EP0000544B1 - Heat stabilized thermoplastic resins containing compounds with phosphorus to phosphorus bonds - Google Patents
Heat stabilized thermoplastic resins containing compounds with phosphorus to phosphorus bonds Download PDFInfo
- Publication number
- EP0000544B1 EP0000544B1 EP78100439A EP78100439A EP0000544B1 EP 0000544 B1 EP0000544 B1 EP 0000544B1 EP 78100439 A EP78100439 A EP 78100439A EP 78100439 A EP78100439 A EP 78100439A EP 0000544 B1 EP0000544 B1 EP 0000544B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- phosphorus
- composition
- polymer
- percent
- organo
- 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.)
- Expired
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- 229910052698 phosphorus Inorganic materials 0.000 title claims description 12
- 239000011574 phosphorus Substances 0.000 title claims description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims description 9
- 150000001875 compounds Chemical class 0.000 title description 9
- 229920005992 thermoplastic resin Polymers 0.000 title description 4
- 239000000203 mixture Substances 0.000 claims description 26
- 229920000642 polymer Polymers 0.000 claims description 12
- 150000002903 organophosphorus compounds Chemical class 0.000 claims description 10
- 229920000515 polycarbonate Polymers 0.000 claims description 8
- 239000004417 polycarbonate Substances 0.000 claims description 8
- 229920001169 thermoplastic Polymers 0.000 claims description 8
- 125000004122 cyclic group Chemical group 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 230000000087 stabilizing effect Effects 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 4
- 125000004104 aryloxy group Chemical group 0.000 claims description 4
- 125000004663 dialkyl amino group Chemical group 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- 125000004437 phosphorous atom Chemical group 0.000 claims description 3
- 229910052717 sulfur Chemical group 0.000 claims description 3
- 239000011593 sulfur Chemical group 0.000 claims description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 24
- 239000003381 stabilizer Substances 0.000 description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- -1 organo phosphorus derivatives Chemical class 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 238000010926 purge Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000155 melt Substances 0.000 description 6
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 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
- IMDXZWRLUZPMDH-UHFFFAOYSA-N dichlorophenylphosphine Chemical compound ClP(Cl)C1=CC=CC=C1 IMDXZWRLUZPMDH-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical compound [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000006188 syrup Substances 0.000 description 2
- 235000020357 syrup Nutrition 0.000 description 2
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 2
- VZMUCIBBVMLEKC-UHFFFAOYSA-N 2-chloro-5,5-dimethyl-1,3,2$l^{5}-dioxaphosphinane 2-oxide Chemical compound CC1(C)COP(Cl)(=O)OC1 VZMUCIBBVMLEKC-UHFFFAOYSA-N 0.000 description 1
- RCMBNTZZKQOSGO-UHFFFAOYSA-N 2-hydroxy-5,5-dimethyl-1,3,2-dioxaphosphinane Chemical compound CC1(C)COP(O)OC1 RCMBNTZZKQOSGO-UHFFFAOYSA-N 0.000 description 1
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 1
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 1
- PFWQHDSRFLRDDN-UHFFFAOYSA-N CC(C)(CO1)COP1(P1(OCC(C)(C)CO1)=O)=O Chemical compound CC(C)(CO1)COP1(P1(OCC(C)(C)CO1)=O)=O PFWQHDSRFLRDDN-UHFFFAOYSA-N 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
- FCSHMCFRCYZTRQ-UHFFFAOYSA-N N,N'-diphenylthiourea Chemical compound C=1C=CC=CC=1NC(=S)NC1=CC=CC=C1 FCSHMCFRCYZTRQ-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920000402 bisphenol A polycarbonate polymer Polymers 0.000 description 1
- XGRJZXREYAXTGV-UHFFFAOYSA-N chlorodiphenylphosphine Chemical compound C=1C=CC=CC=1P(Cl)C1=CC=CC=C1 XGRJZXREYAXTGV-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- OVARTBFNCCXQKS-UHFFFAOYSA-N propan-2-one;hydrate Chemical compound O.CC(C)=O OVARTBFNCCXQKS-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical class OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000001291 vacuum drying Methods 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/5398—Phosphorus bound to sulfur
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
Definitions
- This invention is concerned with the heat and/or oxygen stabilization of thermoplastic resins with organo phosphorus derivatives.
- Organophosphorus compounds are known as stabilizers for thermoplastic material such as tetrakis (2,4-di-t.butylphenyl)-4,4'-bis(phenylyldiphosphonite) or 3,9-di(octadecyloxy)-2,4,8,10-tetra- oxa-3,9-diphosphaspiro-5,5-undecane.
- the invention is directed to a composition
- a is independently 0 or 1, n is 3 to 6, X is oxygen or sulfur, R" R 2 and R 3 are independently dialkylamino, alkoxy, aryloxy, alkyl, aryl, alkaryl, aralkyl, or R 1 and R 2 taken with the P atom represent a cyclic structure having only carbon, phosphorus and oxygen atoms in the cyclic structure.
- a preferred species of the invention is a thermoplastic polycarbonate resin containing a compound of the formula
- blends or compositions of this invention are thus useful to make molded parts as in the injection molding of diverse articles such as; for example, cups, glasses, valve fittings and appliances covers.
- thermoplastic resins or polymers which can be used in the compositions of this invention are illustrated by polyalkylenes such as polyethylene, polypropylene and related copolymers; polyvinyl chloride; vinyl polymers such as polystyrene and related copolymers such as styrene-butadiene- acrylonitrile copolymers; acrylic polymers such as polyacrylonitriles and poly(methylmethacrylates) and related copolymers; polyesters such as poly(ethylene terephthalates); and aromatic polycarbonates such as bisphenol A polycarbonate and copolycarbonates with diverse dihydroxy phenols.
- polyalkylenes such as polyethylene, polypropylene and related copolymers
- polyvinyl chloride vinyl polymers such as polystyrene and related copolymers such as styrene-butadiene- acrylonitrile copolymers
- acrylic polymers such as polyacrylonitriles and poly(methylmethacrylates) and related copoly
- a stabilizing amount of the compounds is defined as a range from about 0.01 to about 1.0 percent by weight and preferably about 0.05 to about 0.25 based on the total weight of the polymer.
- compositions of this invention may also be blended with other conventional additives such as ultra violet light stabilizers, antioxidants, dyes and pigments.
- Stabilizer A bis(5,5-dimethyl-2-oxo-1,3,2-dioxaphosphorinanyl), was prepared as follows. Into a flask fitted with stirrer, nitrogen purge, feeding funnel, thermometer, and reflux condenser were charged 50 ml of dry benzene and 4.6 grams (0.1 mole) sodium:paraffin 50:50 dispersion. The mixture was stirred about 30 minutes at room temperature with a slow nitrogen purge and then a solution containing 15 grams, (0.1 mole) of 2-hydroxy-5,5-dimethyl-1 ,3,2-dioxaphosphorinan dissolved in 50 ml of dry benzene was fed in at such a rate that the temperature was kept below 30°C.
- Stabilizer B was prepared as follows. Into a flask equipped with stirrer, nitrogen purge, thermometer, and reflux condenser were charged 175 ml of benzene. The flask was purged with nitrogen to remove the air and then 25 ml of benzene was distilled off to remove any trace of water. The contents were cooled to 25°C and then with stirring 35.8 grams (0.2 mole) of dichlorophenyl phosphine was added, all at once, followed by the addition in the same manner 49.6 grams (0.4 mole) of trimethyl phosphite.
- the mixture was refluxed for three hours, cooled, and transferred to a Rinco flask where the benzene was removed by distillation using high vacuum and 90°C temperature.
- the resulting product was a colorless liquid, having a weight of 53 grams, and upon standing overnight began to crystallize.
- the product was identified by Phosphorus 31 Nuclear Magnetic Resonance to be the compound having the formula:
- Stabilizer C was prepared as follows. 33 grams (0.15 mole) of chlorodiphenylphosphine and 18.6 grams (0.15 mole) of trimethyl phosphite was fed into a flask equipped with stirrer, thermometer, feeding funnel, nitrogen purge, and reflux condenser containing 150 ml of dry benzene. The reaction mixture was refluxed for three hours under a very slow nitrogen purge. The reactants were cooled, transferred to a rotary evaporator where the benzene was removed by distillation under vacuum. 42 grams of a slightly yellowish syrup was recovered. After standing for several days, the syrup crystallized into a composition having a paste-like consistency. After examination by phosphorus-31 NMR, the product was identified as a mixture of 20 percent of and about 40 percent of
- Stabilizer D was prepared as follows. 1.2 grams (0.05 mole) of magnesium was weighed into a 125 ml flask equipped with magnetic stirrer, thermometer, feeding funnel, N 2 purge and reflux condenser. After purging with N 2 50 ml of tetrahydrofuran was added to the magnesium. The contents were stirred while phenyl dichlorophosphine 8.9 grams (0.05 mole) was fed in dropwise with occasional external cooling with a water bath to maintain a reaction temperature of 50° to 60°C. After phosphine addition was completed the contents were stirred at 50°C for four hours. The reaction mixture was cooled to room temperature (25°C), transferred to a separating funnel and washed with 30 ml of water.
- a copolycarbonate of phenolphthalein and Bisphenol A hereinafter known as Polycarbonate E, was prepared by condensing 51.0 kg (112.5 pounds) of Bisphenol A and 17.0 kg (37.5 pounds) of phenolphthalein with 31 kg (68 pounds) of phosgene. The reaction was carried out in a solution of 544 kg (1200 pounds) of methylene chloride and 73.7 kg (162.5 pounds) pyridine in a 757 liters (200 gallon) glass-lined Pfaudler reactor 'PFAUDLER' is a registered Trade Mark. Para tertiary butyl phenol 0.95 kg (2.10 pounds) was added as a terminator to control molecular weight.
- the pyridine hydrochloride formed in the reaction and any excess pyridine was removed by contacting the polymer solution with a solution of 34 kg (76 pounds) of 12N HCI in 114 liters (30 gallons) of distilled water. An aliquot of the polymer solution in methylene chloride was removed and washed two additional times with 30 volume percent distilled water. The water was separated and removed after each wash. Final traces of water were removed by contacting the solution with silica gel. The polymer solution was then filtered, the polymer precipitated with hexane, and air dried.
- the copolycarbonate was 25 weight percent phenolphthalein and had a molecular weight of 33,000 weight average molecular weight by gel permeation chromatography.
- Stabilizers A, B, C and D prepared as above were blended with Polycarbonate E using ethanol as the solvent.
- Stabilizer F was tetrakis (2, 4-di-t-butylphenyl)-4,4'-bis-(phenyldiphosphonite) available as Sandostab P-FPO®. 'Sandostab' is a registered Trade mark of 'SANDOZ'.
- Stabilizer G has 3,9-(di(octadecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro-5,5-undecane available as Weston 618@.
- the stabilizer level was 1000 parts per million.
- compositions were then air dried followed by vacuum drying at 1 10°C for four hours.
- One gram of each composition was weighed into a separate 13 by 100 mm test tube and purged with nitrogen.
- the test tubes were inserted into a 4.4 cm (1-3/4 inch) deep hole in an aluminum block with the temperature being controlled at 350°C.
- the heat cycle time was 30 minutes.
- a nitrogen pad (a pressure of about 3.7 mm of mercury) was maintained on the samples during the heat cycle.
- the polyethylene composition was next subjected to a multiextrusion test employing the same extruder as above, but with the temperature of 260°C. After each pass through the extruder, the melt index of a sample of the extruded composition was determined. A decrease in the melt index signified a breaking down and crosslinking of the polymer. The best stabilizer would result in the smallest change in the melt index.
- Comparative Run E the same polyethylene as in Example 5 was extruded twice at 260°C, the polyethylene in the comparative run not containing any stabilizer.
- the two compositions were vacuum oven dried and then injection molded.
- the molded samples were heat aged in a circulating air oven at 120°C. They were removed at various times and their yellow index was determined according to ASTM-1925-63T. The results of the tests are shown in Table III.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
- This invention is concerned with the heat and/or oxygen stabilization of thermoplastic resins with organo phosphorus derivatives.
- Organophosphorus compounds are known as stabilizers for thermoplastic material such as tetrakis (2,4-di-t.butylphenyl)-4,4'-bis(phenylyldiphosphonite) or 3,9-di(octadecyloxy)-2,4,8,10-tetra- oxa-3,9-diphosphaspiro-5,5-undecane.
- It has been found that compounds having a phosphorus to phosphorus bond are useful to stabilize thermoplastic polymers or resins from the effects of heat and/or oxygen during the molding of a blend containing the polymers and a compound having one or more phosphorus to phosphorus bonds.
- Such compounds are known per se namely by US 2.403.792 teaching their use as extreme pressure lubricating agent, by East German patent 86.394 disclosing their use as starting products for the preparation of stabilizers and by US patent 3.032.591 relating to their use as polymerization accelerator for epoxy resins or as preignition firing suppressants in motor fuels.
- The invention is directed to a composition comprising a thermoplastic polymer and a stabilizing amount of an organo-phosphorus compound having one of the formulas
- A preferred species of the invention is a thermoplastic polycarbonate resin containing a compound of the formula
- The blends or compositions of this invention are thus useful to make molded parts as in the injection molding of diverse articles such as; for example, cups, glasses, valve fittings and appliances covers.
- The thermoplastic resins or polymers which can be used in the compositions of this invention are illustrated by polyalkylenes such as polyethylene, polypropylene and related copolymers; polyvinyl chloride; vinyl polymers such as polystyrene and related copolymers such as styrene-butadiene- acrylonitrile copolymers; acrylic polymers such as polyacrylonitriles and poly(methylmethacrylates) and related copolymers; polyesters such as poly(ethylene terephthalates); and aromatic polycarbonates such as bisphenol A polycarbonate and copolycarbonates with diverse dihydroxy phenols.
- The compounds having at least one phosphorus-to-phosphorus bond which can be used in the invention are illustrated by, and not limited to, the following:
- Ph signifies the phenyl group,
- Me signifies the methyl group,
- Et signifies the ethyl group, and
- i-Pr signifies the isopropyl group.
- For the purposes of this invention a stabilizing amount of the compounds is defined as a range from about 0.01 to about 1.0 percent by weight and preferably about 0.05 to about 0.25 based on the total weight of the polymer.
- The compositions of this invention may also be blended with other conventional additives such as ultra violet light stabilizers, antioxidants, dyes and pigments.
- Stabilizer A, bis(5,5-dimethyl-2-oxo-1,3,2-dioxaphosphorinanyl), was prepared as follows. Into a flask fitted with stirrer, nitrogen purge, feeding funnel, thermometer, and reflux condenser were charged 50 ml of dry benzene and 4.6 grams (0.1 mole) sodium:paraffin 50:50 dispersion. The mixture was stirred about 30 minutes at room temperature with a slow nitrogen purge and then a solution containing 15 grams, (0.1 mole) of 2-hydroxy-5,5-dimethyl-1 ,3,2-dioxaphosphorinan dissolved in 50 ml of dry benzene was fed in at such a rate that the temperature was kept below 30°C. The contents were stirred for 15 minutes at 25°C and then a solution of 12.0 grams (0.066 mole) of 2-chloro-2-oxo-5,5-dimethyl-1 ,3,2-dioxaphosphorinan dissolved in benzene (50 ml) was fed dropwise at 5 to 7°C. The reaction temperature was controlled by rate of addition and an ice acetone-water bath. After the feed was in, the reactants were stirred and digested at 25°C for three hours. The contents were again cooled to 5°C by an external source at which time 100 ml of an aqueous 5 percent NaHC03 solution was added and stirred for a few minutes. The contents were transferred to a separating funnel and allowed to phase out. At the interface a solid forms. The solid was filtered off then dried. It had a melting point of 222°C. The crude product was recrystallized using CHCI3:ethyl acetate (2:1), filtered then washed with water, filtered again then dried. The white needle crystals weighed 5.15 grams and had a melting point of 255°C. The product was identified by phosphorus-31 Nuclear Magnetic Resonance; Infrared; and Mass Spectroscopy as having the formula:
- Stabilizer B was prepared as follows. Into a flask equipped with stirrer, nitrogen purge, thermometer, and reflux condenser were charged 175 ml of benzene. The flask was purged with nitrogen to remove the air and then 25 ml of benzene was distilled off to remove any trace of water. The contents were cooled to 25°C and then with stirring 35.8 grams (0.2 mole) of dichlorophenyl phosphine was added, all at once, followed by the addition in the same manner 49.6 grams (0.4 mole) of trimethyl phosphite. The mixture was refluxed for three hours, cooled, and transferred to a Rinco flask where the benzene was removed by distillation using high vacuum and 90°C temperature. The resulting product was a colorless liquid, having a weight of 53 grams, and upon standing overnight began to crystallize. The product was identified by Phosphorus 31 Nuclear Magnetic Resonance to be the compound having the formula:
- Stabilizer C was prepared as follows. 33 grams (0.15 mole) of chlorodiphenylphosphine and 18.6 grams (0.15 mole) of trimethyl phosphite was fed into a flask equipped with stirrer, thermometer, feeding funnel, nitrogen purge, and reflux condenser containing 150 ml of dry benzene. The reaction mixture was refluxed for three hours under a very slow nitrogen purge. The reactants were cooled, transferred to a rotary evaporator where the benzene was removed by distillation under vacuum. 42 grams of a slightly yellowish syrup was recovered. After standing for several days, the syrup crystallized into a composition having a paste-like consistency. After examination by phosphorus-31 NMR, the product was identified as a mixture of 20 percent of
- Stabilizer D was prepared as follows. 1.2 grams (0.05 mole) of magnesium was weighed into a 125 ml flask equipped with magnetic stirrer, thermometer, feeding funnel, N2 purge and reflux condenser. After purging with N2 50 ml of tetrahydrofuran was added to the magnesium. The contents were stirred while phenyl dichlorophosphine 8.9 grams (0.05 mole) was fed in dropwise with occasional external cooling with a water bath to maintain a reaction temperature of 50° to 60°C. After phosphine addition was completed the contents were stirred at 50°C for four hours. The reaction mixture was cooled to room temperature (25°C), transferred to a separating funnel and washed with 30 ml of water. The water was removed and the oil layer was allowed to evaporate in air to about 50 percent of the original volume. Then a second addition of 30 ml of water precipitated 2.1 grams of a white solid which, when recrystallized from acetonitrile, gave a product with a melting point of 150°C, consistent with reported literature results. The structure of the compound was determined to be as follows:
- A copolycarbonate of phenolphthalein and Bisphenol A, hereinafter known as Polycarbonate E, was prepared by condensing 51.0 kg (112.5 pounds) of Bisphenol A and 17.0 kg (37.5 pounds) of phenolphthalein with 31 kg (68 pounds) of phosgene. The reaction was carried out in a solution of 544 kg (1200 pounds) of methylene chloride and 73.7 kg (162.5 pounds) pyridine in a 757 liters (200 gallon) glass-lined Pfaudler reactor 'PFAUDLER' is a registered Trade Mark. Para tertiary butyl phenol 0.95 kg (2.10 pounds) was added as a terminator to control molecular weight.
- After polymerization, the pyridine hydrochloride formed in the reaction and any excess pyridine was removed by contacting the polymer solution with a solution of 34 kg (76 pounds) of 12N HCI in 114 liters (30 gallons) of distilled water. An aliquot of the polymer solution in methylene chloride was removed and washed two additional times with 30 volume percent distilled water. The water was separated and removed after each wash. Final traces of water were removed by contacting the solution with silica gel. The polymer solution was then filtered, the polymer precipitated with hexane, and air dried.
- The copolycarbonate was 25 weight percent phenolphthalein and had a molecular weight of 33,000 weight average molecular weight by gel permeation chromatography.
- Stabilizers A, B, C and D prepared as above were blended with Polycarbonate E using ethanol as the solvent.
- Comparative Runs A, B, C and D were made employing no stabilizers and two commercially available stabilizers. Stabilizer F was tetrakis (2, 4-di-t-butylphenyl)-4,4'-bis-(phenyldiphosphonite) available as Sandostab P-FPO®. 'Sandostab' is a registered Trade mark of 'SANDOZ'. Stabilizer G has 3,9-(di(octadecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro-5,5-undecane available as Weston 618@. In Examples 1 through 4 and Comparative Runs C and D, the stabilizer level was 1000 parts per million.
- The compositions were then air dried followed by vacuum drying at 1 10°C for four hours. One gram of each composition was weighed into a separate 13 by 100 mm test tube and purged with nitrogen. The test tubes were inserted into a 4.4 cm (1-3/4 inch) deep hole in an aluminum block with the temperature being controlled at 350°C. The heat cycle time was 30 minutes. A nitrogen pad (a pressure of about 3.7 mm of mercury) was maintained on the samples during the heat cycle.
- After the heat cycle, the sample was cooled. The test tube was broken and the composition was dissolved in methylene chloride. The glass particles were removed by filtration and the filtrate was diluted with more methylene chloride to make up a 100 ml solution. The color was determined on the solution by using a "Spectronic" Bausch and Lomb Photometer at 350 m,u and reported in Table I as percent transmittance.
- 6.8 kg (15 pounds) of high density polyethylene having a melt index of 5.0 and a density of 9.962 was dry blended with 3.4 grams (0.12 ounces) of Stabilizer A. The mixture was then double-pass extruded at 149°C on a 3.2 cm (1-1/4 inch) extruder with a nitrogen purge on the feed hopper of the extruder. After blending and extruding, the melt index of the polyethylene composition containing 500 parts per million of Stabilizer A was determined using ASTM Procedure D-1238.
- The polyethylene composition was next subjected to a multiextrusion test employing the same extruder as above, but with the temperature of 260°C. After each pass through the extruder, the melt index of a sample of the extruded composition was determined. A decrease in the melt index signified a breaking down and crosslinking of the polymer. The best stabilizer would result in the smallest change in the melt index. In Comparative Run E, the same polyethylene as in Example 5 was extruded twice at 260°C, the polyethylene in the comparative run not containing any stabilizer.
- The melt index values after extrusion are reported in Table II.
- 300 grams of Polycarbonate E was slurried with approximately 2 liters of distilled water in a Waring Blendor. While the water-polymer slurry was vigorously agitated, a solution of 1.5 grams of Stabilizer G in 15 milliliters of methylene chloride was slowly added. The polycarbonate powder was then collected on a filter and air dried.
- This procedure was repeated adding 1.5 grams of Stabilizer A to 300 grams of Polycarbonate E to give a composition containing 5000 parts per million of Stabilizer A.
- The two compositions were vacuum oven dried and then injection molded. The molded samples were heat aged in a circulating air oven at 120°C. They were removed at various times and their yellow index was determined according to ASTM-1925-63T. The results of the tests are shown in Table III.
- The data in Table III shows that the polycarbonate composition containing Stabilizer A is superior to a commercial stabilizer as far as reducing the level of color formation as determined by the yellow index.
Claims (6)
1. A composition comprising a thermoplastic polymer and a stabilizing amount from about 0.01 to about 1.0 percent by weight based on the total weight of the polymer of an organo phosphorus compound characterized in that the organo phosphorus compound has the formula
wherein a is independently 0 or 1, X is oxygen or sulfur, R1 and R2 are independently dialkylamino, alkoxy, aryloxy, alkyl, aryl, alkaryl, aralkyl, or R1 and R2 taken with the phosphorus atom represent a cyclic structure having only carbon, phosphorus and oxygen atoms in the cyclic structure.
2. A composition comprising a thermoplastic polymer and a stabilizing amount, from about 0.01 to about 1.0 percent by weight based on the total'weight of the polymer, of an organo phosphorus compound characterized in that the organo phosphorus compound has the formula
wherein n is 3 to 6, R1 is dialkylamino, alkoxy, aryloxy, alkyl, aryl, alkaryl or aralkyl.
3. A composition comprising a thermoplastic polymer and a stabilizing amount, from about 0.01 to about 1.0 percent by weight based on the total weight of the polymer, of an organo phosphorus compound characterized in that the organo phosphorus compound has the formula
wherein a is independently 0 or 1, X is oxygen or sulfur, R1 R2 and R3 are independently dialkylamino, alkoxy, aryloxy, alkyl, aryl, alkaryl, aralkyl, or R1 and R2 taken with the phosphorus atom represent a cyclic structure having only carbon, phosphorus and oxygen atoms in the cyclic structure.
4. The composition as in claim 1 wherein the organophosphorus compound has the formula
5. The composition as in anyone of claims 1 to 3 wherein the thermoplastic polymer is a polycarbonate.
6. The composition as in anyone of claims 1 to 3 wherein the organo-phosphorus compound is present in an amount from 0.05 to 0.25 percent by weight based on the total weight of the polymer.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US817326 | 1977-07-20 | ||
| US05/817,326 US4111899A (en) | 1977-07-20 | 1977-07-20 | Heat stabilized thermoplastic resins containing compounds with phosphorus to phosphorus bonds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0000544A1 EP0000544A1 (en) | 1979-02-07 |
| EP0000544B1 true EP0000544B1 (en) | 1982-08-04 |
Family
ID=25222827
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP78100439A Expired EP0000544B1 (en) | 1977-07-20 | 1978-07-19 | Heat stabilized thermoplastic resins containing compounds with phosphorus to phosphorus bonds |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4111899A (en) |
| EP (1) | EP0000544B1 (en) |
| JP (1) | JPS5422447A (en) |
| CA (1) | CA1085542A (en) |
| DE (1) | DE2861986D1 (en) |
| IT (1) | IT1156872B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6713601B2 (en) | 2000-09-12 | 2004-03-30 | Cyclics Corporation | Species modification in macrocyclic polyester oligomers, and compositions prepared thereby |
| US6787632B2 (en) | 2001-10-09 | 2004-09-07 | Cyclics Corporation | Organo-titanate catalysts for preparing pure macrocyclic oligoesters |
| US6831138B2 (en) | 2002-01-07 | 2004-12-14 | Cyclics Corporation | Polymer-containing organo-metal catalysts |
| US7666517B2 (en) | 2001-06-27 | 2010-02-23 | Cyclics Corporation | Isolation, formulation, and shaping of macrocyclic oligoesters |
| US7750109B2 (en) | 2000-09-01 | 2010-07-06 | Cyclics Corporation | Use of a residual oligomer recyclate in the production of macrocyclic polyester oligomer |
| US7767781B2 (en) | 2000-09-01 | 2010-08-03 | Cyclics Corporation | Preparation of low-acid polyalkylene terephthalate and preparation of macrocyclic polyester oligomer therefrom |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6369140B1 (en) * | 1993-03-25 | 2002-04-09 | Clariant Finance (Bvi) Limited | Phosphorus compounds |
| DE19638924A1 (en) * | 1995-09-28 | 1997-04-03 | Sandoz Ag | Phosphorus compounds |
| US6369157B1 (en) | 2000-01-21 | 2002-04-09 | Cyclics Corporation | Blend material including macrocyclic polyester oligomers and processes for polymerizing the same |
| US6420047B2 (en) | 2000-01-21 | 2002-07-16 | Cyclics Corporation | Macrocyclic polyester oligomers and processes for polymerizing the same |
| WO2002018476A2 (en) | 2000-09-01 | 2002-03-07 | Cyclics Corporation | Methods for converting linear polyesters to macrocyclic oligoester compositions and macrocyclic oligoesters |
| US6420048B1 (en) | 2001-06-05 | 2002-07-16 | Cyclics Corporation | High molecular weight copolyesters from macrocyclic oligoesters and cyclic esters |
| US6436549B1 (en) | 2001-07-16 | 2002-08-20 | Cyclics Corporation | Block copolymers from macrocyclic oligoesters and dihydroxyl-functionalized polymers |
| JP5399394B2 (en) * | 2007-09-04 | 2014-01-29 | ビーエーエスエフ ソシエタス・ヨーロピア | Cyclic phosphines as flame retardants |
| EP2478044B1 (en) * | 2009-09-14 | 2013-07-17 | Basf Se | Halogen-free, flame-proof polymer foams containing at least one oligophosphorus compound |
| DE102010040632A1 (en) | 2009-09-14 | 2011-03-17 | Basf Se | New oligophosphorus compounds, useful as flame retardant in foamed or defoamed polymers, preferably polystyrene foam particles of expandable polystyrene or extruded polystyrene foam panels, which are useful for insulation of buildings |
| US8759411B2 (en) * | 2010-02-01 | 2014-06-24 | Basf Se | Derivatives of diphosphines as flame retardants for polyurethanes |
| US20110196052A1 (en) * | 2010-02-05 | 2011-08-11 | Basf Se | Flame retardants |
| WO2015144667A2 (en) * | 2014-03-27 | 2015-10-01 | Basf Se | Heptaphosphorus-derived compounds as flame retardants |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD86394A (en) * | ||||
| US2403792A (en) * | 1942-03-28 | 1946-07-09 | Cities Service Oil Co | Di-phosphorus esters and process of manufacturing |
| US2952701A (en) * | 1957-04-15 | 1960-09-13 | Eastman Kodak Co | Organophosphorus derivatives of 2, 2-dimethyl-1, 3-propanediol |
| US3003996A (en) * | 1959-05-20 | 1961-10-10 | Eastman Kodak Co | Poly-alpha-olefin compositions containing synergistic stabilizer combination |
| NL260852A (en) * | 1960-02-03 | 1900-01-01 | ||
| US3032591A (en) * | 1961-06-05 | 1962-05-01 | American Cyanamid Co | Substituted cyclotetraphosphines |
| US3201369A (en) * | 1961-05-29 | 1965-08-17 | Allied Chem | Heat stable polycarbonates containing metal salts of oxyacids of phosphorus |
| DE1240276B (en) * | 1964-09-23 | 1967-05-11 | Hoechst Ag | Process for stabilizing polyolefins |
| US3450670A (en) * | 1967-01-27 | 1969-06-17 | Gen Electric | Stabilized polyphenylene ether composition |
| US3597511A (en) * | 1968-02-07 | 1971-08-03 | Dow Chemical Co | Process for making bis-alkylene pyrophosphates |
| GB1365502A (en) * | 1971-03-10 | 1974-09-04 | Ici Ltd | Aromatic polymers |
| US3897391A (en) * | 1971-11-01 | 1975-07-29 | Gen Electric | Process for preparing polycarbonate |
| NL7510243A (en) * | 1974-09-04 | 1976-03-08 | Hoechst Ag | STABILIZED POLYALKIN FORM MASS. |
-
1977
- 1977-07-20 US US05/817,326 patent/US4111899A/en not_active Expired - Lifetime
-
1978
- 1978-07-17 CA CA307,528A patent/CA1085542A/en not_active Expired
- 1978-07-19 EP EP78100439A patent/EP0000544B1/en not_active Expired
- 1978-07-19 DE DE7878100439T patent/DE2861986D1/en not_active Expired
- 1978-07-20 IT IT50385/78A patent/IT1156872B/en active
- 1978-07-20 JP JP8890078A patent/JPS5422447A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7750109B2 (en) | 2000-09-01 | 2010-07-06 | Cyclics Corporation | Use of a residual oligomer recyclate in the production of macrocyclic polyester oligomer |
| US7767781B2 (en) | 2000-09-01 | 2010-08-03 | Cyclics Corporation | Preparation of low-acid polyalkylene terephthalate and preparation of macrocyclic polyester oligomer therefrom |
| US6713601B2 (en) | 2000-09-12 | 2004-03-30 | Cyclics Corporation | Species modification in macrocyclic polyester oligomers, and compositions prepared thereby |
| US7666517B2 (en) | 2001-06-27 | 2010-02-23 | Cyclics Corporation | Isolation, formulation, and shaping of macrocyclic oligoesters |
| US6787632B2 (en) | 2001-10-09 | 2004-09-07 | Cyclics Corporation | Organo-titanate catalysts for preparing pure macrocyclic oligoesters |
| US6831138B2 (en) | 2002-01-07 | 2004-12-14 | Cyclics Corporation | Polymer-containing organo-metal catalysts |
Also Published As
| Publication number | Publication date |
|---|---|
| US4111899A (en) | 1978-09-05 |
| DE2861986D1 (en) | 1982-09-30 |
| CA1085542A (en) | 1980-09-09 |
| JPS5422447A (en) | 1979-02-20 |
| IT1156872B (en) | 1987-02-04 |
| IT7850385A0 (en) | 1978-07-20 |
| EP0000544A1 (en) | 1979-02-07 |
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