WO2013135701A1 - Synthèse de polyphénolbisulfures - Google Patents

Synthèse de polyphénolbisulfures Download PDF

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WO2013135701A1
WO2013135701A1 PCT/EP2013/055006 EP2013055006W WO2013135701A1 WO 2013135701 A1 WO2013135701 A1 WO 2013135701A1 EP 2013055006 W EP2013055006 W EP 2013055006W WO 2013135701 A1 WO2013135701 A1 WO 2013135701A1
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alkyl
aryl
formula
cycloalkyl
alkynyl
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PCT/EP2013/055006
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German (de)
English (en)
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Christoph Fleckenstein
Hartmut Denecke
Sabine Fuchs
Matthias Mueller
Manfred Doering
Michael Cisielski
Jochen Wagner
Peter Deglmann
Sameer Nalawade
Peter Gutmann
Klaus Hahn
Klemens Massonne
Andreas Kleinke
Roland Helmut Kraemer
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Basf Se
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/22—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of hydropolysulfides or polysulfides
    • C07C319/24—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of hydropolysulfides or polysulfides by reactions involving the formation of sulfur-to-sulfur bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/37—Thiols
    • C08K5/372—Sulfides, e.g. R-(S)x-R'
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/06—Polystyrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
    • C08L81/04—Polysulfides
    • 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 a process for the preparation of polyphenol disulfides. Further, the invention relates to polyphenol disulfides obtainable by the process, a flame retardant system containing the polyphenol disulfide and a halogen-free organic phosphorus compound, and a polymer composition containing the flame retardant system.
  • 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
  • a typical representative of these classic flame retardants is hexabromocyclododecane. Due to the bioaccumulation and persistence of some polyhalogenated hydrocarbons, it is a major effort in the plastics industry to replace halogenated flame retardants with halogen-free ones.
  • halogen-free phosphorus-containing flame retardants in combination with halogen-free sulfur-containing synergists.
  • polyphenol disulfides as synergists to halogen-free phosphorus-containing
  • Poly (tert-butylphenol disulfide) and poly (tert-pentylphenol disulfide) are important representatives of this class of compounds and can be obtained commercially, for example, as VULTAC® TB7 or VULTAC® 2 and 3, respectively. According to US 3,968,062 it is assumed that these are complex mixtures of polysulfides.
  • poly (tert-butylphenol disulfide) is prepared by heating para-tert-butylphenol with sulfur monochloride using trichlorethylene as solvent, the temperature of the heating mantle being between 15 and 155 ° C.
  • trichlorethylene a low-boiling solvent such as trichlorethylene is recommended according to the above-mentioned US patent application to sublimated para-tert. Butylphenol attributed to the reaction vessel.
  • polyphenol disulfides of the prior art are efficient synergists to halogen-free phosphorus-containing flame retardants, there is still room for improvement. conditions, in particular as regards their production and their performance properties.
  • thermoplastic polymers eg. As polystyrene, and the proportion of low molecular weight, volatile components contained therein. This is associated with a partially occurring during their use in polymers at elevated temperature odor development, eg. B. in the extrusion or cutting of foam blocks.
  • the object of the invention is to provide a process for the preparation of polyphenol disulfides which exhibit good thermal stability and a low proportion of low molecular weight, readily volatile components and, during their use in polymers, no odor at elevated temperature.
  • R 1 , R 2 , R 3 , R 4 and n have the following meanings: R 1 , R 2 , R 3 are identical or different C 1 -C 6 -alkyl, C 2 -C 1 8 alkenyl, C 2 -C 8 alkynyl, C 6 -C 2 aryl, C3-Cio-cycloalkyl, C6-Ci2-aryl-Ci-CI8-alkyl, a heteroaryl, the N one or more hetero atoms from the group , O and S, 0- (C 1 -C 8 ) -alkyl, 0- (C 2 -C 8 ) -alkenyl, O- (C 2 -C 8 ) -alkynyl, O- (C 6 -C 2 ) aryl, 0- (C 3 -Cio) cycloalkyl, (C6-Ci
  • R 4 is identical or different SH, Ci-C 8 alkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, C 6 -C 2 aryl, C3-Cio-cycloalkyl, C6-Ci 2 - aryl-Ci-C 8 alkyl, a heteroaryl group which contains one or more heteroatoms from the group N, O and S, 0- (Ci-C 8) -alkyl, 0- (C 2 -C 8) alkenyl, O- (C 2 -C 8) -alkynyl, 0- (C6-Ci2) aryl, 0- (C 3 -Cio) cycloalkyl, (C6-Ci2) aryl (Ci-Ci 8 ) -Alkyl-O, S-
  • n is an integer from 0 to 1000, preferably an integer from 1 to 1000; with the proviso that R 4 in at least one of the one or more mercaptophenols of formula (II) SH is when n is greater than zero.
  • Polyphenol disulfide prepared in accordance with the present invention has a higher level of dimeric and polymeric phenolic disulfides, a lower level of monosulfide units, a lower level of polysulfide units, and a lower level of elemental sulfur compared to prior art polyphenol disulfides.
  • the polyphenol disulfides prepared by the process according to the invention are characterized by a satisfactory thermal stability. Associated with this is also during their use in polymers at elevated temperature barely or not at all occurring odor development, eg. B. in the extrusion or cutting of foam blocks.
  • the inventive method is preferably carried out at relatively low temperatures, which is advantageous from an economic and environmental point of view. Among other things, this also counteracts the sublimation of unreacted phenol.
  • polyphenol disulfide of the formula (I) comprises dimeric phenol disulfides and polymeric phenol disulfides.
  • a dimeric phenol disulfide according to the invention or a diphenol disulfide according to the invention is understood as meaning a compound of the formula (I) in which n is 0.
  • a polymeric phenol disulfide according to the invention is understood as meaning a compound of the formula (I) in which n is not 0 and where not more than 5%, preferably .about.3%, are particularly preferred. At least ⁇ 1%, very particularly preferably ⁇ 0.5% of the (n + 1) disulfide bridges contained in the formula (I) are replaced by a mono- or oligosulfide bridge.
  • an oligosulfide bridge is understood as meaning a linear chain consisting of 3 or more, in particular 3 to 8, sulfur atoms.
  • polymeric phenol disulfides according to the invention are the compounds listed in the examples poly (tert-butylphenol disulfide) and poly (tert-pentylphenoldisulfid).
  • R 2 is preferably identical or different C 1 -C 6 -alkyl, C 2 -C 18 -alkenyl, C 2 -C 18 -alkynyl, C 6 -C 12 -aryl, C 1 -C 10 -cycloalkyl, O- (C 1 -C 8 ) -alkyl, O- (C 2 -C 8) alkenyl, 0- (C 2 -C 8) -alkynyl, 0- (C6 - Ci2) aryl, or 0- (C 3 -Cio) cycloalkyl.
  • R 1 , R 3 are preferably identical or different H, Ci-Cis-alkyl, C2-Ci8-alkenyl, C2-C18-
  • R 4 is preferably SH or H.
  • n is preferably an integer from 0 to 500, preferably an integer from 1 to 500.
  • R 2 is particularly preferably identical or different Ci-Ci6-alkyl or C6-Ci2-aryl.
  • R 1 , R 3 are particularly preferably identical or different H, Ci-Cis-alkyl, C3-Cio-cycloalkyl
  • R 4 is preferably SH or H.
  • n is more preferably an integer from 0 to 250, preferably an integer from 1 to 250.
  • R 2 is very particularly preferably identical or different C 1 -C 10 -alkyl or C 6 -C 12 -aryl.
  • R 1 , R 3 are most preferably H.
  • R 4 is very particularly preferably SH or H.
  • n is very particularly preferably an integer from 0 to 150, preferably an integer from 1 to 150.
  • R 2 is particularly preferably identical or different t-C4Hg or t-CsHu.
  • R 1 , R 3 are particularly preferably H.
  • R 4 is particularly preferably SH or H.
  • n is more preferably an integer from 3 to 100. Particular preference is given to polyphenol disulfides of the formula (I) in which all symbols have the particularly preferred meanings.
  • Another example of a compound of formula (I) is di (ortho-phenylphenol) disulphide:
  • the polyphenol disulfide of the formula (I) is di (tert-pentylphenol) disulphide, di (para-phenylphenol) disulphide or di (ortho-phenylphenol) disulphide:
  • polyphenol disulfide of formula (I) is di- (tert-pentylphenol) disulphide or di (para-phenylphenol) disulphide. According to a further embodiment, the polyphenol disulfide of the formula (I) is di- (orthophenylphenol) disulphide.
  • One or more, preferably one to three, more preferably one or two mercaptophenols of the formula (II) are used in the process according to the invention.
  • mercaptophenols of the formula (II) which lead to the formation of the preferred polyphenol disulfides of the formula (I).
  • Particular preference is given to mercaptophenols of the formula (II) which lead to the formation of the particularly preferred polyphenol disulfides of the formula (I).
  • mercaptophenols of the formula (II) which lead to the formation of the very particularly preferred polyphenol disulfides of the formula (I).
  • very particularly preferred mercaptophenols of the formula (II) are 4- (tert-butyl) -2-mercaptophenol, 4- (tert-butyl) -2,6-dimercaptophenol, 4- (tert-pentyl) -2- mercaptophenol, 4- (tert-pentyl) -2,6-dimercaptophenol, 4- (phenyl) -2-mercaptophenol and 4- (phenyl) -2,6-dimercaptophenol.
  • mercaptophenols of the formula (II) which lead to the formation of the more particularly preferred polyphenol disulfides of the formula (I).
  • These are the compounds 4- (tert-butyl) -2-mercaptophenol, 4- (tert-butyl) -2,6-dimercaptophenol, 4- (tert-pentyl) -2-mercaptophenol and 4- (tert-butyl) -2-mercaptophenol.
  • 4- (tert-butyl) -2-mercaptophenol 4- (tert-butyl) -2,6-dimercaptophenol
  • 4- (tert-pentyl) -2-mercaptophenol 4- (tert-butyl) -2-mercaptophenol.
  • tert-pentyl) -2,6-dimercaptophenol 4- (tert-butyl) -2-mercaptophenol,6-dimercaptophenol.
  • Another example of a mercaptophenol of formula (II) is 6- (phenyl) -2-mercaptophenol.
  • 4- (tert-pentyl) -2-mercaptophenol, 4- (phenyl) -2-mercaptophenol or 6- (phenyl) -2-mercaptophenol is used as mercaptophenol of the formula (II).
  • 4- (tert-pentyl) -2-mercaptophenol or 4- (phenyl) -2-mercaptophenol is used as mercaptophenol of the formula (II).
  • two mercaptophenols of the formula (II) are used, wherein R 4 is SH in one of these two mercaptophenols and H in the other.
  • two mercaptophenols of the formula (II) are used, wherein R 4 is SH in one of these two Mercaptophenole and in the other H, and wherein the symbols R 1 , R 2 , R 3 and n in these two Mercaptophenolen the have the same meaning.
  • One or more, preferably one to three, more preferably one or two, oxidizing agents are used in the process according to the invention. Very particular preference is given to the use of one (1) oxidizing agent.
  • Suitable oxidizing agents are, for example, molecular oxygen, peroxides such as hydrogen peroxide, urea-hydrogen peroxide adduct, tert-butyl hydroperoxide or cumene hydroperoxide; Peroxymonosulphates such as sodium, potassium or ammonium peroxymonosulphates; Oxon; Peroxide isulfates such as sodium, potassium or ammonium peroxydisulfates; Peroxyborates such as sodium or potassium peroxyborate; Peroxycarbonates such as sodium or potassium peroxycarbonate; Periodic acid such as sodium or potassium periodate; Vanadium pentoxide or osmium tetroxide.
  • peroxides such as hydrogen peroxide, urea-hydrogen peroxide adduct, tert-butyl hydroperoxide or cumene hydroperoxide
  • Peroxymonosulphates such as sodium, potassium or ammonium peroxymonosulphates
  • Oxon Peroxide isulfates such as
  • Preferred oxidants are molecular oxygen and hydrogen peroxide.
  • a particularly preferred oxidizing agent is molecular oxygen.
  • Molecular oxygen is preferably used in the form of air.
  • oxygen-depleted air is also preferred, the oxygen content being depleted to 15% by volume, preferably up to 7% by volume, particularly preferably up to 5% by volume.
  • Oxygen enriched air can also be used.
  • the degree of oligomerization of the compound of the formula (I) can be influenced.
  • molecular oxygen is used as the oxidant, it is generally used in excess.
  • the process according to the invention is carried out in the presence of one or more bases.
  • the process according to the invention is carried out in the absence of a base.
  • the process according to the invention is carried out in the presence of one or more bases.
  • one or more bases Preferably one to three, especially preferred used one or two bases. Very particular preference is given to the use of one (1) base.
  • Suitable bases are, for example, hydroxides such as sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide or ammonium hydroxides; Carbonates, such as lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, magnesium carbonate, calcium carbonate, barium carbonate or ammonium carbonates; Phosphates such as sodium phosphate, potassium phosphate, calcium phosphate or ammonium phosphates; Acetates such as lithium acetate, sodium acetate, potassium acetate, calcium acetate, zinc acetate, copper acetate or ammonium acetates, amines such as triethylamine, diethylamine, Hünig's base, imidazole, N-methylimidazole, pyridine, lutidine or collidine.
  • hydroxides such as sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide or ammonium hydroxides
  • Carbonates such as lithium carbonate, sodium carbonate, potassium carbonate,
  • ammonium encompasses NH 4 + and alkylammonium ions, in particular NH 4 + , tetramethyl, tetraethyl, tetrapropyl and tetrabutylammonium ions.
  • a particularly preferred base is ammonium hydroxide.
  • the mercaptophenol of the formula (II) and the base are customarily reacted with one another in a molar ratio of 1: 0.1 to 1: 100, preferably 1: 1 to 1:10, particularly preferably 1: 1 to 1: 5.
  • the degree of oligomerization of the compound of the formula (I) can be influenced.
  • the process according to the invention is carried out in the presence of a solvent.
  • Suitable solvents are, for example, water; Alcohols, such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methylpropanol or tert-butanol; dipolar aprotic solvents such as ⁇ , ⁇ -dimethylformamide (DMF), ⁇ , ⁇ -diethylformamide, N, N-
  • Alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methylpropanol or tert-butanol
  • dipolar aprotic solvents such as ⁇ , ⁇ -dimethylformamide (DMF), ⁇ , ⁇ -diethylformamide, N, N-
  • DMAC Dimethylacetamide
  • NMP N-methyl-2-pyrolidinone
  • ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethylurea 1, 3-dimethyl-2-imidazolidinone (DMI), 1, 3-dimethyl-3,4,5,6-tetrahydro-2 (1 H) -pyrimidinone (DMPU ), Dimethylsulfoxide, diethylsulfoxide, sulfolane, acetonitrile, propionitrile, butyronitrile or benzonitrile; Esters such as methyl acetate, ethyl acetate, n-butyl acetate or isobutyl acetate; Ethers, such as diethyl ether, diisopropyl ether, dibutyl ether, methyl tert-butyl ether
  • MTBE tetrahydrofuran
  • THF dioxane
  • DME 1,2-dimethoxyethane
  • aromatic hydrocarbons such as benzene, toluene, ethylbenzene, cumene, xylenes or mesitylene
  • aliphatic hydrocarbons such as hexane or cyclohexane
  • Carbonates such as diethyl carbonate or ethylene carbonate.
  • a particularly preferred solvent is ethanol.
  • the process according to the invention is carried out at a temperature in the range from -10 to 150.degree.
  • the relatively low temperatures see US Pat. No. 3,968,062 counteract the sublimation of unreacted mercaptophenol of the formula (II).
  • reaction is carried out in the process according to the invention over a period of 0.1 h to 10 d.
  • atmospheric pressure is understood to mean a pressure in the range from 1003 to 1023 mbar, preferably 1013 mbar.
  • inventive method can also be carried out at elevated pressure, in particular when gaseous oxidants such as molecular oxygen are used as the oxidant.
  • the work-up of the reaction mixtures is carried out, for example, by filtration, aqueous work-up and / or distillation.
  • the products are obtained as viscous oils or solids which, for example, under reduced pressure (preferably 10 -5 to 100 mbar, particularly preferably 10 -4 to 10 mbar) and / or at elevated temperature (preferably 120 to 250 ° C, particularly preferably 150 to 230 ° C) can be freed of residual solvent and / or unreacted mercaptophenol.
  • reduced pressure preferably 10 -5 to 100 mbar, particularly preferably 10 -4 to 10 mbar
  • elevated temperature preferably 120 to 250 ° C, particularly preferably 150 to 230 ° C
  • Adhesive base can be used to remove products obtained as solids, for example by washing with C 1 -C 3 alcohols and / or water.
  • the products can also be purified, for example, by crystallization or precipitation.
  • the one or more mercaptophenols of the formula (I I) used in the process according to the invention are commercially available or can be synthesized on the basis of methods known from the literature.
  • the mercaptophenols of the formula (II) are prepared by reacting polyphenol sulfides of the formula (I II)
  • a reducing agent e.g. Zinc in combination with hydrochloric acid
  • R 1 , R 2 , R 3 and R 4 in the formula (III) have the same meaning as in the mercaptophenol of the formula (II)
  • the symbols k, I and m in the formula (III) have the following meanings: k is an integer from 0 to 1000, preferably an integer from 1 to 1000;
  • I is an integer from 0 to 7;
  • n is an integer from 0 to 7.
  • Polyphenol sulfides of the formula (III) are known, for example, from US Pat. Nos. 3,968,062, AT 508,304 and WO 201 1/000019 and the non-prepublished international patent application
  • mercaptophenols of the formula (II) where R 4 * H are prepared by a process comprising the following steps: i) reaction of a phenol of the formula (IV),
  • Phenols of the formula (IV) are either commercially available or can be synthesized on the basis of methods known from the literature.
  • Suitable reducing agents for the reaction of phenolsulfonic acids of the formula (V) to form mercapto-phenols of the formula (II) with R4 * H are, for example, molecular hydrogen in combination with a catalyst, e.g. Raney nickel, or hydrazine in combination with a catalyst, e.g. Raney nickel. Also suitable are, for example, iron in combination with hydrochloric acid, or zinc in combination with hydrochloric acid.
  • Another object of the invention is a Polyphenoldisulfid of formula (I), obtainable by the inventive method.
  • the invention in such a polyphenol disulfide with n * 0 at most 5%, preferably -i 3%, more preferably ⁇ 1%, most preferably ⁇ 0.5% of the (n + 1) disulfide bridges contained in the formula (I) by a Mono or Oligosulfidmaschine replaced.
  • the invention further provides a flame retardant system comprising i) at least one polyphenol disulfide of the formula (I) according to the invention; and ii) at least one halogen-free organic phosphorus compound having a phosphorus content in the range of 0.5 to 40% by weight, based on the phosphorus compound.
  • Another object of the invention is a polymer composition containing one or more polymers and the flame retardant system according to the invention.
  • the polyphenol disulfides prepared by the process according to the invention are suitable, for example, as flame retardant synergists in polymers. Preferred is the use in foams, in particular in polystyrene-based foams.
  • the flame retardant synergist prepared according to the invention is used in admixture with one or more flameproofing agents and optionally with further synergists for the production of flame-retardant (or flame-retardant) polymers, in particular thermoplastic polymers.
  • the flame retardants and synergists are preferably physically mixed with the corresponding polymer in the melt and then either finished ready as a polymer mixture and then further processed in a second process step together with the same or a different polymer.
  • styrene polymers the addition of the flame retardants and synergists before, during and / or after the preparation by suspension polymerization is preferred.
  • Foamed or unfoamed styrene polymers including ABS, ASA, SAN, AMSAN, SB and HIPS polymers, polyimides, polysulfones, polyolefins such as polyethylene and polypropylene, polyacrylates, polyetheretherketones, polyurethanes, polycarbonates, polyphenylene oxides, unsaturated polyester resins, Phenol resins, polyamides, polyethersulfones, polyether ketones and polyether sulfides, each individually or in mixture as polymer blends be used.
  • thermoplastic polymers such as foamed or unfoamed styrene homopolymers and copolymers, in each case individually or in a mixture as polymer blends.
  • styrene polymer encompasses polymers based on styrene, alpha-
  • Methylstyrene or mixtures of styrene and alpha-methylstyrene The same applies to the styrene content in SAN, AMSAN, ABS, ASA, MBS and MABS (see below).
  • Inventive styrene polymers are based on at least 50 parts by weight of styrene and / or alpha-methylstyrene monomers.
  • 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 used with polyphenylene ether (PPE).
  • GPPS glassy polystyrene
  • HIPS toughened polystyrene
  • 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 in proportions of not more than 30 parts by weight, preferably in the range of 1 to 10 Parts by weight, based on 100 parts by weight of the polymer melt.
  • PA polyamides
  • PE polyolefins
  • PMMA polymethyl methacrylate
  • PC polycarbonate
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PES polyethersulfones
  • PES polyether ketones or polyether sulfides
  • 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.
  • flame-retardant polymer foams in particular based on styrene polymers, preferably EPS and XPS.
  • EPS expandable styrene polymers
  • 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.
  • Atmospheric oxygen (Scheme 4), analogous to the synthesis of poly (4- (t-butyl) -2,6-dimercaptophenol) (see Example 3).
  • b determines fractional precipitation and subsequent analysis of the different fractions; Proportion stated in wt .-%, based on the product sample; c determined by thermogravimetric analysis (under N2, 20-800 ° C, heating rate 10 K / min); d determines total chlorine determination via tube combustion, subsequent difference formation with chloride value; Content given in wt .-%, based on the product sample.
  • poly-tert-alkylphenol disulfide (B1 and B2) prepared according to the invention shows that the poly-tert-alkylphenol disulfide prepared according to the invention has a higher proportion dimeric and polymeric phenol disulfides and a lower proportion of monosulfide units and a has a lower content of elemental sulfur and covalently bound chlorine.
  • poly-tert-alkylphenol disulfide prepared according to the invention is characterized by a higher temperature stability. As flame retardants and synergists
  • the flame retardants FR1 to FR2 and the synergists S1 to S4 were used.
  • FR1 Available commercially as Disflamoll ® TP from Lanxess.
  • FR2 Synthesized as described in WO201 1/083009.
  • the fire behavior of the foam panels was determined at a foam density of 15 kg / m 3 in accordance with DIN 4102.
  • Vultac® TB7 and Vultac® 3 were used.
  • Expandable styrene polymers (extrusion process):
  • 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 molecular weight of the granules was 220,000 g / mol (Mw) and 80,000 g / mol (Mn) (determined by GPC, Rl detector, PS as standard).
  • the granules were prefoamed by the action of flowing steam and, after 12 hours' storage, were further welded by a further treatment with steam in a closed mold to form foam blocks with a density of 15 kg / m 3 .
  • foam blocks were subsequently by means of hot wire cut with a Styrofoam incandescent cutting machine from Charlotte Kaiser, 67071 Ludwigshafen, (power: 180 VA, primary: 230 V, secondary: 0 - 12 V, 15 A) in the corresponding standard test specimens, z. B. tailored to determine the fire behavior according to DIN 4102.
  • 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.
  • Table 3 Fire behavior of inventive polymer composition (examples) and of comparative examples
  • the uniformly kneaded in the extruder at 200 ° C gel is passed through a calming zone and extruded after a residence time of 15 minutes with an outlet temperature of 105 ° C through a 300 mm wide and 1, 5 mm wide nozzle into the atmosphere.
  • the foam is passed through a mold channel connected to the extruder to form a foamed sheet having a cross section of 650 mm x 50 mm and a density of 40 g / l.
  • the molecular weight of the polystyrene was 240,000 g / mol (Mw) and 70,000 g / mol (Mn) (determined by GPC, Rl detector, PS as standard).
  • Mw g / mol
  • Mn 70,000 g / mol
  • Example flame retardant odor on extrusion 200 odor of extruded
  • Table 5 Fire behavior of inventive polymer composition (examples) and of comparative examples
  • Example flame retardant system Brandtest (B2 according to DIN 4102)

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé pour produire un polyphénolbisulfure de formule (I), consistant à faire réagir un ou plusieurs mercaptophénoles de formule (II) avec un ou plusieurs agents d'oxydation, éventuellement en présence d'une ou de plusieurs bases, les symboles R1, R2, R3, R4 et n étant tels que définis dans la description.
PCT/EP2013/055006 2012-03-13 2013-03-12 Synthèse de polyphénolbisulfures WO2013135701A1 (fr)

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Cited By (3)

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Publication number Priority date Publication date Assignee Title
WO2015177347A1 (fr) * 2014-05-22 2015-11-26 Basf Se Mélanges ignifuges sans halogène destinés à des mousses polyoléfines
TWI561507B (en) * 2015-06-29 2016-12-11 Double Bond Chemical Ind Co Ltd Composite antioxidant, resin composition comprising the same and its application
US20220388951A1 (en) * 2019-10-30 2022-12-08 Arkema France Method for evaluating brominated flame retarders

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015177347A1 (fr) * 2014-05-22 2015-11-26 Basf Se Mélanges ignifuges sans halogène destinés à des mousses polyoléfines
TWI561507B (en) * 2015-06-29 2016-12-11 Double Bond Chemical Ind Co Ltd Composite antioxidant, resin composition comprising the same and its application
US20220388951A1 (en) * 2019-10-30 2022-12-08 Arkema France Method for evaluating brominated flame retarders

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