US 20110201662A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2011/0201662 A1 Ishaque et al. (43) Pub. Date: Aug. 18, 2011

(54) METHOD FOR PRODUCING XPS MOULDED Publication Classification PIECES PROVIDED WITH INSECTICIDE (51) Int. Cl. (75) Inventors: Michael Ishaque, Mannheim (DE); AOIN 43/56 (2006.01) Olaf Kriha, Neustadt (DE); Klaus AOIP 7/04 (2006.01) Hahn, Kirchheim (DE); Daniela C08, 9/2 (2006.01) Longo, Sankt Augustin (DE) (52) U.S. Cl...... 514/.407; 264/54 Assignee: (73) BASF SE, Ludwigshafen (DE) (57) ABSTRACT (21) Appl. No.: 13/124,979 Process for the production of insecticide-modified extruded polystyrene foam (XPS) preforms, comprising the steps (22) PCT Fled: Oct. 21, 2009 (a) heating polystyrene (PS) until a polymer melt is formed, (86) PCT NO.: PCT/EP09/63780 (b) introducing a blowing agent into the polymer melt to S371 (c)(1), form a foamable melt, and (2), (4) Date: Apr. 19, 2011 (c) foaming the foamable melt to give an XPS preform, where at least one insecticide from the group of the phe (30) Foreign Application Priority Data nylpyrazoles, chlorfenapyr and hydramethylnone is intro duced into the polymer melt in at least one of steps (a) and/or Oct. 22, 2008 (EP) ...... O8167227.1 (b). US 2011/0201662 A1 Aug. 18, 2011

METHOD FOR PRODUCING XPS MOULDED 0012. In the XPS preforms prepared by the process PIECES PROVIDED WITH INSECTICDE according to the invention, the insecticide is incorporated into the polymer matrix in a particularly stable and uniform man ner. This reduces active Substance losses and exposure to the 0001. The invention relates to a process for the preparation insecticide during the preparation, processing and use of the of insecticide-modified foam preforms of extruded polysty XPS preforms. Moreover, the process according to the inven rene foam (XPS preforms), to insecticidal XPS preforms tion makes it possible to reduce the amount of insecticide obtainable by the process, and to their use in the building required. trade. (0013 Moreover, the insecticide-modified XPS preforms 0002 Polymer foams and foam preforms are used both according to the invention do not have any disadvantages below and above ground as insulation material in the con regarding their mechanical properties and insulation proper struction industry, for example. Insects, in particular termites, ties in comparison with a standard product (without insecti can inflict Substantial feeding damage on Such foams, so that cide). the insulation effect and the mechanical stability of the pre 0014 For the purposes of the invention, polystyrene (PS) forms are limited and further advancing of the pests is made is used as umbrella term for homo- and copolymers of Sty possible. In many cases, an insecticidal protection of pre rene, other vinyl-aromatic monomers and, if desired, further forms is stipulated by the law, since Such insulation materials comonomers. PS is understood as meaning, for example, constitute a preferred environment for termites. standard polystyrene (general purpose polystyrene, GPPS, 0003 JP-2000-001564 describes the use of (+)-5-amino usually transparent), high-impact polystyrene (HIPS, com 1-(2,6-dichloro-O.O.C.-trifluoro-p-tolyl)-4-trifluoromethyl prising, for example, polybutadiene or polyisoprene rubber), sulfinylpyrazole (Common Name: fipronil) for the protection styrene/maleic (anhydride) polymers, acrylonitrile/butadi of polymer foams. To this end, fipronil is employed in con ene/styrene polymers (ABS), styrene/acrylonitrile polymers centrations of from 0.001-1% by weight. Polystyrene, poly (SAN), C.-methylstyrene/acrylonitrile polymer (AMSAN), or ethylene and polypropylene are described as polymer matrix. mixtures of these (component K1). Preferred PS is standard Fipronil is incorporated by applying to the Surface of the polystyrene, i.e. a polystyrene with a molar styrene monomer prefoamed foam particles, or by applying to the blowing content of at least 95%. Furthermore preferred PS is C.-me agent-comprising granules.JP 2001-259271 describes a pro thylstyrene/acrylonitrile polymer (AMSAN). cess in which blowing agent-comprising EPS granules or 00.15 Moreover, PS also comprises blends of one or more prefoamed EPS granules are coated with fipronil and a binder. of the abovementioned polymers (component C1) with one or 0004 WO 00/44224 discloses the preparation of insecti more thermoplastic polymers (component C2) Such as, for cide-modified polymer foam sheets by extruding or pressing example, polyphenylene ethers (PPE), polyamides (PA), an expandable polymer composition which comprises, dis polyolefins such as polypropylene (PP) or polyethylene (PE), persed into it, an insecticide from the pyrethroid group. The polyacrylates such as polymethyl methacrylate (PMMA), process described relates to the preparation of XPS (extruded polycarbonates (PC), polyesters such as polyethylene tereph polystyrene foam). The active substances employed differ thalate (PET) or polybutylene terephthalate (PBT), polyether markedly from the active Substances according to the inven sulfones (PES), polyether ketones (PEK) or polyether sul tion with regard to their structure. Moreover, the insecticidal fides (PES). activity of the foams described therein with respect to insects 0016. The abovementioned polymers of component C1 is not satisfactory. are obtainable by polymerization of one or more vinyl-aro 0005. It is an object of the invention to do away with the matic monomers such as styrene and, if desired, further abovementioned disadvantages and to provide an economical comonomers such as dienes, C. B-unsaturated carboxylic process for the production of XPS preforms with a sustained acids, esters (preferably alkyl esters) or amides of these car and improved insecticidal activity. boxylic acids and alkenes. Suitable polymerization methods 0006. It has been found that insecticidal active substances are known to the skilled worker. according to the invention can be incorporated homoge 0017. It is preferred to choose, as vinyl-aromatic mono neously into a polymer melt without decomposition. mer, at least one compound of the general formula (I) 0007. The invention therefore relates to a process for the preparation of insecticide-modified extruded polystyrene foam (XPS) preforms, comprising the steps (I) 0008 (a) heating polystyrene (PS) until a polymer melt H RI is formed, 0009 (b) introducing a blowing agent into the polymer melt to form a foamable melt, and 0010 (c) foaming the foamable melt to give an XPS re ex 3 preform, (R) where at least one insecticide from the group of the phe nylpyrazoles, chlorfenapyr and hydramethylnone is intro duced into the polymer melt in at least one of steps (a) and/or in which R' and R independently of one another are in each (b). case hydrogen, methyl or ethyl; 0011. The invention furthermore relates to XPS preforms 10018 R is hydrogen, C-Co-alkyl such as methyl, ethyl, obtainable by the process according to the invention, and to n-propyl, isopropyl. n-butyl, isobutyl, sec-butyl, tert-butyl, their use as construction material, in particular as insulation n-pentyl, isopentyl, sec-pentyl, neopentyl, 1,2-dimethylpro material, in the building trade. pyl, isoamyl, n-hexyl, isohexyl, Sec-hexyl, n-heptyl, n-octyl, US 2011/0201662 A1 Aug. 18, 2011

2-ethylhexyl, n-nonyl, n-decyl; preferably C-C-alkyl Such C-Co-alkylesters of acrylic acid, in particular the butylest as methyl, ethyl, n-propyl, isopropyl. n-butyl, isobutyl, sec ers, preferably n-butyl acrylate, and the C-Co-alkylesters of butyl and tert-butyl; and methacrylic acid, in particular methyl methacrylate (MMA). 00.19 k is an integer from 0 to 2. 0034 Suitable carboxamides are in particular the amides I0020) R' and Rare in each case preferably hydrogen, and of the abovementioned compound (II), for example acryla more preferably k=0, Styrene is especially preferred; others mide and methacrylamide. which are especially suitable are C.-methylstyrene, p-methyl 0035 Also suitable as monomers are compounds of the styrene, ethylstyrene, tert-butylstyrene, vinylstyrene, C.-vi general formula (IIIa) and (IIIb), the compounds (IIIa) for nyltoluene, 1,2-diphenylethylene, 1,1-diphenylethylene or mally being OH-substituted carboxamides: mixtures of these. 0021 Suitable diene comonomers are all polymerizable dienes, in particular 1,3-butadiene, 1,3-pentadiene, 1.3-hexa (IIIa) diene, 2,3-dimethylbutadiene, isoprene, piperylene or mix R9 tures of these. Preferred are 1,3-butadiene (short: butadiene), O X-OH isoprene, or mixtures of these. R7 N 0022 Compounds which are preferably suitable as C.B- V unsaturated carboxylic acid or its derivatives are those of the o H general formula (II) H R8 (IIIb) O (II) R7 X

H R8

in which the symbols denote: 10036) R is selected from the group consisting of in which the symbols have the following meanings: 0037 unbranched or branched C-Co-alkyl such as 0023 R is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl. n-butyl, isobutyl, 0024 unbranched or branched C-Co-alkyl such as Sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, methyl, ethyl, n-propyl, isopropyl. n-butyl, isobutyl, neopentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl, iso Sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, neopentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl, iso n-nonyl, n-decyl; especially preferably C-C-alkyl hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, Such as methyl, ethyl, n-propyl, isopropyl. n-butyl, n-nonyl, n-decyl; particularly preferably C-C-alkyl isobutyl, sec-butyl and tert-butyl: Such as methyl, ethyl, n-propyl, isopropyl. n-butyl, 0038 or hydrogen: isobutyl, sec-butyl and tert-butyl: 0.039 very especially preferred are hydrogen and 0025 or hydrogen, methyl; 0026 very especially preferred are hydrogen and 10040) R' is selected from the group consisting of methyl; 0041 unbranched or branched C-Co-alkyl such as I0027) R' is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl. n-butyl, isobutyl, 0028 unbranched or branched C-Co-alkyl such as Sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, methyl, ethyl, n-propyl, isopropyl. n-butyl, isobutyl, neopentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl, iso Sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, neopentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl, iso n-nonyl, n-decyl; especially preferably C-C-alkyl hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, Such as methyl, ethyl, n-propyl, isopropyl. n-butyl, n-nonyl, n-decyl; especially preferably C-C-alkyl isobutyl, sec-butyl and tert-butyl: Such as methyl, ethyl, n-propyl, isopropyl. n-butyl, 0.042 hydrogen is very especially preferred; isobutyl, sec-butyl and tert-butyl, 10043 R’ is selected from among 0029 hydrogen is very especially preferred; 0044 unbranched or branched C-Co-alkyl such as I0030) R' is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl. n-butyl, isobutyl, 0031 hydrogen (in which case compound (II) is the Sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, carboxylic acid itself), neopentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl, iso 0032 or unbranched or branched C-Co-alkyl (in hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, which case compound II is a carboxylic ester) Such as n-nonyl, n-decyl; especially preferably C-C-alkyl methyl, ethyl, n-propyl, isopropyl. n-butyl, isobutyl, Such as methyl, ethyl, n-propyl, isopropyl. n-butyl, Sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, isobutyl, sec-butyl and tert-butyl, neopentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl, iso 0.045 hydrogen is very especially preferred; hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, 004.6 X is selected from the group consisting of n-nonyl, n-decyl; especially preferably C-C-alkyl 0047 hydrogen, Such as methyl, ethyl, n-propyl, isopropyl. n-butyl, (0.048 glycidyl isobutyl, sec-butyl and tert-butyl; and 2-ethylhexyl. 0049 groups with tertiary amino groups, preferably 0033 Preferred compounds of the formula (II) are acrylic NH(CH), N(CH), where b is an integer in the range acid and methacrylic acid. Furthermore preferred are the of from 2 to 6, US 2011/0201662 A1 Aug. 18, 2011

0050 enolizable groups with 1 to 20 C atoms, prefer employ compounding extruders (primary extruders). Step (a) ably acetoacetyl, of the formula of the process according to the invention can be carried out continuously or batchwise, a continuous process being pre ferred. OR 10 0060 Step (b) of the process according to the invention - O comprises the introduction of a blowing agent into the poly styrene molten in step (a), in order to form a foamable melt. O 0061 The blowing agent can be introduced into the molten O polystyrene by any method known to the skilled worker. Suitable examples are extruders or mixers (for example where kneaders). In a preferred embodiment, the blowing agent is I0051) R' is selected from among unbranched or branched mixed with the molten polystyrene under elevated pressure. C-Co-alkyl Such as methyl, ethyl, n-propyl, isopropyl. n-bu Here, the pressure must be high enough that foaming of the tyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec molten polymer material is essentially prevented and a homo pentyl, neopentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl, iso geneous distribution of the blowing agent in the molten poly hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, styrene is obtained. Suitable pressures are from 50 to 500 bar n-decyl; especially preferably C-C-alkyl such as methyl, (absolute), preferably from 100 to 200 bar (absolute), espe ethyl, n-propyl, isopropyl. n-butyl, isobutyl, sec-butyl and cially preferably 120-170 bar (absolute). The temperature in tert-butyl. step (b) of the process according to the invention must be 0052 R in formula (IIIa) or (IIIb), respectively, is very chosen Such that the polymeric material is present in the especially preferably selected from among hydrogen and molten state. Therefore, step (b) of the process according to methyl, and R7 and Rare in each case hydrogen. the invention is generally carried out attemperatures of from 0053 Particularly preferred as compound of the formula 100 to 280° C., preferably from 120 to 260° C. and especially (Va) is methylolacrylamide. preferably from 180 to 220° C. Step (b) can be carried out 0054 The PS may also be prepared using alkenes as continuously or batchwise; step (b) is preferably carried out comonomers. Particularly suitable alkenes are ethylene continuously. (ethene) and propylene (propene). 0062. The addition of the blowing agent can be effected in 0055. Further suitable comonomers for the preparation of the compounding extruder (primary extruder) or in a Subse component C1 are, for example, in each case from 1 to 5% by quent step. weight of (meth)acrylonitrile, (meth)acrylamide, ureido 0063. In a preferred embodiment, the foamable polymer (meth)acrylate, 2-hydroxyethyl(meth)acrylate, 3-hydrox melt is produced in XPS extruders which are known to the ypropyl(meth)acrylate, acrylamidopropanesulfonic acid skilled worker, for example via a tandem arrangement of (branched or unbranched), or the sodium salt of vinylsulfonic compounding extruder (primary extruder) and cooling acid. extruder (secondary extruder). The process can be carried out 0056. The polystyrenes (PS) which can be employed in continuously or batchwise, the polystyrene being melted in accordance with the invention can be prepared by processes the primary extruder (step (a)) and the addition of the blowing known to the skilled worker, for example by free-radical agent (step (b)) for forming a foamable melt also being car polymerization, anionic polymerization or cationic polymer ried out in the primary extruder. ization, neat, in Solution, dispersion or emulsion. Free-radical 0064. Thereafter, the melt which is provided with blowing polymerization is preferred. agent is cooled in the secondary extruder to a temperature of 0057 The polystyrenes which can be employed in the 50-180° C., preferably to a temperature of 80-130°C., which process according to the invention have, in general, weight is suitable for foaming. averaged molecular weights of from 100 000 to 300 000 0065 Suitable blowing agents comprise inorganic, g/mol and an MVR melt volume rate (200° C./5 kg) deter organic and chemically reactive blowing agents. Suitable mined as specified in ISO 113 in the range of from 1 to 10 inorganic blowing agents comprise carbon dioxide, nitrogen, cm. Examples of suitable polystyrenes are PS 158 K, 168 N argon, water, air and helium. A preferred blowing agent is a or 148G from BASF SE. mixture of carbon dioxide and water. 0058. In step (a) of the process according to the invention, 0066. Organic blowing agents comprise aliphatic hydro the polystyrene is heated to give a polymer melt. By forma carbons with 1 to 9 carbon atoms and perhalogenated or tion of a polymer melt, there is understood, for the purposes of partially halogenated aliphatic hydrocarbons with 1 to 4 car the present invention, a plastification of the polystyrene in the bon atoms. Aliphatic hydrocarbons comprise methane, wider sense, i.e. the conversion of the Solid polystyrene into a ethane, propane, n-butane, isobutene, n-pentane, isopentane shapable or flowable state. To this end, it is necessary to heat and neopentane. Fully and partially halogenated aliphatic the polystyrene to a temperature of above the melting point or hydrocarbons comprise fluorocarbon compounds, chlorocar the glass transition temperature. Suitable temperatures are, in bon compounds and chlorofluorocarbon compounds. general, from 50 to 250° C., preferably from 100 to 220° C. Examples of fluorocarbon compounds comprise methyl fluo especially preferably from 180 to 220° C. If a polystyrene ride, perfluoromethane, ethyl fluoride, difluoromethane, 1,1- with a molar styrene monomer content of 95% is employed, it difluoroethane, 1,1,1-trifluoroethane, 1,1,1,2-tetrafluoroet must be heated to a temperature of at least 180°C. in order to hane, pentafluoroethane, difluoromethane, perfluoroethane, give a polymer melt. 2,2-difluoropropane, 1,1,1-trifluoropropane, perfluoropro 0059. The heating of the polystyrene (step (a) of the pro pane, difluoropropane, difluoropropane, perfluorobutane, cess according to the invention) can be carried out by means perfluorocyclopentane. Partially halogenated chlorocarbon of any devices known in the art, Such as by means of an compounds and chlorofluorocarbon compounds which are extruder, mixer (for example kneader). It is preferred to Suitable for use in the process according to the invention US 2011/0201662 A1 Aug. 18, 2011 comprise methyl chloride, methylene chloride, ethyl chlo and 9,10-dihydro-9-Oxa-10-phosphaphenanthrene 10-oxide. ride, 1,1,1-trichloroethane, chlorodifluoromethane, 1,1- A further suitable flame retardant is, for example, hexabro dichloro-1-fluoroethane, 1-chloro-1,1-difluoroethane, 1,1- mocyclododecane (HBCD), in particular the technical grade dichloro-2,2,2-trifluoroethane and 1-chloro-1.2.2.2- products which comprise essentially the Cl-, 3- and Y-isomer tetrafluoroethane. Fully halogenated and preferably an addition of dicumyl peroxide as Synergist. chlorofluorohydrocarbon compounds comprise trichlo 0076. In the process according to the invention, at least one romonofluoromethane, dichlorodifluoromethane, trichlorot insecticide from the group of the phenylpyrazoles, in particu rifluoroethane, 1,1,1-trifluoroethane, pentafluoroethane, lar fipronil (IV), acetoprole, ethiprole (V) and the compound dichlorotetrafluoroethane, chloroheptafluoropropane and of the formula (VI), chlorfeinapyr (VII) and hydramethylnone dichlorohexafluoropropane. (VIII), are admixed to the polymer melt employed. Admixing 0067 Chemically reactive blowing agents comprise can be carried out in steps a) and/or b). aZodicarboxylic diamide, aZodiisobutyronitrile, benzene Sul 0077. The addition of the at least one insecticide is not fone hydrazide, 4.4-oxybenzenesulfonyl semicarbazide, critical here, thus, the at least one insecticide can be effected p-toluenesulfonyl semicarbazide, barium aZodicarboxylate, as a pure Substance, as a formulation or in the form of a N,N'-dimethyl-N,N'-dinitrosotherephthalamide and trihy masterbatch. It is also possible to employ, in step a), a PS drazinotriazine. which already comprises at least one insecticide. 0068 A further preferred blowing agent mixture com 0078 For the purposes of the present invention, pure sub prises from 0 to 100% by weight of carbon dioxide, from 0 to stances are understood as meaning Substances with an active 50% by weight of water and from 0 to 75% by weight of an substance content of at least 80% by weight, preferably at alcohol, for example methanol or ethanol, of a ketone or of an least 90% by weight, more preferably at least 95% by weight ether. and in particular preferably at least 97% by weight, in each 0069. For environmental reasons, it is desirable to employ case based on the total weight of the pure Substances. inorganic blowing agents, if this is possible. Two especially 007.9 Formulations are understood as meaning all known Suitable inorganic blowing agents are carbon dioxide and insecticide formulations with which the skilled worker is Water. familiar. The use of commercially available formulations is 0070 The amount of the blowing agent employed is from also possible. The use of aqueous formulations is preferred. 0.5 to 20% by weight, preferably from 4 to 12% by weight and 0080 Masterbatches are understood as meaning PSs in particular from 2 to 8% by weight, based on the polystyrene which comprise the at least one insecticide at a concentration employed. which is higher than the final concentration. The final con 0071. In a further preferred embodiment, at least one centration is understood as meaning the concentration of the nucleating agent is added to the molten polymeric material. at least one insecticide in the XPS preform. Suitable insecti Nucleating agents which can be employed are finely divided, cide concentrations for a masterbatch are in the range of from inorganic Solids such as talc, metal oxides, silicates or poly 1 to 90% by weight. Preferably, the masterbatch comprises ethylene waxes in amounts of, in general, from 0.1 to 10% by less than 20% by weight, more preferably from 1 to 15% by weight, preferably from 0.1 to 3% by weight, especially pref weight and in particular from 5 to 10% by weight of the at erably from 1 to 1.5% by weight, based on the polymeric least one insecticide, in each case based on the total weight of material. The mean particle diameter of the nucleating agent the masterbatch. is, as a rule, in the range of from 0.01 to 100 um, preferably I0081 Suitable processes for preparing a masterbatch are, from 1 to 60 um. An especially preferred nucleating agent is for example, the incorporation of the at least one insecticide talc, for example talc from Luzenac Pharma. The nucleating into a polymer melt in an extruder or the coating of PS with an agent can be added to the polymer melt by methods known to insecticide or an insecticide mixture. the skilled worker. The addition may be carried out in step (a) I0082 Suitable mixing ratios of the masterbatch and the and/or (b). commercially available PS which is employed in the process 0072. If desired, further additives such as nucleating according to the invention are in the range of from 10:1 to agents, plasticizers, flame retardants, IR absorbers such as 1:1000, especially preferably in the range of from 10:1 to carbon black or graphite, aluminum powder and titanium 1:100 and in particular in the range of from 10:1 to 1:50. dioxide, Soluble and insoluble colorants and pigments may be I0083. The admixing of the at least one insecticide is pref added in step (a) and/or (b). Preferred additives are graphite erably effected in step (a). In one embodiment, the at least one and carbon black. insecticide is added as pure Substance in step (a) and/or (b). In 0073. It is especially preferred to add graphite in amounts a further embodiment, the addition of the at least one insec of in general, from 0.05 to 25% by weight, especially pref ticide is effected in step (a) and/or (b) in the form of an erably in amounts from 2 to 8% by weight, based on the aqueous formulation. polymeric material. Suitable particle sizes for the graphite 0084. In a further embodiment, the at least one insecticide employed are in the range of from 1 to 50 lum, preferably in is incorporated, into a polymer melt, in an extruder at a the range from 2 to 10 Jum. concentration which is higher than the final concentration 0074. In one embodiment, the XPS preform according to (preparation of a masterbatch) and this active-substance the invention can be colored in order to make it readily dis comprising polymer is Subsequently fed to the polymer melt tinguishable from non-insecticide-modified XPS preforms in step (a) and/or (b). The feeding can be effected for example and thus to increase product safety. by mixing into the main stream of the polymers, shortly after 0075. Owing to fire protection regulations in the construc melting or via a secondary stream which serves for conveying tion industry and in other industries, one or more flame retar additives into the main stream. dants are added in step (a) and/or (b). Examples of suitable I0085. In a further embodiment, the preparation of the flame retardants are tetrabromobisphenol A diallyl ether, batch is effected by coating a PS with an insecticide or insec expandable graphite, red phosphorus, triphenyl phosphate ticide mixture. It is preferred to use PS granules for this US 2011/0201662 A1 Aug. 18, 2011 purpose. In this context, the coating process is carried out by known methods with which the skilled worker is familiar. In -continued this context, the insecticide, or the insecticide mixture, can be (VI) used in Solid, dissolved and/or dispersed (for example Sus C NH2 f pended or emulsified) form. The insecticide, or the insecti Sn cide mixture, is applied to the PS to be coated for example by FC N1N1"So V spraying or applying in drums, using customary mixers. NR NH2 Another possibility is the immersion or wetting of the PS in a C Suitable solution, dispersion, emulsion or Suspension. If S desired, further coating additives such as binders, antistatics, (VII) hydrophobicizing agents, flame retardants, finely divided CN silica and inorganic fillers may be added to the insecticide, or Br the insecticide mixture. \ N C 0.086. In one embodiment, the coated PS thus obtained is melted together with commercially available uncoated PS by N methods known to the skilled worker, for example in an FC CHOCH2CH3 extruder, and processed by the process according to the inven (VIII) tion to give XPS preforms. The addition of the coated PS to the commercially available uncoated PS is preferably carried CF out in this context in step (a) of the process according to the H A" N CH invention. It is also possible to mix the coated and the com CH3 M mercially available uncoated PS in a preceding step and then )=N-N=C to feed into step (a). In a preferred embodiment, the at least CDX N VCH one insecticide is added as pure Substance in step (a). In a further preferred embodiment, the at least one insecticide is CH CF added in step (a) in the form of a formulation. 0087. In an especially preferred embodiment, the at least one insecticide is added in step (a) in the form of an aqueous 0090 Fipronil is especially preferred. formulation. 0091. The compounds mentioned, in particular those of 0088. The added amount of the at least one insecticide in the formulae (II), (III), (V) and (VI), and their preparation are step (a) and/or (b) can be chosen at will, but is preferably known and described, for example, in “The Pesticide chosen such that the XPS preform according to the invention Manual", 14" Edition, British Crop Protection Council has insecticide concentrations of from 10 to 1000 ppm, espe (2006). The thiamide of the formula (IV) and its preparation cially preferably from 20 to 1000 ppm and in particular from is described in WO98/28279. Fipronil, hydramethylnone and 50 to 500 ppm, based on the XPS preform. chlorfenapyr are commercially available from BASF SE 0089 Suitable insecticides are phenylpyrazoles, in par (Ludwigshafen, Germany). ticular fipronil ((+)-5-amino-1-(2,6-dichloro-C.C.C.-trif 0092 Besides the abovementioned insecticides, further luoro-p-tolyl)-4-trifluoromethylsulfinylpyrazole), hydram insecticides, biocides or fungicides may be added (in a mix ethylnone and chlorfenapyr. ture). 0093 Suitable mixing partners are, for example, from the (IV) group of the insecticides: C CN I.1. organo (thio)phosphates: acephate, azamethiphos, azin N phos-methyl, chlorpyrifos, chlorpyrifos-methyl, chlorfenvin ? phos, diazinon, dichlorvos, dicrotophos, dimethoate, disulfo FC Na S 29 ton, ethion, fenitrothion, fenthion, isofenphos, isoxathion, malathion, methamidophos, methidathion, methyl-parathion, C NH2 CF mevinphos, monocrotophos, oxydemeton-methyl, paraoxon, (V) parathion, phenthoate, phosalone, phosmet, phosphamidon, CH3CHSO CN phorate, phoxim, pirimiphos-methyl, profenofos, prothiofos, Sulprophos, tetrachlorvinphos, terbufos, triaZophos, trichlor fon; ( \, I.2. carbamates: alanycarb, aldicarb, bendiocarb, benfura HN N1 carb, carbaryl, carbofuran, carbosulfan, fenoxycarb, furathio C C carb, methiocarb, methomyl, oxamyl, pirimicarb, propoXur, thiodicarb, triazamate; I.3. pyrethroids: allethrin, bifenthrin, cyfluthrin, cyhalothrin, cyphenothrin, cypermethrin, alpha-cypermethrin, beta cypermethrin, Zeta-cypermethrin, deltamethrin, esfenvaler CH3 ate, etofenproX, fempropathrin, fenvalerate, imiprothrin, lambda-cyhalothrin, permethrin, prallethrin, pyrethrin I and US 2011/0201662 A1 Aug. 18, 2011

II, resmethrin, silafluofen, tau-fluvalinate, tefluthrin, tet 0097. Further mixing partners which are possible are ramethrin, tralomethrin, transfluthrin, profluthrin, dime amidrazones of the formula (IX), fluthrin; I.4. growth regulators: a) chitin synthesis inhibitors: benzoy lureas: chlorfluaZuron, diflubenZuron, flucycloxuron, (IX) flufenoXuron, hexaflumuron, lufenuron, novaluron, noviflu muron, sulfluramid, teflubenzuron, triflumuron; buprofezin, diofenolan, hexythiaZOX, etoxazole, clofentazine; b) ecdys one antagonists: halofenozide, methoxyfenozide, tebufenozide, azadirachtin; c) juvenoids: pyriproxyfen, methoprene, fenoxycarb; d) lipid biosynthesis inhibitors: spi rodiclofen, spiromesifen, Spirotetramat; I.5. nicotin receptor agonists/antagonists: acetamiprid, where the symbols have the following meanings: clothianidin, dinotefuran, imidacloprid, nitenpyram, thiaclo 0.098 W is C1 or CF; prid, thiamethoxam; 0099 X,Y are identical or different C1 or Br: I.6. GABA antagonists: endosulfan, pyrafluprole, pyriprole; I0100 R'' is (C-C)-alkyl, (C-C)-alkenyl, (C-C)- I.7. macrocyclic lactone insecticides: abamectin, emamectin, alkynyl or (C-C)-cycloalkyl, each of which can be Sub milbemectin, lepimectin, spinosad; stituted by 1 to 3 halogen atoms, or (C-C)-alkyl which is I.8. site-I electron transport inhibitors: Substituted by (C-C)-alkoxy; for example fenazaquin, fenpyroximate pyrimidifen, pyrida I0101) R''. Rare (C-C)-alkyl or together with the car ben, tebufenpyrad, tolfenpyrad, flufenerim, hydramethylnon, bon atom to which they are bonded form (C-C)-cy cloalkyl which can be substituted by 1 to 3 halogenatoms: dicofol; 0102) R' is H or (C-C)-alkyl, I.9. site-II and Site-III electron transport inhibitors: and enantiomers and salts thereof. aceduinocyl, fluacyprim, rotenone; (0103 Preferably, the symbols of the formula (IX) have the I.10. compounds which inhibit oxidative phosphorylation: following meanings: cyhexatin, diafenthiuron, fenbutatin oxide, propargite; I0104 R'' is preferably (C-C)-alkyl, in particular methyl I.11. chitin biosynthesis inhibitors: or ethyl: cyromazine; 0105) R' and R' are preferably methyl or together with I.12. mixed function oxidase inhibitors: the carbon atom to which they are bonded form a cyclo propyl ring which can have attached to it one or two chlo piperonyl butoxide (PBO); rine atoms; I.13. Sodium channel modulators: I0106 R'' is preferably (C-C)-alkyl, in particular indoxacarb, metaflumizone; methyl; I.14. active Substances with unknown or unspecific mecha 0107 W is preferably CF; nisms of action: 0108) X,Y are preferably C1. amidoflumet, benclothiaz, bifenazate, borate, cartap, chlo 0109 Furthermore preferred compounds of the formula rantraniliprole, flonicamid, pyridalyl, pymetrozine, Sulfur, (IX) are those in which X and Y are C1, Wis CF, R', Rand thiocyclam, flubendiamide, cyenopyrafen, cyflumetofen, R'' are methyl and R'' is methyl or ethyl, and also those flupyrazofoS. compounds in which X,Y are C1, W is CF, R', R' together with the carbon atom to which they are bonded form a 2.2- 0094. The commercially available compounds of group dichlorocyclopropyl group, R'' is methylandR'' is methyl or I.1 to I. 15 can be found in “The Pesticide Manual", 14" ethyl. These compounds and their preparation are described Edition, British Crop Protection Council (2006). for example in US 2007/0184983. 0095 Lepimectin is known from “Agro Project, PJB 0110 Preferred mixing partners besides mixtures of the Publications Ltd, November 2004. Benclothiaz, and its prepa compounds employed in accordance with the invention with ration are described in EP-A1 454621. Methidathione and one another—are pyrethroids (I.3), neonicotin receptor ago paraoxone and their preparation is described in “Farm nists/antagonists (I.5), borates, carbaryl, chlorantraniliprole, Chemicals Handbook, Volume 88, Meister Publishing Com chlorpyrifos, diflubenzuron, fenitrothion, flonicamid, pany, 2001. Acetoprole and its preparation are described in flufenoXuron, hexaflumuron, indoxacarb, isofenphos, novi WO 98/28277. Flupyrazofos is described in “Pesticide Sci flumuron, metaflumizone, spinosad, Sulfluramid. Especially ence '54, 1988, pages 237-243 and in U.S. Pat. No. 4,822, preferred are acetamiprid, bifenthrin, cyfluthrin, cyhalothrin, 779. Pyrafluprole and its preparation are described in JP cypermethrin, alpha-cypermethrin, deltamethrin, fenvaler 2002 193709 and in WO 01/00614. Pyriprole and its prepara ate, imidacloprid, lambda-cyhalothrin, permethrin, thiaclo tion are described in WO 98/.45274 and in U.S. Pat. No. prid and thiamethoxam. 6,335,357. Amidoflumet and its preparation are described in 0111 Very especially preferred are mixtures of fipronil U.S. Pat. No. 6,221,890 and in JP 21010907. Flufenerim and with one or more of the abovementioned mixing partners, in its preparation are described in WO 03/007717 and in WO particular fipronil with C-cypermethrin and/or piperonyl 03/007718. Cyflumetofen and its preparation are described in butoxide (PBO). Furthermore especially preferred is the use WO 04/08O18O. offipronil without a further mixing partner. 0096 Anthranilamides of the formula (XIV) and their 0112 The mixing ratio between the insecticides employed preparation are described in WO 01/70671; WO 02/48137; in accordance with the invention and, if appropriate, further WO 03/24222, WO 03/15518, WO 04/67528: WO 04/33468; mixing partners may vary within wide limits and is generally and WO 05/118552. from 0.1:100 to 100:0.1 US 2011/0201662 A1 Aug. 18, 2011

0113. The insecticide, or insecticide mixture, can be kg/m. The XPS sheets according to the invention preferably employed as pure Substance (for example as a technical have cells at least 90% of which, in particular 95 to 100% of grade, or pure, active Substance). The use of commercially which, are of closed-cell type, measured as specified in DIN available formulations is also possible. ISO 4590. 0114. The amount of insecticide, or insecticide mixture, 0.122. As the result of the distribution of the insecticide in which is added to the polymer melt is chosen such that the the polymer melt, the insecticide is firmly incorporated into XPS preforms obtainable therefrom have concentrations of from 10 to 1000 ppm, especially preferably from 20 to 1000 the polymer matrix in the insecticide-modified XPS preforms ppm and very especially preferably from 50 to 500 ppm. according to the invention. This reduces active Substance loss 0115 Step (c) of the method according to the invention and exposure to the insecticide during preparation, process comprises the foaming of the foamable melt in order to obtain ing and use of the XPS preforms. In addition, the process an XPS preform. according to the invention allows the insecticide quantity 0116. To this end, the melt is conveyed through a suitable required to be reduced. device, for example a die plate. The die plate is heated to at (0123. In one embodiment, the insecticide, or insecticide least a temperature of the blowing-agent-comprising polymer mixture, is in the form of a molecular dispersion in the XPS melt. The temperature of the die plate is preferably 50 to 200° preforms according to the invention. C. The temperature of the die plate is especially preferably 0.124. In the form of a molecular dispersion means accord 100 to 150° C. ing to the invention that the active Substance is so finely 0117 The blowing-agent-comprising polymer melt is distributed in the polymer matrix that no crystalline amounts transferred through the die plate into a Zone in which a lower of the active substance can be identified by X-ray diffracto pressure prevails than in the Zone in which the foamable melt metry. Such a state is also referred to as a “solid solution'. is held before extrusion through the die plate. The lower 0.125 Since the detection level for crystalline amounts is pressure can be Superatmospheric or Subatmospheric. Extru approximately 3% by weight in the case of X-ray diffracto sion into a Zone with atmospheric pressure is preferred. metry, the term “no crystalline amounts' means that less than 0118 Step (c) is also carried out at a temperature at which 3% by weight of crystalline amounts are present. The state of the polymeric material to be foamed is present in the molten the molecular dispersion can be determined with the method state, in general attemperatures of from 50 to 150°C., pref referred to as differential scanning calorimetry (DSC). In the erably at from 100 to 125° C. By conveying the blowing case of molecular dispersion, a melting peak can no longer be agent-comprising polymer melt, in Step (c), into a Zone in detected around the melting point of the active substance. The which a lower pressure prevails, the blowing agent is brought detection limit of this method is 1% by weight. into the gaseous state. As a result of the great increase in Volume, the polymer melt is expanded and foamed. 0.126 Solid solutions result in an improved release of the 0119 The geometric shape of the cross-section of the XPS active Substance. An important demand made of Solid solu preforms obtainable by the process according to the invention tions is that they are also stable upon storage over prolonged is determined essentially by the choice of the die plate and can periods, i.e. that the active Substance does not crystallize. be varied within wide ranges. Thus, it is possible to employ, Moreover, the capacity of the solid solution, in other words for example, die plates whose outlet opening has one of the the ability to form stable solid solutions with the highest following shapes: circle, triangle, quadrangle (square, rect possible active Substance contents, is also important. angle, rhombus, trapezoid, parallelogram, lozenge, quad 0127. The invention also relates to the use of the XPS rangle enscribed in a circle, deltoid, quadrangle circum preforms according to the invention. scribed about a circle), pentagon, hexagon, heptagon, I0128 Preferred is the use of the XPS preforms produced in octagon, nonagon, decagon and n-agonal shapes with n=11 to accordance with the invention in the construction industry, for 100, and also ellipse and circle. Others which are suitable example as insulation material below and above ground for include complex shapes such as pentagram, hexagram, Super avoiding or reducing damage of the preforms by pests such as, ellipse, spherical lune, spherical triangle and cycloid, and all for example insects, which can inflict Substantial feeding shapes which result from combinations of the shapes men damage to the preforms, so that the insulation effect and the tioned here with one another. mechanical stability of the preforms are limited and further 0120) The XPS preforms obtainable by the process penetration of the pests is made possible. The preforms pro according to the invention preferably have a right-angled duced inaccordance with the invention are especially Suitable cross section. The thickness of the XPS preform is deter for avoiding or reducing damage by termites. mined by the height of the slit of the die plate. The width of the I0129. The invention is illustrated in greater detail by the XPS preform is determined by the width of the die-plate slit. examples, without being limited thereby. The length of the preform is determined in a downstream step by methods known to the skilled worker, Such as bonding, Preparation of Termiticidal Extruded PS Foams: welding, sawing and cutting. Particularly preferred are XPS preforms with a sheet-like geometry (XPS sheets). Sheet-like EXAMPLE ACCORDING TO THE INVENTION means that the dimension of the thickness(height) is Small in comparison with the dimension of the width and the dimen 1. Coating PS Granules sion of the length of the preform. 0121. As a rule, the XPS preforms according to the inven 0.130 6985g of polystyrene granules (Polystyrol 158k, tion have a compressive strength, measured as specified in BASF SE) were admixed with 15 ml of a suspension DIN EN 826, in the range of from 0.3 to 1.0 N/mm. prefer concentrate comprising 500 g/l of fipronil in a stirrer ably in the range of from 0.35 to 0.7 N/mm. The density of from Alexanderwerk. The mixture was subsequently the foam sheets is preferably in the range of from 25 to 50 dried at RT. US 2011/0201662 A1 Aug. 18, 2011

2. Preparation of Termiticide-(Fipronil)-Comprising 0.136 The extrusion temperature is no more than 200° C. Foams in the Extruder The mixture is foamed through a slot die of 22 mm width at a throughput of 7 kg/h. I0131 The components of Table 1 are mixed in a twin screw extruder (ZSK25): Determination of the Active Substance in the XPS Foam: TABLE 1. I0137 The content was analyzed by means of GC/MS. To Product 1 this end, 0.5g of the XPS are dissolved in acetonitrile and an (reference aliquot of this solution, in diluted form, is Subjected to quan without active Substance) Product 2 Product 3 Product 4 titative analysis by means of GC/MS (Agilent GC: 6890N with an MSD 5973 detector). The results are shown in Tables PS 158K granules 6805 64SS 6105 5405 3 and 4. PS 158K- O 350 700 1400 fipronil of Example 1 TABLE 3 Additive mixture 195 195 195 195 (color, graphite, Product 1 2 3 4 flame retardant, talc) Fipronil (ppm O 21 168 204 Carbon dioxide 231 231 231 231 Ethanol 161 161 161 161 Amount produced 7392g 7392 g 7392g 7392 g TABLE 4

0132 Here, fipronil-coated PS granules are the fipronil Product 5 6 7 8 source (product of Example 1) which is metered in and which is mixed with the other components in the respective mixing Deltamethrin ppm 65 113 209 398 ratios. The extrusion temperature is no more than 200°C. The mixture is foamed through a slot die of 22 mm width at a throughput of 7 kg/h. Biological Test of the XPS Foams: Comparative Example 0.138. The biological test method selected was similar to the biological test method of Su et al. (1993) for the determi 3. Coating PS Granules nation of the activity of Soil termiticides. Using a drilling machine equipped with a tap borer, cylinders (approximately 0.133 100g of a deltamethrinactive substance formulation (Decis Micro) (deltamethrin 62.5 ga.i./kg, Bayer CropSci 2.5 cm in diameter and 5.0 cm in length) were cut from ence) were mixed with 100 ml of water. The mixture was blocks. Each polystyrene cylinder was wedged into a TeniteR) placed into a stirrer from Alexanderwerk together with 6150 polyester tube of diameter 2.5 cm. This tube was then con g of polystyrene (PS 158k; BASFSE) and mixed. The mix nected via a Tygon connecting hose to another tube which ture was dried overnight. comprised 80 female worker termites and one soldier termite. The 5.0 cm polystyrene cylinders were placed between two 3 4. Preparation of cm agar segments. The food and nesting material for the Termiticide-(Deltamethrin)-Comprising Foams in the termites, used bothin the tube with the termites and in the tube Extruder with the polystyrene cylinder, was Ponderosa pine shavings and paper strips. The two tubes were kept at 25°C. during the 0134. The components of Table 2 are mixed in a twin screw extruder (ZSK25): test time of 7 days. 0.139. The distance tunneled through the outer surface of TABLE 2 the cylinder along the inner wall of the tube was recorded over 24 hours. Short (<10 mm) straight tunnels on the outer side of Product 5 Product 6 Product 7 Product 8 the cylinder were measured with a ruler. Longer, curved tun PS 158K granules 645S 6105 5405 40OS nels were measured by placing a section of a rubber band PS 158K- 350 700 1400 2800 along the course of the tunnel and then measuring the length deltamethrin of Example 3 of the rubber band. The test was terminated after seven days. Additive mixture 195 195 195 195 On termination, the mortality was determined, as was the (color, graphite, length of the distance tunneled through the interior of the flame retardant, talc) cylinder, by threading small pieces of 0.5 mm insulated tele Carbon dioxide 231 231 231 231 phone wire through the tunnels and after withdrawal of the Ethanol 161 161 161 161 wire measuring its length with a ruler. To determine the length Amount produced 7392 g 7392 g 7392g 7392g of tunneling through the interior of the cylinder for any par ticular day, the ratio of the total length of the tunnel on the 0135. Here, the deltamethrin-coated PS granules (product outer surface of the cylinder to the length of the tunnel for the of 3) acts as the deltamethrin source, which is metered in and particular day was calculated and the total length determined mixed with the further components in the respective mixing for tunneling in the interior of the cylinder was divided by this ratios. ratio. US 2011/0201662 A1 Aug. 18, 2011

20. The process according to claim 16, wherein the at least TABLE 5 one insecticide is incorporated into the polymer melt in the form of a masterbatch. Average Mean External Mean Internal Mean Total mortality Tunneling Tunneling Tunneling 21. The process according to claim 20, wherein the mas Treatment (%) (cm) (cm) (cm) terbatch has an insecticide concentration of from 1 to 15% by Product 2 46.6 3.0 O.8 3.9 weight. Product 3 87.7 1.1 0.4 1.5 22. The process according to claim 20, wherein the mas Product 4 85.2 1.5 0.4 1.9 Product 1 23.9 5.7 3.4 9.1 terbatch is mixed in step (a) with the polymer melt in a ratio reference of from 10:1 to 1:100. without 23. The process according to claim 16, wherein the insec fipronil Product 5 23.7 3.0 1.3 4.3 ticide is fipronil. Product 6 26.2 1.9 1.3 3.2 24. The process according to claim 16, wherein at least one Product 7 23.1 1.3 1.4 2.7 further insecticide is mixed in besides at least one of the Product 8 24.4 0.4 O.S O.8 abovementioned insecticides. 25. The process according to claim 24, wherein the further 1.-15. (canceled) insecticide is selected from the group of the pyrethroids, 16. A process for the production of insecticide-modified neonicotin receptor agonists/antagonists, borates, carbaryl, extruded polystyrene foam (XPS) preforms, comprising the chlorantraniliprole, chlorpyrifos, diflubenzuron, feni steps trothion, flonicamid, flufenoXuron, hexaflumuron, indoxac (a) heating polystyrene (PS) until a polymer melt is arb, isofenphos, noviflumuron, metaflumizone, spinosad and formed, sulfluramid. (b) introducing a blowing agent into the polymer melt to 26. The process according to claim 16, wherein the con form a foamable melt, and centration of the at least one insecticide in the XPS preforms (c) foaming the foamable melt to give an XPS preform, is 10 to 1000 ppm. wherein at least one insecticide from the group of the phenylpyrazoles, chlorfenapyr and hydramethylnone is 27. An XPS preform, obtainable by the process according introduced into the polymer melt in at least one of steps to claim 16. (a) and/or (b). 28. An insulation material comprising the XPS preform 17. The process according to claim 16, wherein the at least according to claim 27. one insecticide is incorporated into the polymer melt in step 29. A material for the protection of buildings against ter (a). mites comprising the XPS preform according to claim 27. 18. The process according to claim 16, wherein the at least 30. A method of protecting a building against termites one insecticide is incorporated into the polymer melt as pure comprising the step of building the XPS preform according to Substance, as formulation or in the form of a masterbatch. claim 27 into the foundation, the external walls or the roof of 19. The process according to claim 16, wherein the at least the building to be protected. one insecticide is incorporated into the polymer melt in the form of an aqueous formulation. c c c c c