocks can also be used simultaneously, that is to say those made up of ethylene oxide units, PPG blocks that is to say those made up of propylene oxide units and PTMG blocks that is to say those made up of units tetramethylene glycol also called polytetrahydrofuran.
  • PEG blocks or blocks obtained by oxyethylation of bisphenols, such as for example bisphenol A are used. These latter products are described in patent EP 613 919.
  • the amount of polyether blocks in (B) is advantageously from 10 to 50% by weight of (B) and preferably from 35 to 50%.
  • copolymers of the invention can be prepared by any means allowing the polyamide blocks and the polyether blocks to be attached. In practice, essentially two methods are used, one said in 2 steps, the other in one step.
  • the 2-step process consists first of all in preparing the polyamide blocks with carboxylic ends by condensation of the polyamide precursors in the presence of a chain-limiting dicarboxylic acid, then in a second step in adding the polyether and a catalyst. If the polyamide precursors are only lactams or alpha omega aminocarboxylic acids, a dicarboxylic acid is added. If the precursors already comprise a dicarboxylic acid, it is used in excess relative to the stoichiometry of the diamines. The reaction is usually carried out between 180 and 300 ° C, preferably 200 to 260 ° C, the pressure in the reactor is established between 5 and 30 bars, it is maintained for approximately 2 hours.
  • the pressure is slowly reduced by putting the reactor into the atmosphere and then the excess water is distilled, for example an hour or two.
  • the polyamide with carboxylic acid ends having been prepared, the polyether and a catalyst are then added.
  • the polyether can be added one or more times, as can the catalyst.
  • the polyether is first added, the reaction of the OH ends of the polyether and of the COOH ends of the polyamide begins with ester bond formations and elimination of water; Water is removed as much as possible from the reaction medium by distillation and then the catalyst is introduced to complete the bonding of the polyamide blocks and of the polyether blocks.
  • This second step is carried out with stirring preferably under a vacuum of at least 5 mm Hg (650 Pa) at a temperature such that the reagents and copolymers obtained are in the molten state.
  • this temperature can be between 100 and 400 ° C and most often 200 and 300 ° C.
  • the reaction is followed by measuring the torque exerted by the molten polymer on the agitator or by the measurement of the electric power consumed by the agitator. The end of the reaction is determined by the value of the target torque or power.
  • the catalyst is defined as being any product making it possible to facilitate the bonding of the polyamide blocks and of the polyether blocks by esterification.
  • the catalyst is advantageously a derivative of a metal (M) chosen from the group formed by titanium, zirconium and hafnium.
  • M represents titanium, zirconium or hafnium and the Rs, identical or different, denote alkyl radicals, linear or branched, having from 1 to 24 carbon atoms.
  • the alkyl radicals C-] to C24 from which are chosen the radicals R of the tetraalkoxides used as catalysts in the process according to the invention are for example such as methyl, ethyl, propyl, isopropyl, butyl, ethylhexyl, decyl, dodecyl, hexadodecyl .
  • the preferred catalysts are the tetraalkoxides for which the radicals R, identical or different, are alkyl radicals C-
  • the catalyst used in this process according to the invention can consist solely of one or more of the tetraalkoxides of formula M (OR) 4 defined above, it can also be formed by the association of one or more of these tetraalkoxides with one or more alkali or alkaline earth alcoholates of formula (R- O) pY in which R-
  • the amounts of alkali or alkaline earth alcoholate and of zirconium or hafnium tetraalkoxides as the the combined to form the mixed catalyst can vary within wide limits. However, it is preferred to use amounts of alcoholate and tetraalkoxides such that the molar proportion of alcoholate is substantially equal to the molar proportion of tetraalkoxide.
  • the proportion by weight of catalyst that is to say of the tetraalkoxide (s) when the catalyst does not contain alkali or alkaline earth alcoholate or else of all of the tetraalkoxide (s) and of alkali or alkaline alcoholates earthy when the catalyst is formed by the association of these two types of compounds, advantageously varies from 0.01 to 5% of the weight of the mixture of the polyamide dicarboxylic with the polyoxyalkylene glycol, and is preferably between 0.05 and 2% of this weight.
  • salts of the metal (M) in particular the salts of (M) and of an organic acid and the complex salts between the oxide of (M) and / or l hydroxide of (M) and an organic acid.
  • the organic acid can be formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauryac acid, acid myristic, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, cyclohexane carboxylic acid, phenylacetic acid, benzoic acid, salicylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, phthalic acid and crotonic acid.
  • Acetic and propionic acids are particularly preferred.
  • M is zirconium.
  • zirconyl salts These salts can be called zirconyl salts.
  • the Applicant without being bound by this explanation, believes that these zirconium and organic acid salts or the complex salts mentioned above release ZrO ++ during the process.
  • the product sold under the name of zirconyl acetate is used.
  • the quantity to be used is the same as for the derivatives M (OR) 4 .
  • all the reagents used in the two-step process are mixed, that is to say the polyamide precursors, the chain-limiting dicarboxylic acid, the polyether and the catalyst. These are the same reagents and the same catalyst as in the two-step process described above. If the polyamide precursors are only lactams, it is advantageous to add a little water.
  • the copolymer has essentially the same polyether blocks, the same polyamide blocks, but also a small part of the various reactants which have reacted randomly which are distributed statistically along the polymer chain.
  • the reactor is closed and heated with stirring as in the first step of the two-step process described above.
  • the pressure is established between 5 and 30 bars.
  • the reactor is placed under reduced pressure while maintaining vigorous stirring of the molten reactants.
  • the reaction is followed as above for the two-step process.
  • the catalyst used in the one-step process is preferably a salt of the metal (M) and an organic acid or a complex salt between the oxide of (M) and / or the hydroxide of (M) and an acid organic.
  • the unsaturated carboxylic acid anhydride can be chosen, for example, from maleic, itaconic, citraconic, allylsuccinic, cyclohex-4-ene-1, 2-dicarboxylic, 4-methylenecyclohex-4- anhydrides ene-1,2-dicarboxylic, bicyclo (2,2,1) hept-5-ene-2,3-dicarboxylic, and x - methylbicyclo (2,2,1) hept-5-ene 2,2-dicarboxylic .
  • maleic anhydride is used.
  • the number-average molar mass is between 800 and 10,000 and preferably between 1,000 and 3,500.
  • (C1) can be represented by the following formula:
  • copolymers in which MAH denotes maleic anhydride, m varies from 1 to 3 and n varies from 6 to 8.
  • MAH denotes maleic anhydride
  • m varies from 1 to 3
  • n varies from 6 to 8.
  • SMA® Resins sold under the name of SMA® Resins by the company ELF ATOCHEM.
  • copolymers (C2) they can be polyethylenes grafted with an unsaturated carboxylic acid anhydride or copolymers of ethylene and an unsaturated carboxylic acid anhydride which are obtained for example by radical polymerization.
  • polyethylene onto which the unsaturated carboxylic acid anhydride is grafted, polyethylene is understood to mean homo- or copolymers.
  • alpha-olefins advantageously those having from 3 to 30 carbon atoms; as examples of alpha olefins, mention may be made of propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3 -methyl-1-pentene, 1-octene, 1-dececene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1 - eicocene, 1-dococene, 1- tetracocene, 1-hexacocene, 1 - octacocene, and 1-triacontene; these alpha-olefins can be used alone or as a mixture of two or more than two,
  • esters of unsaturated carboxylic acids such as, for example, alkyl (meth) acrylates, the alkyls possibly having up to 24 carbon atoms, examples of alkyl acrylate or methacrylate are in particular methyl methacrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate and n-octyl acrylate.
  • - dienes such as, for example, 1,4-hexadiene.
  • the polyethylene can comprise several comonomers.
  • the polyethylene which can be a mixture of several polymers, comprises at least 50% and preferably 75% (in moles) of ethylene, its density can be between 0.86 and 0.98 g / cm 2.
  • the MFI viscosity index at 190 ° C, 2.16 kg is advantageously between 1 and 1000 g / 10 min.
  • LDPE low density polyethylene
  • HDPE high density polyethylene
  • LLDPE linear low density polyethylene
  • VLDPE very low density polyethylene
  • metallocene catalysis that is to say the polymers obtained by copolymerization of ethylene and of alphaolefin such as propylene, butene, hexene or octene in the presence of a monosite catalyst generally consisting of an atom of zirconium or titanium and two cyclic alkyl molecules linked to the metal. More specifically, metallocene catalysts are usually composed of two cyclopentadienic rings linked to the metal. These catalysts are frequently used with aluminoxanes as cocatalysts or activators, preferably methylaluminoxane (MAO). Hafnium can also be used as the metal to which cyclopentadiene is attached. Other metallocenes can include transition metals from groups IV A, V A, and VI A. Metals of the lanthamide series can also be used. - EPR elastomers (ethylene - propylene - rubber)
  • copolymers of ethylene and of the unsaturated carboxylic acid anhydride that is to say those in which the unsaturated carboxylic acid anhydride is not grafted
  • these are the copolymers of l ethylene, unsaturated carboxylic acid anhydride and optionally another monomer which can be chosen from the comonomers mentioned above for the ethylene copolymers intended to be grafted.
  • the ethylene-maleic anhydride and ethylene - alkyl (meth) acrylate - maleic anhydride copolymers are advantageously used. These copolymers comprise from 0.2 to 10% by weight of maleic anhydride, from 0 to
  • alkyl (meth) acrylate 40% by weight of alkyl (meth) acrylate.
  • Their MFI is between 1 and 50 (190 ° C - 2.16 kg).
  • the alkyl (meth) acrylates have already been described above.
  • the copolymer of ethylene and an unsaturated epoxide can be obtained by copolymerization of ethylene and an unsaturated epoxide or by grafting the unsaturated epoxide onto the polyethylene.
  • the grafting can be carried out in the solvent phase or on the molten polyethylene in the presence of a peroxide. These grafting techniques are known in themselves.
  • the copolymerization of ethylene and an unsaturated epoxide it is possible to use the so-called radical polymerization processes usually operating at pressures between 200 and 2,500 bars.
  • unsaturated epoxides there may be mentioned: aliphatic glycidyl esters and ethers such as allyl glycidyl ether, vinyl glycidyl ether, glycidyl itaconate and maleate, glycidyl (meth) acrylate, and alicyclic glycidyl esters and ethers such as 2-cyclohexene-1-glycidyl ether, cyclohexene-4,5-diglycidyl carboxylate, cyclohexene-4-glycidyl carboxylate, 5-norbomene-2-methyl-2-glycidyl carboxylate and endo cis-bicyclo (2,2,1) -5-heptene-2,3-diglycidyl dicarboxylate.
  • aliphatic glycidyl esters and ethers such as allyl glycidyl ether, vinyl glycidyl ether,
  • the copolymer (C3) is obtained from the grafting of a homo or copolymer polyethylene as described for (C2) except that an epoxy is grafted instead of an anhydride. Being a copolymerization it is also similar to (C2) except that an epoxide is used, there may also be other comonomers as in the case of (C2).
  • the copolymer (C3) is advantageously an ethylene / (meth) alkyl acrylate / unsaturated epoxide copolymer.
  • it can contain up to 40% by weight of alkyl (meth) acrylate and up to 10% by weight of unsaturated epoxide, preferably 0.1 to 8%.
  • the epoxide is advantageously glycidyl (meth) acrylate.
  • the alkyl (meth) acrylate is chosen from methyl (meth) acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate.
  • the amount of alkyl (meth) acrylate is advantageously from 20 to 35%.
  • the MFI is advantageously between 1 and 50 (in g / 10 min at 190 ° C. under 2.16 kg) This copolymer can be obtained by radical polymerization of the monomers.
  • the initial composition contains (A) and an acrylic impact modifier then it suffices to add (B), if the initial composition contains only (A) then it is necessary in addition to (B) to add one of the copolymers (C1 ) to (C3).
  • the amount of (C1), (C2) or (C3) is advantageously such that (B) / (C) by weight is between 2 and 10 and preferably between 4 and 6. A mixture of 2 of these can be used.
  • copolymers or of 3, as for the proportions in the ratio (B) / (C) (C) represents the sum of the quantities of (C1) to (C3) used.
  • Anti-statism increases with the proportion of (B) and for equal amounts of (B) with the proportion of ethylene oxide units contained in (B).
  • compositions in which (C) is an acrylic impact modifier advantageously 8 to 15 parts of (B) are used for 92 to 85 parts of (A) + (C) and preferably 8 to 11 parts of (B) for 92 to 89 parts of O 01 1
  • the invention is particularly useful for impact modified PMMA with an acrylic impact modifier.
  • mineral fillers talc, Ca3CO, kaolin, etc.
  • reinforcements fiberglass, mineral fiber, carbon fiber, etc.
  • stabilizers thermo, UV
  • flame retardants and dyes as long as they are not transparent polymers (A).
  • compositions of the invention are prepared by the usual techniques of thermoplastics such as for example by extrusion or using twin-screw mixers or even using a device of the type Ko-kneader BUSS®.
  • thermoplastics such as for example by extrusion or using twin-screw mixers or even using a device of the type Ko-kneader BUSS®.
  • the Applicant has found that in the case where (B) is added to (A) already containing an acrylic impact modifier, then it is not necessary to make an intimate mixture in an extruder or a mixer, to recover the compositions in the form granules or in the molten state and then introducing them into a molding or extrusion device; indeed it suffices to make a mixture of (A) containing the acrylic impact modifier and of (B) in the dry state in powder or granules (dry blend) then to introduce this mixture into the molding device or injection.
  • the present invention also relates to objects manufactured with the preceding compositions; these are for example films, tubes, plates, packaging, computer or telephone cases.
  • the MFI expressed in volume is used (the density of PMMA is 1.18 g / cm 3).
  • PEBAX® MV 1074SN01 it is a copolyether-block amide having polyamide 12 blocks of average molar mass in number 1500 and PEG blocks of average molar mass in number 1500; the MFI is 14 at 235 ° C / 1 kg and the melting point at 158 ° C.
  • PEBAX® MH 1657 it is a copolyether-block amide having polyamide 6 blocks of average molar mass in number 1500 and PEG blocks of average molar mass in number 1500; the MFI is 14 at 235 ° C / 1kg and the melting point at 204 ° C.
  • compositions are produced and injected directly on a press at temperatures of 210 to 240 ° C in the form of plates with dimensions 100mmx100mmx2mm. These plates make it possible to carry out resistivity measurements according to the IEC-93 standard and multiaxial shock.

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Abstract

The invention concerns an antistatic composition with enhanced impact strength comprising for 100 parts by weight: 95 to 80 parts of (A)+(C); 5 to 20 parts of (B); A being an acrylic polymer; (B) being a copolymer with polyamide blocks and polyether blocks comprising essentially ethylene oxide motifs (C2H4 O) ; (C) being a polymer selected among acrylic impact modifiers, copolymers (C1) with low styrene mass and an unsaturated carboxylic acid anhydride, copolymers (C2) of ethylene and an unsaturated carboxylic acid anhydride, copolymers (C3) of ethylene and an unsaturated epoxide or mixtures thereof.

Description

COMPOSITIONS DE POLYMÈRES ACRYLIQUES ANTISTATIQUES ANTISTATIC ACRYLIC POLYMER COMPOSITIONS
[Domaine de l'invention][Field of the invention]
La présente invention concerne des compositions de polymères acryliques antistatiques et plus précisément une composition comprenant un polymère acrylique (A), un copolymere (B) à blocs polyamides et blocs polyéthers comprenant essentiellement des motifs oxyde d'éthylène — (C2H4— O)— et un polymère (C) choisi parmi les modifiants chocs acryliques et/ou des polymères fonctionnels.The present invention relates to compositions of antistatic acrylic polymers and more specifically a composition comprising an acrylic polymer (A), a copolymer (B) containing polyamide blocks and polyether blocks essentially comprising ethylene oxide units ((C2H4— O) - and a polymer (C) chosen from acrylic impact modifiers and / or functional polymers.
Il s'agit de donner au polymère acrylique (A) des propriétés antistatiques. La formation et la rétention de charges d'électricité statique à la surface de la plupart des matières plastiques sont connues. La présence d'électricité statique sur des films thermoplastiques conduit par exemple ces films à se coller les uns sur les autres rendant leur séparation difficile. La présence d'électricité statique sur des films d'emballage peut provoquer l'accumulation de poussières sur les objets à emballer et ainsi gêner leur utilisation. Les résines acryliques telles que par exemple le PMMA sont utilisées pour faire différents objets et en particulier des objets transparents. L'électricité statique provoque l'accumulation de poussières à la surface de ces objets ce qui est gênant pour la transparence.This is to give the acrylic polymer (A) antistatic properties. The formation and retention of static electricity charges on the surface of most plastics is known. The presence of static electricity on thermoplastic films leads for example these films to stick to each other making their separation difficult. The presence of static electricity on packaging films can cause the accumulation of dust on the objects to be packaged and thus hinder their use. Acrylic resins such as for example PMMA are used to make various objects and in particular transparent objects. Static electricity causes the accumulation of dust on the surface of these objects which is troublesome for transparency.
L'art antérieur a décrit des agents antistatiques tels que des surfactants ioniques du type aminés éthoxylées ou sulfonates qu'on ajoute dans des polymères. Cependant les propriétés antistatiques des polymères dépendent de l'humidité ambiante et elles ne sont pas permanentes puisque ces agents migrent à la surface des polymères et disparaissent. Il a alors été proposé comme agents antistatiques des copolymeres à blocs polyamides et blocs polyéthers hydrophiles, ces agents ont l'avantage de ne pas migrer et donc de donner des propriétés antistatiques permanentes et de plus indépendantes de l'humidité ambiante. Le but de la présente invention est de rendre antistatique de façon permanente des résines acryliques disponibles dans le commerce , c'est à dire (i) des résines essentiellement constituées seulement de polymère acrylique ou (ii) des résines constituées d'un mélange de polymère acrylique et d'un modifiant choc. Un autre but de l'invention est aussi d'améliorer la tenue au choc en particulier le choc multiaxial. S'agissant du PMMA transparent, le but est aussi de ne pas altérer la transparence.The prior art has described antistatic agents such as ionic surfactants of the ethoxylated amine or sulfonate type which are added to polymers. However, the antistatic properties of the polymers depend on the ambient humidity and they are not permanent since these agents migrate to the surface of the polymers and disappear. It was then proposed as antistatic agents copolymers with polyamide blocks and hydrophilic polyether blocks, these agents have the advantage of not migrating and therefore of giving permanent antistatic properties and more independent of ambient humidity. The aim of the present invention is to make commercially available acrylic resins permanently antistatic, ie (i) resins essentially consisting only of acrylic polymer or (ii) resins consisting of a mixture of polymer acrylic and a shock modifier. Another object of the invention is also to improve the impact resistance, in particular multiaxial shock. With regard to transparent PMMA, the aim is also not to alter the transparency.
[ L'art antérieur][The prior art]
La demande de brevet japonais JP 60 023 435 A publiée le 6 février 1985 décrit des compositions antistatiques comprenant 5 à 80% de polyétheresteramide et 95 à 20% d'une résine thermoplastique choisie entre autres parmi le polystyrène, l'ABS et le PMMA, cette résine étant fonctionnalisée par l'acide acrylique ou l'anhydride maléique. Des exemples montrent des compositions constituées de 60 à 70 parties de PMMA carboxylé et de 40 à 30 parties de polyétheresteramide (pour 100 parties). D'autres montrent des compositions constituées de 30 à 45 parties de PMMA carboxylé, de 40 à 25 parties de PMMA et 30 parties de polyétheresteramide (pour 100 parties). Il n'est rien écrit sur la transparence des compositions à base de PMMA de plus il est nécessaire de disposer de PMMA carboxylé en proportions importantes.Japanese patent application JP 60 023 435 A published on February 6, 1985 describes antistatic compositions comprising 5 to 80% of polyetheresteramide and 95 to 20% of a thermoplastic resin chosen among others from polystyrene, ABS and PMMA, this resin being functionalized with acrylic acid or maleic anhydride. Examples show compositions consisting of 60 to 70 parts of carboxylated PMMA and 40 to 30 parts of polyetheresteramide (per 100 parts). Others show compositions consisting of 30 to 45 parts of carboxylated PMMA, 40 to 25 parts of PMMA and 30 parts of polyetheresteramide (per 100 parts). There is nothing written on the transparency of compositions based on PMMA, moreover it is necessary to have PMMA carboxylated in significant proportions.
La demande de brevet japonais JP 03 237 149 A publiée le 23 octobre 1991 décrit des compositions antistatiques constituées de 40 à 99 % d'une résine acrylique, 1 à 60 % de polyétheresteramide et 0,2 à 15 % d'un polymère greffé ayant des fonctions anhydride maléique ou époxyde et une partie soluble dans la résine acrylique. Le polymère greffé est compliqué à préparer.Japanese patent application JP 03 237 149 A published on October 23, 1991 describes antistatic compositions consisting of 40 to 99% of an acrylic resin, 1 to 60% of polyetheresteramide and 0.2 to 15% of a grafted polymer having maleic anhydride or epoxide functions and a part soluble in acrylic resin. The grafted polymer is complicated to prepare.
Les demandes de brevet japonais JP 08 253640 A publiée le 1 octobre 1996 et JP 04 146 947 A publiée le 20 mai 1992 décrivent des compositions antistatiques et transparentes constituées de résine acrylique, de polyétheresteramide et de sels. Il n'est pas souhaitable d'ajouter des sels dans de telles compositions parce qu'ensuite au cours de l'utilisation des compositions ils peuvent migrer.Japanese patent applications JP 08 253640 A published on October 1, 1996 and JP 04 146 947 A published on May 20, 1992 describe anti-static and transparent compositions made of acrylic resin, polyetheresteramide and salts. It is not desirable to add salts to such compositions because then during the use of the compositions they can migrate.
Les demandes de brevet japonais JP 05 295 213 A publiée le 9 novembre 1993 et JP 05 287 157 A publiée le 2 novembre 1993 décrivent des compositions antistatiques et transparentes constituées de résine acrylique, de polyétheresteramide et éventuellement d'un électrolyte ou d'acide sulphonique.Japanese patent applications JP 05 295 213 A published on November 9, 1993 and JP 05 287 157 A published on November 2, 1993 describe anti-static and transparent compositions made up of acrylic resin, polyetheresteramide and optionally an electrolyte or sulphonic acid .
Elles ont le même inconvénient que les compositions précédentes.They have the same drawback as the previous compositions.
Les demandes de brevet japonais JP 05 078 543 A et JP 04 146 947 A décrivent des compositions antistatiques et transparentes constituées de résine acrylique et de polyétheresteramide. Les propriétés mécaniques de la résine de base sont fortement altérées.Japanese patent applications JP 05 078 543 A and JP 04 146 947 A describe anti-static and transparent compositions made of acrylic resin and polyetheresteramide. The mechanical properties of the base resin are greatly altered.
[Brève description de l'invention][Brief description of the invention]
On a maintenant trouvé de nouvelles compositions de résines acryliques antistatiques. Il suffit pour rendre antistatique de façon permanente des résines acryliques disponibles dans le commerce , c'est à dire (i) des résines essentiellement constituées seulement de polymère acrylique ou (ii) des résines constituées d'un mélange de polymère acrylique et d'un modifiant choc, d'y ajouter un polyétheresteramide et éventuellement certains polymères fonctionnels. Un autre avantage de l'invention est aussi d'améliorer le choc en particulier le choc multiaxial. S'agissant du PMMA transparent, l'avantage est aussi de ne pas altérer la transparence.New compositions of antistatic acrylic resins have now been found. To make antistatic permanently available, commercially available acrylic resins, i.e. (i) resins consisting essentially only of acrylic polymer or (ii) resins consisting of a mixture of acrylic polymer and a impact modifier, to add a polyetheresteramide and optionally certain functional polymers. Another advantage of the invention is also to improve the shock, in particular the multiaxial shock. In the case of transparent PMMA, the advantage is also not to alter the transparency.
La présente invention concerne donc une composition antistatique à tenue au choc améliorée comprenant pour 100 parties en poids :The present invention therefore relates to an antistatic composition with improved impact resistance comprising per 100 parts by weight:
- 95 à 80 parties de (A)+(C),- 95 to 80 parts of (A) + (C),
- 5 à 20 parties de (B),- 5 to 20 parts of (B),
- (A) étant un polymère acrylique,- (A) being an acrylic polymer,
- (B) étant un copolymere à blocs polyamide et blocs polyether comprenant essentiellement des motifs oxyde d'éthylène — (C2H4 — O) — ,- (B) being a copolymer with polyamide blocks and polyether blocks essentially comprising ethylene oxide units - (C2H4 - O) -,
- (C) étant un polymère choisi parmi les modifiants choc acryliques, les copolymeres (C1) de faible masse du styrène et d'un anhydride d'acide carboxylique insaturé, les copolymeres (C2) de l'éthylène et d'un anhydride d'acide carboxylique insaturé, les copolymeres (C3) de l'éthylène et d'un époxyde insaturé ou leurs mélanges.- (C) being a polymer chosen from acrylic impact modifiers, copolymers (C1) of low mass of styrene and of an acid anhydride unsaturated carboxylic, copolymers (C2) of ethylene and an unsaturated carboxylic acid anhydride, copolymers (C3) of ethylene and an unsaturated epoxide or their mixtures.
La demanderesse a découvert que l'invention était particulièrement utile pour le PMMA modifié choc c'est à dire un mélange de (A) et d'un modifiant choc acrylique (C). Il suffit d'y ajouter (B) pour rendre cette composition antistatique sans qu'il soit nécessaire d'y ajouter un ou plusieurs des copolymeres (C1) àThe Applicant has discovered that the invention is particularly useful for impact modified PMMA, ie a mixture of (A) and an acrylic impact modifier (C). It suffices to add thereto (B) to make this composition antistatic without it being necessary to add thereto one or more of the copolymers (C1) to
(C3). De plus la transparence n'est pas sensiblement altérée. Un autre avantage est que le mélange du PMMA modifié choc et de (B) peut être fait en dry blend et introduit directement dans le dispositif d'injection ou de moulage sans qu'il soit nécessaire de faire un mélange intime dans une extrudeuse ou un malaxeur.(C3). In addition, transparency is not significantly altered. Another advantage is that the mixture of impact modified PMMA and (B) can be made as a dry blend and introduced directly into the injection or molding device without the need for intimate mixing in an extruder or a mixer.
[Description détaillée de l'invention][Detailed description of the invention]
A titre d'exemple de polymère acrylique (A) on peut citer les homopolymères d'un (méth)acrylate d'alkyle. Des (méth)acrylates d'alkyle sont décrits dans KIRK-OTHMER, Encyclopedia of chemical technology, 4 ème édition dans le Vol 1 pages 292-293 et dans le Vol 16 pages 475-478. On peut encore citer des copolymeres d'au moins deux de ces (méth)acrylates et des copolymeres d'au moins un (méth)acrylate avec au moins un monomère choisi parmi l'acrylonitrile, le butadiène, le styrène, l'isoprène pourvu que la proportion de (meth)acrylate soit d'au moins 50% en moles, l'invention est particulièrement utile pour le PMMA. Ces polymères acryliques sont soit constitués des monomères et éventuellement des comonomères cités plus haut et ne contiennent pas de modifiant choc soit ils contiennent en plus un modifiant choc acrylique. Les modifiants choc acryliques sont par exemple des copolymeres statistiques ou séquences d'au moins un monomère choisi parmi le styrène, le butadiène, l'isoprène et d'au moins un monomère choisi parmi l'acrylonitrile et les (meth)acrylate d'alkyle, ils peuvent être de type core-shell. Ces modifiants choc acryliques peuvent être mélangés avec le polymère acrylique (A) une fois préparé ou être introduit au cours de la polymérisation de (A) ou préparés simultanément au cours de la polymérisation de (A). Le MFI (melt flow index ou indice de fluidité à l'état fondu) de (A) peut être compris entre 2 et 15 g/10 min mesuré à 230°C sous une charge de 3,8 kg.As an example of an acrylic polymer (A), mention may be made of homopolymers of an alkyl (meth) acrylate. Alkyl (meth) acrylates are described in KIRK-OTHMER, Encyclopedia of chemical technology, 4th edition in Vol 1 pages 292-293 and in Vol 16 pages 475-478. Mention may also be made of copolymers of at least two of these (meth) acrylates and copolymers of at least one (meth) acrylate with at least one monomer chosen from acrylonitrile, butadiene, styrene, isoprene provided that the proportion of (meth) acrylate is at least 50 mol%, the invention is particularly useful for PMMA. These acrylic polymers are either made up of the monomers and possibly of the comonomers mentioned above and do not contain an impact modifier or they additionally contain an acrylic impact modifier. The acrylic impact modifiers are, for example, random or block copolymers of at least one monomer chosen from styrene, butadiene, isoprene and at least one monomer chosen from acrylonitrile and alkyl (meth) acrylates. , they can be of core-shell type. These acrylic impact modifiers can be mixed with the acrylic polymer (A) once prepared or be introduced during the polymerization of (A) or prepared simultaneously during the polymerization of (A). The MFI (melt flow index) of (A) can be between 2 and 15 g / 10 min measured at 230 ° C under a load of 3.8 kg.
La quantité de modifiant choc acrylique peut être par exemple de 0 à 30 parties pour 100 à 70 parties de (A) et avantageusement de 5 à 20 parties pour 95 à 20 parties de (A).The amount of acrylic impact modifier can for example be from 0 to 30 parts per 100 to 70 parts of (A) and advantageously from 5 to 20 parts per 95 to 20 parts of (A).
On ne sortirait pas du cadre de l'invention si (A) était un mélange de deux ou plusieurs des polymères précédents.It would not be departing from the scope of the invention if (A) were a mixture of two or more of the preceding polymers.
Les polymères (B) à blocs polyamides et blocs polyéthers résultent de la copolycondensation de séquences polyamides à extrémités réactives avec des séquences polyéthers à extrémités réactives, telles que, entre autres :The polymers (B) containing polyamide blocks and polyether blocks result from the copolycondensation of polyamide blocks with reactive ends with polyether blocks with reactive ends, such as, inter alia:
1) Séquences polyamides à bouts de chaîne diamines avec des séquences polyoxyalkylènes à bouts de chaînes dicarboxyliques.1) Polyamide sequences with diamine chain ends with polyoxyalkylene sequences with dicarboxylic chain ends.
2) Séquences polyamides à bouts de chaînes dicarboxyliques avec des séquences polyoxyalkylènes à bouts de chaînes diamines obtenues par cyanoéthylation et hydrogénation de séquences polyoxyalkylène alpha-oméga dihydroxylées aliphatique appelées polyétherdiols.2) Polyamide sequences at the ends of dicarboxylic chains with polyoxyalkylene sequences at the ends of diamine chains obtained by cyanoethylation and hydrogenation of polyoxyalkylene alpha-omega dihydroxylated aliphatic sequences called polyetherdiols.
3) Séquences polyamides à bouts de chaînes dicarboxyliques avec des polyétherdiols, les produits obtenus étant, dans ce cas particulier, des polyétheresteramides. Les copolymeres (B) sont avantageusement de ce type.3) Polyamide sequences at the ends of dicarboxylic chains with polyetherdiols, the products obtained being, in this particular case, polyetheresteramides. The copolymers (B) are advantageously of this type.
Les séquences polyamides à bouts de chaînes dicarboxyliques proviennent, par exemple, de la condensation d'acides alpha-oméga aminocarboxyliques, de lactames ou de diacides carboxyliques et diamines en présence d'un diacide carboxylique limiteur de chaîne.The polyamide sequences with dicarboxylic chain ends originate, for example, from the condensation of alpha-omega aminocarboxylic acids, lactams or dicarboxylic acids and diamines in the presence of a chain-limiting dicarboxylic acid.
La masse molaire en nombre Mn des séquences polyamides est comprise entre 300 et 15 000 et de préférence entre 600 et 5 000. La masse Mn des séquences polyether est comprise entre 100 et 6 000 et de préférence entre 200 et 3 000.The number-average molar mass Mn of the polyamide blocks is between 300 and 15,000 and preferably between 600 and 5,000. The mass Mn of the polyether blocks is between 100 and 6,000 and preferably between 200 and 3,000.
Les polymères à blocs polyamides et blocs polyéthers peuvent aussi comprendre des motifs répartis de façon aléatoire. Ces polymères peuvent être préparés par la réaction simultanée du polyether et des précurseurs des blocs polyamides.The polymers containing polyamide blocks and polyether blocks can also comprise units distributed randomly. These polymers can be prepared by the simultaneous reaction of polyether and precursors of polyamide blocks.
Par exemple, on peut faire réagir du polyétherdiol, un lactame (ou un alpha-oméga amino acide) et un diacide limiteur de chaîne en présence d'un peu d'eau. On obtient un polymère ayant essentiellement des blocs polyéthers, des blocs polyamides de longueur très variable, mais aussi les différents réactifs ayant réagi de façon aléatoire qui sont répartis de façon statistique le long de la chaîne polymère.For example, polyetherdiol, a lactam (or an alpha-omega amino acid) and a chain-limiting diacid can be reacted in the presence of a little water. A polymer is obtained which essentially has polyether blocks, polyamide blocks of very variable length, but also the various reactants which have reacted randomly which are distributed statistically along the polymer chain.
Ces polymères à blocs polyamides et blocs polyéthers qu'ils proviennent de la copolycondensation de séquences polyamides et polyéthers préparées auparavant ou d'une réaction en une étape présentent, par exemple, des duretés shore D pouvant être comprises entre 20 et 75 et avantageusement entre 30 et 70 et une viscosité intrinsèque entre 0,8 et 2,5 mesurée dans le métacrésol à 250° C pour une concentration initiale de 0,8 g/100 ml. Les MFI peuvent être compris entre 5 et 50 (235°C sous une charge de 1 kg)These polymers containing polyamide blocks and polyether blocks, whether they originate from the copolycondensation of polyamide and polyether blocks prepared beforehand or from a reaction in one step, exhibit, for example, shore D hardnesses which may be between 20 and 75 and advantageously between 30 and 70 and an intrinsic viscosity between 0.8 and 2.5 measured in metacresol at 250 ° C for an initial concentration of 0.8 g / 100 ml. The MFIs can be between 5 and 50 (235 ° C under a load of 1 kg)
Les blocs polyétherdiols sont soit utilisés tels quels et copolycondensés avec des blocs polyamides à extrémités carboxyliques, soit ils sont aminés pour être transformés en polyether diamines et condensés avec des blocs polyamides à extrémités carboxyliques. Ils peuvent être aussi mélangés avec des précurseurs de polyamide et un limiteur de chaîne pour faire les polymères à blocs polyamides et blocs polyéthers ayant des motifs répartis de façon statistique.The polyetherdiol blocks are either used as such and copolycondensed with polyamide blocks with carboxylic ends, or they are aminated to be transformed into polyether diamines and condensed with polyamide blocks with carboxylic ends. They can also be mixed with polyamide precursors and a chain limiter to make polymers with polyamide blocks and polyether blocks having randomly distributed units.
Des polymères à blocs polyamides et polyéthers sont décrits dans les brevets US 4 331 786, US 4 115 475, US 4 195 015, US 4 839 441 , US 4 864 014, US 4 230 838 et US 4 332 920.Polymers with polyamide and polyether blocks are described in US Patents 4,331,786, US 4,115,475, US 4,195,015, US 4,839,441, US 4,864,014, US 4,230,838 and US 4,332,920.
Selon une première forme de l'invention Les séquences polyamides à bouts de chaînes dicarboxyliques proviennent, par exemple, de la condensation d'acides alpha-oméga aminocarboxyliques, de lactames ou de diacides carboxyliques et diamines en présence d'un diacide carboxylique limiteur de chaîne. A titre d'exemple d'acides alpha oméga aminocarboxyliques on peut citer l'acide aminoundecanoïque, à titre d'exemple de lactame on peut citer le caprolactame et le lauryllactame, à titre d'exemple de diacide carboxylique on peut citer l'acide adipique, l'acide decanedioïque et l'acide dodécanédioïque, à titre d'exemple de diamine on peut citer l'hexamethylène diamine. Avantageusement les blocs polyamides sont en polyamide12 ou en polyamide 6. La température de fusion de ces séquences polyamides qui est aussi celle du copolymere (B) est en général 10 à 15°C en dessous de celle du PA 12 ou du PA 6.According to a first form of the invention The polyamide sequences with dicarboxylic chain ends originate, for example, from the condensation of alpha-omega aminocarboxylic acids, lactams or dicarboxylic acids and diamines in the presence of a chain-limiting dicarboxylic acid. . By way of example of alpha omega aminocarboxylic acids, mention may be made of aminoundecanoic acid, by way of example of lactam one can cite caprolactam and lauryllactam, as an example of a dicarboxylic acid, adipic acid, decanedioic acid and dodecanedioic acid may be mentioned, as an example of diamine, hexamethylene diamine may be mentioned. Advantageously, the polyamide blocks are made of polyamide12 or of polyamide 6. The melting point of these polyamide blocks which is also that of the copolymer (B) is generally 10 to 15 ° C. below that of PA 12 or PA 6.
Selon la nature de (A) il peut être utile d'utiliser un copolymere (B) ayant une température de fusion moins élevée pour ne pas dégrader (A) pendant l'incorporation de (B), c'est ce qui fait l'objet des deuxième et troisième forme de l'invention ci dessous.Depending on the nature of (A) it may be useful to use a copolymer (B) having a lower melting temperature so as not to degrade (A) during the incorporation of (B), this is what makes the object of the second and third forms of the invention below.
Selon une deuxième forme de l'invention les séquences polyamides résultent de la condensation d'un ou plusieurs acides alpha oméga aminocarboxyliques et/ou d'un ou plusieurs lactames ayant de 6 à 12 atomes de carbone en présence d'un diacide carboxylique ayant de 4 à 12 atomes de carbone et sont de faible masse c'est-à-dire Mn de 400 à 1000. A titre d'exemple d'acide alpha oméga aminocarboxylique on peut citer l'acide aminoundécanoïque et l'acide aminododécanoïque. A titre d'exemple d'acide dicarboxylique on peut citer l'acide adipique, l'acide sébacique, l'acide isophtalique, l'acide butanedioïque, l'acide 1 ,4 cyclohexyldicarboxylique, l'acide téréphtalique, le sel de sodium ou de lithium de l'acide sulphoisophtalique, les acides gras dimérisés(ces acides gras dimérisés ont une teneur en dimère d'au moins 98% et sont de préférence hydrogénés) et l'acide dodécanédioïque HOOC-(CH2)10-COOH. A titre d'exemple de lactame on peut citer le caprolactame et le lauryllactame.According to a second form of the invention, the polyamide sequences result from the condensation of one or more alpha omega aminocarboxylic acids and / or of one or more lactams having from 6 to 12 carbon atoms in the presence of a dicarboxylic acid having 4 to 12 carbon atoms and are of low mass, that is to say Mn from 400 to 1000. By way of example of alpha omega aminocarboxylic acid, mention may be made of aminoundecanoic acid and aminododecanoic acid. By way of example of dicarboxylic acid, mention may be made of adipic acid, sebacic acid, isophthalic acid, butanedioic acid, 1,4 cyclohexyldicarboxylic acid, terephthalic acid, sodium salt or lithium sulphoisophthalic acid, dimerized fatty acids (these dimerized fatty acids have a dimer content of at least 98% and are preferably hydrogenated) and dodecanedioic acid HOOC- (CH 2 ) 10-COOH. By way of example of a lactam, mention may be made of caprolactam and lauryllactam.
On évitera le caprolactame à moins de purifier le polyamide du caprolactame monomère qui y reste dissous.Caprolactam should be avoided unless the polyamide is purified from the monomeric caprolactam which remains dissolved therein.
Des séquences polyamides obtenues par condensation du lauryllactame en présence d'acide adipique ou d'acide dodécanédioïque et de masse Mn 750 ont une température de fusion de 127 - 130°C. Selon une troisième forme de l'invention les séquences polyamides résultent de la condensation d'au moins un acide alpha oméga aminocarboxylique (ou un lactame), au moins une diamine et au moins un diacide carboxylique. L'acide alpha oméga aminocarboxylique, le lactame et le diacide carboxylique peuvent être choisis parmi ceux cités plus haut.Polyamide sequences obtained by condensation of lauryllactam in the presence of adipic acid or dodecanedioic acid and of mass Mn 750 have a melting temperature of 127-130 ° C. According to a third form of the invention, the polyamide sequences result 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.
La diamine peut être une diamine aliphatique ayant de 6 à 12 atomes, elle peut être arylique et/ou cyclique saturée.The diamine can be an aliphatic diamine having from 6 to 12 atoms, it can be arylic and / or cyclic saturated.
A titre d'exemples on peut citer l'hexaméthylènediamine, la pipérazine, l'1-aminoethylpipérazine, la bisaminopropylpipérazine, la tetraméthylène diamine, l'octaméthylène diamine, la decaméthylène diamine, la dodecaméthylène diamine, le 1 ,5 diaminohexane, le 2,2,4-triméthyl-1 ,6- diamino-hexane, les polyols diamine, l'isophorone diamine (IPD), le méthyle pentaméthylènediamine (MPDM), la bis(aminocyclohéxyl) méthane (BACM), la bis(3-méthyl-4 aminocyclohéxyl) méthane (BMACM). Dans les deuxième et troisième forme de l'invention les différents constituants de la séquence polyamide et leur proportion sont choisis pour obtenir une température de fusion inférieure à 150°C et avantageusement comprise entre 90 et 135°C. Des copolyamides à basse température de fusion sont décrits dans les brevets US 4 483 975, DE 3 730 504, US 5 459 230 on reprend les mêmes proportions des constituants pour les blocs polyamides de (B). (B) peut être aussi les copolymeres décrits dans US 5 489 667.Examples include hexamethylenediamine, piperazine, 1-aminoethylpiperazine, bisaminopropylpiperazine, tetramethylene diamine, octamethylene diamine, decamethylene diamine, dodecamethylene diamine, 1.5 diaminohexane, 2, 2,4-trimethyl-1, 6-diamino-hexane, polyols diamine, isophorone diamine (IPD), methyl pentamethylenediamine (MPDM), bis (aminocyclohexyl) methane (BACM), bis (3-methyl- 4 aminocyclohexyl) methane (BMACM). In the second and third forms of the invention, the various constituents of the polyamide block and their proportion are chosen to obtain a melting temperature below 150 ° C. and advantageously between 90 and 135 ° C. Copolyamides with low melting temperature are described in US Patents 4,483,975, DE 3,730,504, US 5,459,230, the same proportions of the constituents are used for the polyamide blocks of (B). (B) can also be the copolymers described in US 5,489,667.
Les blocs polyether peuvent représenter 5 à 85 % en poids de (B). Les blocs polyether peuvent contenir d'autres motifs que les motifs oxyde d'éthylène tels que par exemple de l'oxyde de propylène ou du polytetrahydrofurane(qui conduit aux enchaînements polytetraméthylène glycol). On peut aussi utiliser simultanément des blocs PEG c'est à dire ceux constitués de motifs oxyde d'éthylène, des blocs PPG c'est à dire ceux constitués de motifs oxyde de propylène et des blocs PTMG c'est à dire ceux constitués de motifs tetraméthylène glycol appelés aussi polytétrahydrofurane. On utilise avantageusement des blocs PEG ou des blocs obtenus par oxyéthylation de bisphenols, tels que par exemple le bisphenol A. Ces derniers produits sont décrits dans le brevet EP 613 919. La quantité de blocs polyether dans (B) est avantageusement de 10 à 50% en poids de (B) et de préférence de 35 à 50%.The polyether blocks can represent 5 to 85% by weight of (B). The polyether blocks can contain other units than the ethylene oxide units, such as for example propylene oxide or polytetrahydrofuran (which leads to polytetramethylene glycol sequences). PEG blocks can also be used simultaneously, that is to say those made up of ethylene oxide units, PPG blocks that is to say those made up of propylene oxide units and PTMG blocks that is to say those made up of units tetramethylene glycol also called polytetrahydrofuran. Advantageously, PEG blocks or blocks obtained by oxyethylation of bisphenols, such as for example bisphenol A, are used. These latter products are described in patent EP 613 919. The amount of polyether blocks in (B) is advantageously from 10 to 50% by weight of (B) and preferably from 35 to 50%.
Les copolymeres de l'invention peuvent être préparés par tout moyen permettant d'accrocher les blocs polyamide et les blocs polyether. En pratique on utilise essentiellement deux procédés l'un dit en 2 étapes, l'autre en une étape.The copolymers of the invention can be prepared by any means allowing the polyamide blocks and the polyether blocks to be attached. In practice, essentially two methods are used, one said in 2 steps, the other in one step.
Le procédé en 2 étapes consiste d'abord à préparer les blocs polyamide à extrémités carboxyliques par condensation des précurseurs de polyamide en présence d'un diacide carboxylique limiteur de chaîne puis dans une deuxième étape à ajouter le polyether et un catalyseur. Si les précurseurs de polyamide ne sont que des lactames ou des acides alpha oméga aminocarboxyliques, on ajoute un diacide carboxylique. Si les précurseurs comprennent déjà un diacide carboxylique on l'utilise en excédent par rapport à la stœchiométrie des diamines. La réaction se fait habituellement entre 180 et 300°C, de préférence 200 à 260°C la pression dans le réacteur s'établit entre 5 et 30 bars, on la maintient environ 2 heures. On réduit lentement la pression en mettant le réacteur à l'atmosphère puis on distille l'eau excédentaire par exemple une heure ou deux. Le polyamide à extrémités acide carboxylique ayant été préparé on ajoute ensuite le polyether et un catalyseur. On peut ajouter le polyether en une ou plusieurs fois, de même pour le catalyseur. Selon une forme avantageuse on ajoute d'abord le polyether, la réaction des extrémités OH du polyether et des extrémités COOH du polyamide commence avec formations de liaison ester et élimination d'eau ; On élimine le plus possible l'eau du milieu réactionnel par distillation puis on introduit le catalyseur pour achever la liaison des blocs polyamide et des blocs polyether. Cette deuxième étape s'effectue sous agitation de préférence sous un vide d'au moins 5 mm Hg (650 Pa) à une température telle que les réactifs et les copolymeres obtenus soient à l'état fondu. A titre d'exemple cette température peut être comprise entre 100 et 400°C et le plus souvent 200 et 300°C. La réaction est suivie par la mesure du couple de torsion exercée par le polymère fondu sur l'agitateur ou par la mesure de la puissance électrique consommée par l'agitateur. La fin de la réaction est déterminée par la valeur du couple ou de la puissance cible. Le catalyseur est défini comme étant tout produit permettant de faciliter la liaison des blocs polyamide et des blocs polyether par estérification. Le catalyseur est avantageusement un dérivé d'un métal (M) choisi dans le groupe formé par le titane, le zirconium et le hafnium.The 2-step process consists first of all in preparing the polyamide blocks with carboxylic ends by condensation of the polyamide precursors in the presence of a chain-limiting dicarboxylic acid, then in a second step in adding the polyether and a catalyst. If the polyamide precursors are only lactams or alpha omega aminocarboxylic acids, a dicarboxylic acid is added. If the precursors already comprise a dicarboxylic acid, it is used in excess relative to the stoichiometry of the diamines. The reaction is usually carried out between 180 and 300 ° C, preferably 200 to 260 ° C, the pressure in the reactor is established between 5 and 30 bars, it is maintained for approximately 2 hours. The pressure is slowly reduced by putting the reactor into the atmosphere and then the excess water is distilled, for example an hour or two. The polyamide with carboxylic acid ends having been prepared, the polyether and a catalyst are then added. The polyether can be added one or more times, as can the catalyst. According to an advantageous form, the polyether is first added, the reaction of the OH ends of the polyether and of the COOH ends of the polyamide begins with ester bond formations and elimination of water; Water is removed as much as possible from the reaction medium by distillation and then the catalyst is introduced to complete the bonding of the polyamide blocks and of the polyether blocks. This second step is carried out with stirring preferably under a vacuum of at least 5 mm Hg (650 Pa) at a temperature such that the reagents and copolymers obtained are in the molten state. For example, this temperature can be between 100 and 400 ° C and most often 200 and 300 ° C. The reaction is followed by measuring the torque exerted by the molten polymer on the agitator or by the measurement of the electric power consumed by the agitator. The end of the reaction is determined by the value of the target torque or power. The catalyst is defined as being any product making it possible to facilitate the bonding of the polyamide blocks and of the polyether blocks by esterification. The catalyst is advantageously a derivative of a metal (M) chosen from the group formed by titanium, zirconium and hafnium.
A titre d'exemple de dérivé on peut citer les tetraalcoxydes qui répondent à la formule générale M(OR)4, dans laquelle M représente le titane, le zirconium ou le hafnium et les R, identiques ou différents, désignent des radicaux alcoyles, linéaires ou ramifiés, ayant de 1 à 24 atomes de carbone.By way of example of a derivative, mention may be made of the tetraalkoxides which correspond to the general formula M (OR) 4, in which M represents titanium, zirconium or hafnium and the Rs, identical or different, denote alkyl radicals, linear or branched, having from 1 to 24 carbon atoms.
Les radicaux alcoyles en C-] à C24 parmi lesquels sont choisis les radicaux R des tetraalcoxydes utilisés comme catalyseurs dans le procédé suivant l'invention sont par exemple tels que méthyle, éthyle, propyl, isopropyl, butyle, éthylhexyl, décyl, dodécyl, hexadodécyl. Les catalyseurs préférés sont les tetraalcoxydes pour lesquels les radicaux R, identiques ou différents, sont des radicaux alcoyles en C-| à C3. Des exemples de tels catalyseurs sont notamment Zr (OC2H5)4, Zr (0-isoC3H7)4, Zr(OC4H9)4, The alkyl radicals C-] to C24 from which are chosen the radicals R of the tetraalkoxides used as catalysts in the process according to the invention are for example such as methyl, ethyl, propyl, isopropyl, butyl, ethylhexyl, decyl, dodecyl, hexadodecyl . The preferred catalysts are the tetraalkoxides for which the radicals R, identical or different, are alkyl radicals C- | to C 3 . Examples of such catalysts are in particular Z r (OC 2 H5) 4 , Z r (0-isoC 3 H 7 ) 4 , Z r (OC 4 H 9 ) 4 ,
Zr(OC6H13)4> Hf(OC2H5)4, Hf(OC4H9)4, Hf(O-isoC3H7)4.Z r (OC 6 H 13 ) 4> H f (OC 2 H 5 ) 4 , H f (OC 4 H 9 ) 4 , Hf (O-isoC 3 H 7 ) 4 .
Le catalyseur utilisé dans ce procédé suivant l'invention peut consister uniquement en un ou plusieurs des tetraalcoxydes de formule M(OR)4 définis précédemment, il peut encore être formé par l'association d'un ou plusieurs de ces tetraalcoxydes avec un ou plusieurs alcoolates alcalins ou alcalino-terreux de formule (R- O)pY dans laquelle R-| désigne un reste hydrocarboné, avantageusement un reste alcoyle en C<| à C24, et de préférence en C-j à Cβ, Y représente un métal alcalin ou alcalino-terreux et p est la valence de Y. Les quantités d'alcoolate alcalin ou alcalino-terreux et de tetraalcoxydes de zirconium ou de hafnium que l'on associe pour constituer le catalyseur mixte peuvent varier dans de larges limites. On préfère toutefois utiliser des quantités d'alcoolate et de tetraalcoxydes telles que la proportion molaire d'alcoolate soit sensiblement égale à la proportion molaire de tétraalcoxyde. La proportion pondérale de catalyseur, c'est-à-dire du ou des tetraalcoxydes lorsque le catalyseur ne renferme pas d'alcoolate alcalin ou alcalino-terreux ou bien de l'ensemble du ou des tetraalcoxydes et du ou des alcoolates alcalins ou alcalino-terreux lorsque le catalyseur est formé par l'association de ces deux types de composés, varie avantageusement de 0,01 à 5 % du poids du mélange du polyamide dicarboxylique avec le polyoxyalcoylène glycol, et se situe de préférence entre 0,05 et 2 % de ce poids.The catalyst used in this process according to the invention can consist solely of one or more of the tetraalkoxides of formula M (OR) 4 defined above, it can also be formed by the association of one or more of these tetraalkoxides with one or more alkali or alkaline earth alcoholates of formula (R- O) pY in which R- | denotes a hydrocarbon residue, advantageously an alkyl residue at C <| to C 24 , and preferably in Cj to Cβ, Y represents an alkali or alkaline earth metal and p is the valence of Y. The amounts of alkali or alkaline earth alcoholate and of zirconium or hafnium tetraalkoxides as the the combined to form the mixed catalyst can vary within wide limits. However, it is preferred to use amounts of alcoholate and tetraalkoxides such that the molar proportion of alcoholate is substantially equal to the molar proportion of tetraalkoxide. The proportion by weight of catalyst, that is to say of the tetraalkoxide (s) when the catalyst does not contain alkali or alkaline earth alcoholate or else of all of the tetraalkoxide (s) and of alkali or alkaline alcoholates earthy when the catalyst is formed by the association of these two types of compounds, advantageously varies from 0.01 to 5% of the weight of the mixture of the polyamide dicarboxylic with the polyoxyalkylene glycol, and is preferably between 0.05 and 2% of this weight.
A titre d'exemple d'autres dérivés on peut citer aussi les sels du métal (M) en particulier les sels de (M) et d'un acide organique et les sels complexes entre l'oxyde de (M) et/ou l'hydroxyde de (M) et un acide organique. Avantageusement l'acide organique peut être l'acide formique, l'acide acétique, l'acide propionique, l'acide butyrique, l'acide valérique, l'acide caproïque, l'acide caprylique, l'acide lauryque, l'acide myristique, l'acide palmitique, l'acide stearique, l'acide oléique, l'acide linoleique, l'acide linolénique, l'acide cyclohexane carboxylique, l'acide phénylacétique, l'acide benzoïque, l'acide salicylique, l'acide oxalique, l'acide malonique, l'acide succinique, l'acide glutarique, l'acide adipique, l'acide maléique, l'acide fumarique, l'acide phtalique et l'acide crotonique. Les acides acétique et propionique sont particulièrement préférés. Avantageusement M est le zirconium. Ces sels peuvent s'appeler sels de zirconyle. La demanderesse sans être liée par cette explication pense que ces sels de zirconium et d'un acide organique ou les sels complexes cités plus haut libèrent ZrO++ au cours du procédé. On utilise le produit vendu sous le nom d'acétate de zirconyle. La quantité à utiliser est la même que pour les dérivés M(OR)4.By way of example of other derivatives, mention may also be made of the salts of the metal (M) in particular the salts of (M) and of an organic acid and the complex salts between the oxide of (M) and / or l hydroxide of (M) and an organic acid. Advantageously, the organic acid can be formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauryac acid, acid myristic, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, cyclohexane carboxylic acid, phenylacetic acid, benzoic acid, salicylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, phthalic acid and crotonic acid. Acetic and propionic acids are particularly preferred. Advantageously M is zirconium. These salts can be called zirconyl salts. The Applicant, without being bound by this explanation, believes that these zirconium and organic acid salts or the complex salts mentioned above release ZrO ++ during the process. The product sold under the name of zirconyl acetate is used. The quantity to be used is the same as for the derivatives M (OR) 4 .
Ce procédé et ces catalyseurs sont décrits dans les brevets US 4,332,920, US 4,230,838, US 4,331 ,786, US 4,252,920, JP 07145368A, JP 06287547A, et EP 613919.This process and these catalysts are described in US patents 4,332,920, US 4,230,838, US 4,331, 786, US 4,252,920, JP 07145368A, JP 06287547A, and EP 613919.
S'agissant du procédé en une étape on mélange tous les réactifs utilisés dans le procédé en deux étapes c'est-à-dire les précurseurs de polyamide, le diacide carboxylique limiteur de chaîne, le polyether et le catalyseur. Il s'agit des mêmes réactifs et du même catalyseur que dans le procédé en deux étapes décrit plus haut. Si les précurseurs de polyamide ne sont que des lactames il est avantageux d'ajouter un peu d'eau.With regard to the one-step process, all the reagents used in the two-step process are mixed, that is to say the polyamide precursors, the chain-limiting dicarboxylic acid, the polyether and the catalyst. These are the same reagents and the same catalyst as in the two-step process described above. If the polyamide precursors are only lactams, it is advantageous to add a little water.
Le copolymere a essentiellement les mêmes blocs polyéthers, les mêmes blocs polyamides, mais aussi une faible partie des différents réactifs ayant réagi de façon aléatoire qui sont répartis de façon statistique le long de la chaîne polymère.The copolymer has essentially the same polyether blocks, the same polyamide blocks, but also a small part of the various reactants which have reacted randomly which are distributed statistically along the polymer chain.
On ferme et on chauffe le réacteur sous agitation comme dans la première étape du procédé en deux étapes décrit plus haut. La pression s'établit entre 5 et 30 bars. Quand elle n'évolue plus on met le réacteur sous pression réduite tout en maintenant une agitation vigoureuse des réactifs fondus. La réaction est suivie comme précédemment pour le procédé en deux étapes.The reactor is closed and heated with stirring as in the first step of the two-step process described above. The pressure is established between 5 and 30 bars. When it no longer evolves, the reactor is placed under reduced pressure while maintaining vigorous stirring of the molten reactants. The reaction is followed as above for the two-step process.
Le catalyseur utilisé dans le procédé en une étape est de préférence un sel du métal (M) et d'un acide organique ou un sel complexe entre l'oxyde de (M) et/ou l'hydroxyde de (M) et un acide organique.The catalyst used in the one-step process is preferably a salt of the metal (M) and an organic acid or a complex salt between the oxide of (M) and / or the hydroxide of (M) and an acid organic.
S'agissant des copolymeres (C1) l'anhydride d'acide carboxylique insaturé peut être choisi par exemple parmi les anhydrides maléique, itaconique, citraconique, allylsuccinique, cyclohex-4-ène-1 ,2-dicarboxylique, 4 — méthylènecyclohex-4-ène-1 ,2-dicarboxylique, bicyclo(2,2, 1 )hept-5-ène-2,3- dicarboxylique, et x — méthylbicyclo(2,2,1)hept-5-ène-2,2-dicarboxylique. On utilise avantageusement l'anhydride maléique. La masse molaire moyenne en nombre est comprise entre 800 et 10000 et de préférence entre 1000 et 3500. (C1) peut être représenté par la formule suivante :As regards the copolymers (C1), the unsaturated carboxylic acid anhydride can be chosen, for example, from maleic, itaconic, citraconic, allylsuccinic, cyclohex-4-ene-1, 2-dicarboxylic, 4-methylenecyclohex-4- anhydrides ene-1,2-dicarboxylic, bicyclo (2,2,1) hept-5-ene-2,3-dicarboxylic, and x - methylbicyclo (2,2,1) hept-5-ene 2,2-dicarboxylic . Advantageously, maleic anhydride is used. The number-average molar mass is between 800 and 10,000 and preferably between 1,000 and 3,500. (C1) can be represented by the following formula:
dans laquelle MAH désigne l'anhydride maléique , m varie de 1 à 3 et n varie de 6 à 8. Ces copolymeres peuvent être partiellement estérifiés, entre 35 et 75%, par des alcools. Ces produits sont vendus sous le nom de SMA® Resins par la société ELF ATOCHEM. S'agissant des copolymeres (C2) ils peuvent être des polyéthylènes greffés par un anhydride d'acide carboxylique insaturé ou des copolymeres de l'éthylène et d'un anhydride d'acide carboxylique insaturé qu'on obtient par exemple par polymérisation radicalaire. in which MAH denotes maleic anhydride, m varies from 1 to 3 and n varies from 6 to 8. These copolymers can be partially esterified, between 35 and 75%, with alcohols. These products are sold under the name of SMA® Resins by the company ELF ATOCHEM. As regards the copolymers (C2), they can be polyethylenes grafted with an unsaturated carboxylic acid anhydride or copolymers of ethylene and an unsaturated carboxylic acid anhydride which are obtained for example by radical polymerization.
S'agissant des polyéthylènes sur lesquels on vient greffer l'anhydride d'acide carboxylique insaturé on entend par polyéthylène des homo- ou copolymeres.As regards the polyethylenes onto which the unsaturated carboxylic acid anhydride is grafted, polyethylene is understood to mean homo- or copolymers.
A titre de comonomères, on peut citer :As comonomers, we can cite:
- les alpha-oléfines, avantageusement celles ayant de 3 à 30 atomes de carbone, de carbone; à titre d'exemples d'alpha oléfines on peut citer le propylène, le 1 -butène, le 1-pentène, le 3-méthyl-1 -butène, le 1-hexène, le 4- méthyl-1-pentène, le 3-méthyl-1-pentène, le 1-octène, le 1 -décène, le 1- dodécène, le 1-tétradécène, le 1-hexadécène, le 1-octadécène, le 1 — eicocène, le 1-dococène, le 1-tétracocène, le 1-hexacocène, le 1 — octacocène, et le 1- triacontène; ces alpha-oléfines peuvent être utilisées seules ou en mélange de deux ou de plus de deux,- alpha-olefins, advantageously those having from 3 to 30 carbon atoms; as examples of alpha olefins, mention may be made of propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3 -methyl-1-pentene, 1-octene, 1-dececene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1 - eicocene, 1-dococene, 1- tetracocene, 1-hexacocene, 1 - octacocene, and 1-triacontene; these alpha-olefins can be used alone or as a mixture of two or more than two,
- les esters d'acides carboxyliques insaturés tels que par exemple les (méth)acrylates d'alkyle, les alkyles pouvant avoir jusqu'à 24 atomes de carbone, des exemples d'acrylate ou méthacrylate d'alkyle sont notamment le méthacrylate de méthyle, l'acrylate d'éthyle, l'acrylate de n-butyle, l'acrylate d'isobutyle, l'acrylate de 2-éthylhexyle et l'acrylate de n-octyle.esters of unsaturated carboxylic acids such as, for example, alkyl (meth) acrylates, the alkyls possibly having up to 24 carbon atoms, examples of alkyl acrylate or methacrylate are in particular methyl methacrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate and n-octyl acrylate.
- les esters vinyliques d'acides carboxyliques saturés tels que par exemple l'acétate ou le propionate de vinyle.- vinyl esters of saturated carboxylic acids such as, for example, vinyl acetate or propionate.
- les diènes tels que par exemple le 1 ,4-hexadiène.- dienes such as, for example, 1,4-hexadiene.
- le polyéthylène peut comprendre plusieurs comonomères. Avantageusement le polyéthylène qui peut être un mélange de plusieurs polymères, comprend au moins 50% et de préférence 75% (en moles) d'éthylène, sa densité peut être comprise entre 0,86 et 0,98 g/cm^. Le MFI (indice de viscosité à 190°C, 2,16 kg) est compris avantageusement entre 1 et 1000 g/10 min.- the polyethylene can comprise several comonomers. Advantageously, the polyethylene which can be a mixture of several polymers, comprises at least 50% and preferably 75% (in moles) of ethylene, its density can be between 0.86 and 0.98 g / cm 2. The MFI (viscosity index at 190 ° C, 2.16 kg) is advantageously between 1 and 1000 g / 10 min.
A titre d'exemple de polyéthylènes on peut citer :Examples of polyethylenes that may be mentioned:
- le polyéthylène basse densité (LDPE) - le polyéthylène haute densité (HDPE)- low density polyethylene (LDPE) - high density polyethylene (HDPE)
- le polyéthylène linéaire basse densité (LLDPE)- linear low density polyethylene (LLDPE)
- le polyéthylène très basse densité (VLDPE)- very low density polyethylene (VLDPE)
- le polyéthylène obtenu par catalyse métallocène, c'est-à-dire les polymères obtenus par copolymérisation d'éthylène et d'alphaoléfine telle que propylène, butène, héxène ou octène en présence d'un catalyseur monosite constitué généralement d'un atome de zirconium ou de titane et de deux molécules cycliques alkyles liées au métal. Plus spécifiquement, les catalyseurs métallocènes sont habituellement composés de deux cycles cyclopentadiéniques liés au métal. Ces catalyseurs sont fréquemment utilisés avec des aluminoxanes comme cocatalyseurs ou activateurs, de préférence le méthylaluminoxane (MAO). Le hafnium peut aussi être utilisé comme métal auquel le cyclopentadiène est fixé. D'autres métallocènes peuvent inclure des métaux de transition des groupes IV A, V A, et VI A. Des métaux de la série des lanthamides peuvent aussi être utilisés. - les élastomères EPR (éthylène - propylène - rubber)the polyethylene obtained by metallocene catalysis, that is to say the polymers obtained by copolymerization of ethylene and of alphaolefin such as propylene, butene, hexene or octene in the presence of a monosite catalyst generally consisting of an atom of zirconium or titanium and two cyclic alkyl molecules linked to the metal. More specifically, metallocene catalysts are usually composed of two cyclopentadienic rings linked to the metal. These catalysts are frequently used with aluminoxanes as cocatalysts or activators, preferably methylaluminoxane (MAO). Hafnium can also be used as the metal to which cyclopentadiene is attached. Other metallocenes can include transition metals from groups IV A, V A, and VI A. Metals of the lanthamide series can also be used. - EPR elastomers (ethylene - propylene - rubber)
- les élastomères EPDM (éthylène - propylène - diène)- EPDM elastomers (ethylene - propylene - diene)
- les mélanges de polyéthylène avec un EPR ou un EPDM- polyethylene blends with an EPR or an EPDM
- les copolymeres éthylène-(méth)acrylate d'alkyle pouvant contenir jusqu'à 60% en poids de (méth)acrylate et de préférence 2 à 40%. Le greffage est une opération connue en soi.- ethylene- (meth) acrylate copolymers which may contain up to 60% by weight of (meth) acrylate and preferably 2 to 40%. Grafting is an operation known in itself.
S'agissant des copolymeres de l'éthylène et de l'anhydride d'acide carboxylique insaturé c'est-à-dire ceux dans lesquels l'anhydride d'acide carboxylique insaturé n'est pas greffé il s'agit des copolymeres de l'éthylène, de l'anhydride d'acide carboxylique insaturé et éventuellement d'un autre monomère pouvant être choisi parmi les comonomères qu'on a cité plus haut pour les copolymeres de l'éthylène destinés à être greffés. On utilise avantageusement les copolymeres éthylène-anhydride maléique et éthylène - (méth)acrylate d'alkyle - anhydride maléique. Ces copolymeres comprennent de 0,2 à 10 % en poids d'anhydride maléique, de 0 àAs regards the copolymers of ethylene and of the unsaturated carboxylic acid anhydride, that is to say those in which the unsaturated carboxylic acid anhydride is not grafted, these are the copolymers of l ethylene, unsaturated carboxylic acid anhydride and optionally another monomer which can be chosen from the comonomers mentioned above for the ethylene copolymers intended to be grafted. The ethylene-maleic anhydride and ethylene - alkyl (meth) acrylate - maleic anhydride copolymers are advantageously used. These copolymers comprise from 0.2 to 10% by weight of maleic anhydride, from 0 to
40 % en poids de (méth)acrylate d'alkyle. Leur MFI est compris entre 1 et 50 (190°C - 2,16 kg). Les (méth)acrylates d'alkyle ont déjà été décrits plus haut.40% by weight of alkyl (meth) acrylate. Their MFI is between 1 and 50 (190 ° C - 2.16 kg). The alkyl (meth) acrylates have already been described above.
On ne sortirait pas du cadre de l'invention en remplaçant dans (C2) l'anhydride d'acide carboxylique insaturé par un acide carboxylique insaturé tel que l'acide (meth)acrylique cette fonction pouvant être partiellement neutralisée par un métal (Zn, K) ou un alcalin (Li), il s'agit dans ce cas d'ionomères. Des ionomères de ce type sont vendus par la société DUPONT sous la marque Surlyn®.It would not go beyond the scope of the invention to replace in (C2) the unsaturated carboxylic acid anhydride with an unsaturated carboxylic acid such as (meth) acrylic acid, this function being able to be partially neutralized by a metal (Zn, K) or an alkaline (Li), these are ionomers. Ionomers of this type are sold by DUPONT under the brand Surlyn®.
S'agissant des copolymeres (C3) Le copolymere de l'éthylène et d'un époxyde insaturé peut être obtenu par copolymérisation de l'éthylène et d'un époxyde insaturé ou par greffage de l'époxyde insaturé sur le polyéthylène. Le greffage peut être effectué en phase solvant ou sur le polyéthylène en fusion en présence d'un peroxyde. Ces techniques de greffage sont connues en elles- mêmes. Quant à la copolymérisation de l'éthylène et d'un époxyde insaturé, on peut utiliser les procédés dits de polymérisation radicalaire fonctionnant habituellement à des pressions entre 200 et 2 500 bars. A titre d'exemple d'époxydes insaturés, on peut citer : les esters et éthers de glycidyle aliphatiques tels que l'allyl glycidyléther, le vinyle glycidyléther, le maléate et l'itaconate de glycidyle, le (méth)acrylate de glycidyle, et les esters et éthers de glycidyle alicycliques tels que le 2- cyclohexène-1 -glycidyléther, le cyclohexène-4,5-diglycidyl carboxylate, le cyclohexène-4-glycidyl carboxylate, le 5-norbomène-2-méthyl-2-glycidyl carboxylate et l'endo cis-bicyclo(2,2,1)-5-heptène-2,3-diglycidyl dicarboxylate.Regarding the copolymers (C3) The copolymer of ethylene and an unsaturated epoxide can be obtained by copolymerization of ethylene and an unsaturated epoxide or by grafting the unsaturated epoxide onto the polyethylene. The grafting can be carried out in the solvent phase or on the molten polyethylene in the presence of a peroxide. These grafting techniques are known in themselves. As for the copolymerization of ethylene and an unsaturated epoxide, it is possible to use the so-called radical polymerization processes usually operating at pressures between 200 and 2,500 bars. As examples of unsaturated epoxides, there may be mentioned: aliphatic glycidyl esters and ethers such as allyl glycidyl ether, vinyl glycidyl ether, glycidyl itaconate and maleate, glycidyl (meth) acrylate, and alicyclic glycidyl esters and ethers such as 2-cyclohexene-1-glycidyl ether, cyclohexene-4,5-diglycidyl carboxylate, cyclohexene-4-glycidyl carboxylate, 5-norbomene-2-methyl-2-glycidyl carboxylate and endo cis-bicyclo (2,2,1) -5-heptene-2,3-diglycidyl dicarboxylate.
S'agissant du greffage le copolymere (C3) s'obtient à partir du greffage d'un polyéthylène homo ou copolymere comme décrit pour (C2) sauf qu'on greffe un époxyde au lieu d'un anhydride. S'agissant d'une copolymérisation c'est aussi semblable à (C2) sauf qu'on utilise un époxyde, il peut aussi y avoir d'autres comonomères comme dans le cas de (C2).As regards grafting, the copolymer (C3) is obtained from the grafting of a homo or copolymer polyethylene as described for (C2) except that an epoxy is grafted instead of an anhydride. Being a copolymerization it is also similar to (C2) except that an epoxide is used, there may also be other comonomers as in the case of (C2).
Le copolymere (C3) est avantageusement un copolymere éthylène/(méth)acrylate d'alkyle/époxyde insaturé. Avantageusement il peut contenir jusqu'à 40% en poids de (méth)acrylate d'alkyle et jusqu'à 10% en poids d'époxyde insaturé, de préférence 0,1 à 8%.The copolymer (C3) is advantageously an ethylene / (meth) alkyl acrylate / unsaturated epoxide copolymer. Advantageously, it can contain up to 40% by weight of alkyl (meth) acrylate and up to 10% by weight of unsaturated epoxide, preferably 0.1 to 8%.
L'époxyde est avantageusement le (méth)acrylate de glycidyle. Avantageusement le (méth)acrylate d'alkyle est choisi parmi le (méth)acrylate de méthyle, l'acrylate d'éthyle, l'acrylate de n-butyle, l'acrylate d'isobutyle, l'acrylate de 2-éthylhexyle. La quantité de (méth)acrylate d'alkyle est avantageusement de 20 à 35%. Le MFI est avantageusement compris entre 1 et 50 (en g/10 min à 190°C sous 2,16 kg) Ce copolymere peut être obtenu par polymérisation radicalaire des monomères.The epoxide is advantageously glycidyl (meth) acrylate. Advantageously, the alkyl (meth) acrylate is chosen from methyl (meth) acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate. The amount of alkyl (meth) acrylate is advantageously from 20 to 35%. The MFI is advantageously between 1 and 50 (in g / 10 min at 190 ° C. under 2.16 kg) This copolymer can be obtained by radical polymerization of the monomers.
Si la composition initiale contient (A) et un modifiant choc acrylique alors il suffit d'ajouter (B), si la composition initiale contient seulement (A) alors ii est nécessaire en plus de (B) d'ajouter un des copolymeres (C1) à (C3). La quantité de (C1), (C2) ou (C3) est avantageusement telle que (B)/(C) en poids est compris entre 2 et 10 et de préférence entre 4 et 6. On peut utiliser un mélange de 2 de ces copolymeres ou des 3, quant aux proportions dans le rapport (B)/(C) (C) représente la somme des quantités de (C1) à (C3) utilisés.If the initial composition contains (A) and an acrylic impact modifier then it suffices to add (B), if the initial composition contains only (A) then it is necessary in addition to (B) to add one of the copolymers (C1 ) to (C3). The amount of (C1), (C2) or (C3) is advantageously such that (B) / (C) by weight is between 2 and 10 and preferably between 4 and 6. A mixture of 2 of these can be used. copolymers or of 3, as for the proportions in the ratio (B) / (C) (C) represents the sum of the quantities of (C1) to (C3) used.
On ne sortirait pas du cadre de l'invention en ajoutant, dans une composition contenant déjà (A) et un modifiant choc acrylique, non seulement (B) mais aussi au moins l'un des copolymeres (C1) à (C3). On ne sortirait pas du cadre de l'invention en ajoutant, dans une composition contenant (A) et pas de modifiant choc, non seulement (B) et l'un des copolymeres (C1) à (C3) mais aussi un modifiant choc acrylique.It would not go beyond the scope of the invention to add, to a composition already containing (A) and an acrylic impact modifier, not only (B) but also at least one of the copolymers (C1) to (C3). It would not go beyond the scope of the invention to add, in a composition containing (A) and no impact modifier, not only (B) and one of the copolymers (C1) to (C3) but also an acrylic impact modifier .
L'antistatisme augmente avec la proportion de (B) et pour des quantités égales de (B) avec la proportion de motifs oxyde d'éthylène contenus dans (B).Anti-statism increases with the proportion of (B) and for equal amounts of (B) with the proportion of ethylene oxide units contained in (B).
S'agissant des compositions dans lesquelles (C) est un modifiant choc acrylique on utilise avantageusement 8 à 15 parties de (B) pour 92 à 85 parties de (A)+(C) et de préférence 8 à 11 parties de (B) pour 92 à 89 parties de O 01 1As regards the compositions in which (C) is an acrylic impact modifier, advantageously 8 to 15 parts of (B) are used for 92 to 85 parts of (A) + (C) and preferably 8 to 11 parts of (B) for 92 to 89 parts of O 01 1
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(A)+(C). L'invention est particulièrement utile pour le PMMA modifié choc par un modifiant choc acrylique.(A) + (C). The invention is particularly useful for impact modified PMMA with an acrylic impact modifier.
On ne sortirait pas du cadre de l'invention en ajoutant des charges minérales (talc, Ca3CO, kaolin ...), des renforts (fibre de verre, fibre minérale, fibre de carbone, ...), des stabilisants (thermique, UV), des agents ignifugeants et des colorants dans la mesure ou il ne s'agit pas de polymère (A) transparents.We would not go beyond the scope of the invention by adding mineral fillers (talc, Ca3CO, kaolin, etc.), reinforcements (fiberglass, mineral fiber, carbon fiber, etc.), stabilizers (thermal, UV), flame retardants and dyes as long as they are not transparent polymers (A).
Les compositions de l'invention se préparent par les techniques habituelles des thermoplastiques telles que par exemple par extrusion ou à l'aide de mélangeurs bivis ou encore à l'aide d'un appareil du type Ko-malaxeur BUSS®. Cependant la demanderesse a trouvé que dans le cas ou on ajoute (B) dans (A) contenant déjà un modifiant choc acrylique alors il n'est pas nécessaire de faire un mélange intime dans une extrudeuse ou un mélangeur, de récupérer les compositions sous forme de granulés ou à l'état fondu puis de les introduire dans un dispositif de moulage ou d'extrusion; en effet il suffit de faire un mélange de (A) contenant le modifiant choc acrylique et de (B) à l'état sec en poudre ou en granulés (dry blend) puis d'introduire ce mélange dans le dispositif de moulage ou d'injection.The compositions of the invention are prepared by the usual techniques of thermoplastics such as for example by extrusion or using twin-screw mixers or even using a device of the type Ko-kneader BUSS®. However, the Applicant has found that in the case where (B) is added to (A) already containing an acrylic impact modifier, then it is not necessary to make an intimate mixture in an extruder or a mixer, to recover the compositions in the form granules or in the molten state and then introducing them into a molding or extrusion device; indeed it suffices to make a mixture of (A) containing the acrylic impact modifier and of (B) in the dry state in powder or granules (dry blend) then to introduce this mixture into the molding device or injection.
La présente invention concerne aussi les objets fabriqués avec les compositions précédentes ; ce sont par exemple des films, des tubes, des plaques, des emballages, des boîtiers d'ordinateurs ou de téléphone.The present invention also relates to objects manufactured with the preceding compositions; these are for example films, tubes, plates, packaging, computer or telephone cases.
[Exemples][Examples]
On a utilisé les ingrédients suivants :The following ingredients were used:
Pour les PMMA on utilise le MFI exprimé en volume (la densité du PMMA est de 1 ,18 g/cm3.For PMMA, the MFI expressed in volume is used (the density of PMMA is 1.18 g / cm 3).
OROGLAS® V 825T : PMMA ne contenant pas de modifiant choc acrylique caractérisé par un MFI = 2,8 cm3/10 min ( 230°C 3,8 kg) et un choc Charpy à +23°C de 20 kJ / m2. O 01/18111OROGLAS® V 825T: PMMA containing no acrylic impact modifier characterized by an MFI = 2.8 cm3 / 10 min (230 ° C 3.8 kg) and a Charpy shock at + 23 ° C of 20 kJ / m2. O 01/18111
1818
OROGLAS® Ml 4T : PMMA contenant un modifiant choc acrylique caractérisé par un MFI = 2,8 cm3/10 min ( 230°C 3,8 kg) et un choc Charpy à +23°C de 35 kJ / m2.OROGLAS® Ml 4T: PMMA containing an acrylic impact modifier characterized by an MFI = 2.8 cm3 / 10 min (230 ° C 3.8 kg) and a Charpy shock at + 23 ° C of 35 kJ / m2.
OROGLAS® HF 17 : PMMA contenant un modifiant choc acrylique caractérisé par un MFI = 10,3 cm3/10 min ( 230°C 3,8 kg) et un choc Charpy à +23°C de 45 kJ / m2.OROGLAS® HF 17: PMMA containing an acrylic impact modifier characterized by an MFI = 10.3 cm3 / 10 min (230 ° C 3.8 kg) and a Charpy shock at + 23 ° C of 45 kJ / m2.
PEBAX® MV 1074SN01 : il s'agit d'un copolyéther-bloc-amide ayant des blocs polyamide 12 de masse molaire moyenne en nombre 1500 et des blocs PEG de masse molaire moyenne en nombre 1500 ; le MFI est 14 sous 235°C/1 kg et le point de fusion de 158°C.PEBAX® MV 1074SN01: it is a copolyether-block amide having polyamide 12 blocks of average molar mass in number 1500 and PEG blocks of average molar mass in number 1500; the MFI is 14 at 235 ° C / 1 kg and the melting point at 158 ° C.
PEBAX® MH 1657 : il s'agit d'un copolyéther-bloc-amide ayant des blocs polyamide 6 de masse molaire moyenne en nombre 1500 et des blocs PEG de masse molaire moyenne en nombre 1500 ; le MFI est 14 sous 235°C/1kg et le point de fusion de 204°C.PEBAX® MH 1657: it is a copolyether-block amide having polyamide 6 blocks of average molar mass in number 1500 and PEG blocks of average molar mass in number 1500; the MFI is 14 at 235 ° C / 1kg and the melting point at 204 ° C.
Dans les exemples qui suivent, on a utilisé les techniques de caractérisation suivantes :In the following examples, the following characterization techniques were used:
- Propriétés mécaniques et antistatiques : Les compositions sont réalisées et injectées directement sur presse à des températures de 210 à 240°C sous forme de plaques de dimensions 100mmx100mmx2mm. Ces plaques permettent d'effectuer les mesures de résistivite suivant la norme IEC-93 et de choc multiaxial.- Mechanical and antistatic properties: The compositions are produced and injected directly on a press at temperatures of 210 to 240 ° C in the form of plates with dimensions 100mmx100mmx2mm. These plates make it possible to carry out resistivity measurements according to the IEC-93 standard and multiaxial shock.
Dans le tableau 1 la résistivite surfacique Rs est mesurée en ohm/D. Tous les essais sont effectués à 23°C. Les plaques sont conditionnées à 50% d'humidité pendant 15 jours avant d'être testées pour la mesure de la résistivite de surface.In Table 1 the surface resistivity Rs is measured in ohm / D. All tests are carried out at 23 ° C. The plates are conditioned at 50% humidity for 15 days before being tested for the measurement of surface resistivity.
L'ex 4 est comparatif la résistivite n'est baissée que d'un facteur 100 et le choc peu modifié. Dans les ex 5 et 6 la résistivite est baissée respectivement d'un facteur 3000 et 10000 et le choc fortement amélioré. TABLEAU 1Ex 4 is comparative, the resistivity is only reduced by a factor of 100 and the shock little modified. In ex 5 and 6 the resistivity is lowered by a factor of 3000 and 10000 respectively and the shock greatly improved. TABLE 1
Les propriétés optiques sont reportées dans le tableau 2 suivant:The optical properties are reported in the following table 2:
TABLEAU 2TABLE 2

Claims

REVENDICATIONS
1 Composition antistatique à tenue au choc améliorée comprenant pour 100 parties en poids : - 95 à 80 parties de (A)+(C),1 Antistatic composition with improved impact resistance comprising per 100 parts by weight: - 95 to 80 parts of (A) + (C),
- 5 à 20 parties de (B),- 5 to 20 parts of (B),
- (A) étant un polymère acrylique,- (A) being an acrylic polymer,
- (B) étant un copolymere à blocs polyamide et blocs polyether comprenant essentiellement des motifs oxyde d'éthylène — (C2H4 — O) — , - (C) étant un polymère choisi parmi les modifiants choc acryliques, les copolymeres (C1) de faible masse du styrène et d'un anhydride d'acide carboxylique insaturé, les copolymeres (C2) de l'éthylène et d'un anhydride d'acide carboxylique insaturé, les copolymeres (C3) de l'éthylène et d'un époxyde insaturé ou leurs mélanges.- (B) being a copolymer with polyamide blocks and polyether blocks essentially comprising ethylene oxide units - (C2H4 - O) -, - (C) being a polymer chosen from acrylic impact modifiers, copolymers (C1) of low mass of styrene and an unsaturated carboxylic acid anhydride, the copolymers (C2) of ethylene and an unsaturated carboxylic acid anhydride, the copolymers (C3) of ethylene and an unsaturated epoxide or their mixtures.
2 Composition selon la revendication 1 dans laquelle (A) est le PMMA.2 Composition according to claim 1 in which (A) is PMMA.
3 Composition selon la revendication 1 ou 2 dans laquelle le modifiant choc acrylique est un copolymere d'au moins un monomère choisi parmi le styrène, le butadiène, l'isoprène et d'au moins un monomère choisi parmi l'acrylonitrile et les (meth)acrylate d'alkyle.3 Composition according to claim 1 or 2 in which the acrylic impact modifier is a copolymer of at least one monomer chosen from styrene, butadiene, isoprene and at least one monomer chosen from acrylonitrile and (meth ) alkyl acrylate.
4 Composition selon l'une quelconque des revendications précédentes dans laquelle (C1) est un copolymere du styrène et de l'anhydride maléique de masse molaire moyenne comprise entre 800 et 10000.4 Composition according to any one of the preceding claims in which (C1) is a copolymer of styrene and maleic anhydride with an average molar mass of between 800 and 10,000.
5 Composition selon l'une quelconque des revendications 1 à 3 dans laquelle (C2) est choisi parmi les copolymeres éthylène - (méth)acrylate d'alkyle - anhydride maléique, ces copolymeres comprenant de 0,2 à 10 % en poids d'anhydride maléique, de 0 à 40 % en poids de (méth)acrylate d'alkyle. 6 Composition selon l'une quelconque des revendications 1 à 3 dans laquelle (C3) est avantageusement un copolymere éthylène/(méth)acrylate d'alkyle/époxyde insaturé pouvant contenir jusqu'à 40% en poids de (méth)acrylate d'alkyle et jusqu'à 10% en poids d'époxyde insaturé.5 Composition according to any one of claims 1 to 3 in which (C2) is chosen from ethylene - alkyl (meth) acrylate - maleic anhydride copolymers, these copolymers comprising from 0.2 to 10% by weight of anhydride maleic, from 0 to 40% by weight of alkyl (meth) acrylate. 6 Composition according to any one of claims 1 to 3 in which (C3) is advantageously an ethylene / alkyl (meth) acrylate / unsaturated epoxide copolymer which may contain up to 40% by weight of alkyl (meth) acrylate and up to 10% by weight of unsaturated epoxide.
7 Composition selon l'une quelconque des revendications 1 à 3 dans laquelle (A) est le PMMA et (C) un modifiant choc acrylique.7 Composition according to any one of claims 1 to 3 in which (A) is PMMA and (C) an acrylic impact modifier.
8 Composition selon la revendication 7 comprenant 8 à 15 parties de (B) pour 92 à 85 parties de (A)+(C).8 Composition according to claim 7 comprising 8 to 15 parts of (B) for 92 to 85 parts of (A) + (C).
9 Composition selon la revendication 7 comprenant 8 à 11 parties de (B) pour 92 à 89 parties de (A)+(C).9 Composition according to claim 7 comprising 8 to 11 parts of (B) for 92 to 89 parts of (A) + (C).
10 Objets fabriqués dans une composition selon l'une quelconque des revendications précédentes. 10 Objects made in a composition according to any one of the preceding claims.
EP00960806A 1999-09-09 2000-09-06 Antistatic acrylic polymer compositions Withdrawn EP1144505A3 (en)

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Application Number Priority Date Filing Date Title
FR9911281 1999-09-09
FR9911281 1999-09-09
FR9911744 1999-09-20
FR9911744A FR2798666A1 (en) 1999-09-20 1999-09-20 Antistatic acrylic polymer compositions comprise acrylic polymer, copolymer with polyamide blocks and polyether blocks, and polymer selected among acrylic impact modifiers and specified copolymers
PCT/FR2000/002453 WO2001018111A2 (en) 1999-09-09 2000-09-06 Antistatic acrylic polymer compositions

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EP1144505A3 true EP1144505A3 (en) 2002-02-20

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WO2001018111A2 (en) 2001-03-15
US6525134B1 (en) 2003-02-25
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KR20010099799A (en) 2001-11-09
JP2003508622A (en) 2003-03-04
EP1144505A2 (en) 2001-10-17

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