Classifications

• • 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
  • C08K5/5398—Phosphorus bound to sulfur
• • 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
• • 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
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K21/00—Fireproofing materials
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K21/00—Fireproofing materials
  • C09K21/06—Organic materials
  • C09K21/12—Organic materials containing phosphorus

Definitions

• the invention relates to the use of phosphine sulfide derivatives as flame retardants and polymers, in particular foams, which contain these flame retardants.
• the equipment of polymers, especially foams, with flame retardants is important for a variety of applications, such as polystyrene foam expandable polystyrene foam (EPS) or expanded polystyrene foam boards (XPS) for building insulation.
• EPS polystyrene foam expandable polystyrene foam
• XPS expanded polystyrene foam boards
• HBCD hexabromocyclododecane Due to the bioaccumulation and persistence of some polyhalogenated hydrocarbons, it is a major effort in the plastics industry to substitute halogenated flame retardants.
• Flame retardants should, if possible, not only have a high flame retardancy effect in the plastic at low loading for the processing but also sufficient temperature and hydrolysis stability. Furthermore, they should have no bioaccumulation and persistence.
• halogen-free flame retardants with sulfur-phosphorus bonds in particular thiophosphates and thiophosphonates are described.
• halogen-free flame retardants generally have to be used in significantly higher quantities in order to achieve the same flame retardancy of halogen-containing flame retardants. Therefore, halogen-free flame retardants which can be used in thermoplastic polymers, such as polystyrene, often also not be used in polymer foams, since they either interfere with the foaming process or affect the mechanical and thermal properties of the polymer foam. In the preparation of expandable polystyrene by suspension polymerization, the high flame retardancy reduce the stability of the suspension. In addition, the effect of the flame retardants used in thermoplastic polymers in polymer foams is often unpredictable due to the different fire behavior and different fire tests.
• the object of the invention is therefore to provide compounds which on the one hand are halogen-free and, on the other hand, even in small amounts have good flame retardancy properties in polymers, in particular in polymer foams, such as EPS and XPS.
• R 1, R 2 are identical or different CrCl 2 alkyl, C 3 -C 8 cycloalkyl which is unsubstituted or substituted by one or more -C 4 alkyl groups, C 2 -C 2 -alkenyl, C 2 -C 2 - alkynyl, C 6 -C 0 aryl, C 6 -C 0 aryl-Ci-C 4 alkyl; is H, SH, SR 4 , OH, OR 3 or a group:
• X 1 , X 2 are the same or different O or S; Y 1 , Y 2 are the same or different O or S;
• R 4 , R 5 , R 6 , R 7 , R 8 are, identically or differently independently, C 1 -C 2 -alkyl, C 3 -C 8 -cycloalkyl which is unsubstituted or substituted by one or more C 1 -C 4 -alkyl groups, C 2 - Ci2 alkenyl, C2-Ci2 alkynyl, C 6 -C 0 aryl or C 6 -C 0 aryl-Ci-C 4 alkyl; n is 1 if Y 1 or Y 2 is O, and 1, 2, 3, 4, 5, 6, 7 or 8 if Y 1 or Y 2 is S, and m is an integer of 0 to 100 ,
• the invention further provides a process for the flame-retardant finishing of foamed and unfoamed polymers, wherein the polymer is added a flame retardant containing one or more compounds of the formula (I).
• the invention further relates to the use of certain foamed polymer compositions which contain the novel fire retardant as insulation and / or insulating materials.
• the compounds of the formula (I) are halogen-free and have a significantly better activity even in small amounts than previously known halogen-free flame retardants in foams, such as dibenz [c, e] [1,2-oxaphosphorine-6-oxide (DOP, see US Pat eg EP-A 1 791 896).
• R 1 , R 2 are preferably identical or different C 1 -C 8 -alkyl, cyclohexyl, phenyl or benzyl.
• R 3 is preferably H, SH, SR 4 or a group
• X 1 , X 2 are preferred S.
• Y 1 , Y 2 are preferably the same or different O or S.
• R 4 , R 6 , R 7 , R 8 are preferably identical or different and independently of one another C 1 -C 8 -alkyl, cyclohexyl, phenyl or benzyl.
• n is preferably 1 if Y is 1 or Y 2 is O, and 1 or 2 if Y 2 is S;
• m is preferably 0 to 10.
• R 1 , R 2 are more preferably phenyl.
• R 3 is particularly preferably H, SH, S-benzyl or
• Y 1 is more preferably the same or different O or S.
• R 7 , R 8 are particularly preferably phenyl.
• n is more preferably 1 if Y 1 is O and 1 or 2 if Y 1 is S.
• Particular preference is given to compounds of the formula (I) in which all symbols and indices have the particularly preferred meanings.
• Particularly preferred compounds of the formula (I) are the compounds FSM 1 to FSM 6 listed in the examples.
• FSM 1 diphenyldithiophosphinic acid
• the compounds of the formula (I) used according to the invention are generally used in an amount in the range from 0.1 to 25 parts by weight. Quantities of 2 to 15 parts by weight, preferably 2.5 to 10 parts by weight, ensure adequate flame retardancy, especially in the case of foams made from expandable polystyrene.
• the effectiveness of the compounds (I) can be further improved by the addition of suitable flame retardant synergists, such as the thermal radical formers dicumyl peroxide, di-tert-butyl peroxide or biscumyl (2,3-diphenyl-2,3-dimethyl-butane).
• suitable flame retardant synergists such as the thermal radical formers dicumyl peroxide, di-tert-butyl peroxide or biscumyl (2,3-diphenyl-2,3-dimethyl-butane.
• 0.05 to 5 parts by weight of the flame retardant synergist are usually used.
• synergist is elemental sulfur, preferably in a proportion of 0.05 to 4 parts by weight, particularly preferably 0.1 to 2.5 parts by weight.
• the elemental sulfur can also be used in the form of starting compounds which are decomposed under the process conditions to elemental sulfur.
• Suitable materials for encapsulating are, for example, melamine resins (analogous to US Pat. No. 4,440,880) and urea-formaldehyde resins (analogous to US Pat. No. 4,698,215). Further materials and references are to be found in WO 99/10429.
• flame retardants such as melamine, melamine cyanurates, metal oxides, metal hydroxides, phosphates, phosphonates, phosphinates and expandable graphite or synergists, such as Sb 2 0 3 , Sn compounds or nitroxyl radicals containing or releasing compounds can be used.
• Suitable additional halogen-free flame retardants are, for example, commercially available under the names Exolit OP 930, Exolit OP 1312, HCA, HCA-HQ, M-ester Cyagard RF-1241, Cyagard RF-1243, Fyrol PMP, Phoslite IP-A, (aluminum hypophosphite), Melapur 200, Melapur MC APP (ammonium polyphosphate) and Budit 833 available.
• halogen-reduced materials can be obtained by using the compounds (I) according to the invention and adding minor amounts of halogen-containing, in particular brominated flame retardants, such as hexabromocyclododecane (HBCD) or brominated styrene homo- or styrene copolymers / oligomers (cf. Example styrene-butadiene copolymers, as described in WO-A 2007/058736), preferably in amounts ranging from 0.05 to 1, in particular 0.1 to 0.5 parts by weight, are prepared.
• brominated flame retardants such as hexabromocyclododecane (HBCD) or brominated styrene homo- or styrene copolymers / oligomers
• a preferred embodiment is therefore also a use according to the invention wherein the compound (s) of the formula (I) is used in admixture with one or more further flame-retardant compounds and / or one or more synergists.
• the flame retardant of the invention is halogen-free.
• composition of polymer, flame retardant and other additives is particularly preferably halogen-free.
• the flame retardants according to the invention that is, compounds of the formula (I) alone or in admixture with one another and / or in admixture with synergists and / or in admixture with other flame-retardant substances, are used according to the invention for the production of flame-retardant materials, preferably unfoamed or foamed polymers, in particular thermoplastic polymers used.
• the flame retardant is preferably physically mixed with the corresponding polymer in the melt and then finished as a polymer mixture with phosphorus contents between 0.05 parts by weight and 5 parts by weight and then in a second process step together with the same or with another Polymer further processed.
• the addition of the compounds (I) according to the invention before, during and / or after the preparation by suspension polymerization is preferred.
• the invention also provides a, preferably thermoplastic, polymer composition comprising a flame retardant according to the invention containing one or more compounds of the formula (I).
• foamed or unfoamed styrenic polymers including ABS, ASA, SAN, AMSAN, polyesters, polyimides, polysulfones, polyolefins, such as polyethylene and polypropylene, polyacrylates, can be used as the thermoplastic polymer.
• Foamed or unfoamed styrene homopolymers and copolymers are each individually or in mixture as polymer blends.
• the flameproofed polymer foams preferably have a density in the range from 5 to 200 kg / m 3 , particularly preferably in the range from 10 to 50 kg / m 3 , and are preferably more than 80%, particularly preferably 90 to 100% closed-cell.
• the flame-retardant, expandable styrene polymers (EPS) and styrene polymer extrusion foams (XPS) according to the invention can be made into expandable granules by adding the blowing agent and the inventive flame retardant before, during and / or after the suspension polymerization or by mixing a blowing agent into the polymer melt and subsequent extrusion and granulation under pressure (EPS) or by extrusion and relaxation using appropriately shaped nozzles to foam plates (XPS) or foam strands are processed.
• EPS expandable styrene polymers
• XPS styrene polymer extrusion foams
• styrene polymer comprises polymers based on styrene, ⁇ -methylstyrene or mixtures of styrene and ⁇ -methylstyrene, analogously for the styrene fraction in SAN, AMSAN, ABS, ASA, MBS and MABS (see below) are based on at least 50% by weight of styrene and / or alpha-methylstyrene monomers.
• the polymer is an expandable polystyrene (EPS).
• the foam is a styrenic polymer extrusion foam (XPS).
• Expandable styrenic polymers preferably have a molecular weight M w in the range from 120,000 to 400,000 g / mol, particularly preferably in the range from 180,000 to 300,000 g / mol, measured by gel permeation chromatography according to DIN 55672-1 with refractiometric detection (Rl) versus polystyrene standards, on. Due to the reduction in molecular weight by shear and / or temperature, the molecular weight of the expandable polystyrene is usually about 10,000 g / mol below the molecular weight of the polystyrene used.
• styrene polymers to glassy polystyrene (GPPS), toughened polystyrene (HIPS), anionically polymerized polystyrene or toughened polystyrene (A-IPS), styrene-alpha-methylstyrene copolymers, acrylonitrile-butadiene-styrene polymers (ABS), styrene-acrylonitrile Copolymers (SAN), acrylonitrile-alpha-methylstyrene copolymers (AMSAN), acrylonitrile-styrene-acrylic esters (ASA), methyl acrylate-butadiene-styrene (MBS), methyl methacrylate-acrylonitrile-butadiene-styrene (MABS) polymers or mixtures thereof or with polyphenylene ether (PPE) used.
• GPPS glassy polystyrene
• HIPS toughened polystyrene
• the styrene polymers mentioned can be used to improve the intrinsic mechanical properties or the thermal stability, if appropriate by using compatibilizers with thermoplastic polymers, such as polyamides (PA), polyolefins, such as polypropylene (PP) or polyethylene (PE), polyacrylates, such as polymethyl methacrylate (PMMA), Polycarbonate (PC), polyesters, such as polyethylene terephthalate (PET) or polybutylene terephthalate (PBT), polyethersulfones (PES), polyether ketones or polyether sulfides (PES) or mixtures thereof, generally in proportions of not more than 30 parts by weight, preferably in the range from 1 to 10 parts by weight, based on the polymer melt, are mixed.
• thermoplastic polymers such as polyamides (PA), polyolefins, such as polypropylene (PP) or polyethylene (PE), polyacrylates, such as polymethyl methacrylate (PMMA), Polycarbonate (PC), polyesters, such as polyethylene
• mixtures in the abovementioned quantitative ranges are also possible with, for example, hydrophobically modified or functionalized polymers or oligomers, rubbers, such as polyacrylates or polydienes, for example styrene-butadiene block copolymers or biodegradable aliphatic or aliphatic / aromatic copolyesters.
• rubbers such as polyacrylates or polydienes, for example styrene-butadiene block copolymers or biodegradable aliphatic or aliphatic / aromatic copolyesters.
• Suitable compatibilizers are, for example, maleic anhydride-modified styrene copolymers, polymers or organosilanes containing epoxide groups.
• the styrene polymer melt may also be mixed with polymer recyclates of the above-mentioned thermoplastic polymers, in particular styrene polymers and expandable styrene polymers (EPS), in amounts which do not substantially impair their properties, generally in quantities of not more than 50 parts by weight, in particular in amounts of 1 to 20 parts by weight.
• EPS expandable styrene polymers
• the propellant-containing styrene polymer melt usually contains one or more propellants in a homogeneous distribution in a proportion of 2 to 10 parts by weight, preferably 3 to 7 parts by weight, based on 100 parts by weight of Styrene polymer melt.
• Suitable blowing agents are the physical blowing agents commonly used in EPS, such as aliphatic hydrocarbons having 2 to 7 carbon atoms, alcohols, ketones, ethers or halogenated hydrocarbons. Preference is given to using isobutane, n-butane, isopentane, n-pentane. For XPS it is preferred to use C0 2 or mixtures thereof with alcohols and / or C 2 -C 4 -carbonyl compounds, in particular ketones.
• finely distributed internal water droplets can be introduced into the styrene polymer matrix. This can be done, for example, by the addition of water into the molten styrene polymer matrix. The addition of the water can be done locally before, with or after the propellant dosage. A homogeneous distribution of the water can be achieved by means of dynamic or static mixers. In general, 0 to 2, preferably 0.05 to 1, 5 parts by weight of water are sufficient.
• Expandable styrene polymers with at least 90% of the internal water in the form of inner water droplets with a diameter in the range of 0.5 to 15 ⁇ form during foaming foams with sufficient cell count and homogeneous foam structure.
• the added amount of blowing agent and water is chosen such that the expandable styrene polymers (EPS) have an expansion capacity a, defined as bulk density before foaming / bulk density after being applied, at most 125, preferably 25 to 100.
• EPS expandable styrene polymers
• the expandable styrene polymer pellets (EPS) according to the invention generally have a bulk density of at most 700 g / l, preferably in the range from 590 to 660 g / l.
• bulk densities in the range of 590 to 1200 g / l may occur.
• additives, nucleating agents, fillers, plasticizers, soluble and insoluble inorganic and / or organic dyes and pigments may be jointly or spatially separated from the styrene polymer melt, for example via mixers or side extruders. are given.
• the dyes and pigments are added in amounts ranging from 0.01 to 30, preferably in the range of 1 to 5 parts by weight.
• a dispersing aid for example organosilanes, polymers containing epoxy groups or maleic anhydride-grafted styrene polymers.
• Preferred plasticizers are mineral oils, Phthalates, which can be used in amounts of 0.05 to 10 parts by weight. Analogously, these substances can also be added before, during and / or after the suspension polymerization to inventive EPS.
• the blowing agent can be mixed into the polymer melt.
• One possible method comprises the stages a) melt production, b) mixing c) cooling d) conveying and e) granulation.
• stages can be carried out by the apparatuses or apparatus combinations known in plastics processing.
• static or dynamic mixers are suitable, for example extruders.
• the polymer melt can be taken directly from a polymerization reactor or produced directly in the mixing extruder or a separate melt extruder by melting polymer granules.
• the cooling of the melt can take place in the mixing units or in separate coolers.
• pressurized underwater granulation, granulation with rotating knives and cooling by spray misting of tempering liquids or sputtering granulation may be considered for the granulation.
• Apparatus arrangements suitable for carrying out the method are, for example:
• Extruder - Granulator Furthermore, the arrangement can have side extruders for introducing additives, for example solids or thermally sensitive additives.
• the propellant-containing styrene polymer melt is generally conveyed through the nozzle plate at a temperature in the range from 140 to 300.degree. C., preferably in the range from 160 to 240.degree. Cooling down to the range of the glass transition temperature is not necessary.
• the nozzle plate is heated at least to the temperature of the blowing agent-containing polystyrene melt.
• the temperature of the nozzle plate is in the range of 20 to 100 ° C above the temperature of the blowing agent-containing polystyrene melt. This prevents polymer deposits in the nozzles and ensures trouble-free granulation.
• the diameter (D) of the nozzle bores at the nozzle exit should be in the range of 0.2 to 1.5 mm, preferably in the range of 0.3 to 1, 2 mm, more preferably in the range of 0.3 to 0.8 mm.
• a process for the preparation of halogen-free flame-retardant, expandable styrene polymers (EPS), comprising the steps a) mixing an organic blowing agent and 1-25 parts by weight of the flame retardant according to the invention in the polymer melt by means of static or dynamic mixer at a temperature of at least
• EPS expandable styrene polymers
• suspension polymerization is preferably used as the monomer styrene alone. However, up to 20% of its weight may be replaced by other ethylenically unsaturated monomers such as alkylstyrenes, divinylbenzene, acrylonitrile, 1,1-diphenyl ether or alpha-methylstyrene.
• ethylenically unsaturated monomers such as alkylstyrenes, divinylbenzene, acrylonitrile, 1,1-diphenyl ether or alpha-methylstyrene.
• the customary auxiliaries for example peroxide initiators, suspension stabilizers, blowing agents, chain transfer agents, expanding aids, nucleating agents and plasticizers may be added.
• the flame retardant of the invention is added in the polymerization in amounts of 0.5 to 25 wt .-%, preferably from 5 to 15 wt .-%.
• Propellants are added in amounts of 2 to 10 wt .-%, based on monomer. It can be added before, during or after the polymerization of the suspension.
• Suitable propellants are, for example, aliphatic hydrocarbons having 4 to 6 carbon atoms. It is advantageous to use as suspension stabilizers inorganic Pickering dispersants, e.g. Magnesium pyrophosphate or calcium phosphate use.
• pear-shaped, substantially round particles having an average diameter in the range of 0.2 to 2 mm are formed.
• the final expandable styrenic polymer granules may be coated by glycerol esters, antistatic agents or anticaking agents.
• the EPS granules may be mixed with glycerol monostearate GMS (typically 0.25 parts by weight), glycerol tristearate (typically 0.25 parts by weight) finely divided silica Aerosil R972 (typically 0.12 parts by weight) and Zn stearate (typically 0.15 parts by weight), and antistatic coating.
• GMS typically 0.25 parts by weight
• glycerol tristearate typically 0.25 parts by weight
• finely divided silica Aerosil R972 typically 0.12 parts by weight
• Zn stearate typically 0.15 parts by weight
• the expandable styrene polymer granules according to the invention can be prefoamed in a first step by means of hot air or steam to foam particles having a density in the range of 5 to 200 kg / m 3 , in particular 10 to 50 kg / m 3 and welded in a second step in a closed mold to particle moldings become.
• the expandable polystyrene particles can be made into polystyrene foams having densities of from 8 to 200 kg / m 3, preferably from 10 to 50 kg / m 3 .
• the expandable particles are prefoamed. This is usually done by heating the particles with water vapor in so-called pre-expanders.
• the pre-expanded particles are then welded into shaped bodies.
• the prefoamed particles are brought into forms that do not close in a gas-tight manner and subjected to steam. After cooling, the moldings can be removed.
• the foam is an extruded polystyrene (XPS), available from:
• Foams according to the invention based on styrene polymers, in particular EPS and XPS, are suitable, for example, for use as insulating and / or insulating materials, in particular in the construction industry.
• Preferred is a use as halogen-free insulating and / or insulating material, especially in the construction industry.
• Foams according to the invention in particular based on styrene polymers, such as EPS and XPS, preferably exhibit a quenching time (fire test B2 according to DIN 4102 at a foam density of 15 g / l and a deposition time of 72 h) of ⁇ 15 seconds, particularly preferably ⁇ 10 seconds, and thus meet the conditions for passing the said fire test, as long as the flame height does not exceed the measurement mark specified in the standard.
• a quenching time fire test B2 according to DIN 4102 at a foam density of 15 g / l and a deposition time of 72 h
• FSM Flame retardants used 1 to 6 phosphine sulfides Diphenyldithiophosphinic acid FSM1
• FSM1 is commercially available (ABCR).
• FSM2 Parsons, Andrew F .; Sharpe, David J .; Taylor, Philip; Synlett; 2005; 19;
• FSM3 K. Goda; R. Okazaki; K. Akiba; N. Inamoto; Chem. Soc. Japan; 1978;
• FSM4 T.R. Hopkins; P. W. Bird; J. Amer. Chem. Soc. 1956; 78; 4447-4450.
• FSM5 M.G. Zimin; N. G. Zabirov; V. Smirnov; Zhoournal Obschei Khimii; 1980; 50;
• n-pentane 7 parts by weight of n-pentane were mixed into a polystyrene melt of PS 148G BASF SE with a viscosity number VZ of 83 ml / g.
• a polystyrene melt containing the flame retardants listed in the table was mixed via a Steitenstromextruder in the main stream.
• the stated amounts in parts by weight relate to the total amount of polystyrene which corresponds to 100 parts by weight.
• the mixture of polystyrene melt, blowing agent and flame retardant was conveyed at 60 kg / h through a nozzle plate with 32 holes (diameter of the nozzle 0.75 mm). With the help of pressurized underwater granulation, compact granules with a narrow size distribution were produced.
• the granules were prefoamed by the action of flowing steam and, after being stored for 12 hours by further treatment with steam, sealed in a closed mold to form foam blocks of a density of 15 kg / m 3 .
• the determination of the fire behavior of the foam panels was carried out after 72 hours of storage at a foam density of 15 kg / m 3 according to DIN 4102.
• Hexabromocyclododecane (referred to below as HBCD) was used as comparison experiment.
• Table 1 Fire behavior of EPS sheets according to the invention
• the gel kneaded uniformly in the extruder at 180 ° C., was passed through a settling zone and after a residence time of 15 minutes with a discharge temp. temperature of 105 ° C passed through a mold channel connected to the extruder, wherein a foamed sheet web with a cross section 650mm 50 mm and a density of 35g / l was formed.
• the product was cut into plates. The fire behavior of the samples with a thickness of 10 mm after a deposit time of 30 days according to DIN 4102 was tested.
• Table 2 Fire behavior of XPS plates according to the invention

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