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WO2012127463A1 - Composition retardatrice de flamme et polypropylène à haute résistance au choc, à retard de flamme - Google Patents

Composition retardatrice de flamme et polypropylène à haute résistance au choc, à retard de flamme Download PDF

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Publication number
WO2012127463A1
WO2012127463A1 PCT/IL2012/000124 IL2012000124W WO2012127463A1 WO 2012127463 A1 WO2012127463 A1 WO 2012127463A1 IL 2012000124 W IL2012000124 W IL 2012000124W WO 2012127463 A1 WO2012127463 A1 WO 2012127463A1
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Prior art keywords
flame retardant
composition
molecular weight
brominated epoxy
compatibilizer
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Inventor
Sergei V. Levchik
Edward D. Weil
Gerald R. Alessio
Yaniv Hirschsohn
Yoav Bar-Yaakov
Pierre Georlette
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Bromine Compounds Ltd
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Bromine Compounds Ltd
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Publication of WO2012127463A1 publication Critical patent/WO2012127463A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/226—Mixtures of di-epoxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
    • C08G59/308—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen containing halogen atoms
    • 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
    • C08L23/10—Homopolymers or copolymers of propene
    • 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
    • C08L23/16—Ethene-propene or ethene-propene-diene copolymers
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K3/2279—Oxides; Hydroxides of metals of antimony
    • 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
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0066—Flame-proofing or flame-retarding additives
    • 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
    • C08K5/0091—Complexes with metal-heteroatom-bonds
    • 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
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • 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
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • 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
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • 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
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins

Definitions

  • the present invention relates to a flame retardant additive composition and more particularly to a bromine-based flame retardant composition for high impact polypropylene.
  • Flame retarded polypropylene finds applications in various fields such as electrical (wire nuts, lamp sockets, coil bobbins, connectors and wire and cables), housing of electrical appliances, TV yokes, pipes for water discharge, fibers for textile applications, films and sheets for roofing. In most of these applications, flame retardancy is provided by flame retardant systems based on a combination of brominated flame retardants with antimony trioxide as a synergist.
  • the present invention relates to a flame retarded high impact polypropylene resin, obtained by using the class of bromine-containing flame retardants obtainable by reacting tetrabromobisphenol A with epichlorohydrin.
  • the reaction of tetrabromobisphenol A with epichlorohydrin is known to yield various reactive brominated epoxy polymers having high bromine content, which may be used as such, or in the form of their end- capped non-reactive derivatives, as flame retardants in plastic materials.
  • Brominated epoxy polymers were mentioned in the art for polyolefin applications.
  • WO 99/07787 discloses a composition comprising polyolefin based resin and a brominated epoxy polymer.
  • WO 01/0751 1 discloses the use of bromine epoxy polymers with an average molecular weight of 1,000-50,000 in polyolefins in combination with a second brominated flame retarding agent which is a monomeric or dimeric flame retardant containing aliphatic bromine.
  • US 5,705,544 discloses fire- retarded polypropylene and ethylene-propylene copolymers which contain brominated epoxy polymer having an average molecular weight of at least 3,000 g/mol.
  • JP 11- 021392 indicates that polypropylene is combined with brominated flame retardants such as brominated epoxy compounds.
  • JP 08-302102 discloses a flame retarded polypropylene which comprises halogenated bisphenol A epoxy resin having molecular weight of 700- 5000 in combination with tetrabromobisphenol A-S-2,3 dibromophenol.
  • JP 07-173345 describes a polypropylene resin which is rendered flame-retarded by the use of brominated bisphenol A type epoxy resin.
  • brominated epoxy resins useful as flame retardants are sometimes applied in the form of masterbatch compositions, as disclosed in JP 03-227370 and JP 08-109269.
  • Mixtures of brominated epoxy polymers having different molecular weights, for reducing the fiammability of high density polyethylene and high impact polystyrene are described in WO 2011/077439 and WO 2011/1 17865, respectively, where these mixtures are also provided in the form of highly concentrated masterbatch compositions.
  • the high impact polypropylene compositions of the invention do not exhibit surface migration of the flame retardant component after being aged at 70°C for one month and then visually observed for surface migration of the flame retardants.
  • Another advantage offered by the combination of the high molecular weight brominated epoxy polymer with the low-molecular weight brominated epoxy polymer relates to the possibility of producing a concentrate of the flame retardants (a masterbatch composition), allowing the flame retardants to be conveniently incorporated into the high impact polypropylene resin, as discussed in more detail below.
  • This invention further relates to the flame retardant composition
  • the flame retardant composition comprising at least one high molecular weight brominated epoxy polymer, at least one low molecular weight brominated epoxy polymer and a compatibilizer having a polyethylenic structure, and the use of this composition in high impact polypropylene resin which allows to preserve high impact strength of the resin.
  • the present invention is directed to a flame retardant additive composition
  • a flame retardant additive composition comprising:
  • compatibilizer either having a polyethylenic structure or is organotitanate.
  • the present invention provides the flame retardant additive composition set forth above in a masterbatch form, which is produced by heat extrusion of the components of said flame retardant additive composition to form pellets which are dust free and easy to handle for further compounding.
  • the present invention is also directed to a flame retarded high impact polypropylene composition
  • a flame retarded high impact polypropylene composition comprising the flame retardant additive composition of the present invention and an inorganic synergist.
  • the present invention is directed to flame retardant additive compositions that contain a unique combination of a high molecular weight brominated epoxy polymer, a low molecular weight brominated epoxy polymer and a compatibilizer having a polyethylenic structure.
  • Such flame retardant additive compositions can be used in high impact polypropylene resin while maintaining suitable impact properties.
  • the high molecular weight brominated epoxy polymers suitable for use according to the invention are brominated epoxy polymers represented by Formula I
  • n the average degree of polymerization, is in the range between 24 and 115, and more preferably between 80 and 115, and R 1 and R 2 are glycidyl ether groups
  • Preferred high molecular weight brominated epoxy polymers have an average molecular weight between 10000 and 80000.
  • Examples of commercially available high molecular weight brominated epoxy polymers which are suitable for use include F-2100, F-2300H and F-2400 from ICL-IP.
  • Especially preferred is brominated epoxy polymer of Formula (I) having average molecular weight between 40000 and 60000, e.g., F-2400.
  • the high molecular weight brominated polymer is present in an amount from about 10 wt. % to about 50 wt. % of the total weight of the flame retardant composition and more preferably from about 10 wt. % to about 30 wt. % of the total weight of the flame retardant composition.
  • the low molecular weight brominated epoxy polymers suitable for use according to the invention are selected from the group consisting of brominated epoxy polymers and end-capped derivatives thereof, wherein said brominated epoxy polymers and their end-capped derivatives are represented by formula (I) wherein n, the number average degree of polymerization, is in the range between 0.5 and 7.2, and more preferably between 1 and 6, and R 1 and R 1 are independently selected from the group consisting of glycidyl ether groups O
  • Preferred low molecular weight brominated epoxy and end-capped derivatives thereof have molecular weight between 700 and 2,500, e.g. 1000-2100.
  • An example of commercially available low molecular weight brominated epoxy polymer terminated with glycidyl ether groups is F-2016 manufactured by ICL-IP having an average molecular weight of 1600.
  • Examples of commercially available low molecular weight brominated epoxy polymers terminated with tribromophenol which are suitable for use in this invention include F-3014, F-3020 and F-3516 from ICL-IP.
  • some useful low molecular weight brominated polymers terminated with tribromophenol are defined by the characteristic distribution of the individual tribromophenol-terminated compounds, as may be determined by gel permeation chromatography (GPC), and also by their average molecular weight:
  • the low molecular weight brominated polymer is present in an amount from about 30 wt. % to about 80% wt. % of the total weight of the flame retardant composition and more preferably from about 40% wt. % to about 70% wt. % of the total weight of the flame retardant composition.
  • the flame retardants of Formula (I), which are suitable for reducing the flammability of polypropylene compositions according to the invention, can be prepared by methods known in the art (for example, US 4,605,708, EP 467364, EP 1587865 and WO 2007/132463).
  • high impact polypropylene is a copolymer of propylene and ethylene. Copolymerization of propylene and ethylene decreases crystallinity of the resin and increases amorphous areas which results in higher impact properties.
  • high impact polypropylene is an intimate blend of polypropylene and polyethylene, where polyethylene amorphous phases are dispersed in polypropylene continuous phase.
  • This type of blends can be prepared by extrusion or by joint polymerization of ethylene and propylene in one reactor using for example MgCh catalyst technology.
  • high impact polypropylene is a random copolymer of polypropylene and a-olefin such as for example 1-octene or 1- decene. These copolymers have low density and show high impact properties at low temperature.
  • the high impact polypropylene can be terpolymer of propylene, ethylene and a-olefm.
  • compatibilizers having polyethylenic structure refer to compatibilizers which contain polyethylene component or segment(s), whereas compatibilizers having polypropylenic structure contain polypropylene component or segment(s).
  • a compatibilizer which is suitable for use in the invention is a copolymer of ethylene and a second, polar monomer such as maleic anhydride.
  • the compatibilizers are those selected from the group consisting of silanes, titanates, aluminates, zirconates, and mixtures thereof, particularly the organosi lanes, organotitanates, organoaluminates and/or organozirconates.
  • the compatibilizer is selected from the group of organotitanates bearing long linear aliphatic chains of C 8 - C22.
  • Preferred are phosphatotitanante, e.g., tris(dialkylphosphato)titanate, wherein the alkyl is preferably octyl.
  • An example of a suitable phosphatotitanate is neopentyl(diallyl)oxy, tri(dioctyl phosphate) titanate available under trade name Ken-React CAPS L 12/L from Kenrich Petrochemicals.
  • the compatibilizers are selected from polymers of polar and nonpolar structures which are produced by customary polymerization reactions.
  • compatibilizers for use with the current invention include maleic anhydride functionaiized high-density polyethylene (HDPE), maleic anhydride functionaiized low-density polyethylene (LDPE) or maleic anhydride functionaiized linear low density polyethylene (LLDPE).
  • the maleic anhydride functionaiized polyethylene can be produced by reactive extrusion of the PE in the presence of both a radical initiator and maleic anhydride in a twin-screw extruder which results in maleic anhydride grafted polyethylene.
  • the maleic anhydride functionaiized polyethylene can be also produced by random terpolymerization in autoclave of ethylene, maleic anhydride and another polar monomer, for example acrylic ester.
  • the compatibilizer is selected from the group of copolymers of ethylene and another comonomer bearing an epoxy group.
  • An example of such compatibilizers is random copolymer of ethylene and glycidyl methacrylate polymerized under high pressure in an autoclave.
  • the compatibilizer is present in an amount from about 2 wt. % to about 20% wt. % of the total weight of the flame retardant composition and more preferably from about 5% wt. % to about 15% wt. % of the total weight of the flame retardant composition.
  • the flame retardant composition of the present invention can further contain an inorganic synergist, selected from the group consisting of inorganic antimony, inorganic bismuth, inorganic tin, inorganic iron or inorganic zinc compounds.
  • the most preferable are inorganic antimony compounds, e.g. antimony trioxide, antimony pentoxide, sodium antimonite and the like.
  • the inorganic synergist is present in an amount from about 5 wt. % to about 40% wt. % of the total weight of the flame retardant composition and more preferably from about 10% wt. % to about 25% wt. % of the total weight of the flame retardant composition.
  • This invention is further directed to the flame retarded high impact polypropylene composition comprising the flame retardant composition of the invention.
  • the amount of bromine and the amount of inorganic synergist are responsible for providing sufficient level of flame retardancy to the high impact polypropylene composition.
  • the bromine content in the high impact polypropylene composition is from about 4 wt. % to about 10 wt. % of the total weight of the high impact polypropylene composition which ensures V-2 rating according to UL-94 vertical test.
  • the inorganic synergist content is from about 0.5 wt. % to about 3 wt. % of the total weight of the high impact polypropylene composition.
  • the high impact polypropylene composition of the present invention can also include other additives such as antioxidants, stabilizers, fillers anti-dripping agent such as fluorinated homo- or copolymers such as polytetrafluoroehtylene or processing aid agents, pigments etc., as well as other flame retardants.
  • additives such as antioxidants, stabilizers, fillers anti-dripping agent such as fluorinated homo- or copolymers such as polytetrafluoroehtylene or processing aid agents, pigments etc., as well as other flame retardants.
  • the brominated epoxy polymer flame retardant(s) are added to the formulation at a concentration sufficient for adjusting the bromine content within the range indicated above. It is not mandatory that this bromine content be supplied in its entirety by the brominated epoxy polymers mentioned above, and one or more additional brominated flame retardants may be added to the formulation.
  • the mixture of brominated flame retardants incorporated into the polyethylene according to the invention consists of brominated epoxy polymers, said mixture being free of brominated compounds such as decabromodiphenyl oxide or decabromodiphenyl ethane.
  • the high impact polypropylene compositions of the invention may be prepared as follows. The various ingredients of the composition are blended together according to their respective amounts.
  • the ingredients are first dry blended using suitable mixing machines, or may be dosed separately into the extruder.
  • the powder mixture may then be processed and compounded to form homogeneous polypropylene pellets, for example, by using a twin-screw extruder.
  • the polypropylene pellets obtained are dried, and are suitable for feed to an article shaping process such as injection or extrusion molding. Process parameters are described in more detail in the examples that follow.
  • the masterbatch route can be employed.
  • the brominated epoxy polymers as defined by Formula ( ⁇ ) and optionally also the compatibilizer having a polyethylenic structure may be incorporated into the polymeric formulation via a masterbatch form (which may optionally contain the inorganic synergist, preferably antimony trioxide).
  • a masterbatch is a concentrate composition comprising a suitable carrier, and a relatively high proportion of the flame retardant(s).
  • the carrier is a polymer which is intended to facilitate the mixing of the master batch and improve the compatibility of the masterbatch and the biend polymer (the blend polymer is the polymer combined with the master batch; in the present case, the blend polymer is polypropylene).
  • the blend polymer is the polymer combined with the master batch; in the present case, the blend polymer is polypropylene.
  • Another advantage resulting from using the masterbatch is that it is made of dust free pellets, and is hence environmentally friendly.
  • Suitable carrier polymers applied in the master batch are therefore similar or identical to the blend polymer. However, it was found that it is possible to prepare a masterbatch containing the low molecular weight brominated epoxy polymer of Formula (I) or end-capped brominated epoxy polymer of Formula (I) in combination with a carrier material comprising high molecular weight brominated epoxy polymer.
  • a brominated epoxy polymer with a molecular weight of 40,000-60,000 g/mol may be used, such as F-2400, which is commercially available from 1CL-IP.
  • F-2400 which is commercially available from 1CL-IP.
  • the high molecular weight brominated epoxy polymer functions in the masterbatch both as a carrier material and as an active flame retarding agent.
  • the masterbatch of the invention comprises a combination of brominated epoxy polymers, a compatibilizer having a polyethylenic structure and optionally antimony trioxide.
  • concentration of the low molecular weight brominated epoxy polymer of Formula (I) or tribromophenol end-capped brominated epoxy polymer of Formula (I) is from about 30 wt. % to about 80% wt. % of the total weight of the masterbatch and more preferably from about 40% wt. % to about 70% wt. %.
  • the concentration of the high molecular weight brominated epoxy polymer of Formula (I) is from about 10 wt. % to about 50 wt.
  • the concentration the compatililizer having polyethylenic structure is from about 10 wt. % to about 50 wt. % of the total weight of the masterbatch and more preferably from about 10 wt. % to about 30 wt. %, e.g. from 10 wt. % to about 20 wt. %. If antimony trioxide is also incorporated in the masterbatch, then its concentration may be between 0.1 and 30 wt. %.
  • additives may also be included in the masterbatch, including inert carriers such as polypropylene or polyethylene at concentration in the range of 3 to 30 wt. %.
  • the bromine content of the masterbatch is preferably not less than 40 wt. %.
  • the masterbatch composition of the invention is prepared by melting the brominated epoxy flame retarding agents and the compatibilizer in an extruder, e.g., in a twin-screw extruder.
  • the starting materials are employed either as powders or granules.
  • the extruded strands produced are cooled, e.g., with water.
  • a subsequent drying step is employed, followed by strand pelletizing to provide the masterbatch composition in a granular form.
  • a preferred masterbatch composition of the invention comprises high molecular weight brominated epoxy of Formula I with molecular weight from 40000 to 60000 (e.g., F-2400), low molecular weight brominated epoxy of Formula I or its end- capped derivative with molecular weight from 1000 to 2100 (e.g., F-2016 or F-3020) and compatibilizer having polyethylenic structure as set forth above.
  • the invention therefore also relates to a process for preparing a high impact polypropylene composition suitable for the manufacture of electronic and automotive parts, which process comprises: providing a masterbatch which comprises a mixture of a low molecular weight brominated epoxy of Formula (I), a carrier polymer which is one or more high molecular weight brominated epoxy polymers of Formula (I), as set forth above, and optionally a compatibilizer having a polyethylenic structure, an inert polymer carrier and inorganic synergist such as antimony trioxide; and processing said masterbatch with the high impact polypropylene, and optionally also with said compatibilizer and/or synergist if the latter are not present in said masterbatch, to form a high impact polypropylene composition in which the bromine content is preferably in the range between 4 and 10 wt. % and the inorganic synergist (e.g., antimony trioxide) concentration is in the range between 0 and 3 wt. %.
  • the composition of this invention may contain conventional ingredients, such as fillers, smoke-suppressants, glass reinforcement, impact modifiers, pigments, UV stabilizers, heat stabilizers, lubricants and antioxidants.
  • concentration of each of the additives listed above is typically in the range between 0 and 30 wt. %.
  • injection molded components e.g., electronic or automotive components, comprising a high impact polypropylene and a flame retardant additive composition, which composition comprises low molecular weight brominated epoxy polymer or end-capped low molecular weight brominated epoxy polymer, high molecular weight brominated epoxy polymer, and at least one compatibilizer having a polyethylenic structure or a compatibilizer which is phosphatotitanante, and an inorganic synergist such as antimony trioxide.
  • a flame retardant additive composition which composition comprises low molecular weight brominated epoxy polymer or end-capped low molecular weight brominated epoxy polymer, high molecular weight brominated epoxy polymer, and at least one compatibilizer having a polyethylenic structure or a compatibilizer which is phosphatotitanante, and an inorganic synergist such as antimony trioxide.
  • a flame retarded article e.g., an electronic or automotive component, preferably an injection molded electronic component, as described herein, made by the above-described method.
  • Admer AT2543A Mitsubishi Polyethylene-MA modified copolymer Compatibilizer Chemicals
  • Ken-React CAPS L12/L Ken-React CAPS L12/L (Kendrich Neopentyl(diallyl)oxy, Compatabilizer Petrochemicals) tri(dioctyl)phosphate titanate LLDPE
  • Test specimens were prepared by injection molding using an Arburg 270S Allrounder 250-150.
  • the conditions of the injection molding are presented in Table 4.
  • TABLE 4 Regime of injection molding in Arburg 270S Allrounder 250-150
  • Specimens were conditioned at 23°C and 50% RH for 48 hours prior to UL-94 and mechanical property testing.
  • Table 5 shows examples of high impact polypropylene compositions flame retarded with the blend of low molecular weight and high molecular weight brominated epoxy polymers. All compositions contain 8 wt. % Br with 6 wt. % Br coming from low molecular weight brominated epoxy polymer and 2 wt. % coming from high molecular weight brominated polymer. All compositions contain 2.64 wt. % antimony trioxide being compounded as 3 wt. % of 80% masterbatch.
  • Table 6 shows comparative examples of high impact polypropylene compositions containing compatibilizers having polypropylenic and other non-polyethylenic structures.
  • non polyethylenic compatibilizers provide only moderate improvement in Izod impact strength ( ⁇ 175 J/m, comparative examples 2C-13C) compared to the composition without compatibiiizer (70 J/m, comparative example 1C) and these Izod impact values are much lower than those of the non flame retarded polymer (585 J/m, Table 5).
  • composition of the invention [comprising (a) high molecular weight brominated epoxy polymer, (b) low molecular weight brominated epoxy polymer and (c) a compatibilizer having polyethylenic structure] can be produced in a masterbatch form using a twin screw extruder.
  • Examples 13-14 illustrate that the compositions of the invention can be applied in a masterbatch form in the preparation of high impact polypropylene.
  • the resultant polymer formulations meet the UL-94 V-2 rating.
  • the masterbatch route can be employed, as an alternative to the compounding of high impact polypropylene based on the separate addition of the flame retardants and compatibilizer (see Example 15- 16).
  • Test specimens were prepared by injection molding using an Arburg 270S AUrounder 250-150, the injection molding conditions are presented in Table 10. TABLE 10 Regime of injection molding in Arburg 270S Allrounder 250-150
  • Specimens were conditioned at 23°C and 50% RH for 48 hours prior to UL-94 and mechanical property testing.

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

Abstract

L'invention concerne une composition d'additif retardateur de flamme comprenant : au moins un polymère époxy bromé de masse moléculaire élevée ou son dérivé coiffé aux extrémités, au moins un polymère époxy bromé de faible masse moléculaire ou son dérivé coiffé aux extrémités, et au moins un agent compatibilisant, ledit agent compatibilisant soit ayant une structure polyéthylénique, soit étant un organotitanate. L'invention concerne également un mélange-maître retardateur de flamme qui est obtenu par extrusion à chaud de la composition d'additif retardateur de flamme et production de granulés qui sont exempts de poussière et faciles à manipuler pour un compoundage ultérieur. L'invention concerne également une composition de polypropylène à haute résistance au choc, à retard de flamme, comprenant un polypropylène à haute résistance au choc, la composition d'additif retardateur de flamme de la présente invention et un synergiste inorganique.
PCT/IL2012/000124 2011-03-20 2012-03-20 Composition retardatrice de flamme et polypropylène à haute résistance au choc, à retard de flamme Ceased WO2012127463A1 (fr)

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WO2014106841A1 (fr) * 2013-01-06 2014-07-10 Bromine Compounds Ltd. Préparation de composés aromatiques contenant du brome et leur application comme ignifugeants
EP2910959A1 (fr) 2014-02-19 2015-08-26 Alstom Technology Ltd. Localisation des pannes dans des réseaux à courant continu
EP2935430A1 (fr) 2012-12-20 2015-10-28 Polyad Services LLC Compositions de polymère ignifuges
EP2957595A1 (fr) 2014-06-18 2015-12-23 Basf Se Composition d'agents ignifuges destinée à être utilisée dans des mousses polymères de styrène
US10227531B2 (en) 2014-07-08 2019-03-12 Bromine Compounds Ltd. Preparation of bromine-containing polymers and their application as flame retardants
US10336858B2 (en) 2014-07-08 2019-07-02 Bromine Compounds Ltd. Preparation of bromine-containing polymers useful as flame retardants

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JPH03227370A (ja) 1990-01-31 1991-10-08 Dainippon Ink & Chem Inc 難燃剤マスターバッチ
EP0467364A1 (fr) 1990-07-18 1992-01-22 Dainippon Ink And Chemicals, Inc. Composition de résine thermoplastique retardatrice de flamme
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JPH08302102A (ja) 1995-05-12 1996-11-19 Chisso Corp 難燃性ポリプロピレン樹脂組成物
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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2935430A1 (fr) 2012-12-20 2015-10-28 Polyad Services LLC Compositions de polymère ignifuges
JP2016501963A (ja) * 2012-12-20 2016-01-21 ポリアド サービシズ エルエルシー 難燃性ポリマー組成物
US10227482B2 (en) 2012-12-20 2019-03-12 Byk Usa Inc. Flame retardant polymer compositions
WO2014106841A1 (fr) * 2013-01-06 2014-07-10 Bromine Compounds Ltd. Préparation de composés aromatiques contenant du brome et leur application comme ignifugeants
JP2016508146A (ja) * 2013-01-06 2016-03-17 ブロミン・コンパウンズ・リミテツド 臭素含有芳香族化合物の調製およびその難燃剤としての利用
US9481621B2 (en) 2013-01-06 2016-11-01 Bromine Compounds Ltd. Preparation of bromine-containing aromatic compounds and their application as flame retardants
US9988332B2 (en) 2013-01-06 2018-06-05 Bromine Compounds Ltd. Preparation of bromine-containing aromatic compounds and their application as flame retardants
EP2910959A1 (fr) 2014-02-19 2015-08-26 Alstom Technology Ltd. Localisation des pannes dans des réseaux à courant continu
EP2957595A1 (fr) 2014-06-18 2015-12-23 Basf Se Composition d'agents ignifuges destinée à être utilisée dans des mousses polymères de styrène
US10227531B2 (en) 2014-07-08 2019-03-12 Bromine Compounds Ltd. Preparation of bromine-containing polymers and their application as flame retardants
US10336858B2 (en) 2014-07-08 2019-07-02 Bromine Compounds Ltd. Preparation of bromine-containing polymers useful as flame retardants
US10472462B2 (en) 2014-07-08 2019-11-12 Bromine Compounds Ltd. Bromine-containing polymers useful as flame retardants

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