DE19630903A1 - Stabilisation of isocyanate against discoloration over wide temperature range - Google Patents
Stabilisation of isocyanate against discoloration over wide temperature rangeInfo
- Publication number
- DE19630903A1 DE19630903A1 DE1996130903 DE19630903A DE19630903A1 DE 19630903 A1 DE19630903 A1 DE 19630903A1 DE 1996130903 DE1996130903 DE 1996130903 DE 19630903 A DE19630903 A DE 19630903A DE 19630903 A1 DE19630903 A1 DE 19630903A1
- Authority
- DE
- Germany
- Prior art keywords
- tert
- phosphite
- butylphenyl
- tris
- bis
- 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- Withdrawn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
- 239000012948 isocyanate Substances 0.000 title claims abstract description 19
- 150000002513 isocyanates Chemical class 0.000 title claims abstract description 18
- 238000002845 discoloration Methods 0.000 title claims abstract description 8
- 230000006641 stabilisation Effects 0.000 title abstract description 5
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims abstract description 11
- -1 phosphorus compound Chemical class 0.000 claims abstract description 10
- 239000007983 Tris buffer Substances 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 239000001273 butane Substances 0.000 claims abstract description 4
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims abstract description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims abstract description 4
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 claims abstract description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 3
- QEDNBHNWMHJNAB-UHFFFAOYSA-N tris(8-methylnonyl) phosphite Chemical compound CC(C)CCCCCCCOP(OCCCCCCCC(C)C)OCCCCCCCC(C)C QEDNBHNWMHJNAB-UHFFFAOYSA-N 0.000 claims abstract description 3
- GXURZKWLMYOCDX-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.OCC(CO)(CO)CO GXURZKWLMYOCDX-UHFFFAOYSA-N 0.000 claims abstract 2
- 150000003018 phosphorus compounds Chemical class 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- 230000000087 stabilizing effect Effects 0.000 claims description 6
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 4
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 4
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 4
- AIBRSVLEQRWAEG-UHFFFAOYSA-N 3,9-bis(2,4-ditert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP1OCC2(COP(OC=3C(=CC(=CC=3)C(C)(C)C)C(C)(C)C)OC2)CO1 AIBRSVLEQRWAEG-UHFFFAOYSA-N 0.000 claims description 3
- ADRNSOYXKABLGT-UHFFFAOYSA-N 8-methylnonyl diphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OCCCCCCCC(C)C)OC1=CC=CC=C1 ADRNSOYXKABLGT-UHFFFAOYSA-N 0.000 claims description 3
- 235000010290 biphenyl Nutrition 0.000 claims description 3
- 239000004305 biphenyl Substances 0.000 claims description 3
- FQUNFJULCYSSOP-UHFFFAOYSA-N bisoctrizole Chemical compound N1=C2C=CC=CC2=NN1C1=CC(C(C)(C)CC(C)(C)C)=CC(CC=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2N=C3C=CC=CC3=N2)O)=C1O FQUNFJULCYSSOP-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 3
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 claims description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 2
- FRCLQKLLFQYUJJ-UHFFFAOYSA-N P(O)(O)O.P(O)(O)O.C(C)(C)(C)C1=C(C(=CC(=C1)C)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1C(C)(C)C)C)C(C)(C)C Chemical compound P(O)(O)O.P(O)(O)O.C(C)(C)(C)C1=C(C(=CC(=C1)C)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1C(C)(C)C)C)C(C)(C)C FRCLQKLLFQYUJJ-UHFFFAOYSA-N 0.000 claims 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 1
- 125000005442 diisocyanate group Chemical group 0.000 claims 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 claims 1
- ZZNRIAJJKFZXIX-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)henicosane-1,3-diol dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.C(CCCCCCCCCCCCCCCCC)C(O)C(CO)(CO)CO ZZNRIAJJKFZXIX-UHFFFAOYSA-N 0.000 abstract 1
- 229910052698 phosphorus Inorganic materials 0.000 abstract 1
- 239000011574 phosphorus Substances 0.000 abstract 1
- 239000003381 stabilizer Substances 0.000 description 5
- 238000003860 storage Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- SSADPHQCUURWSW-UHFFFAOYSA-N 3,9-bis(2,6-ditert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C)=CC(C(C)(C)C)=C1OP1OCC2(COP(OC=3C(=CC(C)=CC=3C(C)(C)C)C(C)(C)C)OC2)CO1 SSADPHQCUURWSW-UHFFFAOYSA-N 0.000 description 2
- 230000000875 corresponding effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- OCSIKZYSDOXRPA-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)-3-octadecylhenicosane-1,3-diol dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.C(CCCCCCCCCCCCCCCCC)C(O)(C(CO)(CO)CO)CCCCCCCCCCCCCCCCCC OCSIKZYSDOXRPA-UHFFFAOYSA-N 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 150000002990 phenothiazines Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- VHJWFHRVXSGQHS-UHFFFAOYSA-N tris(2,6-ditert-butyl-4-methylphenyl) phosphite Chemical compound CC(C)(C)C1=CC(C)=CC(C(C)(C)C)=C1OP(OC=1C(=CC(C)=CC=1C(C)(C)C)C(C)(C)C)OC1=C(C(C)(C)C)C=C(C)C=C1C(C)(C)C VHJWFHRVXSGQHS-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/655—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms
- C07F9/6551—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a four-membered ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C263/00—Preparation of derivatives of isocyanic acid
- C07C263/18—Separation; Purification; Stabilisation; Use of additives
Landscapes
- 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)
- Polyurethanes Or Polyureas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
Die vorliegende Erfindung betrifft die Stabilisierung von Isocyanaten gegen Ver färbung durch Zusatz von speziellen Phosphorverbindungen in Kombination mit Ionol (2,6-Di-tert.-butyl-4-methyl-phenol).The present invention relates to the stabilization of isocyanates against Ver coloring by adding special phosphorus compounds in combination with Ionol (2,6-di-tert-butyl-4-methylphenol).
Organische Isocyanate bzw. Polyisocyanate haben für die Herstellung von Poly urethankunststoffen große Bedeutung. So werden organische Polyisocyanate zur Herstellung von z. B. Schaumstoffen, Fasern, Filmen, Elastomeren und Lacken ein gesetzt.Organic isocyanates or polyisocyanates have for the production of poly urethane plastics of great importance. So organic polyisocyanates become Production of e.g. B. foams, fibers, films, elastomers and paints set.
Organische Isocyanate unterliegen jedoch bei der Lagerung einer Verfärbung. Die se ist besonders ausgeprägt bei höheren Temperaturen sowie bei längerer Lagerzeit. Zur Verringerung dieser Verfärbung werden dem Isocyanat verschiedene Stabilisatoren zugesetzt. Gebräuchliche Stabilisatoren sind sterisch gehinderte Phe nole, Dialkyldiphenylamine, Phenothiazine, Phosphite bzw. Gemische von Vertre tern aus diesen Substanzklassen (s. z. B. US-A-3 715 301, US-A-4 064 157, DE-A- 16 68 275, DE-A-16 18 845, EP-A-445 608, EP-A-617 041, JP-44 032 765). Stan dardmäßig wird von vielen Anwendern eine Kombination von primären und sekundären Antioxidantien (meist sterisch gehinderte Phenole und Phosphite bzw. Schwefelverbindungen) verwendet. Weitverbreitet ist der Einsatz des Systems Ionol/Triphenylphosphit. Der durch dieses System erzielte Stabilisierungseffekt ist jedoch in keiner Weise befriedigend. Die auftretende Verfärbung wird zwar gemin dert, jedoch nicht vermieden. Auch findet die stabilisierende Wirkung häufig nur in einem schmalen Temperaturbereich statt, darüber und darunter kommt es in vielen Fällen zu deutlicher Verfärbung. Stabilisierende Wirkung über einen breiten Temperaturbereich ist insofern von Bedeutung, als daß einige Isocyanate bei hö heren Temperaturen gelagert, andere bei niedrigen Temperaturen verschifft wer den.However, organic isocyanates are subject to discoloration during storage. The It is particularly pronounced at higher temperatures and at longer ones Storage time. To reduce this discoloration, various isocyanates are used Stabilizers added. Common stabilizers are sterically hindered phe nols, dialkyldiphenylamines, phenothiazines, phosphites or mixtures of Vertre ters from these classes of substances (see, for example, US Pat. No. 3,715,301, US Pat. No. 4,064,157, DE-A- 16 68 275, DE-A-16 18 845, EP-A-445 608, EP-A-617 041, JP-44 032 765). Stan a combination of primary and secondary antioxidants (mostly sterically hindered phenols and phosphites or Sulfur compounds) used. The use of the system is widespread Ionol / triphenyl phosphite. The stabilizing effect achieved by this system is however in no way satisfactory. The discoloration that occurs is reduced changes, but not avoided. Also, the stabilizing effect is often only found in a narrow temperature range, above and below it comes in clear discoloration in many cases. Stabilizing effect over a wide Temperature range is important in that some isocyanates at high stored at higher temperatures, others shipped at low temperatures the.
Daher ergab sich die Aufgabe, neue Stabilisierungssysteme zu finden, die sowohl besser stabilisieren als auch in einem breiteren Temperaturbereich einsetzbar sind als die bekannten Systeme.Therefore, the task arose to find new stabilization systems that both stabilize better than can be used in a wider temperature range than the known systems.
Gegenstand der vorliegenden Erfindung ist daher ein Verfahren zur Stabilisierung von Isocyanaten gegen Verfärbung, das dadurch gekennzeichnet ist, daß man die Isocyanate mit einem Gemisch aus Ionol und einer oder mehreren Phosphorverbin dungen versetzt, wobei die Phosphorverbindungen und das Ionol in einer Konzentration von jeweils 10 bis 5 000 ppm, bevorzugt 100 bis 1 000 ppm, einge setzt werden.The present invention therefore relates to a method for stabilization of isocyanates against discoloration, which is characterized in that the Isocyanates with a mixture of ionol and one or more phosphorus compounds added, the phosphorus compounds and the ionol in one Concentration of 10 to 5,000 ppm, preferably 100 to 1,000 ppm, each be set.
Als zu stabilisierende Isocyanate im Sinne der Erfindung werden genannt:
Hexamethylendiisocyanat, Isophorondiisocyanat, Toluylendiisocyanat und Diphe
nylmethandiisocyanat. Bevorzugt stabilisiert werden Toluylen- und Diphenylme
thandiisocyanat, besonders bevorzugt Diphenylmethandiisocyanat.The following are mentioned as isocyanates to be stabilized in the sense of the invention:
Hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate and diphenyl methane diisocyanate. Toluene and diphenyl methane diisocyanate are preferably stabilized, particularly preferably diphenyl methane diisocyanate.
Als Phosphorverbindungen, die als Stabilisatoren in das erfindungsgemäße Verfah
ren eingesetzt werden können, werden genannt:
Tris[(4-methyl-2,6-du-tert.-butyl)phenyl]phosphit, Tris(2,4-di-tert.-butylphenyl)
phosphit, Tris(nonylphenyl)phosphit, Phenyldiisodecylphosphit, Diphenylisodecyl
phosphit, Bis(2,6-di-tert.-butyl-4-methylphenyl)pentaerythritoldiphosphit, 1,1,3-
Tris(2-methyl-4-di-tridecyl-5-tert.-butylphenyl)butan, Bis(2,4-di-tert.-butylphenyl)
pentaerythritoldiphosphit, Bis(octadecyl)pentaerythritoldiphosphit, 4,4′-Bis[2,2′-me
thylenbis-(4,6-di-tert.-butylphenyl)phosphito]alpha, alpha′-dimethyldiphenylmethan,
Triisodecylphosphit, Diphenylisooctylphosphat, Diphenylphosphat sowie die Ver
bindungen (1) und (2):The following are mentioned as phosphorus compounds which can be used as stabilizers in the process according to the invention:
Tris [(4-methyl-2,6-du-tert-butyl) phenyl] phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (nonylphenyl) phosphite, phenyldiisodecyl phosphite, diphenylisodecyl phosphite, bis ( 2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 1,1,3-tris (2-methyl-4-di-tridecyl-5-tert-butylphenyl) butane, bis (2,4- di-tert-butylphenyl) pentaerythritol diphosphite, bis (octadecyl) pentaerythritol diphosphite, 4,4'-bis [2,2'-methylenebis (4,6-di-tert-butylphenyl) phosphito] alpha, alpha'-dimethyldiphenylmethane , Triisodecyl phosphite, diphenyl isooctyl phosphate, diphenyl phosphate and the compounds (1) and (2):
Besonders bevorzugt sind Tris(2,4-di-tert.-butylphenyl)phosphit, Tris(2,4-di-tert.- butylphenyl)phosphit, Tris(nonylphenyl)phosphit, Bis(2,6-di-tert.-butyl-4- methylphenyl)pentaerythritol-diphosphit, 4,4′-Bis[2,2′-methylenbis-(4,6-di-tert.- butyl-phenyl)phosphito]alpha, alpha′-dimethyldiphenylmethan, 1,1,3-Tris(2-methyl- 4-di-tridecyl-6-tert.-butylphenyl)-butan, Diphenylisodecylphosphit, Diphenyl isooctylphosphat, Bis(2,4-di-tert.-butylphenyl)pentaerythritoldiphosphit und Tris[4- methyl-(2,6-di-tert.-butyl)phenyl]phosphit.Tris (2,4-di-tert-butylphenyl) phosphite, tris (2,4-di-tert.- butylphenyl) phosphite, tris (nonylphenyl) phosphite, bis (2,6-di-tert-butyl-4- methylphenyl) pentaerythritol diphosphite, 4,4′-bis [2,2′-methylenebis (4,6-di-tert.- butylphenyl) phosphito] alpha, alpha′-dimethyldiphenylmethane, 1,1,3-tris (2-methyl- 4-di-tridecyl-6-tert-butylphenyl) butane, diphenyl isodecyl phosphite, diphenyl isooctyl phosphate, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite and tris [4- methyl- (2,6-di-tert-butyl) phenyl] phosphite.
Die zuvor genannten Phosphorverbindungen können als Stabilisatoren einzeln oder im beliebigen Gemisch untereinander eingesetzt werden. Dabei kann das günstigste Mischungsverhältnis der Phosphorverbindungen untereinander leicht durch entspre chende Vorversuche ermittelt werden.The aforementioned phosphorus compounds can be used individually or as stabilizers can be used in any mixture with each other. It can be the cheapest Mixing ratio of the phosphorus compounds with each other easily by corre sponding appropriate preliminary tests can be determined.
Die zu stabilisierenden Isocyanate werden nach bekannten Verfahren hergestellt, wie beispielsweise in Houben-Weyl) Methoden der Organischen Chemie, Bd. E4, 4. Aufl., 1983, S. 738 ff. beschrieben.The isocyanates to be stabilized are produced by known processes, as for example in Houben-Weyl) Methods of Organic Chemistry, Vol. E4, 4th ed., 1983, p. 738 ff.
Die Einbringung der Stabilisatoren in die zu stabilisierenden Isocyanate kann in Substanz oder als Masterbatch gelöst im Isocyanat erfolgen.The stabilizers can be introduced into the isocyanates to be stabilized in Substance or masterbatch dissolved in the isocyanate.
Aus den Vergleichsbeispielen kann entnommen werden, daß Phosphite nicht zwin gend bei Isocyanaten eine stabilisierende Wirkung aufweisen. Es war daher beson ders überraschend, daß eine entsprechende Kombination aus sterisch gehindertem Phenol (Ionol) mit den erfindungsgemäßen Phosphorverbindungen eine gute stabilisierende Wirkung für die genannten Isocyanate aufweisen.It can be seen from the comparative examples that phosphites do not tend to have a stabilizing effect with isocyanates. So it was special surprisingly, that a corresponding combination of sterically hindered Phenol (ionol) with the phosphorus compounds according to the invention a good one have a stabilizing effect for the isocyanates mentioned.
Die Screening-Lagerzeitversuche wurden bei den Temperaturen +5°C, RT (23°C) und +53°C durchgeführt. Diese sollen den Temperaturbereich abdecken, welcher bei Lagerung, Transport und Aufschmelzen der Isocyanate relevant ist. Pro Lager temperatur wurden so viele Proben gelagert, wie Farbzahlmessungen vorgesehen waren. Dies hatte den Vorteil, daß bei der Farbzahlmessung die für spätere Mes sungen vorgesehene Substanzmenge unangetastet blieb. Die Farbzahlmessung er folgte im Reagenzglas durch optischen Vergleich mit einer Hazen-Farbskala (siehe Tabelle).The screening storage time tests were carried out at temperatures + 5 ° C, RT (23 ° C) and + 53 ° C. These are intended to cover the temperature range which is relevant for storage, transport and melting of the isocyanates. Per camp As many samples as the number of color measurements were stored at the temperature were. This had the advantage that when measuring the color number, it was used for subsequent measurements The intended amount of substance remained untouched. The color number measurement followed in the test tube by optical comparison with a Hazen color scale (see Table).
Claims (4)
Tris[(4-methyl-2,6-du-tert.-butyl)phenyl]phosphit, Tris(2,4-di-tert.-butylphe nyl)-phosphit, Tris(nonylphenyl)phosphit, Phenyldiisodecylphosphit, Diphe nylisodecylphosphit, Bis(2,6-di-tert.-butyl-4-methylphenyl)pentaerythritoldi phosphit, 1,1,3-Tris(2-methyl-4-di-tridecyl-5-tert.-butylphenyl)butan, Bis- (2,4-di-tert.-butylphenyl)-pentaerythritoldiphosphit, Bis(octadecyl)pentaery thritoldiphosphit, 4,4′-Bis[2,2′-methylenbis-(4,6-di-tert.-butylphenyl)phos phito]alpha, alpha′-dimethyldiphenylmethan, Triisodecylphosphit, Diphe nylisooctylphosphat, Diphenylphosphat sowie die Verbindungen (1) und (2) 4. The method according to claim 1, characterized in that compounds are used as Phosphor ver:
Tris [(4-methyl-2,6-du-tert-butyl) phenyl] phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (nonylphenyl) phosphite, phenyldiisodecyl phosphite, diphenylisodecyl phosphite, Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol di-phosphite, 1,1,3-tris (2-methyl-4-di-tridecyl-5-tert-butylphenyl) butane, bis- ( 2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (octadecyl) pentaery thritol diphosphite, 4,4′-bis [2,2′-methylenebis (4,6-di-tert-butylphenyl) phos phito] alpha, alpha′-dimethyldiphenylmethane, triisodecyl phosphite, diphenyl isooctyl phosphate, diphenyl phosphate and the compounds (1) and (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE1996130903 DE19630903A1 (en) | 1996-08-01 | 1996-08-01 | Stabilisation of isocyanate against discoloration over wide temperature range |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE1996130903 DE19630903A1 (en) | 1996-08-01 | 1996-08-01 | Stabilisation of isocyanate against discoloration over wide temperature range |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE19630903A1 true DE19630903A1 (en) | 1998-02-05 |
Family
ID=7801383
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE1996130903 Withdrawn DE19630903A1 (en) | 1996-08-01 | 1996-08-01 | Stabilisation of isocyanate against discoloration over wide temperature range |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE19630903A1 (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1195395A1 (en) * | 2000-10-06 | 2002-04-10 | Bayer Ag | Thermoplastically processable polyurethane elastomers with improved inherent colour |
| WO2013060614A1 (en) | 2011-10-28 | 2013-05-02 | Basf Se | Colour-stable curing compositions containing polyisocyanates of (cyclo)aliphatic diisocyanates |
| EP3252096A1 (en) * | 2016-05-31 | 2017-12-06 | Basf Se | Use of pentaerythritol diphosphite compounds for stabilizing polyisocyanate compositions |
| EP3305824A1 (en) | 2016-10-07 | 2018-04-11 | Basf Se | Colour stable curing agent compositions containing polyisocyanates of (cyclo)aliphatic diisocyanates |
| EP3431521A1 (en) | 2017-07-20 | 2019-01-23 | Basf Se | Colour stable curing agent compositions containing polyisocyanates of (cyclo)aliphatic diisocyanates |
| EP3560975B1 (en) | 2018-04-25 | 2021-04-07 | Covestro Intellectual Property GmbH & Co. KG | Ionically hydrophilized polyisocyanates and antioxidants |
| EP3560976B1 (en) | 2018-04-25 | 2021-05-26 | Covestro Intellectual Property GmbH & Co. KG | Ionically hydrophilized polyisocyanates and radical scavenger and/or peroxide decomposition agent |
| WO2021151774A1 (en) | 2020-01-30 | 2021-08-05 | Basf Se | Color-stable curing agent compositions comprising water-dispersible polyisocyanates |
| WO2022128925A1 (en) | 2020-12-18 | 2022-06-23 | Basf Se | Color-stable curing agent compositions comprising polyisocyanates of (cyclo)aliphatic diisocyanates |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4331083A1 (en) * | 1993-09-13 | 1995-03-16 | Basf Ag | Storage-stable polyisocyanate compositions obtainable by phosgene-free processes, a process for their preparation and their use |
-
1996
- 1996-08-01 DE DE1996130903 patent/DE19630903A1/en not_active Withdrawn
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4331083A1 (en) * | 1993-09-13 | 1995-03-16 | Basf Ag | Storage-stable polyisocyanate compositions obtainable by phosgene-free processes, a process for their preparation and their use |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6486243B2 (en) | 2000-10-06 | 2002-11-26 | Bayer Aktiengesellschaft | Thermoplastically processable polyurethane elastomers having an improved intrinsic color |
| EP1195395A1 (en) * | 2000-10-06 | 2002-04-10 | Bayer Ag | Thermoplastically processable polyurethane elastomers with improved inherent colour |
| WO2013060614A1 (en) | 2011-10-28 | 2013-05-02 | Basf Se | Colour-stable curing compositions containing polyisocyanates of (cyclo)aliphatic diisocyanates |
| EP3252096A1 (en) * | 2016-05-31 | 2017-12-06 | Basf Se | Use of pentaerythritol diphosphite compounds for stabilizing polyisocyanate compositions |
| US11001730B2 (en) | 2016-10-07 | 2021-05-11 | Basf Se | Colour-stable curing compositions containing polyisocyanates of (cyclo)aliphatic diisocyanates |
| EP3305824A1 (en) | 2016-10-07 | 2018-04-11 | Basf Se | Colour stable curing agent compositions containing polyisocyanates of (cyclo)aliphatic diisocyanates |
| WO2018065344A1 (en) | 2016-10-07 | 2018-04-12 | Basf Se | Colour-stable curing compositions containing polyisocyanates of (cyclo)aliphatic diisocyanates |
| EP3431521A1 (en) | 2017-07-20 | 2019-01-23 | Basf Se | Colour stable curing agent compositions containing polyisocyanates of (cyclo)aliphatic diisocyanates |
| CN110914327A (en) * | 2017-07-20 | 2020-03-24 | 巴斯夫欧洲公司 | Color-stable curing compositions comprising polyisocyanates of (cyclo) aliphatic diisocyanates |
| WO2019016097A1 (en) | 2017-07-20 | 2019-01-24 | Basf Se | Colour-stable curing compositions containing polyisocyanate (cyclo)aliphatic diisocyanates |
| CN110914327B (en) * | 2017-07-20 | 2023-08-22 | 巴斯夫欧洲公司 | Color stable curing composition of polyisocyanates containing alicyclic diisocyanates |
| EP3560975B1 (en) | 2018-04-25 | 2021-04-07 | Covestro Intellectual Property GmbH & Co. KG | Ionically hydrophilized polyisocyanates and antioxidants |
| EP3560976B1 (en) | 2018-04-25 | 2021-05-26 | Covestro Intellectual Property GmbH & Co. KG | Ionically hydrophilized polyisocyanates and radical scavenger and/or peroxide decomposition agent |
| WO2021151774A1 (en) | 2020-01-30 | 2021-08-05 | Basf Se | Color-stable curing agent compositions comprising water-dispersible polyisocyanates |
| WO2022128925A1 (en) | 2020-12-18 | 2022-06-23 | Basf Se | Color-stable curing agent compositions comprising polyisocyanates of (cyclo)aliphatic diisocyanates |
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