Classifications

• • 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
  • C08L25/06—Polystyrene
• • 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
  • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
  • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
• • 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
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/04—Homopolymers or copolymers of ethene
  • C08L23/08—Copolymers of ethene
• • 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
  • C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L35/06—Copolymers with vinyl aromatic monomers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
• • 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 anti-static styrene polymer compositions and more specifically a composition comprising a styrene polymer (A), a copolymer (B) containing polyamide blocks and polyether blocks essentially comprising ethylene oxide units - (C2H4— O) - and a compatibilizer (C).
• styrene polymer (A) antistatic properties This is to give the styrene 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.
• Styrene resins such as for example polystyrene or ABS are used to make cases for computers, telephones, televisions, photocopiers as well as many objects. Static electricity causes the accumulation of dust but above all can also damage the microprocessors or the components of the electronic circuits contained in these objects.
• antistatic agents such as ionic surfactants of the ethoxylated amino or sulfonate type which are added to polymers.
• 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 prior art]
• Japanese patent application JP 60 170 646 A published on September 4, 1985 describes compositions consisting of 0.01 to 50 parts of polyether block amide and 100 parts of polystyrene, they are useful for making sliding parts and resistant parts to wear. Antistatic properties are not mentioned.
• Patent application EP 167 824 published on January 15, 1986 describes compositions similar to the previous ones and according to one form of the invention, the polystyrene can be mixed with a polystyrene functionalized with an unsaturated carboxylic anhydride. These compositions are useful for making injected parts. Antistatic properties are not mentioned.
• 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.
• the amount of polyetheresteramide in the examples is 30% by weight of the compositions.
• Patent EP 242 158 describes antistatic compositions comprising
• compositions also comprise a vinyl polymer functionalized with a carboxylic acid which may for example be a polystyrene modified with methacrylic acid.
• the prior art shows either mixtures (i) of styrene resin and polyetheresteramide without compatibilizer, or mixtures (ii) of polyetheresteramide and functionalized styrene resin or alternatively mixtures (iii) of polyetheresteramide, non-functionalized styrene resin and functionalized styrene resin.
• mixtures (i) are antistatic if the polyetheresteramide is well chosen but have poor mechanical properties, in particular the elongation at break is much less than that of styrene resin alone.
• mixtures (ii) and (iii) it is necessary to have a functionalized styrene resin, which is complicated and expensive.
• the object of the invention is to make the ordinary styrene resins used to make the objects mentioned above antistatic, these resins not being functionalized. It has now been found that by using particular compatibilizers it is possible to obtain anti-static styrene resin compositions which retain the properties of the basic styrene resin and even have a markedly improved elongation at break.
• the present invention relates to a composition comprising per 100 parts by weight:
• (C) being a compatibilizer chosen from the low-mass copolymers (C1) of styrene and of an unsaturated carboxylic acid anhydride, the copolymers (C2) of ethylene and of an unsaturated carboxylic acid anhydride, copolymers (C3) of ethylene and an unsaturated epoxide, block copolymers (C4) SBS or SIS grafted with a carboxylic acid or an anhydride of an unsaturated carboxylic acid and their mixtures,
• styrene polymer As an example of a styrene polymer (A), mention may be made of polystyrene, polystyrene modified by elastomers, copolymers of styrene and acrylonitrile (SAN), SAN modified by elastomers, in particular ABS which the mixtures of SAN and ABS are obtained, for example, by grafting (graft-polymerization) of styrene and acrylonitrile onto a trunk of polybutadiene or of butadiene-acrylonitrile copolymer.
• SAN styrene polystyrene polystyrene modified by elastomers
• ABS graft-polymerization
• the elastomers mentioned above can for example be EPR (abbreviation of ethylene-propylene-rubber or ethylene-propylene elastomer), EPDM (abbreviation of ethylene-propylene-diene rubber or ethylene-propylene-diene elastomer), polybutadiene, acrylonitrile-butadiene copolymer, polyisoprene, isoprene-acrylonitrile copolymer.
• EPR abbreviation of ethylene-propylene-rubber or ethylene-propylene elastomer
• EPDM abbreviation of ethylene-propylene-diene rubber or ethylene-propylene-diene elastomer
• polybutadiene acrylonitrile-butadiene copolymer
• polyisoprene polyisoprene
• isoprene-acrylonitrile copolymer abbreviation of ethylene-propylene-rubber or ethylene-propy
• part of the styrene can be replaced by unsaturated monomers copolymerizable with styrene, by way of example, we may mention alpha-methylstyrene and (meth) acrylic esters.
• styrene copolymers mention may also be made of chloropolystyrene, poly-alpha-methylstyrene, styrene-chlorostyrene copolymers, styrene-propylene copolymers, styrene-butadiene copolymers, styrene-isoprene copolymers, styrene-chloride copolymers of vinyl, styrene-vinyl acetate copolymers, styrene-alkyl acrylate copolymers (methyl, ethyl, butyl, octyl, phenyl acrylate), styrene-alkyl methacrylate copolymers (methacrylate of methyl, ethyl, butyl, phenyl), styrene - methyl chloroacrylate copolymers and styrene
• the polymers (B) with polyamide blocks and polyether blocks result from the copolycondensation of polyamide sequences with reactive ends with polyether blocks with reactive ends, such as, inter alia: 1) Polyamide sequences with diamine chain ends with polyoxyalkylene sequences with dicarboxylic chain ends.
• 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.
• polyamide blocks and polyether blocks can also include patterns 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 one-step reaction, 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 there may be mentioned aminoundecanoic acid, as an example of a lactam, there may be mentioned caprolactam and lauryllactam, as an example of a dicarboxylic acid, there may be mentioned adipic acid.
• the polyamide blocks are made of polyamide 12 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
• lactam By way of example of 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 aiiphatic diamine having from 6 to 12 atoms, it can be arylic and / or cyclic saturated.
• IPD isophorone diamine
• MPDM methyl pentamethylenediamine
• AFM 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, propyiene 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 propyiene 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 quantity 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 with respect to the stoichiometry of 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 the copolymers obtained are in the molten state.
• this temperature can be between 100 and 400 ° C.
• the reaction is followed by measuring the torsional torque exerted by the molten polymer on the agitator or by measuring 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.
• 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.
• the C1 to C24 alkyl radicals from which the radicals R of the tetraalkoxides used as catalysts in the process according to the invention are chosen are for example such as methyl, ethyl, propyl, isopropyl, butyl, ethylhexyl, decyl, dodecyl, hexadodecyl.
• Preferred catalysts are tetraalkoxides for which the radicals R, which are identical or different, are C al alkyl radicals
• 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) p Y in which R-
• 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 which are combined to constitute the mixed catalyst can vary within wide limits 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 of all of the tetraalkoxide (s) and of alkaline or alkaline alcoholate (s) 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.
• the metal salts are examples of other derivatives that may also be mentioned.
• 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, acid cyclohexane carboxylic, 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.
• 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, acid cyclohexane
• 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.
• the two-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.
• 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-en-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:
• 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.
• compatibilizers (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.
• polyethylenes to 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
• alpha olefins that may be mentioned include propyiene, 1 -butene, 1-pentene, 3-methyl-1 -butene, 1-hexene, 4- methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1 - eicocene, 1-dococene, 1-tetracocene, 1-hexacocene, 1-octacocene, and 1- t acontene; 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,
• - dienes such as, for example, 1,4-hexadiene.
• the polyethylene can comprise several comonomers.
• 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 / c ⁇ MFI (index viscosity at 190 ° C, 2.16 kg) is advantageously between 1 and 1000 g / 10 min.
• polyethylenes that may be mentioned:
• LDPE low density polyethylene
• HDPE high density polyethylene
• LLDPE linear low density polyethylene
• VLDPE very low density polyethylene
• metallocene catalysis ie polymers obtained by copolymerization of ethylene and alphaolefin such as propyiene, butene, hexene or octene in the presence of a single-site catalyst generally consisting of a zirconium or titanium atom 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 the methylaluminoxane (MAO).
• MAO methylaluminoxane
• Hafnium can also be used as the metal to which cyclopentadiene is attached.
• Other metallocenes can include transition metals from groups IV A, VA, and VI A.
• Metals from the lanthamide series can also be used.
• - EPR elastomers ethylene - propyiene - 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 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 solvent phase or on 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 bar.
• unsaturated epoxides there may be mentioned: - aliphatic glycidyl esters and ethers such as allyl glycidylether, vinyl glycidylether, maleate and glycidyl itaconate, 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-norbornene-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 glycidylether, vinyl glycidylether, maleate and
• the compatibilizer (C3) is obtained from the grafting of a homo or copolymer polyethylene as described for (C2) except that an epoxide is grafted instead of an anhydride.
• the compatibilizer (C3) is obtained from the grafting of a homo or copolymer polyethylene as described for (C2) except that an epoxide is grafted instead of an anhydride.
• 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 compatibilizer (C3) is advantageously an ethylene / (meth) 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.
• compatibilizers these are polystyrene / polybutadiene / polystyrene (SBS), polystyrene / polyisoprene / polystyrene (SIS) copolymers. They can be hydrogenated. In other words, they can be polystyrene / poly (ethylene-butene) / polystyrene (SEBS) block copolymers, polystyrene / poly (ethylene-propylene) / polystyrene (SEPS).
• SBS polystyrene / polybutadiene / polystyrene
• SEBS polystyrene
• SEBS polystyrene / poly (ethylene-butene) / polystyrene (SEBS) block copolymers
• SEPS polystyrene / poly (ethylene-propylene) / polystyrene
• block copolymers are advantageously grafted with acrylic acid or maleic anhydride. It would not go beyond the scope of the invention to use one or more compatibilizers (C1), one or more compatibilizers (C2), one or more compatibilizers (C3), one or more compatibilizers (C4) or a mixture of at least two of these compatibilizers.
• Anti-statism increases with the proportion of (B) and for equal amounts of (B) with the proportion of ethylene oxide units contained in (B).
• the amount of (B) + (C) is advantageously from 5 to 20 parts for 95 to 80 parts of (A) and preferably from 10 to 15 for 90 to 85 parts of (A).
• the ratio (B) / (C) is advantageously between 4 and 6.
• mineral fillers talc, Ca3CO, kaolin, etc.
• reinforcements fiberglass, mineral fiber, carbon fiber, etc.
• stabilizers thermo, UV
• flame retardants and dyes talc, Ca3CO, kaolin, etc.
• compositions of the invention are prepared by the usual techniques of thermoplastics such as for example by extrusion or using twin-screw mixers.
• the present invention also relates to objects manufactured with the preceding compositions; these are for example films, tubes, plates, packaging, computer or telephone cases.
• PS it is a shock polystyrene.
• This copolymer is characterized by a melt index at 200 ° C under 5 kg of between 3 and 5 g / 10 min (ISO standard
• Pebax® 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 / 1kg and the melting point at 158 ° C.
• Lotader® AX terpolymer of ethylene, methyl acrylate and glycidyl methacrylate. This terpolymer has an MFI of 6 (190 ° C / 325gr) and a melting point of 63 ° C.
• - Orevac® Copolymer of ethylene and methyl acrylate grafted with maleic anhydride. This product has a melting point of 65 ° C and an MFI of 3.5 under 190 ° C / 2.16 kg conditions. In the following examples, the following characterization techniques were used:
• compositions obtained are injected on a press at temperatures of 200 to 220 ° C in the form of dumbbells or plates. Dumbbells allow tensile tests to be carried out according to ISO R527.
• Plates with dimensions of 100mmx100mmx2mm are injection molded and allow resistivity measurements to be made according to the IEC-93 standard.
• the surface resistivity is measured in ohm / D and the half-discharge time (CDT) in seconds; the properties obtained in tension are also given. 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.
• a Buss co-mixer of length equal to eleven times the diameter (Buss 11 D) is used with a total flow rate of 25 kg / h. This flow represents the sum of the flows ingredients used.
• the set temperatures of the sleeves are those usually used for a polystyrene, that is to say 200 to 220 ° C.
• the rods from the machine are cooled in a water tank and are transformed into granules. These granules are injected in the form of plates or dumbbells at a temperature between 220 and 240 ° C. The results are shown in Table 1 below.

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  • 2000-06-26 US US09/806,710 patent/US6825270B1/en not_active Expired - Fee Related
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