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WO2011132208A1 - Mélange maître ignifugeant pour polymères thermoplastiques, et procédé de production correspondant - Google Patents

Mélange maître ignifugeant pour polymères thermoplastiques, et procédé de production correspondant Download PDF

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Publication number
WO2011132208A1
WO2011132208A1 PCT/IT2010/000175 IT2010000175W WO2011132208A1 WO 2011132208 A1 WO2011132208 A1 WO 2011132208A1 IT 2010000175 W IT2010000175 W IT 2010000175W WO 2011132208 A1 WO2011132208 A1 WO 2011132208A1
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WO
WIPO (PCT)
Prior art keywords
flame retardant
masterbatch
polymer
mixture
approximately
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/IT2010/000175
Other languages
English (en)
Inventor
Josep Campasol
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
VIBA SpA
Original Assignee
VIBA SpA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by VIBA SpA filed Critical VIBA SpA
Priority to PCT/IT2010/000175 priority Critical patent/WO2011132208A1/fr
Priority to PT117175166T priority patent/PT2417187E/pt
Priority to EP11717516A priority patent/EP2417187B1/fr
Priority to HRP20130268AT priority patent/HRP20130268T1/hr
Priority to PCT/EP2011/055345 priority patent/WO2011124606A1/fr
Priority to ES11717516T priority patent/ES2402984T3/es
Publication of WO2011132208A1 publication Critical patent/WO2011132208A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/203—Solid polymers with solid and/or liquid additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • 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
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers

Definitions

  • the present invention relates to a flame retardant masterbatch for thermoplastic polymers and to the process for its production.
  • Thermoplastic polymers have the characteristic that they can be formed (for example by moulding) when they are brought to a sufficiently high temperature, and maintain the shape imparted on them during processing at lower temperatures, for example when returned to ambient temperature; due to this ease of processing they are applied in the production of a vast number of types of manufactured polymer articles.
  • the latter generally consist of a base polymer (or a mixture of polymers), to which particular additives are added in order to confer desired properties to the manufactured article, such as for example a colour, anti-adhesive, anti-static or conductive, or flame retardant properties.
  • the additives could be added taking each time a weight of the same suitable for the polymer batch being processed (the English term "batch" means the quantity of polymer that is processed in a single production phase).
  • thermoplastic polymers are combustible materials, additives commonly used in their formulation are so-called flame retardants.
  • the combustion process of the polymeric materials passes through the phases of: heating; decomposition (pyrolysis); ignition and combustion; and flame propagation (with thermal feedback).
  • the temperature of the material increases at a speed that depends on the intensity of the heat emitted by the source and on the characteristics of the material, such as its thermal conductivity, the latent heat of fusion and vaporization and the decomposition heat.
  • the material starts to degrade, forming gaseous and liquid compounds of lower molecular weight compared to the original polymer chains (decomposition).
  • the speed of this phase depends on the intensity with which the polymeric material heats up.
  • concentration of the decomposition products, mixed with the surrounding air, increases until falling back within the range of inflammability; the presence in this context of an ignition causes the combustion of the mixture to start.
  • the produced heat is partly radiated to the material (thermal feedback), which feeds the above mentioned phases and leads to self-sustaining of the flame for as long as the consumption of the fuel (the polymer and the vapours formed by it) or of the comburant (oxygen) does not cause extinction of the flame.
  • the action of the flame retardants consists in eliminating or limiting one of the factors described above, by acting physically, chemically, or both, upon the liquid (material that melts), solid and gaseous fractions originated in the process.
  • the physically-acting flame retardants act by decreasing the efficiency of the thermal feedback, diluting the combustion mixture, or forming a protective layer on the solid polymeric material, that is thus shielded from the oxygen-rich gaseous phase.
  • the chemically-acting flame retardants can act through gas phase reactions, producing radicals that remove the chemically-active species involved in the maintenance and in the propagation of the flame; or through condensed phase reactions, that can consist in the formation of a protective carbonaceous layer (called "char") on the surface of the polymer, that thermally isolates the latter and reduces the contact between the pyrolysis products and the oxygen, or by forming swellings on the surface of the polymer that deteriorate its thermal exchange characteristics, retarding the thermal feedback process.
  • char protective carbonaceous layer
  • the flame retardants can be added to the polymer either through a genuine chemical reaction that binds them to the chain of the same, simply by physically mixing them with the material, or with intermediate modalities.
  • Numerous types of flame retardants are known, which act through different mechanisms, like aluminium or magnesium hydroxides, boron compounds, phosphorus compounds, or systems based on halogenated compounds.
  • the latter generally used together with a synergistic component like antimony trioxide, are the most widespread, as they offer an optimal balance of proportion quantity, cost and final performances.
  • CNTs carbon nanotubes
  • these compositions have a flame retardant action of the chemical type, and in particular based on the formation, during the combustion of the polymer, of a "char" layer on the surface of the same.
  • CNTs are hollow structures of indefinite length, formed by carbon atoms that are arranged on cylindrical surfaces (one single surface in the case of single-walled nanotubes, forming nanotubes knows as "SWNT”, the English acronym for "Single-Walled NanoTubes", or more concentric walls, forming nanotubes known as "MWNT", “Multi-Walled NanoTubes”).
  • CNTs can be produced with laboratory reactors, for example by chemical-vapour deposition techniques ("CVD"), laser ablation, or others. CNTs are also marketed, albeit in low volumes, by some companies, such as Bayer, Arkema, Hyperion Catalysis International, Unidym and Nanocyl.
  • CVD chemical-vapour deposition techniques
  • laser ablation or others.
  • CNTs are also marketed, albeit in low volumes, by some companies, such as Bayer, Arkema, Hyperion Catalysis International, Unidym and Nanocyl.
  • thermoplastic resins in particular polycarbonates and styrene resins, containing CNTs and a flame retardant chosen among those known.
  • the patent application US 2008/0293877 A1 describes flame retardant compositions containing between 0.05% and 1 % by weight of CNTs in a cross-linked silicone matrix; these compositions are produced by forming a first mixture between the CNTs and a polysiloxane containing vinyl groups; by adding to this mixture a second polysiloxane, containing hydrosilane groups; and by making the two silane compounds cross-link, for example by heating.
  • the flame retardant compositions in this document have the advantage, compared to others previously known, of having a much reduced content of CNTs, but require an elaborate preparation.
  • Aim of the present invention is that of providing a masterbatch to be employed as flame-retardant additive in thermoplastic polymers, and a process for the production of said masterbatch, improved compared to the known technique.
  • thermoplastic polymers comprising a carrier polymer and, as functional components, a mixture between carbon nanotubes and one or more inorganic components chosen among phyllosilicates, silicates with a three-dimensional crystalline structure, CaC0 3 , zinc borates and zinc stannates.
  • Phyllosilicates are minerals that consist of planes of tetrahedra having oxygen atoms at the vertices and a silicon atom at the centre, bound together by sharing an oxygen atom between two of said tetrahedra; the various planes, on the other hand, are bound to each other only by Van der Waals forces or by electrostatic forces due to cations (for example sodium or potassium) that compensate the charge imbalances due to the partial substitution of the silicon atoms with lower valence atoms, generally aluminum; due to this microstructure, phyllosilicates are typically formed by planar crystals formed by "sheets" that can be delaminated with relative ease (for example in the case of micas), or easily slide on top of each other producing minerals greasy to the touch (as in the characteristic case of talc).
  • Silicates with a three-dimensional crystalline structure are those wherein the tetrahedra, or at least part of them, share all four vertices (by sharing the oxygen atoms).
  • Typical examples of silicates with a three-dimensional structure are tectosilicates, which include in particular feldspars, that also result in being the preferred inorganic components, both because of a better synergy of flame retardancy with the CNTs and for cost reasons.
  • the inorganic component must be present in the form of powders, with maximum dimensions under approximately 30 pm and average dimensions (D 50 ) generally smaller than 10 pm; for example, in the case of silicates, powders suitable for use in the present invention are those with an average granulometry between approximately 2 and 7 pm, and preferably around 5 pm.
  • the inorganic component has a synergistic effect on the flame retardant functionality of the CNTs, maintaining and at times improving the flame retardant classifications even with a reduced quantity of CNTs in the masterbatch; the inorganic component furthermore improves the mechanical characteristics of the final manufactured article and, since it allows to reduce the quantity of CNTs required to obtain the specific product requirements, reduces the cost of the masterbatch.
  • the masterbatch contains minimum quantities of CNTs and second component of respectively 0.1 % and 5% by weight, whereas maximum quantities of these components are respectively 5% and 65% by weight, whereas the complement to 100 is constituted by the carrier polymer.
  • the most commonly used carrier polymers are the linear low-, low-, and high-density polyethylenes (respectively identified in the art with the abbreviations LLDPE, LDPE and HDPE), polypropylenes (homopolymer as well as copolymers), and ethylene vinyl acetate (EVA).
  • the single masterbatch units of the invention generally have a weight of less than 0.1 g.
  • the masterbatches of the invention in order to impart flame retardant properties on thermoplastic polymer batches, must be added to the batch in such quantity as to constitute approximately between 10% and approximately 40% by weight of the total mixture.
  • thermoplastic polymers that will constitute the final manufactured articles, to which the flame retardant masterbatches of the invention can be added must be chemically compatible with the carrier polymers of the masterbatch; this condition is obviously fulfilled when the polymer of the manufactured article and the carrier polymer are the same polymer, but it is sufficient for them not to give rise to unmixing, for example LDPE can be employed as carrier polymer for a masterbatch destined to be used in polypropylene.
  • Another general rule for choosing the carrier polymer is that its fluidity (in terms of MFI, "melt flow index”) should be higher or equal to that of the thermoplastic polymer to which the masterbatch must be added.
  • the flame retardant masterbatches of the invention are particularly suitable for use in polyolefins, and even more so in high-density polyethylene (HDPE).
  • HDPE high-density polyethylene
  • efficient flame retardant additives are commercially available, but at a higher cost, to which the additives of the invention constitute an advantageous alternative.
  • the invention concerns a process for the production of the previously described masterbatches, that consists in mechanically mixing the components in turbo-mixers of variable speed, and extruding the mixture on co- rotating twin screw extruders, provided with degassing system, with ratio l/d > 36 and balanced screw profile between grinding zone and dispersion zone.
  • the inventor has verified that with particular mixing and especially extrusion parameters it is possible to create a strong bond between CNTs and additive. This bond in a situation of pyrolysis creates optimum char.
  • the components of the masterbatch i.e. the CNTs, the inorganic component and the carrier polymer
  • a variable speed turbo-mixer not equipped with potentiometer and supplied with a system of mixing paddles with 4 or 5 blades and low profile (for example 3 mm), to encourage the intimate mixing of the components.
  • the proportioning of the components to be employed in the production of the flame retardant masterbatch vary as a function of the thermoplastic polymers to which they are destined and of the required flame retardant classifications.
  • the carrier polymer is employed in the form of powders having a granulometry between 200 and 700 pm, the CNTs in the form of aggregates with a diameter of the order of about ten nanometres and a length of the order of a few microns, and the inorganic component in the form of powders having a granulometry between 1 and 30 pm.
  • the CNTs and the polymer are premixed under mild conditions (rotation speed of the paddle not higher than 500 rpm), after which the inorganic component is added and then mixing, initially in mild conditions, is carried out with rotation speed of the paddles not higher than 500 rpm, and subsequently at a speed between 1000 and 1250 rpm, whilst heightening the system temperature to values between approximately 40 and 70 °C.
  • mild conditions rotation speed of the paddle not higher than 500 rpm
  • the mixer i.e. as granules comprising CNTs in a carrier polymer, granules comprising the inorganic component in a carrier polymer and, if necessary for regulating the quantities and obtaining desired concentrations of the components in the final masterbatch, granules only of the carrier polymer; the polymer used in these granules is preferably the same for all.
  • the thus obtained mixture is fed, still hot, to a co-rotating twin screw extruder, or to a kneader with rotary and oscillatory axis, known in the art as "Buss kneader", produced by the company Buss AG of Pratteln (Switzerland); the extruder or the kneader must have a degassing zone.
  • the thermal profile of the extruder or the kneader is such that, during its movement through the apparatus, the mixture passes from a temperature between approximately 120 and 160 °C at intake up to an output temperature that can be between approximately 190 and 280 °C, as a function of the melting point of the carrier polymer; the particular profile is optimized as a function of this polymer, according to principles known in the art.
  • the extrudate obtained at outlet of the extrusion (or kneading) section is then cut into the required sizes, for example with a die of the traditional type on the head of the extruder to obtain granules of cylindrical form (2 mm x 3 mm), or by water cutting (for example with systems known in the art as "under water” or “water ring”) to obtain discs or round granules (1 mm of diameter).
  • the thus obtained masterbatches then undergo processes standard in the art of screening, to eliminate granules of the wrong size, and drying for the final drying.
  • the dried product is eventually packaged in paper and/or aluminium bags.
  • the CNTs and LDPE are fed to a turbo-mixer (produced by the company Caccia of Samarate, VA) and a first mild mixing phase is set at 500 rpm for 30 seconds.
  • the mixing is then interrupted, the turbo-mixer is opened, its walls are cleaned (letting the powder adherent to the walls fall back into the mixed mass) and the feldspar is added.
  • mixing is at 500 rpm for 30 seconds, to then change to a mixing phase at 1250 rpm for 5 minutes, in the meantime heating the system until the mixture has a temperature of 70 °C.
  • the product of the mixing is presented as perfectly homogeneous, not very powdery and smooth.
  • the mixture thus obtained is fed directly to the loading hopper placed on a co- rotating twin screw extruder (model 40EV033 by the company Comae of Cerro Maggiore, MI), in which the temperature increases along the direction of movement of the mixture from a value of 160 °C in the inlet chamber to up to 230 °C at the exit of the extruder.
  • a co- rotating twin screw extruder model 40EV033 by the company Comae of Cerro Maggiore, MI
  • the "spaghetto" is cut into cylindrical pieces at the head of the extruder using a 4-bladed cutter and subjected to three subsequent screening operations to recover only the pieces with dimensions between 2 x 3 mm, that are then packaged in bags.

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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)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne, d'une part une nouvelle formulation de mélanges maîtres ignifugeants, et d'autre part un procédé de production correspondant.
PCT/IT2010/000175 2010-04-08 2010-04-23 Mélange maître ignifugeant pour polymères thermoplastiques, et procédé de production correspondant Ceased WO2011132208A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
PCT/IT2010/000175 WO2011132208A1 (fr) 2010-04-23 2010-04-23 Mélange maître ignifugeant pour polymères thermoplastiques, et procédé de production correspondant
PT117175166T PT2417187E (pt) 2010-04-08 2011-04-06 Composição padrão retardadora de chama para polímeros termoplásticos e processo para a sua produção
EP11717516A EP2417187B1 (fr) 2010-04-08 2011-04-06 Mélange maître d'ignifugeant pour polymères thermoplastiques et procédé de production associé
HRP20130268AT HRP20130268T1 (hr) 2010-04-08 2011-04-06 Teško zapaljive pigmentne disperzije (masterbatch) za termoplastiäśne polimere i postupak njihove proizvodnje
PCT/EP2011/055345 WO2011124606A1 (fr) 2010-04-08 2011-04-06 Mélange maître d'ignifugeant pour polymères thermoplastiques et procédé de production associé
ES11717516T ES2402984T3 (es) 2010-04-08 2011-04-06 Mezcla madre retardante de llama para polímeros termoplásticos y proceso para su producción

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/IT2010/000175 WO2011132208A1 (fr) 2010-04-23 2010-04-23 Mélange maître ignifugeant pour polymères thermoplastiques, et procédé de production correspondant

Publications (1)

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WO2011132208A1 true WO2011132208A1 (fr) 2011-10-27

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PCT/IT2010/000175 Ceased WO2011132208A1 (fr) 2010-04-08 2010-04-23 Mélange maître ignifugeant pour polymères thermoplastiques, et procédé de production correspondant

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102604186A (zh) * 2012-02-27 2012-07-25 北京化工大学 一种高韧性导电纳米复合材料及其制备方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003078315A2 (fr) * 2002-03-20 2003-09-25 Facultes Universitaires Notre-Dame De La Paix Nanocomposites: produits, procedes d'obtention et utilisations

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003078315A2 (fr) * 2002-03-20 2003-09-25 Facultes Universitaires Notre-Dame De La Paix Nanocomposites: produits, procedes d'obtention et utilisations

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102604186A (zh) * 2012-02-27 2012-07-25 北京化工大学 一种高韧性导电纳米复合材料及其制备方法

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