Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/0014—Use of organic additives
  • C08J9/0038—Use of organic additives containing phosphorus
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/0066—Use of inorganic compounding 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
  • C08K5/49—Phosphorus-containing compounds
  • C08K5/51—Phosphorus 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
  • C08K5/49—Phosphorus-containing compounds
  • C08K5/51—Phosphorus bound to oxygen
  • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
• • 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
  • 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
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2325/00—Characterised by the use 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; Derivatives of such polymers
  • C08J2325/02—Homopolymers or copolymers of hydrocarbons
  • C08J2325/04—Homopolymers or copolymers of styrene

Definitions

• the invention relates to halogen-free, flame-retardant polymer foams based on styrene polymers, a process for the production of non-flammable, flameproof polymer foams and their use in the construction industry.
• the equipment of flame retardant foams is important for a variety of applications, such as expandable polystyrene (EPS) polystyrene foam or polystyrene foam extrusion (XPS) for building insulation.
• EPS expandable polystyrene
• XPS polystyrene foam extrusion
• flame retardants in plastics mainly polyhalogenated hydrocarbons, optionally used in combination with suitable synergists, such as organic peroxides or nitrogen-containing compounds.
• suitable synergists such as organic peroxides or nitrogen-containing compounds.
• HBCD hexabromocyclododecane
• Flame retardants should, if possible, in addition to a high flame retardancy in the plastic at low loading for processing also have sufficient temperature and hydrolysis stability. Furthermore, they should have no bioaccumulation and persistence.
• DE 1 694 945 a process for the production of foams is described in which sulfur is incorporated as a flame retardant alone or in combination with brominated phosphorus compounds in the foam.
• EP 0 806 451 describes flame-retarded styrenic polymer compositions containing a combination of organic phosphorus compounds and elemental sulfur. In order to achieve a satisfactory flame retardancy, a loading of at least 10 parts by weight of phosphorus compound and sulfur based on 100 parts by weight of the polymer is usually required.
• WO 99/1 0429 also describes flame-retardant polymer electrolyte compositions containing a combination of organic phosphorus compounds and elemental sulfur. In order to achieve a satisfactory flame retardance, total quantities of usually at least 10 parts by weight of phosphorus compound and sulfur based on 100 parts by weight of polymer are also required.
• the flame retardant polymer compositions described in the prior art have satisfactory flame retardant properties. However, the significantly higher amounts of flame retardants used in the prior art, which are used in thermoplastic polymers such as polystyrene, can interfere with the foaming process in the case of polymer foams or adversely affect the mechanical and thermal properties of the foam.
• the invention therefore relates to a polymer foam having a density in the range from 5 to 120 kg / m 3 , comprising a) a polymer component containing at least one styrene polymer
• b1 at least one phosphorus compound of the formula (I) having a phosphorus content in the range from 5 to 80% by weight, based on the phosphorus compound,
• R 1 is C 1 -C 6 -alkyl, C 1 -C 8 -alkyl, C 2 -C 6 -alkenyl, C 1 -C 6 -alkoxy, C 2 -
• R 2 is C Ci 6 alkyl, C 0 Ci hydroxyalkyl, C 2 -C 6 alkenyl, C Ci 6 alkoxy, C 2 -
• Y 1 , Y 2 are the same or different O or S;
• R 4 , R 5 , R 9 , R 10 , R 11 , R 12 , R 13 are identical or different and are C 1 -C 2 -alkyl, C 3 -C 8 -cycloalkyl, which in some cases or both CrC 4 -
• alkyl C 2 -C 2 -alkenyl, C 2 -C 2 alkynyl, C 6 -C 0 - aryl or C 6 -C 0 aryl-Ci-C 4 alkyl;
• R 6 , R 7 , R 8 are identical or different and independently of one another are C 1 -C 6 -alkyl
• Y 1 or Y 2 is S, and m is an integer from 0 to 100; s, t, u are independently 0 or 1; and b2) elemental sulfur.
• the invention furthermore relates to processes for producing halogen-free, flame-retarded polymer foams, the polymer composition being admixed with 0.1 to 5 parts by weight of the flame retardant mixture b) (based on 100 parts by weight of the polymer component).
• the invention likewise relates to the use of the polymer foam according to the invention as insulating and insulating material, in particular in the construction industry.
• R 1 is preferably CRCI 6 alkyl, CRCI 0 hydroxyalkyl, C 2 -C 6 alkenyl, C 6 C -
• R 2 is preferably CRCI 6 alkyl, CRCI 0 hydroxyalkyl, C 2 -C 6 alkenyl, C 6 C -
• R 3 is preferably H, SH, SR 4 , OH, OR 5 or a group:
• X 1 , X 2 and X 3 are preferably the same or different independently of one another O or
• Y 1 , Y 2 are preferably the same or different O or S.
• R 4 , R 5 are preferably identical or different d-Ci 2 alkyl, C 3 -C 8 cycloalkyl, which is unsubstituted or by one or more CrC 4 alkyl groups is substituted, C 2 -C 2 -alkenyl, C 2 -C 2 alkynyl, C 6 -C 0 aryl or C 6 -C 0 aryl-Ci- C4 alkyl.
• R 6, R 7, R 1 are preferably identical or different independently of each other Ci C 6 - alkyl, C 2 -C 6 alkenyl, d-de-alkoxy, d-de-alkenoxy, C 3 -C 0 cycloalkyl, C 3 -Cio cycloalkoxy, C 6 -C 0 aryl, C 6 -C 0 aryloxy, Ce-do-aryl-d-de-alkyl, Ce-Cio-aryl-d-Cie-alkoxy, SR 9, COR 10 , COOR 11 , CONR 12 R 13 .
• n is preferably 1 if Y 1 or Y 2 O, and 1 or 2 if Y 2 is S and m is preferably an integer of 0 to 10.
• s, t, u are preferably 1.
• X 1 , X 2 and X 3 are identical or different and independently of one another O or S; Y 1 , Y 2 are the same or different O or S;
• R 4 , R 5 are preferably C 3 -d 2 -alkyl, C 3 -C 8 -cycloalkyl which is unsubstituted or substituted by one or more C 1 -C 4 -alkyl groups, C 2 -d 2 -alkenyl , C 2 -d 2 -alkynyl or C 6 -do-aryl-dC 4 -alkyl
• R 6 , R 7 , R 8 are identical or different and independently of one another are C 1 -C 6 -alkyl,
• R 1 is C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 1 -C 6 -alkoxy, C 2 -C 6 -alkenoxy, C 3 -Ci 0 -
• Cycloalkyl C 3 -C 0 cycloalkoxy, C 6 -C 0 aryl, C 6 -C 0 aryloxy, C 6 -C 0 aryl C Ci 6 alkyl, C 6 -Cio-aryl-Ci-Ci 6- alkoxy;
• R 2 is C Ci 6 alkyl, C 2 -C 6 alkenyl, C Ci 6 alkoxy, C 2 -C 6 -alkenoxy, C 3 -C 0 - cycloalkyl, C 3 -C 0 cycloalkoxy, C 6 - Ci 0 -aryl, C 6 -cio-aryl-Ci-Ci 6 -alkyl, C 6 -
• X 1 , X 2 and X 3 are identical or different and independently of one another O or S; Y 1 , Y 2 are the same or different O or S;
• R 4 same or different C 3 -C 8 cycloalkyl, the one or more -C 4 alkyl is unsubstituted or substituted d urch, C 2 -C 2 - alkenyl, C 2 -C 12 alkynyl;
• R 6 , R 7 , R 8 are identical or different and independently of one another are C 1 -C 6 -alkyl, C 2 -
• R 1 is C Ci 6 alkyl, C 2 -C 6 alkenyl, d-de-alkoxy, C 3 -C 6 -alkenoxy, C 3 -C 0 -
• Cycloalkyl C 3 -C 0 cycloalkoxy, C 6 -C 0 aryl, C 6 -C 0 aryloxy, C 6 -C 0 aryl C Ci 6 alkyl, C 6 -Cio-aryl-Ci-Ci 6- alkoxy;
• R 2 is C Ci 6 alkyl, C 2 -C 6 alkenyl, C Ci 6 alkoxy, C 2 -C 6 -alkenoxy, C 3 -C 0 -
• Cycloalkyl C 3 -C 0 cycloalkoxy, C 6 -Cio-aryl, C 6 -Cio-aryl-Ci-C 6 alkyl, C 6 - Cio-aryl-Ci-C 6 alkoxy;
• X 1 , X 2 and X 3 are identical or different and independently of one another O or S; Y 1 , Y 2 are the same or different O or S;
• R 6 , R 7 , R 8 are identical or different and independently of one another are C 1 -C 6 -alkyl, C 2 -
• the synergistic flame retardant combination b) according to the invention contains no trimethyl phosphate and / or no tetramethylphosphine disulfide.
• R 1 is particularly preferably C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy, cyclohexyl, phenyl,
• R 2 is particularly preferably -C 8 alkyl, -C 8 alkoxy, cyclohexyl, phenyl, benzyl,
• R 3 is more preferably H, SH, SR 4 , OH, OR 5 or a group
• X 1 and X 3 are particularly preferably the same or different O or S.
• Y 1 is particularly preferably O or S.
• R 4 , R 5 are more preferably identical or different C 1 -C 8 -alkyl, cyclohexyl,
• R 7, R 8 are particularly preferably identical or different -C 8 alkyl, -C 8 alkoxy,
• n is more preferably 1 if Y 1 is O and 1 or 2 if Y 1 is S.
• s and t are particularly preferred 1. Particular preference is given to compounds of the formula (I) in which the symbols and indices have the particularly preferred meanings.
• R 1 is particularly preferably C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy, cyclohexyl, phenyl,
• R 2 is particularly preferably -C 8 alkyl, -C 8 alkoxy, cyclohexyl, phenyl, benzyl,
• R 3 is more preferably H, SH, SR 4 , OH, OR 5 or a group
• X 1 and X 3 are more preferably the same or different O or S;
• Y 1 is more preferably O or S; R 4 , R 5 are particularly preferably identical or different C 3 -C 8 alkyl, cyclohexyl or
• R 7, R 8 are particularly preferably identical or different -C 8 alkyl, -C 8 alkoxy,
• Cyclohexyl, phenyl, phenoxy, benzyl and benzyloxy and n is more preferably 1 if Y 1 is O and 1 or 2 if Y 1 is S. s and t are particularly preferred 1. Particular preference is furthermore given to compounds of the formula (I) in which the symbols and indices in the formula (I) have the following meanings:
• R 1 is particularly preferably C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy, cyclohexyl, phenyl,
• R 2 is particularly preferably -C 8 alkyl, -C 8 alkoxy, cyclohexyl, phenyl, benzyl,
• R 3 is more preferably H, SH, SR 4 , OH, OR 5 or a group
• X 1 and X 3 are more preferably the same or different O or S; Y 1 is more preferably O or S;
• R 4 , R 5 are particularly preferably cyclohexyl
• R 7, R 8 are particularly preferably identical or different -C 8 alkyl, -C 8 alkoxy,
• Cyclohexyl, phenyl, phenoxy, benzyl and benzyloxy and n is more preferably 1 if Y 1 is O and 1 or 2 if Y 1 is S. s and t are particularly preferred 1. Particular preference is furthermore given to compounds of the formula (I) in which the symbols and indices in the formula (I) have the following meanings:
• R 1 is particularly preferably C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy, cyclohexyl, phenyl,
• R 2 is particularly preferably -C 8 alkyl, -C 8 alkoxy, cyclohexyl, phenyl, benzyl,
• R 3 is more preferably a group
• X 1 and X 3 are more preferably the same or different O or S; Y 1 is more preferably O or S;
• R 7, R 8 are particularly preferably identical or different -C 8 alkyl, -C 8 alkoxy,
• Cyclohexyl, phenyl, phenoxy, benzyl and benzyloxy and n is more preferably 1 if Y 1 is O and 1 or 2 if Y 1 is S. s and t are particularly preferred 1.
• R 1 is particularly preferably phenyl, phenyloxy.
• R 2 is particularly preferably phenyl.
• X 1 and X 3 are particularly preferably the same or different O or S.
• Y 1 is particularly preferably O or S.
• R 4 , R 5 are particularly preferably identical or different cyclohexyl, phenyl or benzyl.
• R 7 , R 8 are particularly preferably identical or different phenyl, phenoxy.
• n is preferably 1 if Y 1 is O and 1 or 2 if Y 1 is S.
• s and t are particularly preferred 1.
• Particular preference is given to compounds of the formula (I) in which the symbols and indices have the particularly preferred meanings.
• R 1 is particularly preferably phenyl, phenoxy
• R 2 is particularly preferably phenyl
• R 3 is particularly preferably H, SH, SR 4 , OH, OR 5 or a group
• X 1 and X 3 are particularly preferably the same or different O or S;
• Y 1 is particularly preferably O or S
• R 4 , R 5 are particularly preferably identical or different benzyl; R 7 , R 8 are particularly preferably identical or different phenyl, phenoxy and n is more preferably 1, if Y 1 is O, and 1 or 2, if Y 1 is S. s and t are particularly preferred 1.
• X 1 and X 3 are particularly preferably the same or different O or S;
• Y 1 is particularly preferably O or S
• R 7 , R are particularly preferably identical or different phenyl, phenoxy and n is more preferably 1, if Y 1 is O, and 1 or 2, if Y 1 is S. s and t are particularly preferred 1.
• Particularly preferred compounds of the formula (I) are the compounds FSM 1 to FSM 6 listed in the Examples. Preference is given to using 1 compound of the formula (I) as flame retardant.
• a mixture of two or more, more preferably two to four, in particular two compounds of formula (I) is used as a flame retardant.
• the compounds of formula (I) are partially available commercially, e.g. FSM1 of ABCR GmbH & Co KG, Düsseldorf, Germany, FSM4 as Disflamoll temperature of Lanxess, FSM6 as HCA of Sanko, and FSM7 as Cyagard RF-1241 of Cytech.
• the flame retardants FMS 2, 3 and 4 can be prepared, for example, according to the following references:
• FSM2 J.I. G. Cadogan; J. B. Husband; H. McNab; J. Chem. Soc. Perkin Trans. I .; 1983; 1489 to 1495.
• FSM3 M.G. Zimin, N.G. Zabirov; V. Smirnov; Zhournal Obschei Khimii; 1980; 50; 1 ; 24 to 30.
• Another preferred phosphorus compound (as component b1)) is bis (hydroxymethyl) isobutylphosphine oxide (FSM6).
• the weight ratio of component b1) (phosphorus compound) to component b2) (sulfur) is generally 1: 0.1-10, preferably 1: 0.2-7, particularly preferably 1: 0.3-5 and in particular 1: 0 , 3 - 3.
• the parts by weight of component b) and of components b1) and b2) are in each case based on 100 parts by weight of polymer (component a) within the scope of the invention.
• the synergistic flame retardant mixture is generally in amounts of 0.1 to 5.0 parts by weight, preferably 0.5 to 4.5 parts by weight, more preferably 1, 0 to 4.0 parts by weight, especially 2.5 to 4.0 parts by weight, based to 100 parts by weight of component a) in the polymer foam.
• the polymer composition generally contains from 0.1 to 5% by weight, preferably from 0.2 to 3% by weight, particularly preferably from 0.3 to 2.5% by weight, of elemental sulfur.
• elemental sulfur is preferably distributed largely homogeneously in the polymer foam, which can be achieved, for example, by admixture during extrusion or by static or dynamic mixers (eg kneaders).
• 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 literature citations can be found in WO 99/10429.
• the polymer foam according to the invention may optionally contain further 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).
• 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, based on 100 parts by weight of component a) are usually contained.
• further flame retardants such as melamine, Melamincyanurate, 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 may be included.
• Suitable additional halogen-free flame retardants are, for example, commercially available under the name Exolit OP 930, Exolit OP 1312, HCA-HQ, M-ester, Cyagard RF-1243, Fyrol PMP, Phoslite IP-A (aluminum hypophosphite), Melapur 200, Melapur MC, APP (ammonium polyphosphate) and Budit 833 available.
• halogen-reduced polymer compositions can be obtained by the use of the compounds (I) according to the invention and the addition of lesser amounts of halogen-containing, in particular brominated flame retardants such as hexabromocyclododecane (HBCD) or brominated styrene homo- or styrene copolymers / oligomers (
• HBCD hexabromocyclododecane
• styrene homo- or styrene copolymers / oligomers for 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 (based on 100 wt. Parts of component a)) are produced.
• the flame retardant mixture according to the invention is halogen-free.
• the composition of polymer, flame retardant mixture and other additives is particularly preferably halogen-free.
• the polymer foam according to the invention generally has a density in the range from 5 to 120 kg / m 3 , preferably 8 to 60 kg / m 3 , particularly preferably 10 to 35 kg / m 3 .
• the polymer component a) contains at least one styrene polymer.
• styrene polymer comprises polymers based on styrene, alpha-methylstyrene or mixtures of styrene and alpha-methylstyrene; This applies analogously to the styrene content in SAN, AMSAN, ABS, ASA, MBS and MABS (see below).
• Inventive styrenic polymers are based on at least 50 parts by weight of styrene and / or alpha-methylstyrene monomers.
• Crystal clear polystyrene GPPS
• impact polystyrene HI PS
• anionically polymerized polystyrene or impact polystyrene A-IPS
• styrene-alpha-methylstyrene copolymers acrylonitrile-butadiene-styrene polymers
• ABS acrylonitrile-butadiene-styrene polymers
• SAN styrene-acrylonitrile copolymers
• AMSAN acrylonitrile-alpha-methylstyrene copolymers
• ASA acrylonitrile-styrene-acrylic esters
• MCS methyl acrylate-butadiene-styrene
• MABS methacrylate-acrylonitrile-butadiene-styrene
• the styrene polymers mentioned can be used to improve the 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).
• 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), Polyethersulfon en (P ES), polyether ketones or Polyethersulfiden (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, blended.
• 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.
• foams according to the invention comprising, preferably consisting of polystyrene, in particular those obtained from expandable polystyrene (EPS) and also extruded polystyrene foams (XPS).
• EPS expandable polystyrene
• XPS extruded polystyrene foams
• Expandable styrene polymers preferably have a molecular weight M w in the range from 120,000 to 400,000 g / mol, more preferably in the range from 180,000 to 300,000 g / mol, measured by gel permeation chromatography according to DIN 55672-1 with refractometric detection (RI) in relation to polystyrene standards, on. Due to the molecular weight reduction 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.
• the invention also provides a process for the preparation of the polymer foam according to the invention, wherein the polymer component a) the flame retardant mixture (component b)) is added and the mixture is foamed to a polymer foam.
• the addition can be carried out by adding the synergistic flame retardant mixture (component b)) i) in the finished polymer, or
• the polymerization is carried out, for example, by bulk polymerization, solution polymerization or by emulsion, suspension or dispersion polymerization in the presence of component b), ie by addition to the monomers. before, during or after the polymerization.
• the suspension polymerization is preferred.
• the monomer styrene In the 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. Incidentally, the monomers from which the preferred polymers are obtainable are preferred. Preference is given to the preparation of the polymer composition according to the invention by adding it to the finished polymer i).
• a polymer melt is produced for this purpose and component b) is mixed in before, during or after the melt production.
• the 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 from 1 to 20 Parts by weight, based on 100 parts by weight of the polymer component a).
• 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 from 1 to 20 Parts by weight, based on 100 parts by weight of the polymer component a).
• EPS expandable styrene polymers
• additives, nucleating agents, fillers, plasticizers, soluble and insoluble inorganic and / or organic dyes and pigments for example IR absorbers such as carbon black, graphite or aluminum powder may be jointly or spatially separated, for example via mixers or side extruders, added to the polymer melt become.
• 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, based on 100 parts by weight of component a).
• a dispersing assistant for example organosilanes, epoxy-group-containing polymers or maleic anhydride-grafted styrene polymers.
• Preferred plasticizers are mineral oils, phthalates, which can be used in amounts of from 0.05 to 10 parts by weight, based on 100 parts by weight, and of component a). Analogously, these substances can also be added before, during or after the suspension polymerization to inventive EPS.
• the halogen-free, flameproofed polymer foams preferably have a density in the range from 8 to 60 kg / m 3 , particularly preferably in the range from 10 to 35 kg / m 3 and are preferably more than 80%, particularly preferably 90 to 100% closed-cell ,
• Foams of expandable styrene polymers (EPS foams) and styrene polymer extrusion foams (XPS) according to the invention can be prepared by mixing a blowing agent and the inventive flame retardant into the polymer melt, extrusion and granulation under pressure to expandable granules (EPS) and subsequent expansion of the granules to the EPS foam or by extrusion and relaxation of the polymer melt using appropriately shaped nozzles to foam plates (XPS) or foam strands are processed.
• EPS foams expandable styrene polymers
• XPS styrene polymer extrusion foams
• the foam is an EPS foam.
• the foam is a styrene polymer extrusion foam (XPS).
• the blowing agent-containing polymer melt generally contains one or more blowing agents 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 the 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, preference is given to using 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 polymer matrix. This can be done, for example, by the addition of water into the molten 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. As a rule, from 0 to 2, preferably from 0.05 to 1.5, parts by weight of water, based on 100 parts by weight of component a), 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 amount of blowing agent and water added is selected so that the expandable styrene polymers (EPS) have an expansion capacity a, defined as bulk density, before foaming / bulk density after foaming at most 125, preferably 15 to 100.
• 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. When using fillers, depending on the type and amount of the filler, bulk densities in the range of 590 to 1200 g / l may occur.
• additives and auxiliaries may be added.
• the additives and auxiliaries optionally present in the polymer composition are preferred.
• the rubber in the polymer melt may be blended.
• One possible method comprises the stages a) melt production, b) mixing, c) cooling, d) conveying, e) granulating and f) expanding.
• steps a) to e) 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 be done 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: a) Polymerization reactor - static mixer / cooler - granulator
• the arrangement may include side extruders for incorporation of additives, e.g. of solids or thermally sensitive additives.
• the propellant-containing polymer melt is usually 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 at least heated to the temperature of the molten polymer melt on the tempering medium.
• the temperature of the nozzle plate is in the range of 20 to 100 ° C above the temperature of the propellant-containing polymer 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 from 0.2 to 1.5 mm, preferably in the range from 0.3 to 1.2 mm, particularly preferably in the range from 0.3 to 0 , 8 mm lie.
• D diameter of the nozzle bores at the nozzle exit
• a process for preparing a halogen-free flame-retardant EPS foam comprising the steps of a) incorporating an organic blowing agent and preferably 1-25 parts by weight of the flame retardant according to the invention (based on 100 parts by weight of component a)) the polymer melt by means of static or dynamic mixer at a temperature of at least 150 ° C,
• 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 auxiliaries, nucleating agents and plasticizers may be added.
• the flame retardant according to the invention is used in the polymerization in amounts of from 0.5 to 25 parts by weight, preferably from 5 to 15 parts by weight, added.
• Blowing agents are added in amounts of 2 to 10 parts by weight, 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 inorganic Pickering dispersants, for example magnesium pyrophosphate or calcium phosphate, as suspension stabilizers.
• pear-shaped, substantially round particles having an average diameter in the range of 0.2 to 2 mm are formed.
• the styrenic polymer granules may be coated by glycerol esters, antistatic agents, or anti-caking agents.
• the EPS granules may be coated with glycerol monostearate GMS (typically 0.25%), glycerol tristearate (typically 0.25%) finely divided silica Aerosil R972 (typically 0.12%) and Zn stearate (typically 0.15%), and antistatic ,
• the invention also provides expandable styrene polymer granules, which are formulated in such a way (for example by the amount of blowing agent contained), that from them an EPS foam according to the invention is obtainable.
• Step (e) of the method according to the invention is usually carried out separately of the steps (a) - (d), for example by a user.
• the expandable styrene polymer granules according to the invention can be pre-foamed in a first step by means of hot air or steam in the so-called pre-expanders to foam particles having a density in the range of 5 to 120 kg / m 3 , in particular 8 to 60 kg / m 3 and in a second step a closed mold to particle moldings are welded.
• 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 polymer foam is an extruded polystyrene (XPS), obtainable by:
• 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.
• Inventive foams based on styrene polymers 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 sec, particularly preferably ⁇ 10 sec, and meet
• 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
• the determination of the fire behavior of the foam boards was carried out at a foam density of 15 kg / m 3 according to DIN 4102.
• HBCD hexabromocyclododecane
• the stated amounts in parts by weight relate to 100 parts by weight of polystyrene.
• the mixture of polystyrene melt, blowing agent and flame retardant was fed at 60 kg / h through a nozzle plate with 32 bores (diameter of the nozzles 0.75 mm). changed. 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 (M w ) or 80,000 g / mol (M n ) determined by GPC, Rl detector, PS as standard).
• 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.
• V13 4 - HBCD 0 0 passed / 6.4 s
• V16 8 - HBCD 4 0 passed / 7.3 s
• V17 8 - HBCD 0 4 passed / 5.8 s
• the uniformly kneaded in the extruder at 180 ° 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 molding channel connected to the extruder to form a foamed sheet having a cross section of 650 mm x 50 mm and a density of 35 g / l.
• the molecular weight of the polystyrene was 240,000 g / mol c / M w ) or 70,000 g / mol (M n ) (determined by GPC, RI detector, PS as standard)
• the product was cut into plates.
• the fire behavior of the samples was tested with thicknesses of 10 mm after a deposition time of 30 days according to DIN 4102.

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• 2011
  • 2011-02-03 EP EP11703640A patent/EP2531552A2/de not_active Withdrawn
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  • 2011-02-03 CN CN2011800083795A patent/CN102741332A/zh active Pending
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