WO2004113437A1 - Compositions thermoplastiques d'ingenierie contenant des agents de couplage de polymeres d'olefines oxydees - Google Patents

Compositions thermoplastiques d'ingenierie contenant des agents de couplage de polymeres d'olefines oxydees Download PDF

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WO2004113437A1
WO2004113437A1 PCT/IB2004/002043 IB2004002043W WO2004113437A1 WO 2004113437 A1 WO2004113437 A1 WO 2004113437A1 IB 2004002043 W IB2004002043 W IB 2004002043W WO 2004113437 A1 WO2004113437 A1 WO 2004113437A1
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ethylene
olefin polymer
polymer material
propylene
weight
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PCT/IB2004/002043
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Vu A. Dang
Tam T. M. Phan
Cheng Q. Song
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Basell Poliolefine Italia S.P.A.
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Publication of WO2004113437A1 publication Critical patent/WO2004113437A1/fr

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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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    • C08K5/00—Use of organic ingredients
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    • 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
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    • 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
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    • 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
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    • 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
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/016—Flame-proofing or flame-retarding additives
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
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    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
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    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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    • C08L2205/00—Polymer mixtures characterised by other features
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    • 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
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
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    • 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
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • C08L23/30—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by oxidation
    • 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
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    • 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
    • C08L51/06—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 grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond

Definitions

  • the present invention relates to engineering thermoplastic compositions containing oxidized olefin polymer coupling agents for non-halogenated flame retardants or fillers, and blends of these engineering thermoplastic compositions with non-oxidized olefin polymer material.
  • Engineering thermoplastics possess properties such as high tensile strength, heat and chemical resistance and good abrasion characteristics that make them highly desirable for a variety of processing applications.
  • engineering thermoplastics are extremely versatile, since depending on the application, they can have properties similar to that of rubber, or be as strong as aluminum. It is well known that engineering thermoplastics can be combined with conventional polyolefms to augment properties such as hardness.
  • U.S. Patent Application No. 10/305,816 describes compatibilizing agents for blends of engineering thermoplastics and polyolefms using oxidized olefin polymer materials. It is also known that non-halogenated flame retardants and fillers can be used in polyolefm compositions to improve desirable physical properties.
  • the present invention relates to a non-halogenated flame retardant- containing or filler-containing engineering thermoplastic composition
  • a non-halogenated flame retardant- containing or filler-containing engineering thermoplastic composition comprising:
  • B 10.0 to 85.0 wt% of (i) a non-halogenated flame retardant, (ii) a filler chosen from fiberglass, carbon fibers,- graphite fibers, whiskers, metal fibers, aramides, talc, wollastonite, calcium carbonate, mica, glass microspheres, glass wool, rock wool, stainless steel wool, steel wool, gypsum, alumina, alumina-silica, and silica, and (iii) mixtures thereof; and C. 10.0 to 85.0 wt% of an engineering thermoplastic; wherein the sum of components A + B+ C is equal to 100 wt%.
  • the present invention relates to a non-halogenated flame retardant-containing or filler-containing engineering thermoplastic composition
  • a non-halogenated flame retardant-containing or filler-containing engineering thermoplastic composition comprising:
  • Olefin polymers suitable as a starting material for the oxidized olefin polymers, and for the non-oxidized olefin polymer material used in the engineering thermoplastic compositions of the invention include propylene polymer materials, ethylene polymer materials, butene-1 polymer materials, and mixtures thereof.
  • the propylene polymer material can be:
  • (C) a random terpolymer of propylene and two olefins chosen from ethylene and C 4 -C 8 ⁇ -olefins, containing 1 to 30 wt% of said olefins, preferably 1 to 20 wt%, and having an isotactic index greater than 60%, preferably greater than 70%;
  • the ethylene polymer material is chosen from (A') homopolymers of ethylene, (B 5 ) random copolymers of ethylene and an alpha-olefin chosen from C 3-10 alpha-olefins having a polymerized alpha- olefin content of 1 to 20% by weight, preferably 1% to 16%, (C) random terpolymers of ethylene and two C 3 -C 10 alpha olefins having a polymerized alpha-olefin content of 1% to 20% by weight, preferably, 1% to 16%, and (D') mixtures thereof.
  • A' homopolymers of ethylene
  • B 5 random copolymers of ethylene and an alpha-olefin chosen from C 3-10 alpha-olefins having a polymerized alpha- olefin content of 1 to 20% by weight, preferably 1% to 16%
  • C random terpolymers of ethylene and two C 3 -C 10 alpha olef
  • the useful polybutene-1 homo or copolymers are chosen from (A") homopolymers of butene-1, (B”) copolymers or terpolymers of butene-1 with ethylene, propylene or C 5 -C 10 alpha-olefins, the comonomer content ranging from 1 mole% to 15 mole%; and (C”) mixtures thereof.
  • the useful polybutene-1 homo or copolymers can be isotactic or syndiotactic and have a melt flow rate (MFR) from 0.1 to 150 dg/min, preferably from 0.3 to 100, and most preferably from 0.5 to 75.
  • MFR melt flow rate
  • butene-1 polymer materials their methods of preparation and their properties are known in the art.
  • Suitable polybutene-1 polymers can be obtained, for example, by using Ziegler-Natta catalysts with butene-1, as described in WO 99/45043, or by metallocene polymerization of butene-1 as described in WO 02/102811.
  • the butene-1 polymer materials contain up to 15 mole % of copolymerized ethylene or propylene. More preferably, the butene-1 polymer material is a homopolymer having a crystallinity of at least 30% by weight measured with wide-angle X-ray diffraction after 7 days, more preferably 45% to 70%, most preferably 55% to 60%.
  • the starting material for the oxidized olefin polymer material and the non-oxidized olefin polymer material in the compositions of the invention can be the same or different from each other.
  • the olefin polymer starting material is first exposed to high-energy ionizing radiation under a blanket of inert gas, preferably nitrogen.
  • the ionizing radiation should have sufficient energy to penetrate the mass of polymer material being irradiated to the extent desired.
  • the ionizing radiation can be of any kind, but preferably includes electrons and gamma rays. More preferred are electrons beamed from an electron generator having an accelerating potential of 500 to 4,000 kilovolts. Satisfactory results are obtained at a dose of ionizing radiation of 0.1 to 15 megarads ("Mrad"), preferably 0.5 to 9.0 Mrad.
  • Mrad megarad
  • rad is usually defined as that quantity of ionizing radiation that results in the absorption of 100 ergs of energy per gram of irradiated material regardless of the source of the radiation using the process described in U.S. Pat. No. 5,047,446.
  • Energy absorption from ionizing radiation is measured by the well-known convention dosimeter, a measuring device in which a strip of polymer film containing a radiation-sensitive dye is the energy absorption sensing means.
  • rad means that quantity of ionizing radiation resulting in the absorption of the equivalent of 100 ergs of energy per gram of the polymer film of a dosimeter placed at the surface of the olefin polymer material being irradiated, whether in the form of a bed or layer of particles, or a film, or a sheet.
  • the irradiated olefin polymer material is then oxidized in a series of steps.
  • the first treatment step consists of heating the irradiated polymer in the presence of a first controlled amount of active oxygen greater than 0.004% by volume but less than 15% by volume, preferably less than 8% by volume, more preferably less than 5% by volume, and most preferably from 1.3% to 3.0% by volume, to a first temperature of at least 25°C but below the softening point of the polymer, preferably 25°C to 140°C, more preferably 25°C to 100°C, and most preferably 40°C to 80°C. Heating to the desired temperature is accomplished as quickly as possible, preferably in less than 10 minutes.
  • the polymer is then held at the selected temperature, typically for 5 to 90 minutes, to increase the extent of reaction of the oxygen with the free radicals in the polymer.
  • the holding time which can be determined by one skilled in the art, depends upon the properties of the starting material, the active oxygen concentration used, the irradiation dose, and the temperature. The maximum time is determined by the physical constraints of the fluid bed.
  • the irradiated polymer is heated in the presence of a second controlled amount of oxygen greater than 0.004% but less than 15% by volume, preferably less than 8% by volume, more preferably less than 5% by volume, and most preferably from 1.3% to 3.0% by volume, to a second temperature of at least 25°C but below the softening point of the polymer.
  • a second controlled amount of oxygen greater than 0.004% but less than 15% by volume, preferably less than 8% by volume, more preferably less than 5% by volume, and most preferably from 1.3% to 3.0% by volume.
  • the second temperature is from 100°C to less than the softening point of the polymer, and greater than the first temperature of the first step.
  • the polymer is then held at the selected temperature and oxygen concentration conditions, for 10 to 300 minutes, preferably 20 to 180 minutes, to increase the rate of chain scission and to minimize the recombination of chain fragments so as to form long chain branches, i.e., to minimize the formation of long chain branches.
  • the holding time is determined by the same factors discussed in relation to the first treatment step.
  • a single oxygen treatment step according to the conditions set forth in the first treatment step above can be used.
  • a two oxygen treatment step process is preferred.
  • the oxidized olefin polymer material is heated under a blanket of inert gas, preferably nitrogen, to a third temperature of at least 80°C but below the softening point of the polymer, and held at that temperature for 10 to 120 minutes, preferably 60 minutes. A more stable product is produced if this step is carried out. It is preferred to use this step if the oxidized olefin polymer is going to be stored rather than used immediately, or if the radiation dose that is used is on the high end of the range described above.
  • the polymer is then cooled to a fourth temperature of 70°C over a period of 10 minutes under a blanket of inert gas, preferably nitrogen, before being discharged from the bed.
  • inert gas preferably nitrogen
  • a preferred method of carrying out the treatment is to pass the irradiated olefin polymer through a fluid bed assembly operating at a first temperature in the presence of a first controlled amount of oxygen, passing the polymer through a second fluid bed assembly operating at a second temperature in the presence of a second controlled amount of oxygen, and then maintaining the polymer at a third temperature under a blanket of nitrogen, in a third fluid bed assembly.
  • a continuous process using separate fluid beds for the first two steps, and a purged, mixed bed for the third step is preferred.
  • the process can also be carried out in a batch mode in one fluid bed, using a fluidizing gas stream heated to the desired temperature for each treatment step.
  • the fluidized bed method does not require the conversion of the irradiated polymer into the molten state and subsequent re-solidification and comminution into the desired form.
  • the fluidizing medium can be, for example, nitrogen or any other gas that is inert with respect to the free radicals present, e.g., argon, krypton, and helium.
  • the concentration of peroxide groups formed on the polymer can be controlled by varying the radiation dose during the preparation of the irradiated polymer and the amount of oxygen to which such polymer is exposed after irradiation.
  • the oxygen level in the fluid bed gas stream is controlled by the addition of dried, filtered air at the inlet to the fluid bed. Air must be constantly added to compensate for the oxygen consumed by the formation of peroxides in the polymer.
  • the oxidized olefin polymer materials can be prepared according to the following procedures.
  • the olefin polymer starting material is treated with 0.1 to 10 wt% of an organic peroxide initiator while adding a controlled amount of oxygen so that the olefin polymer material is exposed to greater than 0.004% but less than 21% by volume, preferably less than 15%, more preferably less than 8% by volume, and most preferably 1.0% to 5.0% by volume; at a temperature of at least 25°C but below the softening point of the polymer, preferably 25°C to 140°C.
  • the polymer is then heated to a temperature of at least 25°C up to the softening point of the polymer, preferably from 100°C to less than the softening point of the polymer, at an oxygen concentration that is within the same range as in the first treatment step.
  • the total reaction time is typically 0.5 hour to four hours.
  • the polymer is treated at a temperature of at least 80°C but below the softening point of the polymer, typically for 0.5 hour to about two hours, in an inert atmosphere such as nitrogen to quench any active free radicals.
  • Suitable organic peroxides include acyl peroxides, such as benzoyl and dibenzoyl peroxides; dialkyl and aralkyl peroxides, such as di-tert-butyl peroxide, dicumyl peroxide; cumyl butyl peroxide; l,l,-di-tert-butylperoxy-3,5,5-trimethylcyclohexane; 2,5-dimethyl- l,2,5-tri-tert-butylperoxyhexane,and bis(alpha-tert-butylperoxy isopropylbenzene), and peroxy esters such as bis(alpha-tert-butylperoxy pivalate; tert-butylperbenzoate; 2,5- dimethylhexyl-2,5-di(perbenzoate); tert-butyl-di(perphthalate); tert-butylperoxy-2- ethylhexanoate
  • the oxidized olefin polymer material used in compositions of the invention preferably contains greater than 1 mmol total peroxide per kilogram of oxidized olefin polymer material. More preferably, the oxidized olefin polymer material contains from greater than 1 to 200 mmol total peroxide per kilogram of oxidized olefin polymer material, most preferably from 5 to 100 mmol total peroxide per kilogram of oxidized olefin polymer material.
  • the oxidized olefin polymer material in compositions of the invention contain peroxide linkages that degrade during compounding to form various oxygen-containing polar functional groups, e.g., carboxylic acids, ketones and esters.
  • the number average and weight average molecular weight of the oxidized olefin polymer is usually lower than that of the corresponding olefin polymer material used to prepare same, due to the chain scission reactions during irradiation and oxidation. If the polymer peroxide is subjected to further processing involving heating to the melt temperature, e.g., extrusion, the peroxide groups decompose but the product still contains the other oxygen- containing groups mentioned above.
  • the number average molecular weight (Mschreib) of the oxidized olefin polymers is greater than 10,000. If the M n is lower than 10,000, the dispersing agent could potentially "bloom" at the surface of the finished product.
  • Ionomers of the oxidized olefin polymer can be prepared by methods well known in the art, where at least some of the carboxylic acid groups in the oxidized olefin polymers are neutralized in a slurry process, a melt process, by reactive extrusion, or by grafting with monomer salts. Melt neutralization is preferred.
  • Suitable basic compounds used for neutralization can be metal oxides, hydroxides or salts of alkali and alkali-earth metals and zinc, preferably sodium hydroxide, sodium carbonate, sodium bicarbonate, sodium carbonate monohydrate, sodium dihydrogenphosphate, sodium dihydrogenpyrophosphate, sodium hydrogenphosphate, sodium hydrogenphosphate heptahydrate, sodium pyrophosphate, sodium pyrophosphate decahydrate, sodium triphosphate, potassium hydroxide, potassium carbonate, potassium bicarbonate, potassium carbonate sesquihydrate, potassium hydrogenphosphate, potassium hydrogenphosphate trihydrate, potassium pyrophosphate, lithium hydroxide, lithium carbonate, lithium bicarbonate, lithium hydroxide monohydrate, lithium phosphate, zinc oxide, aluminum hydroxide, etc.
  • the starting material for making the oxidized olefin polymer material, and the non-oxidized olefin polymer material is a propylene homopolymer having an isotactic index greater than 80%. More preferably, the starting material is a propylene homopolymer having an isotactic index greater than 80%.
  • the oxidized olefin polymer material is preferably prepared by irradiation followed by exposure to oxygen as described herein above.
  • the oxidized olefin polymer material or ionomer of the oxidized olefin polymer material is present in an amount from 5.0 wt% to 80.0 wt%, preferably in an amount from 10.0 wt% to 75.0 wt%, more preferably in an amount from 15.0 wt% to 70.0 wt%.
  • the oxidized olefin polymer material or the ionomer of the oxidized olefin polymer material is present in amount from 2.0 wt% to 80.0 wt%, preferably in an amount from 5.0 wt% to 75.0 wt%, more preferably in an amount from 10.0 wt% to 70.0 wt%.
  • the engineering thermoplastics in compositions of the invention can be any thermoplastic resin, neat or unreinforced or unfilled, which maintains dimensional stability and most mechanical properties above 100°C and below 0°C, and includes plastics that can be formed into functional parts that can bear loads and withstand abuse in temperature environments commonly tolerated by traditional engineering materials such as wood, metals, glass, and ceramics.
  • Engineering thermoplastics suitable for use in the present invention include, for example, polyamides, polyesters, polycarbonates, polyimides, acrylonitrile- butadiene-styrene copolymers, and styrene-acrylonitrile copolymers, all of which are commercially available.
  • Suitable polyamides are well known and widely available. Such materials typically can be obtained by polymerizing a monoamino-monocarboxylic acid or a lactam thereof having at least two carbon atoms between the amine and carboxylic acid group, or by polymerizing substantially equimolecular proportions of a diamine that contains at least two carbon atoms between the amine groups and a dicarboxylic acid; or by polymerizing a monoaminocarboxylic acid or a lactam thereof as defined above together with substantially equimolecular proportions of a diamine and dicarboxylic acid.
  • the dicarboxylic acid may be used in the form of a functional derivative thereof, for example, an ester or acid chloride.
  • the polyamide can also be obtained by polymerizing the salt of a diamine and a dicarboxylic acid.
  • substantially equimolecular proportions (of the diamine and of the dicarboxylic acid) is used to cover both strict equimolecular proportions and slight departures therefrom that are involved in conventional techniques for stabilizing the viscosity of the resulting polyamides.
  • a monomer having a monoamine group or monocarboxylic acid group could also be added to control the molecular weight of the polyamide.
  • Examples of the monoamino-monocarboxylic acids or lactams thereof that are useful in preparing the polyamides include those compounds containing from 2 to 16 carbon atoms between the amino and carboxylic acid groups, the carbon atoms forming a ring with the - CO-NH- group in the case of a lactam.
  • Particular examples of aminocarboxylic acids and lactams include, for example, 6-aminocaproic acid, butyrolactam, pivalolactam, caprolactam, capryllactam, enantholactam, undecanolactam, dodecanolactam, and 3- and 4-aminobenzoic acids.
  • Diamines suitable for use in the preparation of the polyamides include alkyl, aryl and alkyl-aryl diamines.
  • Such diamines include, for example, those represented by the general formula:
  • n is an integer from 2 to 16, such as trimethylenediamme, tetramethylenediamme, pentamethylenediamme, octamethylenediamine and especially hexamethylenediamme, as well as trimethylhexamethylenediamine, meta-phenylenediamine, and meta-xylylenediamine.
  • the dicarboxylic acids can be aromatic, for example, isophthalic and terephthalic acids, or aliphatic, wherein the aliphatic dicarboxylic acids are of the formula:
  • Y represents a divalent aliphatic group containing at least 2 carbon atoms.
  • acids are sebacic acid, octadecanedioic acid, suberic acid, glutaric acid, pimelic acid and adipic acid.
  • polystyrene resin polystyrene resin
  • nylons polystyrene resin
  • polypyrrolidone polycaprolactam
  • nylon 6 polycapryllactam
  • nylon 11 polyhexamethylene adipamide
  • nylon 6 polyundecanolactam
  • nylon 11 polydodecanolactam
  • nylon 12 polyhexamethylene azelaiamide
  • nylon sebacamide polyhexamethylene sebacamide
  • polyhexamethylene isophthalamide nylon 6 1
  • polyhexamethylene terephthalamide nylon T
  • polyamide of hexamethylenediamme and n-dodecanedioic acid polyamides resulting from terephthalic acid and/or isophthalic acid and trimethylhexamethylenediamine
  • polyamides resulting from adipic acid and meta- xylenediamines polyamides resulting from adipic acid and meta- xylenediamines
  • Copolymers of the foregoing polyamides or prepolymers thereof are also suitable for use in the practice of the present invention.
  • Such copolyamides include the following: hexamethylene adipamide/caprolactam (nylon 6, 6/6) hexamethylene adipamide/hexamethylene isophthalamide (nylon 6, 6/6, 1) hexamethylene adipamide/hexamethylene terephthalamide (nylon 6, 6/6, T) hexamethylene adipamide/hexamethylene azelaiamide (nylon 6, 6/6, 9) hexamethylene adipamide/hexamethylene azelaiamide/caprolactam (nylon 6, 6/6, 9/6)
  • Mixtures and/or copolymers of two or more of the foregoing polyamides or prepolymers thereof, respectively, are also within the scope of the present invention.
  • polyamides are the polyamides 6; 6,6; 11; 12 and mixtures of at least one crystalline polyamide, e.g., 6; 6,6, arid at least one amorphous polyamide, e.g., 6, 1; 6, 1,T; and most preferably polyamide 6, polyamide 11, or polyamide 12.
  • polyamides here is intended to include the toughened or supertough polyamides.
  • Supertough polyamides, or supertough nylons, as they are more commonly known, are available commercially, e.g., from E. I. du Pont de Nemours and Company (Zytel ST resins), Wilson Fiberfille (NY resins), Badische Aniline and Sodafabrik (Ultramid resins), among others, or may be prepared in accordance with a number of U.S. patents including, among others, U.S.P. 4,174,358; 4,474,927; 4,346,194 and 4,251,644.
  • These supertough nylons are prepared by blending one or more polyamides with one or more polymeric or copolymeric elastomeric toughening agents.
  • Suitable toughening agents are disclosed in the U.S. patents identified above as well as in U.S.P. 3,884,882 and 4,147,740, and Galucci et al., "Preparation and Reactions of Epoxy-Modified Polyethylene,” J. Appl. Poly. Sci., 27, 425-437 (1982.
  • these elastomeric polymers and copolymers can be straight chain or branched as well as graft polymers and copolymers, including core- shell graft copolymers, and are characterized as having incorporated therein either by copolymerization or by grafting on the preformed polymer, a monomer having functional and/or active or highly polar groupings capable of interacting with or adhering to the polyamide matrix so as to enhance the toughness of the polyamide polymer.
  • Polyesters suitable for use in the present invention are well known and widely available. They possess chain units that contain an unsubstituted or substituted aromatic ring in the polymer chain. Examples of substituents on the aromatic ring include, for example, halogen, such as chlorine or bromine, and C C 4 alkyl, such as methyl, ethyl, propyl, or butyl.
  • Suitable polyesters can be prepared, for example, by reacting aromatic dicarboxylic acids, their esters or their ester-forming derivatives with hydroxy compounds in a conventional manner.
  • aromatic dicarboxylic acids are naphthalene dicarboxylic acids, terephthalic acid and isophthalic acid as well as mixtures of these.
  • the aromatic dicarboxylic acids or their derivatives can be partly replaced, preferably in an amount of up to 10 mol %, by other dicarboxylic acids.
  • These other dicarboxylic acids include aliphatic or cycloaliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid and cyclohexane dicarboxylic acid, for example.
  • Preferably used dihydroxy compounds are glycols having 2 to 6 carbon atoms, in particular ethylene glycol; butane- 1,4-diol; but-2-ene-l,4-diol; hexane-l,6-diol; hexane-1,4- diol; cyclohexane- 1,4-diol; l,4-di-(hydroxymethyl)-cyclohexane; 2,2-di-(4"-hydroxyphenyl)- propane, and neopentyl glycol or mixtures of these.
  • polyesters are polyalkylene terephthalates, which are derived from alkanediols having 2-6 carbon atoms. Polyethylene terephthalate and polybutylene terephthalate are particularly preferred.
  • the relative viscosity of the polyesters is in general from 1.2 to 1.8, measured in a 0.5% strength by weight solution in a phenol/o- dichlorobenzene mixture (weight ratio 3:2) at 25°C.
  • Suitable polycarbonates include aromatic polycarbonates, which are well known in the art and are commercially available. These polycarbonates can be prepared by a variety of conventional and well known processes, which include transesterification, melt polymerization, and interfacial polymerization.
  • the polycarbonates are generally prepared by reacting a dihydric phenol with a carbonate precursor such as, for example, phosgene. Suitable processes for preparing the polycarbonates of the present invention are described in, for example, US 4,123,436 and 3,153,008. However, other known processes for producing polycarbonates are suitable.
  • Particularly preferred polycarbonates are aromatic polycarbonates prepared by reacting bisphenol-A [2,2-bis(4-hydroxyphenyl)phenyl)propane] with phosgene.
  • the engineering thermoplastic is present in an amount from 10.0 wt% to 85.0 wt%, preferably in an amount from 15.0 wt% to 80.0 wt%, more preferably in an amount from 20.0 wt% to 75.0 wt%.
  • the engineering thermoplastic is present in amount from 5.0 wt% to 85.0 wt%, preferably in an amount from 10.0 wt% to 80.0 wt%, more preferably in an amount from 15.0 wt% to 75.0 wt%.
  • Suitable fillers include reinforcing fibers such as fiberglass, carbon fibers, graphite fibers, metal fibers, whiskers and aramides; inert fillers such as talc, wollastonite, mica, calcium carbonate, glass microspheres, glass wool, rock wool, stainless steel wool, steel wool, and gypsum; ceramic fibers such as alumina, alumina silica and silica; and mixtures thereof.
  • the inert fillers of the invention are preferably present as finely divided solids with a particle size range of from 0.8 to 40 microns.
  • a non-halogenated flame retardant When a non-halogenated flame retardant is present, its primary function is as a flame retardant, but when present in amounts of 10 wt% or more it also functions as a filler.
  • the particle size is less than five microns. Suitable examples include quaternary phosphonium compounds, magnesium hydroxide, and aluminum hydroxide or its hydrates.
  • the non- halogenated flame retardant, filler or mixture thereof is present in an amount from 10.0 wt% to 85.0 wt%, preferably in an amount from 15.0 wt% to 80.0 wt%, more preferably in an amount from 20.0 wt% to 75.0 wt%.
  • the non-halogenated flame retardant, filler or mixture thereof is present in amount from 10.0 wt% to 85.0 wt%, preferably in an amount from 15.0 wt% to 80.0 wt%, more preferably in an amount from 20.0 wt% to 75.0 wt%.
  • the non-oxidized olefin polymer material is present in an amount from 2.0 wt% to 80.0 wt%, preferably 5.0 to 75.0 wt%, more preferably in an amount from 10.0 wt% to 70.0 wt%.
  • the engineering thermoplastic, oxidized olefin polymer material, ionomer of the oxidized olefin polymer material, additives and non-oxidized olefin polymer material in the compositions of the invention can be combined in conventional operations well known in the art; including, for example, drum tumbling, or with low or high speed mixers, where the components are in the solid or melt phase.
  • compositions can be combined in any order, for example, all the components can be combined in a single operation, or sub-combinations of the materials can be combined separately, and then blended; for example, a non-halogenated flame retardant or filler may be combined with the oxidized olefin polymer material to form a concentrate, with this concentrate then being combined with the engineering thermoplastic, oxidized olefin polymer and non-oxidized olefin polymer.
  • oxidized olefin polymers can be used as a universal carrier to deliver the additive to a variety of polymer compositions.
  • Conventional coupling agents and additives can also be incorporated in the compositions of the invention.
  • the resulting composition is then compounded in the molten state to disperse the additive in any conventional manner well known in the art, in batch or continuous mode; for example, by using a mixer, a kneading machine, or a single or twin screw extruder.
  • the material can then be pelletized.
  • a polypropylene homopolymer having an MFR of 0.4 dg/min and I.I. of 95.4% commercially available from Basell USA I c was irradiated at 0.5 Mrad under a blanket of nitrogen. The irradiated polymer was then treated with 3.0% by volume of oxygen at 140° C for 60 minutes and the oxygen was then removed. The polymer was then heated at 140°C under a blanket of nitrogen for 60 minutes, cooled and collected. The MFR of the resultant polymer material was 2500 dg/min. Control Example 1 and Example 2
  • Control Example 1 and Example 2 all ingredients are simultaneously dry-blended and bag mixed with Irganox B225 antioxidant commercially available from Ciba Specialty Chemicals Corporation and calcium stearate.
  • PPG 3793 fiber glass is commercially available from PPG industries.
  • United MP 1000 is a maleated grafted polypropylene commercially available from Crompton Corporation.
  • Polyamide PA-6 is a nylon-6 commercially available as Capron 8202 NL from BASF.
  • the non-oxidized propylene polymer homopolymer has an MFR of 4 and an I.I. of 95.0% commercially available from Basel USA Inc. Glass filled materials were compounded on a ZSK 40 mm Werner Pfieiderer supercompounder, available from Coperion. Extrusion temperature was 245 °C for all zone with a crew speed of 250 rpm. All materials were injected molded on a 5 oz Battenfeld injection molding machine commercially available from SMS Plastic Technology.
  • Control Example 1 and Example 2 are set forth in Table II.
  • Control Example 3 and Example 4 are set forth in Table III.
  • Magshield S is a magnesium hydroxide flame retardant commercially available from Martin Marietta.
  • MP 1000 is a maleated grafted polypropylene commercially available from Crompton Corporation.
  • Polyamide PA-6 is a nylon-6m commercially available as Capron 8202 NL from BASF.
  • Control Example 5 and Example 6 are set forth in Table IN.
  • the oxidized olefin polymer coupling agents of the invention maintain flame retardancy performance at levels approximately that of Control Example 5 while improving mechanical properties.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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Abstract

Ces compositions thermoplastiques d'ingénierie contenant des agents de couplage de polymères d'oléfines oxydées contiennent : A. 5,0 à 80,0 % en poids d'un matériau polymère d'oléfine oxydée ou un ionomère d'un matériau polymère d'oléfine oxydée ; b. 10,0 à 85,0 % en poids de (i) un produit ignifugeant non-halogéné, (ii) une charge sélectionnée parmi la fibre de verre, les fibres de carbone, les fibres de graphite, les barbes, les fibres métalliques, les aramides, le talc, la wollastonite, le carbonate de calcium, le mica, les microsphères de verre, la laine de verre, la laine de roche, la laine d'acier inoxydable, la laine d'acier, la pierre à plâtre, l'oxyde d'aluminium, l'oxyde d'aluminium-silice, la silice et (iii) des mélanges de ceux-ci ; et C. 10,0 à 85,0 % en poids d'une matière thermoplastique d'ingénierie ; la somme des composants A + B + C étant égale à 100 % en poids.
PCT/IB2004/002043 2003-06-23 2004-06-17 Compositions thermoplastiques d'ingenierie contenant des agents de couplage de polymeres d'olefines oxydees WO2004113437A1 (fr)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2887312A1 (fr) * 2005-06-17 2006-12-22 Skf Ab Butee de debrayage
FR2887311A1 (fr) * 2005-06-17 2006-12-22 Skf Ab Butee de debrayage
WO2010128013A1 (fr) * 2009-05-06 2010-11-11 Lanxess Deutschland Gmbh Réduction de l'influence de l'hydrophilie sur la conductibilité électrique de matières moulables électriquement conductrices en polyamide
CN105238039A (zh) * 2015-10-12 2016-01-13 天津市飞荣达科技有限公司 无卤阻燃的电磁屏蔽尼龙6复合材料及其制造方法
CN108264685A (zh) * 2017-12-25 2018-07-10 温州鑫泰新材料股份有限公司 一种改性pp阻燃材料空调吸塑隔热板
BE1027332B1 (fr) * 2019-10-15 2021-08-27 Energy Res Inst Shandong Academy Sciences Matériau de nylon renforcé ignifuge sans halogène et procédé de préparation et applications
WO2022200095A1 (fr) * 2021-03-23 2022-09-29 Basf Se Composition de polyamide présentant une résistance à l'hydrolyse accrue, son procédé de préparation, son application et article fabriqué à partir de cette dernière
CN115850876A (zh) * 2022-11-17 2023-03-28 深圳市华鹰塑胶原料有限公司 聚烯烃改性塑料及其制备方法

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JPH03285936A (ja) * 1990-04-02 1991-12-17 Mitsui Petrochem Ind Ltd ポリオレフィン樹脂組成物
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JPH03285936A (ja) * 1990-04-02 1991-12-17 Mitsui Petrochem Ind Ltd ポリオレフィン樹脂組成物
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2887312A1 (fr) * 2005-06-17 2006-12-22 Skf Ab Butee de debrayage
FR2887311A1 (fr) * 2005-06-17 2006-12-22 Skf Ab Butee de debrayage
WO2010128013A1 (fr) * 2009-05-06 2010-11-11 Lanxess Deutschland Gmbh Réduction de l'influence de l'hydrophilie sur la conductibilité électrique de matières moulables électriquement conductrices en polyamide
CN105238039A (zh) * 2015-10-12 2016-01-13 天津市飞荣达科技有限公司 无卤阻燃的电磁屏蔽尼龙6复合材料及其制造方法
CN108264685A (zh) * 2017-12-25 2018-07-10 温州鑫泰新材料股份有限公司 一种改性pp阻燃材料空调吸塑隔热板
BE1027332B1 (fr) * 2019-10-15 2021-08-27 Energy Res Inst Shandong Academy Sciences Matériau de nylon renforcé ignifuge sans halogène et procédé de préparation et applications
WO2022200095A1 (fr) * 2021-03-23 2022-09-29 Basf Se Composition de polyamide présentant une résistance à l'hydrolyse accrue, son procédé de préparation, son application et article fabriqué à partir de cette dernière
CN115850876A (zh) * 2022-11-17 2023-03-28 深圳市华鹰塑胶原料有限公司 聚烯烃改性塑料及其制备方法

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