Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
  • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
  • C07D487/04—Ortho-condensed systems
• • 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
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
  • C07D207/46—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with hetero atoms directly attached to the ring nitrogen atom
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
  • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
  • C07D209/44—Iso-indoles; Hydrogenated iso-indoles
  • C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
  • C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
  • C07D221/04—Ortho- or peri-condensed ring systems
  • C07D221/06—Ring systems of three rings
  • C07D221/14—Aza-phenalenes, e.g. 1,8-naphthalimide
• • 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
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/32—Compounds containing nitrogen bound to oxygen
• • 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
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
  • C08K5/3415—Five-membered rings
  • C08K5/3417—Five-membered rings condensed with carbocyclic rings
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
  • C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
  • C09D123/10—Homopolymers or copolymers of propene
  • C09D123/12—Polypropene
• • 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
  • C09K21/10—Organic materials containing nitrogen
• • 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
  • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
  • C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'

Definitions

• the present invention relates to the use of organic compound
• Oxyimides as flame retardants for plastics there is also provided a flame retardant plastic composition which includes an oxyimide flame retardant.
• a flame retardant plastic composition which includes an oxyimide flame retardant.
• moldings prepared from a flame-retardant polymer composition according to the invention are given.
• plastics such as As plastics based on polyolefins, polystyrene, polyamides, polyurethanes or polyesters, are flammable and relatively easily flammable. In order to reduce or eliminate the risk of fire of plastics in certain applications, it is therefore imperative to reduce the flammability and to use flame-retardant or flame-retardant plastic compositions. This will be done in usually flame retardants added to the plastic with the aim to prevent the ignition for a certain time or to significantly delay the spread of fire.
• Traditional flame retardants are based on chlorine- and bromine-containing compounds (usually in combination with antimony trioxide), on phosphorus-containing, on nitrogen-containing compounds and / or on inorganic hydroxides. Recently, for environmental and / or toxicological reasons, halogen-free flame retardant solutions are preferred. For the production of flame-retardant plastics, there are a variety of
• Flame retardants which are usually used substrate-specific for a particular polymer and a specific application according to the underlying standards. Flame-retardant plastics are used, for example, in electrical and electronic applications, in the transport / automotive sector and in construction.
• a very effective nitrogen-based flame retardant class developed in recent years, preferably for polyolefins, is based on alkoxyamines (WO 99/00450, WO 2008101845, WO 2011086114). Cleavage of the alkoxyamines gives rise to free radicals in the event of a fire, which intervene in the degradation process of the polymer and thus bring about the flameproofing effect (C.R. Wilen, R. Pfaendner, J. Appl.
• Alkoxyamines can also be used advantageously in synergistic combinations with other flame retardants (WO 02/074847, WO 03/016388, WO 2010026230, WO 2009080554, WO 2011003773, WO 2011117266). Furthermore, it was found that hydroxylamine
• Stabilizers can bring about a synergistic improvement of the effect of bromine-containing, phosphorus-containing and inorganic flame retardants (WO 02/074847).
• the flame retardants known from the prior art mentioned above do not all meet today's requirements. Thus, for example, they must still be used in a relatively high concentration with respect to the plastic composition to be protected, which may, for example, lead to a deterioration in the mechanical properties of the plastic.
• Other criteria include the thermal Stability, discoloration, formation of toxic gases in case of fire, easy accessibility on an industrial scale, among others.
• the object of the present invention was to provide novel flame retardants and synergistic flame retardant components which are effective at low concentrations and comparatively easily accessible.
• This object is related to the use of organic oxyimides as flame retardants for plastics according to the features of claim 1, with respect to a flame-retardant plastic composition with the features of claim 12, with respect to a method for producing this plastic composition having the features of claim 15 and a molded part of a paint or a coating which can be produced from a flameproofed polymer composition, having the features of patent claim 16.
• the respective dependent claims represent advantageous developments.
• the formula I is understood to mean that the imaged structural element is contained in the organic oxyimide.
• the oxyimides used according to the invention are not to be equated with isocyanurates or compounds derived therefrom or classes of compounds.
• the oxyimide used according to the invention is halogen-free, ie the corresponding compound contains no halogen atoms. It has been shown that the organic oxyimides used according to the invention have good activity, as described above, in order to render plastics flame-retardant.
• oxyimides containing at least one structural element of the following formula II
• R 1 is hydrogen or an optionally substituted alkyl, cycloalkyl, aryl, heteroaryl or acyl radical, used as a flame retardant.
• bridged oxyimides containing at least one structural element of the following formula III
• R 2 is an optionally substituted alkylene, cycloalkylene, arylene, heteroarylene or bridging acyl radical can be used.
• R is selected from radicals of the group consisting of
• n 1 to 18, -CH (CH 3 ) -, -C (CH 3 ) 2 -, -O-, -S-, -SO 2 -, -NHCO-, - CO - and the groups shown below
• m is 0 or 1 to 18.
• radicals R can be given by the following structural elements:
• the organic oxyimide has one of the following structural formula:
• R 1 and R 2 have the abovementioned meaning.
• a particularly preferred radical R 1 is hydrogen or an acyl radical.
• R 2 has the meaning given above.
• Hydroxylamines with, for example, an acid chloride or by transesterification from the corresponding acid esters with e.g. Volatile alcohols such. the methyl esters.
• these hydroxylamine derivatives can also be in the form of linear
• Oligomers or polymers e.g. bifunctional
• the syntheses of these polymers is described, for example, in H. Imajo et al. J. Pol. Be: Pol. Chem. 18, 2189-2196 (1980) or in H. Imajo et al. J. Pol. See: Pol. Chem. 19, 1855-1861 (1981).
• these polymers can also be synthesized in the form of branched or crosslinked structures by partially or completely replacing a difunctional component with a tri-, tetra- or higher-functionalized compound, e.g. a trifunctional acid component or a trifunctional hydroxylamine.
• copolymers can be synthesized according to the invention by, for example, a difunctional Hydroxylimid partially by a diol compound such as ethylene glycol, butanediol-1-4, 1,6-hexanediol, hydroquinone, 4,4 'dihydroxybiphenyl is replaced. Accordingly, for example copolyesters or copolyurethanes are accessible. Moreover, by partially replacing the difunctional hydroxylimides with difunctional compounds of structures other than diols, such as diamines, copolymers of mixed structures such as polyesteramides are available.
• the inventively used th organic oxyimides are preferably used for the following plastics, particularly preferably in thermoplastic, elastomeric or thermosetting plastics, especially thermoplastic polymers:
• Polymers of olefins or diolefins e.g. Polyethylene (LDPE, LLDPE, VLDPE, ULDPE, MDPE, HDPE, UHMWPE),
• Metallocene PE polypropylene, polyisobutylene, poly-4-methyl-pentene-1, polybutadiene, polyisoprene, polycyclooctene, polyalkylene-carbon monoxide copolymers, as well as copolymers in the form of random or block structures such as e.g. Polypropylene-polyethylene (EP), EPM or EPDM, ethylene-vinyl acetate (EVA), ethylene-acrylic esters, e.g. Ethylene-butyl acrylate, ethylene-acrylic acid and its salts (ionomers), as well as terpolymers such as e.g. Ethylene acrylic acid glycidyl acrylate, graft polymers such as e.g. Polypropylene-g-maleic anhydride, polypropylene-g-acrylic acid, polyethylene-g-acrylic acid,
• Polystyrene polymethylstyrene, polyvinylnaphthalene, styrene-butadiene (SB), styrene-butadiene-styrene (SBS), styrene-ethylene-butylene-styrene (SEBS), styrene-ethylene-propylene-styrene, styrene-isoprene, styrene-isoprene-styrene (SIS ), Styrene-butadiene-acrylonitrile (ABS), styrene-acrylonitrile-acrylate (ASA), styrene-ethylene, styrene-maleic anhydride polymers including corresponding graft copolymers such as Styrene on butadiene,
• halogen-containing polymers such as e.g. Polyvinyl chloride (PVC), polychloroprene and polyvinylidene chloride (PVDC), copolymers of vinyl chloride and vinylidene chloride or vinyl chloride and vinyl acetate, chlorinated polyethylene, polyvinylidene fluoride,
• Polymers of unsaturated esters such as e.g. Polyacrylates and polymethacrylates such as polymethyl methacrylate (PMMA),
• Polyacetals e.g. Polyoxymethylene POM
• copolymers e.g. butanal
• Polymers of cyclic ethers e.g. Polyethylene glycol, polypropylene glycol, polyethylene oxide, polypropylene oxide,
• Polyurethanes hydroxy-terminated polyethers or polyesters and aromatic or aliphatic isocyanates, in particular linear polyurethanes, polyureas,
• Polyamides such as e.g. Polyamide-6, 6.6, 6.10, 4.6, 4.10, 6.12, 12.12, polyamide 11, polyamide 12, and (partially) aromatic polyamides, e.g. Polyphthalamides, e.g. prepared from terephthalic acid and / or isophthalic acid and aliphatic diamines or from aliphatic dicarboxylic acids such as e.g. Adipic acid or
• Sebacic acid and aromatic diamines e.g. 1,4- or 1,3-diaminobenzene,
• Polyimides polyamide-imides, polyetherimides, polyesterimides, poly (ether) ketones, polysulfones, polyethersulfones, and
• Polyarylsulfones polyphenylene sulfide, polybenzimidazoles, polyhydantoins,
• Polyesters of aliphatic or aromatic dicarboxylic acids and diols or of hydroxy carboxylic acids such as e.g.
• PET Polyethylene terephthalate
• PBT polybutylene terephthalate
• PBT polypropylene terephthalate
• polyethylene naphthylate poly-1,4-dimethylolcyclohexane terephthalate
• polyhydroxybenzoate polyhydroxynaphthalate
• polylactic acid polyethylene terephthalate (PET)
• PET polybutylene terephthalate
• PBT polypropylene terephthalate
• polyethylene naphthylate poly-1,4-dimethylolcyclohexane terephthalate
• polyhydroxybenzoate polyhydroxynaphthalate
• polylactic acid polylactic acid
• Polycarbonates polyestercarbonates, as well as blends such as e.g.
• PC / ABS PC / PBT
• PC / PET / PBT PC / PET / PBT
• Cellulose derivatives such as e.g. Cellulose nitrate, cellulose acetate, cellulose propionate, cellulose butyrate
• non-thermoplastic or thermosetting plastics p non-thermoplastic or thermosetting plastics p
• mixtures, combinations or blends of two or more of the aforementioned polymers are non-thermoplastic or thermosetting plastics p
• polymers specified under a) to o) are copolymers, these may be present in the form of random, block or tapered structures.
• polymers specified under a) to o) are stereoregular polymers, these may be present in the form of isotactic, stereotactic, but also atactic forms.
• the polymers specified under a) to o) can have both amorphous and (partly) crystalline morphologies.
• the polyolefins mentioned under a) may also be crosslinked, e.g. crosslinked polyethylene, which is referred to as X-PE.
• the polyolefins mentioned under a) can have any stereostructures, i.
• the organic oxyimides used according to the invention are used for polyolefins, in particular for the polyolefins mentioned under a).
• the present flame retardants can be used in the following clever, non-thermoplastic plastics: q) epoxy resins consisting of di- or polyfunctional epoxy compounds in combination with e.g. aminic, anhydride or catalytically active hardeners,
• phenolic resins e.g. Phenol-formaldehyde resins, urea-formaldehyde resins, melamine-formaldehyde resins,
• the flame retardants of the invention are used in polyolefins, preferably polypropylene and / or polyethylene and their copolymers and blends.
• the oxyimide used according to the invention can be used in combination with at least one further flame retardant, resulting in synergistic effects.
• the at least one further flame retardant is preferably selected from the group consisting of a) inorganic flame retardants such as Al (OH) 3 , Mg (OH) 2 , AIO (OH), MgC0 3 , phyllosilicates such as montmorillonite, not or organically modified, Double salts, such as Mg-Al silicates,
• POSS Polyhedral Oligomeric Silsesquioxane compounds, huntite, hydromagnesite or halloysite, and Sb 2 0 3 , Sb 2 0 5 , MoO 3 , zinc stannate, zinc hydroxystannate,
• nitrogen-containing flame retardants e.g. Melamine, melanin, melamine, melamine derivatives, melamine condensation products or melamine salts, benzoguanamine, polyisocyanurates, alantoin, phosphacenes, in particular melamine cyanurate, melamine phosphate, dimelamine phosphate, melamine pyrophosphate, melamine polyphosphate, melamine-metal phosphates, such as e.g. Melamine aluminum phosphate, melamine zinc phosphate,
• nitrogen-containing flame retardants e.g. Melamine, melanin, melamine, melamine derivatives, melamine condensation products or melamine salts, benzoguanamine, polyisocyanurates, alantoin, phosphacenes, in particular melamine cyanurate, melamine phosphate, dimelamine phosphate, melamine pyrophosphate, melamine polyphosphate, melamine-metal phosphate
• Phosphorhaitigen flame retardants such. red phosphorus, phosphates, e.g. Resorcinol diphosphate, bisphenol A diphosphate and their oligomers, triphenyl phosphate,
• Ethylenediamine diphosphate such as salts of hypophosphorous acid and its derivatives such as diethyl aluminum phosphinate or aluminum phosphinate, aluminum phosphite, aluminum phosphonate, phosphonate esters, oligomeric and polymeric derivatives of methane phosphonic acid, 9,10-dihydro-9-oxa-10-phosphorylphenanthrene-10-oxide (DOPO) and their substituted compounds,
• phosphinates such as salts of hypophosphorous acid and its derivatives such as diethyl aluminum phosphinate or aluminum phosphinate, aluminum phosphite, aluminum phosphonate, phosphonate esters, oligomeric and polymeric derivatives of methane phosphonic acid, 9,10-dihydro-9-oxa-10-phosphorylphenanthrene-10-oxide (DOPO) and their substituted compounds,
• DOPO 9,10-dihydro-9-oxa-10-phosphorylphenanthrene-10
• Chlorine and bromine based halogenated flame retardants e.g. polybrominated diphenyloxides, e.g.
• Decabromodiphenyloxide tris (3-bromo-2,2-bis (bromomethyl) propyl phosphate, tris (tribromoneopentyl) phosphate, tetrabromophthalic acid, 1,2-bis (tribromophenoxy) ethane,
• Borates such as e.g. Zinc borate or calcium borate,
• Anti-drip agents e.g. polytetrafluoroethylene
• silicon-containing compounds such as e.g. Polyphenylsiloxane.
• halogen-containing flame retardants mentioned under b) are often commercial products which are e.g. from the companies Albemarle, Chemtura / Great Lakes or ICL are commercially available.
• Free-radical formers in the context of the present invention are compounds which can generate radicals by thermal and light-induced cleavage.
• Suitable free-radical formers for the applications present here are those which have sufficient thermal stability for the plastics or coating processing processes, ie none at the time of processing or form only very small amounts of free radicals and spontaneously generate radicals only at higher temperatures, as they occur only in case of fire.
• the respective processing processes and temperatures for coatings and plastic processing processes are known to the person skilled in the art. Plastics processing processes and associated temperatures can also be found in the specialist literature such as H. Domininghaus, P. Eisner, P. Eyerer. T. Hirth, Kunststoffe, 8th edition, Springer 2012.
• the radical generator is particularly preferably selected from the group consisting of a) N-alkoxyamines according to the structural formula shown below
• R 3 is hydrogen or an optionally substituted alkyl, cycloalkyl, aryl, heteroaryl or acyl radical, in particular a C 1 to C 4 alkyl radical,
• R 4 is an alkoxy, aryloxy, cycloalkoxy, aralkoxy or
• Z is hydrogen or an optionally substituted alkyl, cycloalkyl, aryl, heteroaryl or acyl radical, where the two radicals Z can also form a closed ring, which may optionally be substituted by ester, ether, amine, amide, carboxy or urethane groups,
• R is an alkyl, cycloalkyl or aryl radical
• R 6 is identical or different at each occurrence and denotes a linear or branched alkyl radical
• R 7 is the same or different at each occurrence and is hydrogen or a linear or branched alkyl radical
• R 8 is the same or different at each occurrence and is an alkyl, alkoxy, aryloxy, cycloalkyloxy, aralkoxy or acyloxy radical,
• R 7 has the abovementioned meaning, preferably methyl
• R 7 has the meaning indicated above, preferably methyl, and 2 ⁇ n ⁇ 100.
• Typical examples of the aforementioned N-alkoxyamines of the stated structure are: 1-cyclohexyloxy-2,2,6,6-tetramethyl-4-octadecylaminopiperidine; Bis (1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate; 2,4-bis [(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) butylamino] -6- (2-hydroxyethylamino-S-triazine; bis (1-cyclohexyloxy-2,2,6 , 6-tetramethylpiperidin-4-yl) adipate;
• the at least one further flame retardant may in particular also be a phosphorus-containing flame retardant.
• Preferred phosphorus-containing flame retardants are phosphinates of the following structures:
• R 1 and R 2 are identical or different and are selected from linear or branched C 1 -C 6 -alkyl and / or aryl;
• R 1 is alkyl
• R 2 is alkyl and M is Al or Zn.
• a particularly preferred example of a phosphinate according to the invention are the commercially available products Exolit OP (RTM) from Clariant SE.
• phosphorus-containing flame retardants are metal salts of hypophosphorous acid having a structure according to the formula
• Met is a metal selected from Groups I, II, III and IV of the Periodic Table of the Elements, and n is a number from 1 to 4 corresponding to the charge of the corresponding metal ion Met.
• Met n + is, for example, Na + , Ca 2+ , Mg 2+ , Zn 2+ , Ti 4+ or Al 3+ , with Ca 2+ , Zn 2+ and Al 3+ being particularly preferred.
• phosphorus-containing flame retardants are phosphonates or phosphonic diaryl esters of a structure according to the following formula:
• Corresponding structures may also be present in the form of phosphonate oligomers, polymers and co-polymers.
• Linear or branched phosphonate oligomers and polymers are known in the art.
• branched phosphonate oligomers and polymers reference is made to US Pat. Nos. 2,716,101, 3,326,852, 4,328,174, 4,331,614, US Pat.
• Phophonates are available, for example, under the tradename Nofia (RTM) from FRX Polymers.
• phosphorus-containing flame retardants are compounds based on oxaphosphorine oxide and derivatives thereof having, for example, the following structures:
• synergistic phosphorus-containing flame retardants are cyclic phosphonates of a structure according to one of the following formulas:
• a 1 and A 2 independently represent a substituted or unsubstituted, straight or branched alkyl group of 1 to 4 carbon atoms, substituted or unsubstituted benzyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, and wherein A 3 and A 4 are independently each is methyl or ethyl and A 5 is a straight or branched alkyl group of 1 to 4 carbon atoms or a phenyl or benzyl group, each of which may have up to 3 methyl groups.
• Cyclic phosphonates are commercially available, for example, from Thor GmbH under the trade name Aflammit (RTM) or can be prepared according to EP 2450401.
• the at least one further flame retardant may in particular also be a nitrogen-containing flame retardant.
• Preferred nitrogen-containing flame retardants are melamine polyphosphate, melamine cyanurate, melamine-metal phosphates, poly- [2,4- (piperazin-1,4-yl) -6- (morpholin-4-yl) -l, 3,5-triazine] and ammonium polyphosphate. These compounds are commercial products and available under the tradenames Melapur (RTM) from BASF SE, Budit (RTM) from Budenheim Chemical Factory, Exolit (RTM) from Clariant, Safire (RTM) from Floridienne or MCA PPM Triazines from MCA Technologies GmbH.
• oxyimide used according to the invention with at least one further flame retardant
• oxyimide: flame retardant preferably from 5:95 to 50:50, particularly preferably from 10:90 to 30:70 are used.
• organic oxyimides based on the plastics, to 0.01 to 30 wt .-%, preferably to 0.1 to 20 wt .-%, particularly preferably to 1 to 10 wt .-% are used.
• the present invention relates to a flame-retardant plastic composition containing or consisting of 50 to 98 parts by weight preferably 70 to 95 parts by weight of at least one plastic, in particular at least one thermoplastic polymer,
• organic oxyimide is halogen-free, c) 1 to 25 parts by wt. preferably 2.5 to 15 parts by wt. of at least one further flame retardant.
• the flame-retardant plastic composition may additionally
• At least one additive from the class of phenolic antioxidants, phosphites, acid scavengers, hindered amines, dispersants and combinations thereof.
• additives selected from the group consisting of UV absorbers, light stabilizers, stabilizers, hydroxylamines, benzofuranones, metal deactivators, filler deactivators, nucleating agents, impact modifiers, plasticizers, lubricants, rheology modifiers, processing aids, pigments, dyes, optical brighteners , antimicrobial agents, antistatic agents, slip agents, antiblocking agents, coupling agents, dispersants, compatibilizers, oxygen scavengers, acid scavengers, marking agents or antifogging agents.
• additives selected from the group consisting of UV absorbers, light stabilizers, stabilizers, hydroxylamines, benzofuranones, metal deactivators, filler deactivators, nucleating agents, impact modifiers, plasticizers, lubricants, rheology modifiers, processing aids, pigments, dyes, optical brighteners , antimicrobial agents, antistatic agents, slip agents, antiblocking agents, coupling agents, dispers
• compositions contain particular acid scavengers, for example based on salts of long-chain acids such as calcium stearate, magnesium stearate, zinc stearate, calcium lactate or of hydrotalcites and / or stabilizers from the group of phenolic antioxidants and phosphites / phosphonites and / or light stabilizers from the group of hindered amines (HALS) and / or dispersants.
• acid scavengers for example based on salts of long-chain acids such as calcium stearate, magnesium stearate, zinc stearate, calcium lactate or of hydrotalcites and / or stabilizers from the group of phenolic antioxidants and phosphites / phosphonites and / or light stabilizers from the group of hindered amines (HALS) and / or dispersants.
• HALS hindered amines
• Suitable light stabilizers for example compounds on the basis of 2- (2 'hydroxyphenyl) benzotriazoles are, 2-hydroxybenzophenones, esters of benzoic acids, acrylates, oxamides, and 2- (2-hydroxyphenyl) -l, 3,5-triazines.
• Suitable 2- (2 'hydroxyphenyl) benzotriazoles are for example 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3', 5'-di-butyl-2'-hydroxyphenyl ieri-) benzotriazole, 2- (5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5 '- (1,1,3,3-tetramethylbutyl) phenyl) benzotriazole, 2- (3'',5'-di-tert-butyl-2'-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-methylphenyl-5-chlorobenzotriazole, 2- (3 'sec-butyl-5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-4'-octyloxyphenyl) benzotriazole, 2- (3'
• Suitable acrylates are, for example, ethyl ⁇ -cyano- ⁇ , ⁇ -diphenyl acrylate, isooctyl ⁇ -cyano- ⁇ , ⁇ -diphenyl acrylate, methyl ⁇ -carbomethoxycinnamate, methyl ⁇ -cyano- ⁇ -methyl-p-methoxycinnamate, Butyl- ⁇ -cyano- ⁇ -methyl-p-methoxycinnamate, methyl- ⁇ -carbomethoxy-p-methoxycinnamate and N- ( ⁇ -carbomethoxy- ⁇ -cyanovinyl) -2-methylindoline.
• esters of benzoic acids are, for example, tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate,
• Dibenzoylresorcinol bis (4-ieri-butylbenzoyl) resorcinol, benzoylresorcinol, 2,4-di-ii-butylphenyl-3,5-di-ieri-butyl-4-hydroxybenzoate, hexadecyl-3,5-di-ieri-butyl 4-hydroxybenzoate, octadecyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-irei-butylphenyl-3,5-di-ieri-butyl-4-hydroxybenzoate.
• Suitable oxamides are, for example, 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butoxanilide, 2,2'-didodecyloxy-
• Suitable 2- (2-hydroxyphenyl) -1, 3,5-triazines are, for example, 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1, 3,5-triazine, 2- (2-hydroxy) 4-octyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1, 3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1 , 3,5-triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1, 3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl ) -4,6-bis (4-methylphenyl-l, 3,5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -
• Suitable metal deactivators are, for example, ⁇ , ⁇ '-diphenyloxamide, N-salicylal-N'-salicyloylhydrazine, N, N'-bis (salicyloyl) hydrazine, N, N'-bis (3,5-di-tert-butyl-4-) hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1, 2,4-triazole, bis (benzylidene) oxalyldihydrazide, oxanilide, isophthaloyl dihydrazide,
• metal deactivators are the following structures:
• Suitable phenolic antioxidants are, for example:
• Alkylated monophenols e.g. 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di- tert -butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2- (a-methylcyclohexyl) -4,6-dimethylphenol, 2, 6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-ieri-butyl-4-methoxymethylphenol, linear or branched nonylphenols, such as 2,6-Dinonyl-4-methylphenol, 2,4-dimethyl-6- (1-methylundec-1-yl) phenol, 2,4-dimethyl-6- (1-methyl
• Alkylthiomethylphenols e.g. 2,4-dioctylthiomethyl-6-te / t-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-didodecylthiomethyl-4-nonylphenol;
• Hydroquinones and alkylated hydroquinones e.g. 2,6-di-tertiary-butyl-4-methoxy-phenol, 2,5-di-tert-butyl-hydroquinone, 2,5-di-alpha-amyl-hydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6- Di-ieri-butylhydroquinone, 2,5-di-uteri-butyl-4-hydroxyanisole, 3,5-di-ieri-butyl-4-hydroxyanisole, 3,5-di-ieri-butyl-4-hydroxyphenylstearate, bis ( 3,5-di-ieri-butyl-4-hydroxyphenyl) adipate;
• Tocopherols e.g. ⁇ -, ⁇ -, ⁇ -, ⁇ -tocopherol and mixtures of these (vitamin E);
• Hydroxylated thiodiphenyl ethers e.g. 2,2'-thiobis (6-ieri-butyl-4-methylphenol), 2,2'-thiobis (4-octylphenol), 4,4'-thiobis (6-ieri-butyl-3-methylphenol), 4, 4'-Thiobis (6-ieri-butyl-2-methylphenol), 4,4'-thiobis (3,6-di-5ec-amylphenol), 4,4'-bis (2,6-dimethyl-4-hydroxyphenyl )disulfide;
• Alkylidene bisphenols such as 2,2'-methylenebis (6-ieri-butyl-4-methylphenol), 2,2'-methylenebis (6-ieri-butyl-4-ethylphenol), 2,2'-methylenebis [4-methyl] 6- ( ⁇ -methylcyclohexyl) phenol], 2,2'-methylenebis (4-methyl-6-cyclohexylphenol), 2,2'-methylenebis (6-nonyl-4-methylphenol), 2,2'-methylenebis (4 , 6-di-ethyl-butylphenol), 2,2'-ethylidenebis (4,6-di-ieri-butylphenol), 2,2'-ethylidenebis (6- tert-butyl-4-isobutylphenol), 2,2'-methylenebis [6- (a-methylbenzyl) -4-nonylphenol], 2,2'-methylenebis [6- (a, a-dimethylbenzyl) -4-nonylphenol]
• N and S benzyl compounds e.g. 3,5,3 ', 5'-tetra-ieri-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tridecyl-4-hydroxy-3,5-di-ieri-butylbenzylmercaptoacetate , Tris (3,5-di-ieri-butyl-4-hydroxybenzyl) amine, bis (4-yl-butyl-3-hydroxy-2,6-dimethylbenzyl) dithioterephthalate, bis (3,5-di-tert-butyl) butyl-4-hydroxybenzyl) sulfide, isooctyl-3,5-di-ieri-butyl-4-hydroxybenzylmercaptoacetate;
• Hydroxybenzylated malonates e.g. Dioctadecyl 2,2-bis (3,5-di-i-butyl-2-hydroxybenzyl) malonate, dioctadecyl-2- (3-yl-butyl-4-hydroxy-5-methylbenzyl) malonate, didodecylmercaptoethyl-2,2 bis (3,5-di-ieri-butyl-4-hydroxybenzyl) malonate, bis [4- (l, l, 3,3-tetramethylbutyl) phenyl] -2,2-bis (3,5-di-C butyl-4-hydroxybenzyl) malonate;
• Aromatic hydroxybenzyl compounds such as e.g. 1, 3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,4-bis (3,5-di-tert-butyl) 4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene, 2,4,6-tris (3,5-di-i-butyl-4-hydroxybenzyl) phenol;
• Triazine compounds such as 2,4-bis (octylmercapto) -6- (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6-bis (3,5-di-te / t-butyl-4- hydroxyanilino) -l, 3,5-triazine, 2-octylmercapto-4,6-bis (3,5-di-tert-butyl-4-hydroxyphenoxy) -l, 3,5-triazine, 2,4, 6-tris (3,5-di-tert-butyl-4-hydroxyphenoxy) -1,2,3-triazine, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl ) isocyanurate, 1,3,5-tris (4-yl-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 2,
• Benzyl phosphonates e.g. Dimethyl 2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl 3,5-di-i-di-4-hydroxybenzylphosphonate, dioctadecyl-3,5-di-i-butyl-4-hydroxybenzylphosphonate, Dioctadecyl-5-ieri-butyl-4-hydroxy-3-methylbenzylphosphonate, the calcium salt of the monoethyl ester of 3,5-di-tertiarybutyl-4-hydroxybenzylphosphonic acid;
• Acylaminophenols e.g. 4-hydroxylauranilide, 4-hydroxystearanilide, octyl-N- (3,5-di-i-butyl-4-hydroxyphenyl) carbamate;
• Esters of ⁇ - (3,5-di-ieri-butyl-4-hydroxyphenyl) propionic acid with mono- or polyhydric alcohols e.g. Methanol, ethanol, n-octanol, i-octanol,
• Trimethylolpropane 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane.
• Esters of ⁇ - (5-yl-butyl-4-hydroxy-3-methylphenyl) propionic acid with mono- or polyhydric alcohols e.g. Methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol,
• Trimethylolpropane 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane, 3,9-bis [2- ⁇ 3- (3-tert-butyl-4-hydroxy-5-) methylphenyl) propionyloxy ⁇ -1, 1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane;
• Esters of ⁇ - (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid with mono- or polyhydric alcohols e.g. Methanol, ethanol, octanol, octadecanol, 1,6-
• Esters of 3,5-di-ieri-butyl-4-hydroxyphenyl) acetic acid with monohydric or polyhydric alcohols e.g. Methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol,
• vitamin C Ascorbic acid (vitamin C).
• Particularly preferred phenolic antioxidants are:
• Octadecyl 3- (3,5-di-ieri-butyl-4-hydroxyphenyl) propionate, pentaerythritol tetrakis [3- (3,5-di-i-butyl-4-hydroxyphenyl) propionate, tris (3,5-) di-tert-butyl-4-hydroxyphenyl) isocyanurate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-i-butyl-4-hydroxyphenyl) isocyanurate, l, 3, 5-trimethyl-2,4,6-tris (3,5-di-ieri-butyl-4-hydroxybenzyl) benzene, triethylene glycol bis [3- (3-yl-butyl-4-hydroxy-5- methylphenyl) propionate, N, N'-hexane-l, 6-diyl-bis [3- (3,5-di-ieri-butyl-4-hydroxyphenyl) propionic acid amide.
• Suitable phosphites / phosphonites are, for example:
• Triphenyl phosphite diphenyl alkyl phosphites, phenyl dialkyl phosphites,
• Tri (nonylphenyl) phosphite Tri (nonylphenyl) phosphite, trilauryl phosphites, trioctadecyl phosphite,
• Diisodecyloxypentaerythritol diphosphite bis (2,4-di-ieri-butyl-6-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tris (ieri-butylphenyl) pentaerythritol diphosphite, tristearylsorbitol triphosphite, tetrakis (2,4-di-ieri-butylphenyl) 4,4'-biphenylenediphosphonite, 6-isoctyloxy-2A8,10-tetra-ieri-butyl-12H-dibenzo [d, g] -l, 3,2-dioxaphosphocine, bis (2,4-di-ieri-butyl -6-methylphenyl) methyl phosphite, bis (2,4-di-ieri-butyl-6-methylphenyl) ethyl phosphite, 6-fluoro
• Particularly preferred phosphites / phosphonites are:
• Suitable stabilizers are amine antioxidants.
• Suitable aminic antioxidants are, for example:
• aminic antioxidants are hydroxylamines or N-oxides (nitrones), e.g. ⁇ , ⁇ -dialkylhydroxylamine, N, N-dibenzylhydroxylamine, ⁇ , ⁇ -dilaurylhydroxylamine, N, N-distearylhydroxylamine, N-benzyl-a-phenylnitrone, N-octadecyl-a-hexadecylnitrone, and Genox EP (Chemtura) according to the formula:
• Suitable stabilizers are thiosynergists.
• Thiosynergists are, for example, distearyl thiodipropionate,
• Suitable stabilizers are copper salts, e.g. Copper (I) iodide, copper (I) bromide or copper complexes such as e.g. Triphenylphosphine-copper (I) complexes.
• copper salts e.g. Copper (I) iodide, copper (I) bromide or copper complexes such as e.g. Triphenylphosphine-copper (I) complexes.
• Suitable hindered amines are, for example, 1,1-bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, bis (l, 2,2,6,6-pentamethyl-4-piperidyl) sebazate, bis (l octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (l, 2,2,6,6-pentamethyl) 4-piperidyl) -n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensation product of 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, linear or cyclic condensation products of N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-yl-octylamino-2,6-di-chloro-1, 3,5-triazine , Tris (2
• Polyacrylates e.g. Long chain side chain copolymers, polyacrylate block copolymers, alkylamides: e.g. N, N'-l, 2-ethanediyl-bisoctadecanamide sorbitan ester, e.g. Monostearyl sorbitan esters, titanates and zirconates, reactive copolymers having functional groups, e.g. Polypropylene-co-acrylic acid, polypropylene-co-maleic anhydride, polyethylene-co-glycidyl methacrylate, polystyrene-old-maleic anhydride-polysiloxanes: e.g.
• Dimethylsilanediol-ethylene oxide copolymer, polyphenylsiloxane copolymer, amphiphilic copolymers e.g. Polyethylene block polyethylene oxide, dendrimers, e.g. hydroxyl-group-containing dendrimers.
• Suitable nucleating agents are, for example, talc, alkali or alkaline earth salts of mono- and polyfunctional carboxylic acids such as e.g. Benzoic acid, succinic acid, adipic acid, e.g. Sodium benzoate, zinc glycerolate, aluminum hydroxy-bis (4-te / t-butyl) benzoate, benzylidene sorbitols, e.g. 1.3: 2.4
• Suitable fillers and reinforcing agents are for example synthetic or natural materials such as calcium carbonate, silicates, glass fibers, glass beads (solid or hollow), talc, mica, kaolin, barium sulfate, metal oxides and metal hydroxides, carbon black, graphite, carbon nanotubes, graphene, wood flour or fibers of natural products such as cellulose or synthetic fibers.
• Other suitable fillers are hydrotalcites or zeolites or sheet silicates such as montmorillonite, bentonite, beidelite, mica, hectorite, saponite, vermiculite, ledikite, magadite, lllite, kaolinite, wollastonite, attapulgite.
• Suitable pigments may be inorganic or organic in nature.
• Suitable inorganic pigments are, for example, titanium dioxide, zinc oxide,
• Zinc sulphide iron oxide, ultramarine, carbon black.
• Suitable organic pigments are, for example, anthraquinones, anthanthrones, benzimidazolones, quinacridones, diketopyrrolopyrroles, dioxazines, indanthrones, isoindolinones, azo compounds, perylenes, phthalocyanines or pyranthrones.
• Other suitable pigments are metal-based effect pigments or pearlescent pigments
• Optical brighteners are, for example, bisbenzoxazoles, phenylcoumarins or bis (styryl) biphenyls and in particular optical brighteners of the formulas:
• Suitable filler deactivators are, for example, epoxides such as e.g. Bisphenol A diglycidyl ether, polysiloxanes, polyacrylates in particular
• Block copolymers such as polymethacrylic polyalkylene oxide.
• Suitable antistatic agents are, for example, ethoxylated alkylamines, fatty acid esters, alkylsulfonates and polymers such as e.g. Polyether amides.
• the present invention relates to a molding composition, a molding, a paint or a coating produced from a previously described flame-retardant plastic composition, in particular in the form of injection molded parts, films or films, coatings or paints, foams,
• compositions of the present invention may be used for marine applications (pontoons, planks, boats), automotive applications (bumpers, batteries, cowlings, fuel tanks, cables, conduits, etc.), aircraft parts, railway parts, bicycle and motorcycle parts, space applications such as satellite parts, housing parts for Electrical appliances such as computers, telephones, printers, audio and video systems, plugs, printed circuits, switches, lamp covers, refrigerators, coffee machines, vacuum cleaners, power generation rotor blades, fans, roofing membranes, construction films, pipes such as sewage pipes and gas pipes Fittings, drainage systems, profiles such as window profiles or conduits, wood composites, furniture, flooring, cladding panels, artificial turf, stadium seats, carpets, nets, ropes, furniture parts, mats, garden chairs, crates, containers and barrels.
• the invention also relates to a method for producing a previously described plastic composition according to the invention, in which the at least one organic oxyimide before, after or simultaneously with the at least one further flame retardant in the at least one plastic, preferably the at least one thermoplastic polymer is incorporated.
• Single-screw extruders, twin-screw extruders, planetary roller extruders, ring extruders, co-kneaders which are preferably equipped with a vacuum degassing.
• the processing can be done under air or under
• Various flame retardants and additives can be added separately or as a mixture, in the form of liquids, powders, granules or compacted products or likewise in the form of masterbatches or concentrates containing, for example, SO 80% of the compositions according to the invention.
• the invention likewise relates to a flameproofing composition consisting of an organic oxyimide containing at least one structural element of the formula I depicted below,
• Trimesyl trichloride in 19 mL of distilled acetone was added dropwise. After completion of the addition The mixture is stirred for 1 h at 5 ° C, then the reaction mixture is stirred for 12 h at room temperature. The precipitated, white solid is filtered off and washed with 5% hydrochloric acid and with water. There will be 3.9 g (78%) of a white Product received.
• the residence time of the mixture in bypass operation is 60 s.
• the desired mixture of polymer and additives (see Table 1 below) is first mixed manually in a beaker and fed in small portions to the micro-extruder. If the volume of the device is filled with melt, the material remains in the device for a further 60 s (dwell time) and is then drained off.
• the resulting plastic strands are granulated (Pell-Tec SD 50 pure).
• Test specimens for the fire test are produced from the granules at a temperature of 220 ° C and a pressure of 2 t using a hydraulic 10t press (Werner & Pfleiderer). For this purpose, the granules are filled into the mold and these transferred into the already preheated press. At a pressure of 0.5 t, the granules are first melted for 60 seconds. After the melting time, the pressure is increased to 2 1 and held constant for a further 3 min. While maintaining the contact pressure, the mold is cooled to 60 ° C and then removed the specimens.
• the specimens have the following dimensions according to the standard: 125 x 12.5 x 1.5 mm.
• Table 1 Compositions in polypropylene and results of the fire test
• Table 2 Compositions in polypropylene and results of the fire test
• Alkoxyamine Flamestab NOR 116 from BASF SE
• Example 36 Analogously to Examples 1-35 according to the invention, a thermoplastic polyurethane (Elastollan 1185A from BASF SE) was processed with 8% diethylaluminum phosphinate and 4% of compound 3 at 190 ° C. and compressed at 200 ° C. to test specimens. The classification V-2 with a total burning time (4 specimens) of 1.3 seconds is obtained.
• a thermoplastic polyurethane (Elastollan 1185A from BASF SE) was processed with 8% diethylaluminum phosphinate and 4% of compound 3 at 190 ° C. and compressed at 200 ° C. to test specimens.
• the classification V-2 with a total burning time (4 specimens) of 1.3 seconds is obtained.
• Phosphate phosphoric acid
• P, P '- [l, l'-biphenyl] -4,4'-diyl ⁇ , ⁇ , ⁇ ', ⁇ '-tetraphenyl ester ADK rod FP 800 from Adeka

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