DE3140520A1 - Self-extinguishing thermoplastic moulding compositions - Google Patents
Self-extinguishing thermoplastic moulding compositionsInfo
- Publication number
- DE3140520A1 DE3140520A1 DE19813140520 DE3140520A DE3140520A1 DE 3140520 A1 DE3140520 A1 DE 3140520A1 DE 19813140520 DE19813140520 DE 19813140520 DE 3140520 A DE3140520 A DE 3140520A DE 3140520 A1 DE3140520 A1 DE 3140520A1
- Authority
- DE
- Germany
- Prior art keywords
- poly
- parts
- self
- polymers
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000004415 thermoplastic moulding composition Substances 0.000 title abstract 2
- 229920000642 polymer Polymers 0.000 claims abstract description 18
- 239000013256 coordination polymer Substances 0.000 claims abstract description 11
- 229920001795 coordination polymer Polymers 0.000 claims abstract description 11
- 229920001955 polyphenylene ether Polymers 0.000 claims abstract description 9
- 239000003063 flame retardant Substances 0.000 claims description 13
- 239000000654 additive Substances 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 10
- 230000000996 additive effect Effects 0.000 claims description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- 238000009757 thermoplastic moulding Methods 0.000 claims description 5
- 150000003018 phosphorus compounds Chemical class 0.000 claims 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 14
- 150000002903 organophosphorus compounds Chemical class 0.000 abstract description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 15
- 239000000203 mixture Substances 0.000 description 14
- -1 vinyl aromatic compound Chemical class 0.000 description 14
- 238000000465 moulding Methods 0.000 description 13
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 238000012545 processing Methods 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- 125000004122 cyclic group Chemical group 0.000 description 6
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 150000001340 alkali metals Chemical class 0.000 description 5
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical group [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000004793 Polystyrene Substances 0.000 description 4
- BEQVQKJCLJBTKZ-UHFFFAOYSA-M diphenylphosphinate Chemical compound C=1C=CC=CC=1P(=O)([O-])C1=CC=CC=C1 BEQVQKJCLJBTKZ-UHFFFAOYSA-M 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000000214 vapour pressure osmometry Methods 0.000 description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Chemical group CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- 239000007983 Tris buffer Substances 0.000 description 3
- YTMRJBAHYSIRMZ-UHFFFAOYSA-N dioctylphosphinic acid Chemical compound CCCCCCCCP(O)(=O)CCCCCCCC YTMRJBAHYSIRMZ-UHFFFAOYSA-N 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- ZUYQAYFMISSPTF-UHFFFAOYSA-N methoxy-oxo-phenylphosphanium Chemical compound CO[P+](=O)C1=CC=CC=C1 ZUYQAYFMISSPTF-UHFFFAOYSA-N 0.000 description 3
- 229920006380 polyphenylene oxide Polymers 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- 150000003440 styrenes Chemical class 0.000 description 3
- 230000035900 sweating Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229920001169 thermoplastic Polymers 0.000 description 3
- 239000004416 thermosoftening plastic Substances 0.000 description 3
- 125000003944 tolyl group Chemical group 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 229920005669 high impact polystyrene Polymers 0.000 description 2
- 239000004797 high-impact polystyrene Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- SPWDQSXYMZXSIV-UHFFFAOYSA-N 11,12-dimethyldocosane Chemical group CCCCCCCCCCC(C)C(C)CCCCCCCCCC SPWDQSXYMZXSIV-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- UQRONKZLYKUEMO-UHFFFAOYSA-N 4-methyl-1-(2,4,6-trimethylphenyl)pent-4-en-2-one Chemical group CC(=C)CC(=O)Cc1c(C)cc(C)cc1C UQRONKZLYKUEMO-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000008045 alkali metal halides Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 125000000853 cresyl group Chemical group C1(=CC=C(C=C1)C)* 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- KSHDLNQYVGBYHZ-UHFFFAOYSA-N dibutylphosphinic acid Chemical compound CCCCP(O)(=O)CCCC KSHDLNQYVGBYHZ-UHFFFAOYSA-N 0.000 description 1
- MLCHBQKMVKNBOV-UHFFFAOYSA-M dioxido(phenyl)phosphanium Chemical compound [O-]P(=O)C1=CC=CC=C1 MLCHBQKMVKNBOV-UHFFFAOYSA-M 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
- C08G79/14—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing two or more elements other than carbon, oxygen, nitrogen, sulfur and silicon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L85/00—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers
- C08L85/02—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers containing phosphorus
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
Selbstverldschende thermoplastische FormmassenSelf-sealing thermoplastic molding compounds
Die Erfindung betrifft selbstverlöschende thermoplastische Formmassen, enthaltend A) 70 bis 10 Gew.-Teile eines Polymerisates einer vinylaromatischen Verbindung, B) 30 bis 90 Gew.-Teile eines Polyphenylenethers, C) 1 bis 20 Gew.-Teile eines Flammschutzzusatzes sowie D) - gegebenenfalls - übliche Zusatzstoffe in wirksamen Mengen, die nach Entzündung mit einer heißen Flamme in wenigen Sekunden verlöschen und nicht brennend abtropfen.The invention relates to self-extinguishing thermoplastic molding compositions, containing A) 70 to 10 parts by weight of a polymer of a vinyl aromatic compound, B) 30 to 90 parts by weight of a polyphenylene ether, C) 1 to 20 parts by weight of a flame retardant additive and D) - if necessary - customary additives in effective amounts, which after inflammation Extinguish with a hot flame in a few seconds and do not drip off burning.
Thermoplastische Formmassen, die sich zur Herstellung von Formteilen eignen, die schlagfest modifizierte Styrolpolymerisate und Polyphenylenether enthalten und selbstverlöschend sind, sind z.B. aus der DE-AS 20 37 510 und der US-PS 3 809 729 bekannt. Diese Formmassen enthalten zur Flammfestausrüstung sowohl eine aromatische Phosphorkomponente als auch eine aromatische Halogenverbindung. Aufgrund der korrosiv wirkenden Verbrennungsgase bei Einsatz von halogenhaltigen Substanzen sind aber halogenfreie selbstverlöschende Formmassen erstrebenswert.Thermoplastic molding compounds, which are used for the production of molded parts which contain impact-resistant modified styrene polymers and polyphenylene ethers and are self-extinguishing, are for example from DE-AS 20 37 510 and US-PS 3,809 729 known. These molding compounds contain both an aromatic compound for the flame retardant finish Phosphorus component as well as an aromatic halogen compound. Due to the corrosive effective combustion gases when using halogen-containing substances are halogen-free self-extinguishing molding compounds are desirable.
Es können aber auch ohne Zusatz von Halogenverbindungen unter Verwendung von aromatischen Phosphaten und cyclischen Phosphonaten bzw. Phosphaten, wie beispielsweise in den US-PSen 3 883 613, 4 154 775 und der DE-OS 28 36 771 9 beschrieben3 selbstverlöschende Formmassen erhalten werden; diese besitzen aber eine wesentlich verschlechterte Wärneformbeständigkeit, schwitzen bei der Verarbeitung aus und verursachen eine starke Gelb färbung der nach der Verarbeitung resultierenden Formteile.But it can also be used without the addition of halogen compounds of aromatic phosphates and cyclic phosphonates or phosphates, such as in U.S. Patents 3,883,613, 4,154,775 and DE-OS 2,836,771 9 described 3 self-extinguishing molding compositions are obtained; but these have an essential deteriorated heat resistance, exudes during processing and causes a strong yellow coloration of the molded parts resulting after processing.
Der vorliegenden Erfindung lag daher die Aufgabe zugrunde, thermoplastische Formmassen auf der Grundlage von Styrolpolymerisaten und Polyphenylenethern zu schaffen, die nach Entzündung mit einer heißen Flamme in wenigen Sekunden verlöschen, nicht brennend abtropfen, keine Halogen-Flamm schutzmittel enthalten, eine hohe Wärmeformbeständigkeit besitzen, ohne Ausschwitzen zu verarbeiten sind und eine geringe Eigenfarbe aufweisen.The present invention was therefore based on the object of thermoplastic To create molding compounds based on styrene polymers and polyphenylene ethers, which go out in a few seconds after ignition with a hot flame, not drip while burning, do not contain halogen flame retardants, high heat resistance can be processed without exuding and have a low inherent color.
Diese Aufgabe wird in den erfinduflgsgemäßen Formmassen dadurch gelöst daß als Flammschutzmittel anorganische KoordinationspolZmere eingesetzt werden, die organische Phosphorverbindung mit Phosphor in der Hauptkette und in -der Oxidationsstufe + 1 enthalten.This object is achieved in the molding compositions according to the invention that inorganic coordination polymers are used as flame retardants, the organic phosphorus compound with phosphorus in the main chain and in the oxidation state + 1 included.
Gegenstand der Erfindung sind dementsprechend selbstverlöschende thermoplastische Formmassen, enthaltend A) 70 bis 10 Gew.-Teile eines Polymersats einer monovinylaromatischen Verbindung, B) 30 bis 90 Gew.-Teile eines Polyphenylenethers, C) 1 bis 20 Gew.-Teile eines Flammschutzzusatzes, sowie D) - gegebenenfalls - übliche Zusatzstoffe in wirksamen Mengen.The invention accordingly relates to self-extinguishing thermoplastics Molding compositions containing A) 70 to 10 parts by weight of a polymer of a monovinylaromatic Compound, B) 30 to 90 parts by weight of a polyphenylene ether, C) 1 to 20 parts by weight a flame retardant additive, as well as D) - if necessary - usual additives in effective Amounts.
Die erfindungsgmäBen Formmassen sind dadurch gekennzeichnet, daß als Flammschutzzusatz anorganische Koordinationspolymere eingesetzt werden, die organische Phosphorverbindungen mit Phosphor in der Oxidationsstufe + 1 als zentrale Bausteine enthalten.The molding compositions according to the invention are characterized in that as Flame retardant additive inorganic coordination polymers are used, the organic Phosphorus compounds with phosphorus in the + 1 oxidation state as central building blocks contain.
Unter Formmassen sollen Mischungen verstanden werden, die sich durch thermoplastische Verarbeitung innerhalb bestimmter Temperaturbereiche zu Formteilen oder zu Halbzeug verarbeiten lassen. Die Formmassen können als Granulat vorliegen, sie können aber auch pulverförmig oder durch Tablettierung vorgeformt oder in Form von Platten oder Bahnen vorliegen.Molding compositions are to be understood as meaning mixtures which are characterized by thermoplastic processing into molded parts within certain temperature ranges or have it processed into semi-finished products. The molding compounds can be in the form of granules, but they can also be preformed in powder form or by tableting or in the form of panels or webs.
Die Komponente A) der erfindungsgemäBen Formmassen soll wenigstens ein Polymerisat einer monovinylaromatischen Verbindung sein, wobei bis zu 40 Gew.% an Styrol durch andere Comonomere ersetzt sein können. Als monovinylaromatische Verbindungen kommen dabei insbesondere Styrol in Betracht, ferner die kern- oder seitenketten-alkylierten Styrole Vorzugsweise wird aber Styrol allein verwendet.Component A) of the molding compositions according to the invention should at least be a polymer of a monovinylaromatic compound, with up to 40 wt.% on styrene can be replaced by other comonomers. As monovinyl aromatic Compounds come into consideration in particular styrene, furthermore the core or Side-chain alkylated styrenes Preferably, however, styrene is used alone.
Als Comonomere kommen beispielsweise Äcrylnitril, Maleinsäureanhydrid und Ester der Acrylsäure bzw. Methacrylsäure in Frage. Es können auch mehrere Comonomere gleichzeitig verwendet werden. Bei der Komponente A) kann es sich aber auch insbesondere um schlagfest modifiziertes Polystyrol handeln.Examples of comonomers are acrylonitrile and maleic anhydride and esters of acrylic acid or methacrylic acid in question. Several comonomers can also be used can be used at the same time. In the case of component A), however, it can also be in particular be impact-resistant modified polystyrene.
Die meist angewandten Verfahren zur Herstellung schlagzäh modifizierter Styrolpolymerisate sind die Polymerisation in Masse oder Lösung, wie es beispielsweise in der US-PS 2 694 692 beschrieben ist und Verfahren zur Masse--Suspensionspolymerisation, wie sie beispielsweise in der US-PS 2-862 906 beschrieben sind. Selbstverständlich sind auch andere Verfahren anwendbar.The most commonly used process for the production of impact modified Styrene polymers are polymerization in bulk or solution, as it is for example is described in US-PS 2,694,692 and process for mass - suspension polymerization, as described, for example, in US Pat. No. 2-862,906. Of course other methods can also be used.
L Als Kautschuke werden die üblicherweise für die Schlagfestmodifizierung von Styrolpolymerisaten gebräuchlichen natürlichen oder synthetischen Kautschuke eingesetzt.L. The rubbers are usually used for the Impact modification of styrene polymers common natural or synthetic rubbers are used.
Geeignete Kautschuke im Sinne der Erfindung sind neben Naturkautschuk z.B. Polybutadien, Polyisopren und Mischpolymerisate des Butadiens und/oder Isoprens mit Styrol und anderen Comonomeren, die eine Glastemperatur unter -20°C besitzen. Besondere eignen sich Butadien-Polymerisate mit einem 1,4-cis-Gehalt, der zwischen 25 und 98 % liegt. Ebenso können aber auch EPDM-, Butyl- und Polyacrylsäurealkylester-Kautschuke eingesetzt werden.Suitable rubbers for the purposes of the invention are natural rubber e.g. polybutadiene, polyisoprene and copolymers of butadiene and / or isoprene with styrene and other comonomers that have a glass transition temperature below -20 ° C. Butadiene polymers with a 1,4-cis content between 25 and 98%. However, EPDM, butyl and polyacrylic acid alkyl ester rubbers can also be used can be used.
Als Komponente B) kommen Polyphenylenether auf der Basis von in ortho-Position disubstituierten Polyphenylenoxiden in Frage, wobei der Ethersauerstoff der einen Einheit an den Benzolkern der benachbarten Einheit gebunden ist.Polyphenylene ethers based on in the ortho position are used as component B) disubstituted polyphenylene oxides in question, the ether oxygen of the one Unit is bound to the benzene nucleus of the neighboring unit.
Dabei sollen mindestens 50 Einheiten miteinander verknüpft sein. Die Polyphenylenether können in ortho-Stellung zum Sauerstoff, Wasserstoff, Halogen, Kohlenwasserstoffe, die kein 0<-ständiges tertiäres Wasserstoffatom besitzen, Ealogenkohlenwasserstoffe, Phenyl rest und Kohlenwasserstoff-oxy-Reste tragen. So kommen in Frage: Poly(2,5-dichlor-1,4-phenylen)ether, Poly(2,6-diphenyl-1,4-phenylen)-ether, Poly(2,6-dimethoxy-1,4-phenylen)ether, Poly(2,6-dimethyl-1,4-phenylen)ether, Poly(2 ,6-dibrom-1,4-phenylen)-ether, Bevorzugterweise wird der Poly(2,6-dimethyl-1,4--phenylen)ether eingesetzt. Besonders bevorzugt sind dabei Poly(2,6-dimethyl-1 ,4-phenylen)ether mit einer Grenzviskosität von 0,40 bis 0,65 dl/g (gemessen in Chloroform bei 30°C).At least 50 units should be linked to one another. the Polyphenylene ethers can be in the ortho position to the oxygen, hydrogen, halogen, Hydrocarbons that do not have a 0 <tertiary hydrogen atom, Carrying halogenated hydrocarbons, phenyl residues and hydrocarbon-oxy residues. So are possible: poly (2,5-dichloro-1,4-phenylene) ether, poly (2,6-diphenyl-1,4-phenylene) ether, Poly (2,6-dimethoxy-1,4-phenylene) ether, poly (2,6-dimethyl-1,4-phenylene) ether, poly (2 , 6-dibromo-1,4-phenylene) ether, the poly (2,6-dimethyl-1,4-phenylene) ether is preferred used. Poly (2,6-dimethyl-1,4-phenylene) ethers are particularly preferred with an intrinsic viscosity of 0.40 to 0.65 dl / g (measured in chloroform at 30 ° C).
Die Polyphenylenether können z.B. in Gegenwart von komplexbildenden Mitteln wie Kupferbromid und sek.-Dibutylamin aus den Phenolen hergestellt werden.The polyphenylene ethers can, for example, in the presence of complexing agents Agents like copper bromide and sec-dibutylamine are made from the phenols.
Als Flammschutzzusatz Komponente C) der erfindungsgemäßen Formmassen werden anorganische Koordinationspolymere folgender allgemeiner Strukturformeln (I), (II), (III), (IV) eingesetzt: Die Phosphinatgruppen können zudem in ein und derselben Verbindung als lineare und als verbrückende Bausteine, so wie es in den allgemeinen Formel (IV) beschrieben ist, auftreten.Inorganic coordination polymers of the following general structural formulas (I), (II), (III), (IV) are used as the flame retardant additive component C) of the molding compositions according to the invention: The phosphinate groups can also occur in one and the same compound as linear and bridging building blocks, as described in general formula (IV).
J Diese anorganischen Koordinationspolymeren sind gekennzeichnet durch Metallatome M als koordinative Verknüpfungsstelle und organischen Phosphorverbindungen mit Phosphor in der Oxidationsstufe + 1 als zentralen Bausteinen.J These inorganic coordination polymers are characterized by metal atoms M as the coordinative point of attachment and organic phosphorus compounds with phosphorus in the + 1 oxidation state as central building blocks.
Lineare Koordinationspolymere vom Typ I enthalten Alkali-Metalle, insbesondere Lithium, Natrium, Kalium und/oder Rubidium als Koordinationselement M1. Die Reste R1 und R2 können gleich oder verschieden sein. Da die erfindungsgemaßen Flammschutzmittel Jedoch Bausteine aus organischen Phosphorverbindungen mit Phosphor in der Oxidationsstufe + 1 - unter Oxidationsstufe ist der in U. Hofmann und W. Rüdorfs "Lehrbuch Anorganische Chemie", Vieweg--Verlag, Braunschweig, (1969) auf Seite 308 wiedergegebene Begriff zu verstehen - enthalten, stellen die Reste R1 und R2 substituierte und/oder unsubstituierte Phenylreste und/oder verzweigte und/oder unverzweigte Alkylgruppen mit 1 bis 18 C-Atomen dar. Typische Beispiele für die Reste R1 und R2 sind die Phenyl, Tolyl-, Kresyl-, Mesityl-, Nonylphenyl-, und Naphthyl-Gruppen sowie die Methyl-, Ethyl-, n-Butyl-, tert.-Butyl-, Ethylhexyl-, Dodecyl-, Octadecyl--Gruppe u.a.Type I linear coordination polymers contain alkali metals, in particular lithium, sodium, potassium and / or rubidium as a coordination element M1. The radicals R1 and R2 can be identical or different. Since the inventive Flame retardants However, building blocks from organic phosphorus compounds with phosphorus in the oxidation state + 1 - under the oxidation state is the one described in U. Hofmann and W. Rüdorfs "Textbook Inorganic Chemistry", Vieweg - Verlag, Braunschweig, (1969) Page 308 to understand the term reproduced - contain, represent the radicals R1 and R2 substituted and / or unsubstituted phenyl radicals and / or branched and / or unbranched alkyl groups with 1 to 18 carbon atoms. Typical examples of the R1 and R2 radicals are the phenyl, tolyl, cresyl, mesityl, nonylphenyl and naphthyl groups and the methyl, ethyl, n-butyl, tert-butyl, ethylhexyl, dodecyl, octadecyl groups i.a.
Typische Beispiele für diese linearen Poly-alkalimetallphosphinate (s. allgemeine Formel I) Poly[natrium(I)-methyl-phenylphosphinat] (M = Na; R1 = CH2; R2 = C6H5) Poly[kalium(I)-methyl-phenylphosphinat] (M = K; R1 = CH3; R2 = C6H5) Poly[lithium[I]-methyl-phenylphosphinat] (M = Li; R1 = CH2; R2 = C6H5) Poly[natrium(I)-dodecyl-phenylphosphinat] (M = Na; R¹ = C12H25; R² = C6H5) Poly[natrium(I)-bisphenylphosphinat] (M = Na; R1 = R2 = C6H5) Poly[natrium(I)-bisdodecylphosphinat] (M = Na; R1 = R2 = C12H25) Poly[natrium(I)-phenyl-tolyl-phosphinat] (M = Na; R1 = C6H5; R2 = C6H4-CH3) Der Polymerisationsgrad n der linearen Koordinationspolymeren von Typ der Polyalkalimetallphosphinate I beträgt 2 bis 30 und wurde mittels Dampfdruckosmometrie in einem Mechrolab-Osmometer an 0,5-%igen Lösungen der Polymeren in Pyridin bestimmt.Typical examples of these linear poly-alkali metal phosphinates (see general formula I) Poly [sodium (I) methyl phenylphosphinate] (M = Na; R1 = CH2; R2 = C6H5) Poly [potassium (I) -methyl-phenylphosphinate] (M = K; R1 = CH3; R2 = C6H5) Poly [lithium [I] methyl phenyl phosphinate] (M = Li; R1 = CH2; R2 = C6H5) poly [sodium (I) dodecyl phenyl phosphinate] (M = Na; R¹ = C12H25; R² = C6H5) poly [sodium (I) bisphenylphosphinate] (M = Na; R1 = R2 = C6H5) poly [sodium (I) bisdodecyl phosphinate] (M = Na; R1 = R2 = C12H25) poly [sodium (I) phenyl tolyl phosphinate] (M = Na; R1 = C6H5; R2 = C6H4-CH3) The degree of polymerization n of the linear coordination polymers of the type of polyalkali metal phosphinates I is 2 to 30 and was determined by means of vapor pressure osmometry determined in a Mechrolab osmometer on 0.5% solutions of the polymers in pyridine.
Die Herstellung der linearen Polymetallphosphinate erfolgt beispielsweise durch die Umsetzung von Alkalimetallhalo-' geniden mit neutralen Estern organisch substituierter Phosphinsäuren wird es z.B. von C.M. Mikulski et.al in J. Inorg.The production of the linear polymetallic phosphinates takes place, for example organic through the reaction of alkali metal halides with neutral esters substituted phosphinic acids it is e.g. Mikulski et al in J. Inorg.
Nucl. Chem. 43, (1981) 225 beschrieben wird.Nucl. Chem. 43, (1981) 225.
Cyclische Koordinationspolymere vom Typ II sind wohlbekannt.Type II cyclic coordination polymers are well known.
Ihre Herstellung wird beispielsweise von G.H. Dahl und B.P. Bock in Inorg. Chem. 6, (1967) 1439 und W. Sbrensen und T.W. Cambell in Präparative Methoden der Polymeren--Chemie, Verlag Chemie, Weinheim (1962) S. 198 oder von H.O. Gilmän in Inorg. Chem., 13, (1974) 1921 ausführlich beschrieben. Als zentrale Verknüpfungsstellen M2 kommen in Frage Si, Ge, Pb, Zn, Cd, Cu, Co, Ni, Fe, V, V=O, Ti=O, mit R = R1 = Alkyl, Zr=O, Hf=O. They are manufactured, for example, by GH Dahl and BP Bock in Inorg. Chem. 6, (1967) 1439 and W. Sbrensen and TW Cambell in Preparative Methods of Polymers - Chemie, Verlag Chemie, Weinheim (1962) p. 198 or by HO Gilmän in Inorg. Chem., 13, (1974) 1921 in detail. The central connection points M2 are Si, Ge, Pb, Zn, Cd, Cu, Co, Ni, Fe, V, V = O, Ti = O, with R = R1 = alkyl, Zr = O, Hf = O.
Zr, Die Reste R1 und R2 entsprechen denen in den zuvor beschriebenen linearen Poly-(alkalimetallphosphinaten).Zr, The radicals R1 and R2 correspond to those in those described above linear poly (alkali metal phosphinates).
Typische Beispiele dieser erfindungsgemäsen cyclischen Poly(metallphosphinate) vom Typ II sind Ti(IV)phosphinat--Polymere mit R1 = R2 = Phenyl, Tolyl, Methyl oder Decyl, Zr(IV)phosphinat-Polymere mit R1 = R2 = Phenyl und/oder Dodecyl. Weitere erfindungsgemäße Beispiele sind Poly[Zn(II)-dibutyl-co-dioctyl-phosphinat] (M2 = Zn; R1 = R2 = n-C4Hg/und n-C8H17) Poly[Zn(II)-bis(diphenylphosphinat)] (M2 = Zn, R1 = R2 = C6H5) PolyEMn(II)-bis(dioctylphosphinat)] (M2 = Mn, R1 = R2 = octyl) PQlyiPb(II)-bis(diphenylphosphinat)] (M2 = Pb, R1 = R2 = C6H5) Der Polymerisationsgrad n der cyclischen Polymetallphosphinate liegt zwischen 3 und 30, vorzugsweise zwischen 4 und 20. Die Bestimmung von n erfolgte dampfdruckosmometrisch in einem Mechrolab-Osmometer an 0,5 %igen Lösungen in Chloroform.Typical examples of these cyclic poly (metal phosphinates) according to the invention Type II are Ti (IV) phosphinate polymers with R1 = R2 = phenyl, tolyl, methyl or Decyl, Zr (IV) phosphinate polymers with R1 = R2 = phenyl and / or dodecyl. Further Examples according to the invention are poly [Zn (II) -dibutyl-co-dioctyl-phosphinate] (M2 = Zn; R1 = R2 = n-C4Hg / and n-C8H17) poly [Zn (II) bis (diphenylphosphinate)] (M2 = Zn, R1 = R2 = C6H5) PolyEMn (II) -bis (dioctylphosphinate)] (M2 = Mn, R1 = R2 = octyl) PQlyiPb (II) -bis (diphenylphosphinate)] (M2 = Pb, R1 = R2 = C6H5) The degree of polymerization n of the cyclic polymetallic phosphinates is between 3 and 30, preferably between 4 and 20. n was determined vapor pressure osmometry in a Mechrolab osmometer on 0.5% solutions in chloroform.
Cyclische Koordinationspolymere vom Typ III sind ebenfalls bekannt. Ihre Herstellung wird beispielsweise von PO Nannelli et.al. in J. Polym, Sci., Part A-1 (1971), S. 3027 oder in J. Polym. Sci., Polym. Chem. Ed., 11 (1973) S. 2691 ausführlich beschrieben. Als zentrale Verknüpfungsstellen M3 kommen in Frage Al und Cr(III).Type III cyclic coordination polymers are also known. Their production is for example by PO Nannelli et.al. in J. Polym, Sci., Part A-1 (1971), p. 3027 or in J. Polym. Sci., Polym. Chem. Ed., 11 (1973) S. 2691 described in detail. As central connection points M3 come into question Al and Cr (III).
Die Reste R1 und R2 entsprechen denen der zuvor beschriebenen linearen Poly(alkalimetallphosphinate).The radicals R1 and R2 correspond to those of the linear ones described above Poly (alkali metal phosphinates).
Typische Beispiele dieser erfindungsgemäßen cyclischen Poly(metallphosphinate) des Typs III sind Poly(Cr(III)tris(methylphenylphosphinat) 3 (M3 = Cr, R1 = CH3, R2 = C6X5) Poly(Cr(III)bis(dioctylphosphinat)-co-dimethylphosphinat3 (M3 = Cr, R1 = R2 = C8H17 und 0113) Poly[Cr(III)tris(diphenylphosphinat)] (M3Cr, R1 = R2 = C6H5) Poly[Al(III)tris(diphenylphosphinat)] (M3 = Al, R1 = R2 = C6H5) Der Polymerisationsgrad n der cyclischen Poly(metallphosphinate) des Typs III liegt zwischen 3 und 30, vorzugsweise zwischen 4 und 20. Die Bestimmung von n erfolgte dampfdruckosmometrisch in einem Mechrolab-Osmometer an 0,5 %igen Lösungen der Polymere in Chloroform oder Tetrahydrofuran.Typical examples of these cyclic poly (metal phosphinates) according to the invention of type III are poly (Cr (III) tris (methylphenylphosphinate) 3 (M3 = Cr, R1 = CH3, R2 = C6X5) Poly (Cr (III) bis (dioctylphosphinate) -co-dimethylphosphinate3 (M3 = Cr, R1 = R2 = C8H17 and 0113) poly [Cr (III) tris (diphenylphosphinate)] (M3Cr, R1 = R2 = C6H5) Poly [Al (III) tris (diphenylphosphinate)] (M3 = Al, R1 = R2 = C6H5) The degree of polymerization n of the cyclic poly (metal phosphinates) of type III is between 3 and 30, preferably between 4 and 20. n was determined by vapor pressure osmometry in one Mechrolab osmometer on 0.5% solutions of the polymers in chloroform or tetrahydrofuran.
Alternierend tricyclische und lineare Koordinationspolymere vom Typ IV werden beispielsweise von V. Giancotti et al.Alternating tricyclic and linear coordination polymers of the type IV are for example by V. Giancotti et al.
in Die Makromolekulare Chemie, 120 (1968), S. 96 oder von T.S. Wei et al. in Phys. Rev. 1312 (1975), 5297 ausführlich beschrieben. Als zentrale Verbindungsstellen M4 kommen in Frage Be, Zn und Co. Die Reste R¹ und R² entsprechen denen der zuvor beschriebenen linearen Poly(alkalimetallphosphinate).in Die Makromolekulare Chemie, 120 (1968), p. 96 or by T.S. White et al. in phys. Rev. 1312 (1975), 5297 described in detail. As central liaison points M4 are Be, Zn and Co. The radicals R¹ and R² correspond to those of the previous one described linear poly (alkali metal phosphinates).
9 Typische Beispiele dieser erfindungsgemäßen alternierend tricyclischen und linearen Polymeren des Typs IV sind PolyEBe(II)-bis(di-n-butylphosphinat) 3 Poly(Co(II)-co-Zn(II)-bis(dioctylphosphinat) 3. 9 Typical examples of these alternating tricyclic ones according to the invention and linear polymers of type IV are PolyEBe (II) bis (di-n-butylphosphinate) 3 Poly (Co (II) -co-Zn (II) -bis (dioctylphosphinate) 3.
Der Polymerisationsgrad n der alternierend tricyclischen und linearen Polymeren des Typs IV liegt zwischen 3 und 30, vorzugsweise zwischen 4 und 20. Die Bestimmung von n erfolgt dampfdruckosmometrisch in einem Mechrolab-Osmometer an 0,5 %igen Lösungen der Polymeren in Chlorofonm.The degree of polymerization n of the alternating tricyclic and linear Type IV polymers is between 3 and 30, preferably between 4 and 20. The N is determined by vapor pressure osmometry in a Mechrolab osmometer 0.5% solutions of the polymers in chlorofonm.
Die Mischungen können als Komponente D weitere Zusatzstoffe, wie Pigmente, Füllstoffe3 Oligo- und Polymere, Antistatika, Antioxidantien und Schmiermittel enthalten.As component D, the mixtures can contain further additives, such as pigments, Fillers3 Contain oligomers and polymers, antistatic agents, antioxidants and lubricants.
Man stellt die erfindungsgemäßen thermoplastischen Formmassen wie üblich auf Vorrichtungen, die ein homogenes Mischen zulassen, wie Knetern, Extrudern oder Walzenmischgeräten her.The thermoplastic molding compositions according to the invention are produced as Usually on devices that allow homogeneous mixing, such as kneaders, extruders or roller mixers.
Neben der Eigenschaft der Selbstverlöschung besitzen Form-.In addition to the property of self-extinction, form.
teile aus den erfindungsgemäßen Formmassen hohe Wärmeformbeständigkeiten und eine ausgezeichnete helle Eigenfarbe.parts of the molding compositions according to the invention have high heat resistance and an excellent light inherent color.
Während der Verarbeitung wird kein Ausschwitzen des Flammschutzzusatzes und damit auch keine Abscheidungen auf den Innenwänden von Verarbeitungsmaschinen, z.B. Spritzgußmaschinen, festgestellt. Alle zum Vergleich durchgeführten, nicht erfindungsgemäßen Formmassen besitzen dagegen wesent-1 ich niedere Wärmeformbeständigkeiten und eine starke Gelbfärbung, zudem beobachtet man bei der Verarbeitung häufig ein Ausschwitzen des Flammschutzzusatzes.There is no exudation of the flame retardant additive during processing and therefore no deposits on the inner walls of processing machines, e.g. injection molding machines. All performed for comparison, not In contrast, molding compositions according to the invention have substantially low heat resistance and a strong yellow color, in addition one often observes during processing Exudation of the flame retardant additive.
Die Flammschutzprüfung erfolgt im vertikalen Brandtest nach den Vorschriften der Underwriter Laboratories zwecks Einordnung in eine der Brandklassen 94 VE-O, 94 VE-1 oder 94 VE-2.The flame retardancy test is carried out in the vertical fire test according to the regulations the Underwriter Laboratories for the purpose of classification in one of the fire classes 94 VE-O, 94 VE-1 or 94 VE-2.
Die Wàrmeformbeständigkeit wurde nach Vicat nach DIN 53 460/B ermittelt.The heat resistance was determined according to Vicat according to DIN 53 460 / B.
Die Gelbfärbung der Formteile wurde anhand des Gelbwertes (DIN ) beurteilt. Das Ausschwitzen des Flammschutzmittels während der Verarbeitung wurde visuell beurteilt.The yellow coloration of the molded parts was assessed using the yellowness index (DIN). The exudation of the flame retardant during processing was assessed visually.
In den Tabellen ist Aus schwitzen mit + und kein Ausschwitzen mit - festgehalten.In the tables, sweating out is shown with + and no sweating with - held.
Beispiele und Vergleichsversuche Die in der Tabelle angegebenen Gewichtsteile an Polystyrol, Poly(2,6-dimethyl-1,4-phenylen)ether und an Flammschutzzusatz werden auf einem Zweiwellenextruder bei 3000C geschmolzen, homogenisiert, gemischt und granuliert.Examples and comparative experiments The parts by weight given in the table on polystyrene, poly (2,6-dimethyl-1,4-phenylene) ether and on flame retardant additives melted on a twin-screw extruder at 3000C, homogenized, mixed and granulated.
Zur Beurteilung des Ausschwitzens wurde auf einer Schneckenspritzgußmaschine Krauss-Maffei Typ KM 265-1120 eine Kühlschrankbox gespritzt. Die Temperatur im Plastifizierextruder in Höhe der Einspritzdüse betrug 2800C, die Temperatur im Werkzeug betrug 7000. Nach 10 Spritzgußvorgängen (Gesamtcycluszeit Jeweils 35 sec) wurden die Innenwände des Werkzeugs auf Formbelag und die Spritzteile selbst auf Abscheidungen untersucht.The exudation was assessed on a screw injection molding machine Krauss-Maffei type KM 265-1120 injected a refrigerator box. The temperature in the plasticizing extruder at the level of the injection nozzle was 2800C, the temperature in the mold was 7000. After 10 injection molding processes (total cycle time 35 seconds in each case) the inner walls were of the tool for mold deposits and the molded parts themselves for deposits.
J Tabelle Beispiele/ HIPS/PPO-Blend Kompo. A+B Struktur- Komponente C Brand- Vicat Gelb- Aus-Vergleichs- Komp. A Komp. B (Gew.-Tle) formel (Gew.-Tle) klasse wert schwitversuch (Tle) (Tle) n. [°C] zen HIPS PPO UL 94 1 30 70 90 I Poly-[Na(I)-bis- VE 0 163 -diphenylphosphinat], 10 2 50 50 90 II Poly-[Ti(IV)-oxo- VE 1 164 -bisdiphenylphosphinat], 10 3 50 50 85 II Poly-[Ti(IV)-oxo- VE 0 145 -bisdiphenylphosphinat], 15 4 60 40 80 II Poly-[Ti(IV)-oxo- VE 0 129 -bisdiphenylphosphinat], 20 5 40 60 90 II Poly-[Ti(IV)-oxo- VE 0 157 -bisdiphenylphosphinat], 10 6 30 70 92 II Poly-[Ti(IV)-oxo- VE 0 165 -bisdiphenylphosphinat], 8 7 50 50 82 II Poly-[Ti(IV)-oxo- VE 0 144 -bisdiphenylphosphinat], 18 8 30 70 90 II Poly-[Ti(IV)-oxo- VE 0 164 -bisdiphenylphosphinat], 10 9 30 70 88 III Poly-[Al(III)-tris- VE 0 166 -diphenylphosphinat], 12 10 30 70 90 IV Poly-[Co(II)-Co- VE 0 167 --Zn(II)-bis-diphenylphosphinat], 10 A 50 50 92 - Triphenylphosphinat VE 0 117 +J Table examples / HIPS / PPO blend compo. A + B structure Component C Brand Vicat Yellow Comp. A Comp. B (parts by weight) formula (Parts by weight) class value sweating test (parts) (parts) n. [° C] zen HIPS PPO UL 94 1 30 70 90 I poly- [Na (I) -bis- VE 0 163 -diphenylphosphinate], 10 2 50 50 90 II poly- [Ti (IV) -oxo- VE 1 164 -bisdiphenylphosphinate], 10 3 50 50 85 II Poly- [Ti (IV) -oxo- VE 0 145 -bisdiphenylphosphinate], 15 4 60 40 80 II poly- [Ti (IV) -oxo- VE 0 129 -bisdiphenylphosphinate], 20 5 40 60 90 II Poly- [Ti (IV) -oxo- VE 0 157 -bisdiphenylphosphinate], 10 6 30 70 92 II Poly- [Ti (IV) -oxo- VE 0 165 -bisdiphenylphosphinate], 8 7 50 50 82 II Poly- [Ti (IV) -oxo- VE 0 144 -bisdiphenylphosphinate], 18 8 30 70 90 II poly- [Ti (IV) -oxo- VE 0 164 -bisdiphenylphosphinate], 10 9 30 70 88 III Poly- [Al (III) -tris- VE 0 166 -diphenylphosphinate], 12 10 30 70 90 IV Poly- [Co (II) -Co- VE 0 167 - Zn (II) -bis-diphenylphosphinate], 10 A 50 50 92 - Triphenylphosphinate VE 0 117 +
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0192154A2 (en) | 1985-02-12 | 1986-08-27 | BASF Aktiengesellschaft | Self-extinguishing thermoplastic composition not containing halogen |
| WO1998039381A1 (en) * | 1997-03-04 | 1998-09-11 | Ticona Gmbh | Flameproof polymer moulding material |
| DE10323116A1 (en) * | 2003-05-22 | 2004-12-16 | Clariant Gmbh | Titanium-containing phosphinate flame retardants |
| EP1712270A1 (en) * | 2005-04-13 | 2006-10-18 | Gkss-Forschungszentrum Geesthacht Gmbh | Composite material, especially composite membrane and process of manufacture |
| DE102008038410A1 (en) | 2007-09-11 | 2009-03-12 | Basf Se | Thermoplastic molding material, useful e.g. for preparing fibers, foil and molded body, comprises thermoplastic polyesters, flame retardant e.g. expandable graphite and fluorine containing polymer and additives |
| DE102008038411A1 (en) | 2007-09-11 | 2009-03-12 | Basf Se | Thermoplastic molding material, useful e.g. for preparing fibers, foil and molded body, comprises thermoplastic polyamide, flame retardant e.g. expandable graphite and fluorine containing polymer, and additives |
| WO2011009877A1 (en) | 2009-07-24 | 2011-01-27 | Basf Se | Flameproofed polyamide molding compounds |
| WO2011039292A1 (en) | 2009-10-01 | 2011-04-07 | Basf Se | Method for producing functionalized expandable graphite intercalation compounds |
| WO2011039301A1 (en) | 2009-10-01 | 2011-04-07 | Basf Se | Functionalized expandable graphite intercalation compounds |
| WO2011051121A1 (en) | 2009-10-27 | 2011-05-05 | Basf Se | Heat aging-resistant polyamides with flame retardancy |
| WO2011138384A1 (en) | 2010-05-05 | 2011-11-10 | Basf Se | Component comprising an insert part and plastics jacketing and process for the production thereof |
| WO2012013564A1 (en) | 2010-07-30 | 2012-02-02 | Basf Se | Flameproofed molding compounds |
| WO2012049264A2 (en) | 2010-10-15 | 2012-04-19 | Basf Se | Method for producing flame-proofed thermoplastic molding compounds |
| WO2012080388A1 (en) | 2010-12-16 | 2012-06-21 | Basf Se | Rubber-modified flame-retardant moulding compositions and production thereof |
| US8481624B2 (en) | 2007-09-28 | 2013-07-09 | Styrolution GmbH | Methods for producing flameproofed thermoplastic moulding compounds |
-
1981
- 1981-10-13 DE DE19813140520 patent/DE3140520A1/en not_active Withdrawn
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0192154A2 (en) | 1985-02-12 | 1986-08-27 | BASF Aktiengesellschaft | Self-extinguishing thermoplastic composition not containing halogen |
| WO1998039381A1 (en) * | 1997-03-04 | 1998-09-11 | Ticona Gmbh | Flameproof polymer moulding material |
| DE10323116A1 (en) * | 2003-05-22 | 2004-12-16 | Clariant Gmbh | Titanium-containing phosphinate flame retardants |
| EP1712270A1 (en) * | 2005-04-13 | 2006-10-18 | Gkss-Forschungszentrum Geesthacht Gmbh | Composite material, especially composite membrane and process of manufacture |
| DE102008038410A1 (en) | 2007-09-11 | 2009-03-12 | Basf Se | Thermoplastic molding material, useful e.g. for preparing fibers, foil and molded body, comprises thermoplastic polyesters, flame retardant e.g. expandable graphite and fluorine containing polymer and additives |
| DE102008038411A1 (en) | 2007-09-11 | 2009-03-12 | Basf Se | Thermoplastic molding material, useful e.g. for preparing fibers, foil and molded body, comprises thermoplastic polyamide, flame retardant e.g. expandable graphite and fluorine containing polymer, and additives |
| US8481624B2 (en) | 2007-09-28 | 2013-07-09 | Styrolution GmbH | Methods for producing flameproofed thermoplastic moulding compounds |
| WO2011009877A1 (en) | 2009-07-24 | 2011-01-27 | Basf Se | Flameproofed polyamide molding compounds |
| WO2011039301A1 (en) | 2009-10-01 | 2011-04-07 | Basf Se | Functionalized expandable graphite intercalation compounds |
| WO2011039292A1 (en) | 2009-10-01 | 2011-04-07 | Basf Se | Method for producing functionalized expandable graphite intercalation compounds |
| WO2011051121A1 (en) | 2009-10-27 | 2011-05-05 | Basf Se | Heat aging-resistant polyamides with flame retardancy |
| WO2011138384A1 (en) | 2010-05-05 | 2011-11-10 | Basf Se | Component comprising an insert part and plastics jacketing and process for the production thereof |
| WO2012013564A1 (en) | 2010-07-30 | 2012-02-02 | Basf Se | Flameproofed molding compounds |
| WO2012049264A2 (en) | 2010-10-15 | 2012-04-19 | Basf Se | Method for producing flame-proofed thermoplastic molding compounds |
| US9034949B2 (en) | 2010-10-15 | 2015-05-19 | Styrolution Europe Gmbh | Method for producing flame-proofed thermoplastic molding compounds |
| WO2012080388A1 (en) | 2010-12-16 | 2012-06-21 | Basf Se | Rubber-modified flame-retardant moulding compositions and production thereof |
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