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WO2001068765A2 - Compositions polymere styrenique antistatiques - Google Patents

Compositions polymere styrenique antistatiques Download PDF

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Publication number
WO2001068765A2
WO2001068765A2 PCT/SG2001/000041 SG0100041W WO0168765A2 WO 2001068765 A2 WO2001068765 A2 WO 2001068765A2 SG 0100041 W SG0100041 W SG 0100041W WO 0168765 A2 WO0168765 A2 WO 0168765A2
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Prior art keywords
blocks
copolymer
copolymers
weight
advantageously
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WO2001068765A3 (fr
Inventor
Ganeshram Gopalakrishnan
Foong Jen Ho
Wai Shyan Yeo
Chen Shiong Foong
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Atofina South East Asia Pte Ltd
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Atofina South East Asia Pte Ltd
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Publication of WO2001068765A3 publication Critical patent/WO2001068765A3/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • 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
    • 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
    • C08L33/062—Copolymers with monomers not covered by C08L33/06
    • C08L33/068—Copolymers with monomers not covered by C08L33/06 containing glycidyl groups
    • 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
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers

Definitions

  • the present invention relates to antistatic styrenic polymer compositions and more specifically to a composition comprising " a styrenic polymer (A), a copolymer (B) containing polyether blocks comprising essentially ethylene oxide units -(C2H4-0)-, a compatibilizer (C) and an antistatic mixture (D) based on fibres.
  • the aim of the invention is to give the styrenic polymer (A) antistatic, properties.
  • the formation and retention of static-electricity charges on the surface of most plastics are known.
  • the presence of static electricity on thermoplastic films results, for example, in these films sticking to one another, making them difficult to separate.
  • the presence of static electricity on packaging films may cause the accumulation of dust on the articles to be packaged and thus impede their use.
  • Styrenic resins such as polystyrene or ABS, are used for making compartmentalized boxes and for making trays on which loose electronic components are placed prior to their assembly on cards, and it is necessary for these boxes and these trays to be antistatic, so that they do not irretrievably damage the components.
  • Antistatic styrenic resins are also used to make reels and pieces for photocopy machines.
  • Plastic Reels uses a 3-piece concept. A special locking mechanism enables 2 pieces of 13" flange and. a hub to be assembled easily. Flanges and hubs are packed in a compact format and assembled when needed, this reducing storage space at user's end. Hubs are available in different widths of 8.5 to 56.5mm. Reels and hubs are manufactured by injection moulding. These plastic reels are used for IC packaging. IC's are packed in a flexible strap and then this strap can wound on these reels.
  • antistatic agents such as ionic surfactants of the ethoxylated amine or sulphonate type, which are added to polymers.
  • antistatic properties of the polymers depend on the ambient moisture level and are not permanent since these agents migrate to the surface of the polymers and disappear. It has therefore been proposed to use, as antistatic agents, copolymers containing polyamide blocks and hydrophilic polyether blocks, these agents having the advantage of not migrating and therefore of giving permanent antistatic properties which are also independent of the ambient moisture level.
  • Japanese Patent Application JP 60 170 646 A published on 4 September 1985 describes compositions consisting of from 0.01 to 50 parts of a polyether- block-amide and 100 parts of polystyrene; these are useful for making sliding parts and wear-resistant parts. No mention is made of antistatic properties.
  • Patent Application EP 167 824 published on 15 January 1986 describes compositions similar to those mentioned previously, and in one embodiment of the invention polystyrene may be blended with a polystyrene functionalized by an unsaturated carboxylic anhydride. These compositions are useful for making injection mouldings. No mention is made of antistatic properties.
  • Japanese Patent Application JP 60 023 435 A published on 6 February 1985 describes antistatic compositions comprising from 5 to 80% of polyetheresteramide and from 95 to 20% of a thermoplastic resin chosen, inter alia, from polystyrene, ABS and P A, this resin being functionalized by acrylic acid or maleic anhydride.
  • the quantity of polyetheresteramide in the examples is 30% by weight of the compositions.
  • Patent EP 242 158 describes antistatic compositions comprising from 1 to 40% of polyetheresteramide and from 99 to 60% of a thermoplastic resin chosen from styrenic resins, PPO and polycarbonate. According to a preferred embodiment the compositions also comprise a vinyl polymer functionalized by a carboxylic acid. This may, for example, be a methacrylic-acid-modified polystyrene.
  • Patent EP 829 520 describes substrates such as PVC, HDPE, LLDPE, polypropylene, ABS and polystyrene, rendered antistatic by adding an antistatic mixture consisting of a copolymer having polyamide blocks and polyether blocks, a salt such as sodium perchlorate and a fibrous material or a material which forms fibres in the course of introducing the mixture into the substrate.
  • the proportion by weight of the antistatic mixture is from 0.1 to 15%, preferably from 1 to 15%, of the substrate.
  • the proportion by weight of the salt is from 0.05 to 10%), preferably from 0.5 to 5%, of the quantity of copolymer containing polyamide blocks and polyether blocks.
  • the ratio by weight of the quantity of fibres to copolymer containing polyamide blocks and polyether blocks is from 20/1 to 1/10, preferably from 10/1 to 1/3.
  • 3.84 g of copolymer containing polyamide blocks and polyether blocks 0.16 g of sodium perchlorate and 4 g of Nylon-6 fibres are added to 191.8 g of polystyrene. This corresponds to about 4% of antistatic mixture in 96% of polystyrene, the fibres representing half of the mixture.
  • 4.8 g of copolymer containing polyamide blocks and polyether blocks 0.2 g of sodium perchlorate and 5 g of Nylon-6 fibres are added to 189 g of polystyrene. This corresponds to about 5% of antistatic mixture in 95% of polystyrene, the fibres representing half of the mixture.
  • the surface resistivities are of the order of lO ⁇ ohms.
  • the blends of styrenic resin and polyetheresteramide without compatibilizer are antistatic if the polyetheresteramide is carefully chosen, but they have poor mechanical properties, in particular the elongation at break is far inferior to that of styrenic resin by itself.
  • the blends of polyetheresteramide and functionalized styrenic resin and the blends of polyetheresteramide, non-functionalized styrenic resin and functionalized styrenic resin it is necessary to use a functionalized styrenic resin, and this is complicated and expensive.
  • One aim of the invention is to render antistatic the ordinary styrenic resins used for making the abovemention ⁇ d articles, these resins not being functionalized.
  • the present invention relates to a composition
  • a composition comprising, per 100 parts by weight :
  • a compatibilizer chosen from low-mass copolymers (C1) of styrene and of an unsaturated carboxylic anhydride, copolymers (C2) of ethylene and of an unsaturated carboxylic anhydride, copolymers (C3) of ethylene and of an unsaturated epoxide, blocks copolymers (C4) of butadiene and styrene and mixtures of these,
  • styrenic polymer A
  • polystyrene elastomer-modified polystyrene, copolymers of styrene and acrylonitrile (SAN), elastomer-modified SAN, in particular ABS, which is obtained, for example, by grafting (graft polymerization) of styrene and acrylonitrile on a backbone of polybutadiene or of butadiene ' -acrylonitrile copolymer, and mixtures of SAN and ABS.
  • SAN acrylonitrile
  • Elastomers Possible examples of the abovementioned elastomers are EPR (the abbreviation for ethylene-propylene rubber or ethylene-propylene elastomer), EPDM (the abbreviation for ethylene- propylene-diene rubber or ethylene-propyiene-diene elastomer), polybutadiene, acrylonitrile-butadiene copolymer, polyisoprene and isoprene-acrylonitrile copolymer.
  • EPR the abbreviation for ethylene-propylene rubber or ethylene-propylene elastomer
  • EPDM the abbreviation for ethylene- propylene-diene rubber or ethylene-propyiene-diene elastomer
  • polybutadiene acrylonitrile-butadiene copolymer
  • polyisoprene and isoprene-acrylonitrile copolymer are examples of the abovementioned elastomers.
  • part of the styrene may be replaced by unsaturated monomers copoiymerizable with styrene, for example alpha-methylstyrene or (meth)acrylates.
  • unsaturated monomers copoiymerizable with styrene for example alpha-methylstyrene or (meth)acrylates.
  • styrene copolymers which may be mentioned are chloropolystyrene, poly-alpha-methylstyrene, styrene-chlorostyrene copolymers, styrene-propylene copolymers, styrene- butadiene copolymers, styrene-isoprene copolymers, styrene-vinyl chloride copolymers, styrene-vinyl acetate copolymers, styrene-alkyl acrylate copolymers (methyl, e
  • copolymer (B) By way of example of copolymer (B) mention may be made of copolymers (B1) containing polyamide blocks and polyether blocks, copolymers (B2) containing polyester blocks and polyether blocks and copolymers (B3) containing polyurethane blocks and polyether blocks (polyetherurethane).
  • the polyether blocks may represent from 5 to 85% by weight of (B).
  • the polyether blocks may contain units other than ethylene oxide units, for example propylene oxide units or polytetrahydrofuran units (leading to polytetramethylene glycol chain linkages). It is also possible to use at the same time PEG blocks, i.e. blocks consisting of ethylene oxide units, PPG blocks, i.e. blocks consisting of propylene oxide units, and PTMG blocks, i.e. blocks consisting of tetramethylene glycol units, also called polytetrahydrofuran. It is advantageous to use PEG blocks or blocks obtained by oxyethylation of bisphenols, such as bisphenol A. The latter products are described in patent EP 613 919.
  • the number-average molar mass M» of the polyether sequences is between 100 and 6000, preferably between 200 and 3000.
  • the quantity of polyether blocks in (B) is preferably from 10 to 50% by weight of (B).
  • the copolymers (B2) containing polyester blocks and polyether blocks are copolymers having polyether units derived from polyetherdiols, such as polyethylene glycol (PEG), dicarboxylic acid units, such as terephthalic acid, and glycol (ethanediol) units or 1,4-butanediol units.
  • PEG polyethylene glycol
  • dicarboxylic acid units such as terephthalic acid
  • glycol (ethanediol) units or 1,4-butanediol units glycol (ethanediol) units or 1,4-butanediol units.
  • copolymers (B3) containing polyurethane blocks and polyether blocks mention may be made of polyetherurethanes, "such as those containing diisocyanate units, units derived from polyetherdiols and units derived from ethanediol or from 1 ,4-butanediol.
  • the polymers (B1) containing polyamide blocks and polyether blocks result from copolycondensation of polyamide blocks having reactive end groups with polyether blocks having reactive end groups, such as for example:
  • polyamide blocks having dicarboxylic chain ends with polyetherdiols are advantageously of this type.
  • the polyamide blocks having dicarboxylic chain ends stem, for example, from the condensation of alpha-omega aminoacrboxylic acids, of lactams or of dicarboxylic acids and diamines in the presence of a chain-limiting dicarboxylic acid.
  • the number-average molar mass M consult of the polyamide blocks is between 300 and 15,000, preferably between 600 and 5000.
  • the mass M n of the polyether blocks is between 100 and 6000, preferably between 200 and 3000.
  • polymers containing polyamide blocks and polyether blocks may also contain randomly distributed units. These polymers may be prepared by simultaneous reaction of the polyether and of the precursors of the polyamide blocks
  • polymers containing polyamide blocks and polyether blocks which stem from copolycondensation of polyamide and polyether blocks prepared previously or from a one-step reaction have a Shore D hardness which may, for example, be between 20 and 75, 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 MFI values may be between 5 and 50 (235°C under a load of 1 kg).
  • the polyetherdiol blocks are used either as they are and copolycond.ensed with polyamide blocks having carboxylic end groups or are aminated in order to be converted into polyether diamines and condensed with polyamide blocks having carboxylic end groups.
  • polymers containing polyamide blocks and polyether blocks may also be mixed with precursors of polyamide and a chain-limiting compound to make the polymers containing polyamide blocks and polyether blocks and having randomly distributed units.
  • Polymers containing polyamide blocks and polyether blocks are described in patents US 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.
  • the polyamide blocks having dicarboxylic chain ends stem, for example, from condensation of alpha- omega aminoacrboxylic acids, of lactams or of 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 lactams mention may be made of caprolactam and laurolactam, by way of example of dicarboxylic acids mention may be made of adipic acid, decanedioic acid and dodecanedioic acid and by way of example of a diamine mention may be made of hexamethylenediamine.
  • the polyamide blocks are advantageously of Nylon-12 or Nylon-6.
  • the melting point of these polyamide blocks, which is also that of the copolymer (B1), is generally from 10 to 15°C below that of Nylon-12 or Nylon-6.
  • the polyamide blocks result from 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 from 4 to 12 carbon atoms and have low mass, i.e. an M n of from 400 to 1000.
  • alpha-omega aminocarboxylic acids mention may be made of aminoundecarioic acid and aminododecanoic acid.
  • dicarboxylic acids mention may be made of adipic acid, sebacic acid, isophthalic acid, butanedioic acid, 1 ,4-cyclohexyldicarboxylic acid, terephthalic acid, the sodium or lithium salt of sulphoisophthalic acid, dimerized fatty acids (these dimerized fatty acids have a content of at least 98% of dimer and are preferably hydrogenated) and dodecanedioic acid HOOC-(CH2) ⁇ o- COOH -
  • lactams mention may be made of caprolactam and laurolactam.
  • Caprolactam should be avoided unless the polyamide is purified to remove residual dissolved caprolactam monomer.
  • Polyamide blocks obtained by condensation of laurolactam in the presence of adipic acid or dodecanedioic acid and having a mass M ⁇ of 750 have a melting point of 127-130°C.
  • polyamide blocks result from 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 may be chosen from those mentioned above.
  • the diamine may be an aliphatic diamine having from 6 to 12 atoms, and may be an aryl diamine and/or a saturated cyclic diamine.
  • hexamethylenediamine piperazine, 1-aminoethylpiperazine, bisaminopropylpiperazine, tetramethylenediamine, octamethylenediamine, decamethyienediamine, dodecamethylenediamine, 1 ,5 diaminohexane, 2,2,4-trimethyl-1 ,6- diaminohexane, diamine polyols, isophoronediamine (IPD), methylpentamethylenediamine (MPDM), bis(aminocyclohexyl)methane (BACM) and bis(3-methyl-4-aminocyclohexyl)methane (BMACM).
  • IPD isophoronediamine
  • MPDM methylpentamethylenediamine
  • BMACM bis(
  • the various constituents of the polyamide block and their proportion are chosen so as to obtain a melting point below 150°C, advantageously between 90 and 135°C.
  • Low-melting-point copolyamides are described in patents US 4 483 975, DE 3 730 504 and US 5 459 230, and the same proportions of the constituents are used for the polyamide blocks of (B).
  • (B) may also be the copolymers described in US 5 489 667.
  • the copolymers of the invention may be prepared by any means which allows the polyamide blocks and the polyether blocks to be linked together.
  • use is essentially made of two processes, known as the 2-stage process and 1 -stage process.
  • the 2-stage process consists in firstly preparing the polyamide blocks having carboxylic end groups by condensation of the precursors of polyamide in the presence of a chain-limiting dicarboxylic acid, and then in a second step adding the polyether and a catalyst. If the precursors of polyamide are not- lactams or alpha-omega aminocarboxylic acids, a dicarboxylic acid is added.
  • the precursors already comprise a dicarboxylic acid this is used in excess with respect to the stoichiometry of the diamines.
  • the reaction usually takes place at between 180 and 300°C, preferably from 200 to 260°C, and the pressure in the reactor is set between 5 and 30 bar and maintained for approximately 2 hours. The pressure is reduced slowly to atmospheric pressure and then the excess water is distilled off for, for example, one or two hours.
  • the polyether and a catalyst are added.
  • the polyether may be added in one or more portions, and the same applies to the catalyst.
  • the polyether is added first, and the reaction of the OH end groups of the polyether with the COOH end groups of the polyamide begins, with the formation of ester linkages and elimination of water. The water is removed as far as possible by distillation from the reaction mixture, and then the catalyst is introduced in order to complete the linking of the polyamide blocks to the polyether blocks.
  • This second step takes place with stirring, preferably under a vacuum of at least 5 mm Hg (650 Pa) at a temperature such that the reactants and the copolymers obtained are in the molten state.
  • this temperature may be between 100 and 400°C, usually between 200 and 300°C.
  • the reaction is monitored by measuring the torque exerted by the polymer melt on the stirrer or by measuring the electrical power consumed by the stirrer. The end of the reaction is determined by the value of the torque or of the target power.
  • the catalyst is defined as being any product promoting the linking of the polyamide blocks to the polyether blocks by esterification.
  • the catalyst is advantageously a derivative of a metal (M) chosen from the group consisting of titanium, zirconium and hafnium.
  • -C24-alkyl radicals from which the radicals R are chosen in the tetraalkoxides used as catalysts in the process according " to the invention include methyl, ethyl, propyl, isopropyl, butyl, ethylhexyl, decyl, dodecyl and hexadodecyl.
  • Preferred catalysts are the tetraalkoxides in which the radicals R are identical or different and are C-
  • Particular examples of catalysts of this type are Zr(OC2H5)4, Zr(O-isoC*3H7)4,
  • the catalyst used in this process according to the invention may consist of only one, or of a number, of the tetraalkoxides of formula M(OR)4 defined above. It may also be formed by a combination of one or more of these tetraalkoxides with one or more alkali metal alcoholates or alkaline earth metal alcoholates of the formula (R ⁇ O)pY in which R- denotes a hydrocarbon residue, advantageously a C-1-C24 alkyl residue, preferably a C-
  • the quantitites of alkali metal alcoholate or alkaline earth metal alcoholate and of tetraalkoxides of zirconium or of hafnium which are combined to constitute the mixed catalyst may vary within wide limits. However, it is preferable for the quantities of alcoholate and of tetraalkoxides used to be such that the molar proportion of alcoholate is approximately equal to the molar proportion of tetraafkoxide.
  • the proportion by weight of catalyst that is to say of the tetraalkoxide(s) if the catalyst does not contain an alkali metal alcoholate or alkaline earth metal alcoholate or else all of the tetraalkoxide(s) and of the alkali metal alcoholate(s) or alkaline earth metal alcoholate(s) if the catalyst is formed by a combination of these two types of compounds, advantageously varies from 0.01 to 5% by weight of the mixture of the dicarboxylic polyamide 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 an organic acid and the complex salts between the oxide of (M) and/or the hydroxide of (M) and an organic acid.
  • the organic acid may advantageously be formic, acetic, propionic, butyric, valeric, caproic, caprylic, lauric, myristic, palmitic, stearic, oleic, linoleic, linolenic, cyclohexanecarboxylic, phenylacetic, benzoic, salicylic, oxalic, malonic, succinic, glutaric, adipic, maleic, fumaric, phthalic and crotonic acid. Acetic and propionic acids are particularly preferred.
  • M is advantageously zirconium. These salts may be called zirconyl salts.
  • all the reactants used in the two- step process are mixed together, that is to say the precursors of polyamide, the chain-limiting dicarboxylic acid, the polyether and the catalyst. They are the same reactants and the same catalyst as in the two-step process described above. If the precursors of polyamide are not lactams it is advantageous to add a little water.
  • the copolymer has essentially the same polyether blocks and the same polyamide blocks, but also a small portion of the various reactants that have reacted randomly and are distributed randomly 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 established is between 5 and
  • 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 organic acid.
  • copolymer (B) use is made of utilise Pebax® MV1074 or Pebax® MH1657 marketed by ELF ATOCHEM, Pelestat® 7530 or Pelestat® 7490 or Pelestat® 6321 marketed by Sanyo Chemicals Japan or C- 2300 marketed by BF Goodrich.
  • the unsaturated carboxylic acid anhydride may be chosen, for example from maleic, itaconic, citraconic, allylsuccinic, cyclohex-4-ene-1 ,2-dicarboxylic, 4-methylenecyclohex-4-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 anhydride. It is advantageous to use maleic anhydride.
  • the number-average molar mass is between 800 and 10,000, preferably between 1000 and 3500.
  • (C1) may be represented by the following formula:
  • MAH denotes maleic anhydride
  • m varies from 1 to 3
  • n varies from 6 to 8.
  • SMA® Resins by ELF ATOCHEM.
  • compatibilizers (C2) these may be polyethylenes grafted by an unsaturated carboxylic anhydride or copolymers of ethylene and of an unsaturated carboxylic anhydride, obtained, for example, by free-radical polymerization.
  • alpha-olefins advantageously those having from 3 to 30 carbon atoms; by way of 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-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1 — eicosene, 1-docosene, 1-tetracosene, 1- hexacosene, 1 — octacosene and 1-triacontene; these alpha-olefins may be used alone or as a mixture of two or more of the same,
  • alkyl (meth)acrylates such as for example alkyl (meth)acrylates, where the alkyl radicals may have up to 24 carbon atoms and
  • alkyl acrylates and methacrylates are in particular methyl methacrylate, ethyl acrylate, n-butyl acrylate, isobutyi acrylate and 2-ethylhexyl acrylate,
  • - dienes such as ,4-hexadiene
  • the polyethylene may contain a number of comonomers.
  • the polyethylene which may be a mixture of a number of polymers, advantageously contains at least 50%, preferably 75% (in moles) of ethylene and its density may be between 0.86 and 0.98 g/cm 3 .
  • the MFI index of the viscosity at 190°C and 2.16 kg is advantageously between 1 and 1000 g/10 min.
  • LDPE low-density polyethylene
  • HDPE high-density polyethylene
  • LLCPE linear low-density polyethylene
  • VLDPE very-low-density polyethylene
  • metallocene catalysis that is to say polymers obtained by copolymerizing ethylene and alpha-olefin, such as propylene, butene, hexene or octene, in the presence of a single-site catalyst generally consisting of a zirconium or titanium atom and of two cyclic alkyl molecules linked to the metal. More specifically, metallocene catalysts are usually composed of two cyclopentadiene rings linked to the metal. These catalysts are frequently used with aluminoxanes as cocatalysts or activators, preferably methylaluminoxane (MAO). Hafnium may also be used as the metal to which the cyclopentadiene is bonded. Other metallocenes may include transition metals from groups IV A, V A, or VI A. Metals from the lanthanide series may also be used.
  • copolymers of ethylene and unsaturated carboxylic anhydride that is to say those in which the unsaturated carboxylic anhydride is not grafted
  • these are copolymers of ethylene, unsaturated carboxylic anhydride and possibly another monomer which may be chosen from the comonomers mentioned above as ethylene copolymers for grafting.
  • ethylene-maleic anhydride copolymers or ethylene-alkyl (meth)acrylate-maleic anhydride copolymers contain from 0.2 to 10% by weight of maleic anhydride and from 0 to 40%o by weight of alkyl (meth)acrylate.
  • Their MFI is between 1 and 50 (190°C - 2.16 kg).
  • alkyl (meth)acrylates have been described above.
  • the unsaturated carboxylic anhydride in (C2) with an unsaturated carboxylic acid, such as (meth)acrylic acid, and this function may be partially neutralized by an alkali metal (Li) or another metal (Zn), giving ionomers.
  • lonomers of this type are marketed by the company DUPONT with the trade mark Surlyn®.
  • the compatibilizers (C3) the copolymer of ethylene and an unsaturated epoxide can be obtained by copolymerizing ethylene and an unsaturated epoxide, or by grafting the unsaturated epoxide onto the polyethylene.
  • the grafting may be carried out in a solvent phase or on the polyethylene melt in the presence of a peroxide. These grafting techniques are known per se. As regards the copolymerization of ethylene with an unsaturated epoxide, use may be made of what are known as free-radical polymerization processes, which usually operate at pressures between 200 and 2500 bar.
  • unsaturated epoxides By way of example of unsaturated epoxides, mention may be made of: - aliphatic glycidyl ethers and esters, such as allyl glycidyl ether, vinyl glycidyl ether, glycidyl maleate, glycidyl itaconate and glycidyl (meth)acrylate, and alicyclic glycidyl ethers and esters, such as 2-cyclohexen-1- yl glycidyl ether, diglycidyl cyclohexene-4,5-dicarboxylate, glycidyl cyclohexene-4-carboxylate, glycidyl 2-methyl- 5-norbornene-2- carboxylate and diglycidyl endo-cis-bicyclo[2.2.1]hept-5-ene-2,3- dicarboxylate.
  • the compatibilizer (C3) is obtained by grafting a polyethylene homo- or copolymer as described for (C2) except that an epoxide is grafted instead of an anhydride.
  • copolymerization this is also similar to the case of (C2) except that an epoxide is used, and there may also be other comonomers present, as in the case of (C2).
  • the compatibilizer (C3) is advantageously an ethylene/alkyl (meth)acrylate/unsaturated epoxide copolymer. It may advantageously contain up to 40% by weight of alkyl (meth)acrylate and up to 10% by weight of unsaturated epoxide, preferably from 0.1 to 8%.
  • the epoxide is advantageously glycidyl (meth)acrylate.
  • the alkyl (meth)acrylate is advantageously chosen from methyl
  • (meth)acrylate ethyl acrylate, n-butyl acrylate, isobutyl acrylate and 2-ethylhexyl acrylate.
  • the quantity of alkyl (meth) acrylate is advantageously from 20 to 35%.
  • the MFI is advantageously between 1 and 50 (g/10 min at 190°C under a load of 2.16 kg). This copolymer may be obtained by free-radical polymerization of the monomers.
  • compatibilizers are copolymers with styrene blocks and blocks made of butadiene or isoprene or of a mixture butadiene /isoprene. They can be linear blocks copolymers or star blocks copolymers. These copolymers are described in ULLMANN'S ENCYCLOPEDIA OF INDUSTRIAL CHEMISTRY , fith edition (1995) Vol A26, pages 655-659. They can be hydrogenated. They can bemputationnalized, advantageously by grafted functions as explained for (C2) an (C3).
  • compatibilizers C1
  • compatibilizers C2
  • compatibilizers C3
  • compatibilizers C4
  • the antistatic behaviour increases with the proportion of (B) and, for equal amounts of (B), with the proportion of ethylene oxide units present in (B).
  • these fibres may also be in the form of nonwoven or felt.
  • These fibres advantageously have a length of from 0.01 to 200 mm, preferably from 0.1 to 20 mm.
  • the size of these fibres is advantageously from 0.5 to 500 dtex, preferably from 1 to 100 dtex (where dtex corresponds to g/10,000 m).
  • the material of these fibres is advantageously polyamide or polyester, with the proviso that it is insoluble in (A).
  • (D1) which is not in the form of fibres prior to entering the composition of the invention, but in the form of pellets use is made of pellets of polyamide or of polyester, with the proviso that they are insoluble in (A). During the course of mixing with the other constituents of the composition, (D1) turns into fibres.
  • the copolymer (D2) is described in EP 829 520, in which it is called b2. It is advantageously from the same family as (B1 ), and may be identical to or different from (B1). With regard to (D3), this compound is described in EP 829 520, in which it is called b3.
  • These are advantageously salts of alkali metals or alkaline earth metals, of zinc or of ammonium.
  • the organic salts advantageously have from 1 to 4 carbon atoms, and examples of these are salts of acetic, trifluoroacetic, methanesulphonic or trifluoromethanesulphonic acid.
  • the inorganic salts are, for example, LiCIO 4 , NaCI0 4 , LiBF 4 , NaBF 4 , KBF 4 , KClO 4 .
  • the proportion by weight of the salt (D3) is from 0.05 to 10%, preferably from 0.5 to 5%, of the quantity of copolymer (D2).
  • the ratio by weight of the quantity of fibres (D1) to the quantity of copolymer (D2) is from 20/1 to 1/10, preferably from 10/1 to 1/3. In one particular embodiment this ratio (D1)/(D2) is between 2/1 and 1/2. In another embodiment the ratio (D1)/(D2+D3) by weight is between 0.8 and 1.2.
  • the mixture (D) may also comprise polyamides, advantageously Nylon-6 if the polyamide blocks of (D2) are of Nylon-6, and advantageously Nylon-12 if the polyamide blocks of (D2) are of Nylon-12.
  • mixtures (D) use is made of IRGASTAT®P22 and IRGASTAT®P18 marketed by Ciba Specialty Chemicals.
  • mineral fillers talc, CaC ⁇ 3, kaolin, etc.
  • reinforcing materials glass fibre, mineral fibre, carbon fibre, etc.
  • stabilizers heat, UV
  • flame-retardants or colorants talc, CaC ⁇ 3, kaolin, etc.
  • compositions of the invention are prepared by the techniques usual for thermoplastics, such as extrusion, or with the aid of twin-screw mixers.
  • the compositions could be directedly injected or moulded but generaly they are cooled and recovered as pellets. These pellets are then further melted in an extruder and processed as any thermoplastic.
  • the compositions of the invention remain antistatic whichever they are further extruded, or injected or thermoformed.
  • the present invention also relates to the articles manufactured with the above compositions, for example films, tubes or pipes, sheets, packaging, casings for computers or telephones and uses described in the previous chapter [field of the invention], [Examples]
  • the ingredients used in the examples below are as follows:
  • HIPS this is an impact-modified polystyrene.
  • This copolymer is characterized by a melt flow index between 3 and 5 g/10 min (ISO 1133:91 ) at 200°C under a load of 5 kg. It is also characterized by a Vicat temperature of
  • this is a copolyether-block-amide having Nylon-12 blocks of number-average molar mass 1500 and PEG blocks of number-average molar mass 1500; the MFI is 14 at 235 c C/1kg and the melting point is
  • Pebax®1657 this is a copolyether-block-amide having Nylon-6 blocks of number-average molar mass 1500 and PEG blocks of number-average molar mass 1500; the MFI is 14 at 235°C/1 kg and the melting point is 204°C.
  • Lotader® AX terpolymer of ethylene, methyl acrylate and glycidyl methacrylate. This copolymer has an MFI of 6 (190°C/325 g) and a melting point of 63°C.
  • - K-resin KK 38 SBS block copolymer.
  • - lrgastat®P22 mixture (D) in which (D2) is a block copolymer with PA 6 blocks and PEG blocks.
  • Plaques of dimensions 100 mm x 100 mm x 2 mm are injection-moulded and can be used to carry out surface resistivity measurements with the aid of two electrodes.
  • This very simple apparatus allows surface resistivities of up to 2.10 ⁇ 2 ohms to be measured and classifies higher values as "insulative".
  • This apparatus is sufficient and very simple to use for rapid classification of antistatic polystyrenes for trays or compartmentalized boxes in which loose electronic components are placed prior to their assembly on cards. The surface resistivity is measured in ohm per unit area.
  • An extruder of length equal to eleven times the diameter with a total throughput of 25 kg/h is used. This throughput represents the total of the throughputs of the ingredients used.
  • the temperature settings for the barrels are those normally used for a polystyrene, that is to say from 200 to 220°C.
  • the strands discharged from the machine are cooled in a water tank and converted into pellets. These pellets are injection-moulded to give plaques or dumbbells at a temperature between 220 and 240°C.
  • Tables 1-3 below, in which the quantities are weights Tables 1 and 2 are comparative, and Table 3 is in accordance with the invention.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne une composition comprenant, par 100 parties en poids, 95 à 80 % avantageusement 92 à 84 % d'un polymère styrénique (A) ; 3 à 11 % avantageusement 5 à 8 % d'un copolymère (B) contenant des blocs polyéther comprenant sensiblement des unités d'oxyde d'éthylène -(C2H4-0)- ; 1 à 3 % d'un compatibiliseur (C) choisi parmi des copolymères de faible masse (C1) de styrène et d'un anhydride carboxylique insaturé, des copolymères (C2) d'éthylène et d'un anhydride carboxylique insaturé, d'un copolymère (C3) d'éthylène et d'un époxyde insaturé, des copolymères séquencés (C4) de butadiène et de styrène et leurs mélanges ; 1 à 6 % avantageusement de 2 à 5 % d'un mélange (D). Ce mélange (D) contient un polymère (D1) sous forme de fibres ou formant des fibres pendant le mélange des constituants des compositions, et insoluble dans (A) ; un copolymère (D2) contenant des blocs polyéther comprenant sensiblement des unités d'oxyde d'éthylène -(C2H4-0); un sel organique ou inorganique (D23) de faible masse molaire.
PCT/SG2001/000041 2000-03-13 2001-03-13 Compositions polymere styrenique antistatiques Ceased WO2001068765A2 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2093238A1 (fr) 2008-02-21 2009-08-26 Total Petrochemicals France Procédé de préparation d'élastomères hydroperoxydés et leur utilisation en tant que polymères de monovinyle aromatiques à fort impact
WO2011050150A1 (fr) * 2009-10-23 2011-04-28 Exxonmobil Research And Engineering Company Copolymère poly(alpha-oléfine/alkylène glycol), son procédé de fabrication et formulation de lubrifiant le comprenant

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2466478B2 (fr) * 1979-10-02 1986-03-14 Ato Chimie Procede de preparation de copolyetheresteramides aliphatiques elastomeres
EP0242158B1 (fr) * 1986-04-14 1994-01-19 Toray Industries, Inc. Compositions de résine thermoplastique intrinsèquement antistatique
DE4235505A1 (de) * 1992-10-21 1994-04-28 Cheil Ind Inc Antistatische thermoplastische Styrolharzzusammensetzung
US5652326A (en) * 1993-03-03 1997-07-29 Sanyo Chemical Industries, Ltd. Polyetheresteramide and antistatic resin composition
EP0789049A1 (fr) * 1996-02-09 1997-08-13 Ciba SC Holding AG Polymères rendus antistatiques
ATE279479T1 (de) * 1996-09-16 2004-10-15 Ciba Sc Holding Ag Antistatische zusammensetzung

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2093238A1 (fr) 2008-02-21 2009-08-26 Total Petrochemicals France Procédé de préparation d'élastomères hydroperoxydés et leur utilisation en tant que polymères de monovinyle aromatiques à fort impact
WO2011050150A1 (fr) * 2009-10-23 2011-04-28 Exxonmobil Research And Engineering Company Copolymère poly(alpha-oléfine/alkylène glycol), son procédé de fabrication et formulation de lubrifiant le comprenant
US8455415B2 (en) 2009-10-23 2013-06-04 Exxonmobil Research And Engineering Company Poly(alpha-olefin/alkylene glycol) copolymer, process for making, and a lubricant formulation therefor

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