DE19813136C1 - 3,5-Di-tert-butyl-4-hydroxyphenylpropionic acid esters - Google Patents
3,5-Di-tert-butyl-4-hydroxyphenylpropionic acid estersInfo
- Publication number
- DE19813136C1 DE19813136C1 DE19813136A DE19813136A DE19813136C1 DE 19813136 C1 DE19813136 C1 DE 19813136C1 DE 19813136 A DE19813136 A DE 19813136A DE 19813136 A DE19813136 A DE 19813136A DE 19813136 C1 DE19813136 C1 DE 19813136C1
- Authority
- DE
- Germany
- Prior art keywords
- tert
- butyl
- polyisocyanates
- acid esters
- hydroxyphenylpropionic acid
- 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 - Fee Related
Links
Classifications
-
- 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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyurethanes Or Polyureas (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
Die vorliegende Erfindung betrifft die Verwendung von 3,5-Di-tert.-butyl-4-hydroxy phenylpropionsäureestern zur Stabilisierung von Polyisocyanaten.The present invention relates to the use of 3,5-di-tert-butyl-4-hydroxy Phenylpropionsäureestern for the stabilization of polyisocyanates.
Die organischen Isocyanate haben für die Herstellung von Polyurethan-Kunststoffen hohe Bedeutung erlangt. So werden z. B. die organischen Polyisocyanate mit Polyolen (Polyether- und Polyesterpolyole) für die Schaumstoff-, Faser-, Film-, Elastomer- und Lack-Herstellung eingesetzt.The organic isocyanates have for the production of polyurethane plastics gained great importance. So z. As the organic polyisocyanates with polyols (Polyether and polyester polyols) for the foam, fiber, film, elastomer and Lacquer preparation used.
Die organischen Polyisocyanate neigen jedoch bei Lagerung, auch bei niedrigen Temperaturen, zur Verfärbung. Diese Eigenschaft ist besonders ausgeprägt, wenn die Lagerung bei höheren Temperaturen erfolgen muß, z. B. wenn die festen Polyiso cyanate für eine homogene Reaktionsführung mit Reaktionspartnern, wie Polyether polyolen, Polyesterpolyolen oder Glykolen, zu Urethanen umgesetzt werden sollen. Auch bei der Präpolymerherstellung muß die NCO-OH-Reaktion bei höheren Temperaturen durchgeführt werden. Dabei wird beobachtet, daß die Isocyanate sich sehr schnell verfärben, wenn keine Stabilisierung vorgenommen wurde.However, the organic polyisocyanates tend to be stored, even at low levels Temperatures, for discoloration. This property is particularly pronounced when the Storage at higher temperatures must be done, for. B. if the solid polyiso cyanates for a homogeneous reaction with reactants, such as polyethers polyols, polyester polyols or glycols to be converted to urethanes. Even in prepolymer production, the NCO-OH reaction at higher Temperatures are carried out. It is observed that the isocyanates themselves discolor very quickly if no stabilization has been made.
Es wurde bereits vorgeschlagen, verschiedene Stabilisatoren organischen Polyiso cyanaten zuzusetzen, um die Verfärbungsneigung der organischen Polyisocyanate zu verringern. Bekannte Stabilisatoren sind z. B. sterisch gehinderte Phenole, Di alkyldiphenylamine, Phenothiazine, Phosphite bzw. Gemische von Vertretern aus diesen Substanzklassen (vgl. z. B. US 3 715 301, US 4 064 157, DE-OS 16 68 275, DE-AS 16 18 845).It has already been proposed various stabilizers organic polyiso cyanates add to the discoloration tendency of the organic polyisocyanates to decrease. Known stabilizers are z. As sterically hindered phenols, di Alkyldiphenylamine, phenothiazines, phosphites or mixtures of representatives of these classes of substances (cf., for example, US Pat. Nos. 3,715,301, 4,064,157, DE-OS 16 68 275, US Pat. DE-AS 16 18 845).
Am häufigsten findet 2,6-Di-tert.-butyl-4-methylphenol (BHT) allein oder in Kombi nation mit weiteren Verbindungen der angeführten Stabilisatorenklassen Verwendung zur Stabilisierung von organischen Polyisocyanaten. Most commonly, 2,6-di-tert-butyl-4-methylphenol (BHT) is found alone or in combination nation with further compounds of the listed stabilizer classes use for the stabilization of organic polyisocyanates.
Nachteil von BHT ist die relativ hohe Flüchtigkeit und Migrationstendenz in Poly urethane umhüllende Substrate sowie die daraus resultierende starke Gelbfärbung der Substrate in NOX-belasteter Atmosphäre. Stabilisatoren ohne diese Nachteile sind da her von Interesse und es war Aufgabe der vorliegenden Erfindung, solche Materialien bereitzustellen.Disadvantage of BHT is the relatively high volatility and migration tendency in poly urethane enveloping substrates and the resulting strong yellowing of the substrates in NO X -belasteter atmosphere. Stabilizers without these disadvantages are therefore of interest and it is an object of the present invention to provide such materials.
Gegenstand der vorliegenden Erfindung ist die Verwendung von 3,5-Di-tert.-butyl-4- hydroxy-phenylpropionsäure-estern als Stabilisatoren für organische Polyisocyanate, insbesondere für aromatische Polyisocyanate.The present invention is the use of 3,5-di-tert-butyl-4- hydroxy-phenylpropionic acid esters as stabilizers for organic polyisocyanates, in particular for aromatic polyisocyanates.
Als Ester der genannten Phenylpropionsäure kommen vor allem in Frage: der Methyl-, Ethyl-, Propyl- und Tert.-Butylester, insbesondere der Methylester (BHPME).As esters of said phenylpropionic acid are in particular: the methyl, Ethyl, propyl and tert-butyl esters, in particular the methyl ester (BHPME).
Umsetzungen mit Polyisocyanaten verlangen eine ausgewogene Reaktivität, die auch durch Spuren anderer Verbindungen, wie z. B. Antioxidantien, nicht beeinflußt werden sollen.Reactions with polyisocyanates require a balanced reactivity, too by traces of other compounds, such as. As antioxidants, are not affected should.
Überraschenderweise hat sich gezeigt, daß schon geringste Mengen von 3,5-Di-tert.- butyl-4-hydroxyphenylpropionsäure-ester von 0,001 bis 0,1 Gew.-%, vorzugsweise 0,001 bis 0,003 Gew.-%, bezogen auf Polyisocyanat, wirksam sind.Surprisingly, it has been shown that even the smallest amounts of 3,5-di-tert.- Butyl-4-hydroxyphenylpropionic acid ester of 0.001 to 0.1 wt .-%, preferably 0.001 to 0.003 wt .-%, based on polyisocyanate, are effective.
BHPME der z. B. durch basisch katalysierte Addition von Acrylsäuremethylester an 2,6-Di-tert.-butylphenol hergestellt wird und im Handel erhältlich ist, eignet sich bei allen gebräuchlichen Polyisocyanaten, einschließlich aliphatischen, aromatischen und cycloaliphatischen Polyisocyanaten. Als Beispiele sind zu erwähnen: Ethylendiiso cyanat, Tetramethylendiisocyanat, Hexamethylendiisocyanat, 4,4'-Methylen-bis-(cy clohexyldiisocyanat), m-Phenylendiisocyanat, p-Phenylendiisocyanat, Toluylen-2,4-di isocyanat, Toluylen-2,6-diisocyanat, 4,4'-Methylen-bis-(phenylisocyanat), 2,3'-Methylen-bis-(phenylisocyanat), 2,3-Methylen-bis-(phenylisocyanat), Toluylen- 2,4,6-triisocyanat. BHPME the z. B. by basic catalyzed addition of methyl acrylate 2,6-di-tert-butylphenol is prepared and commercially available, is useful in all common polyisocyanates, including aliphatic, aromatic and cycloaliphatic polyisocyanates. Examples include: ethylenediiso cyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, 4,4'-methylene bis (cy clohexyl diisocyanate), m-phenylene diisocyanate, p-phenylene diisocyanate, toluene-2,4-di isocyanate, tolylene-2,6-diisocyanate, 4,4'-methylene-bis- (phenyl isocyanate), 2,3'-methylene bis (phenyl isocyanate), 2,3-methylene bis (phenyl isocyanate), tolylene 2,4,6-triisocyanate.
Die erfindungsgemäßen Phenylpropionsäureester können auch in Kombination mit be kannten Isocyanatstabilisatoren eingesetzt werden.The phenylpropionic acid esters according to the invention can also be used in combination with be knew wasocyanate stabilizers can be used.
Die so stabilisierten organischen Polyisocyanate zeigen eine sehr stark verminderte Neigung zur Verfärbung bei Lagerung bei erhöhten Temperaturen und können mit Vorteil für die Herstellung von Polyurethanen eingesetzt werden. Die Polyurethane werden ihrerseits für Schaum-, Film-, Lack- oder Elastomerherstellung verwendet.The thus stabilized organic polyisocyanates show a very greatly reduced Tendency to discoloration when stored at elevated temperatures and can with Advantage be used for the production of polyurethanes. The polyurethanes are in turn used for foam, film, paint or elastomer production.
Gegenstand der vorliegenden Erfindung soll anhand der folgenden Beispiele noch näher erläutert werden (%-Angaben bedeuten jeweils Gew.-% sowie alle Temperatur angaben °C). The present invention is based on the following examples still are explained in more detail (percentages in each case wt .-% and all temperature specifications ° C).
Aus dieser Zusammenstellung geht hervor, daß 10 ppm BHPME-Zusatz eine bessere Stabilisatorwirkung zeigt als 100 ppm Zusatz von BHT.From this compilation shows that 10 ppm BHPME addition a better Stabilizer effect shows as 100 ppm addition of BHT.
* Farbzahl nach DIN 53 409 (Juli '67) bzw. ISO (Juli 1988)* Color number according to DIN 53 409 (July '67) or ISO (July 1988)
Die Proben wurden einem UV-Bestrahlungstest unterzogen, um das Vergilbungs verhalten zu untersuchen. Nach 70 Stunden Belichtung wurden von diesen Proben Farbzahlen nach APHA vermessen. The samples were subjected to a UV irradiation test to determine the yellowing to investigate behavior. After 70 hours exposure were from these samples Measure color numbers according to APHA.
Das Isocyanat wurde 5 mal auf 60°C erwärmt und wieder abgekühlt.The isocyanate was heated 5 times to 60 ° C and cooled again.
Claims (4)
Priority Applications (10)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19813136A DE19813136C1 (en) | 1998-03-25 | 1998-03-25 | 3,5-Di-tert-butyl-4-hydroxyphenylpropionic acid esters |
PCT/EP1999/001689 WO1999048863A1 (en) | 1998-03-25 | 1999-03-15 | Stabilisation of organic polyisocyanates |
EP99913256A EP1082296A1 (en) | 1998-03-25 | 1999-03-15 | Stabilisation of organic polyisocyanates |
CN99804416A CN1294575A (en) | 1998-03-25 | 1999-03-15 | Stabilisation of organic polyisocyanates |
KR1020007010539A KR20010042135A (en) | 1998-03-25 | 1999-03-15 | Stabilisation of Organic Polyisocyanates |
BR9909029-5A BR9909029A (en) | 1998-03-25 | 1999-03-15 | Stabilization of organic polyisocyanates |
AU31451/99A AU3145199A (en) | 1998-03-25 | 1999-03-15 | Stabilisation of organic polyisocyanates |
CA002325034A CA2325034A1 (en) | 1998-03-25 | 1999-03-15 | Stabilisation of organic polyisocyanates |
JP2000537847A JP2002507594A (en) | 1998-03-25 | 1999-03-15 | Stabilizers for organic polyisocyanates |
TW088104181A TW461898B (en) | 1998-03-25 | 1999-03-18 | Stabilisation of organic polyisocyanates |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19813136A DE19813136C1 (en) | 1998-03-25 | 1998-03-25 | 3,5-Di-tert-butyl-4-hydroxyphenylpropionic acid esters |
Publications (1)
Publication Number | Publication Date |
---|---|
DE19813136C1 true DE19813136C1 (en) | 1999-07-15 |
Family
ID=7862279
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DE19813136A Expired - Fee Related DE19813136C1 (en) | 1998-03-25 | 1998-03-25 | 3,5-Di-tert-butyl-4-hydroxyphenylpropionic acid esters |
Country Status (10)
Country | Link |
---|---|
EP (1) | EP1082296A1 (en) |
JP (1) | JP2002507594A (en) |
KR (1) | KR20010042135A (en) |
CN (1) | CN1294575A (en) |
AU (1) | AU3145199A (en) |
BR (1) | BR9909029A (en) |
CA (1) | CA2325034A1 (en) |
DE (1) | DE19813136C1 (en) |
TW (1) | TW461898B (en) |
WO (1) | WO1999048863A1 (en) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11548975B2 (en) | 2016-10-14 | 2023-01-10 | Asahi Kasei Kabushiki Kaisha | Isocyanate composition and method for producing isocyanate polymer |
EP3527593A4 (en) | 2016-10-14 | 2019-10-30 | Asahi Kasei Kabushiki Kaisha | Isocyanate composition, production method for isocyanate composition, and production method for isocyanate polymer |
CN108003072B (en) * | 2017-12-04 | 2020-08-28 | 万华化学(宁波)有限公司 | Isocyanate stabilizer and preparation method thereof |
CN110872238B (en) * | 2018-08-31 | 2022-07-12 | 万华化学集团股份有限公司 | Isocyanate stabilizer and preparation method thereof |
CN111228245A (en) * | 2020-02-27 | 2020-06-05 | 华侨大学 | Application of phenolic compound and pharmaceutically acceptable salt thereof in preparation of anti-hepatitis B virus medicine |
TWI754527B (en) * | 2021-01-27 | 2022-02-01 | 宏正自動科技股份有限公司 | Fixing connector |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1618845B (en) * | Sumitomo Chemical Co. Ltd., Osaka (Japan) | Process for the production of storage-stable, liquid toluylene diisocyanate raw mixtures | ||
DE1668275A1 (en) * | 1966-09-23 | 1971-09-23 | Ici Ltd | Process for the stabilization of organic isocyanates |
US3715301A (en) * | 1971-06-30 | 1973-02-06 | Texaco Inc | Multi-hydrotorting of coal |
US4064157A (en) * | 1976-03-29 | 1977-12-20 | The Dow Chemical Company | Stabilization of polyisocyanates against discoloration |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE59101819D1 (en) * | 1990-03-07 | 1994-07-14 | Bayer Ag | Stabilization of organic polyisocyanates. |
EP1023377B1 (en) * | 1997-09-30 | 2003-12-03 | UNIROYAL CHEMICAL COMPANY, Inc. | Stabilized polyether polyol and polyurethane foam obtained therefrom |
-
1998
- 1998-03-25 DE DE19813136A patent/DE19813136C1/en not_active Expired - Fee Related
-
1999
- 1999-03-15 BR BR9909029-5A patent/BR9909029A/en not_active Application Discontinuation
- 1999-03-15 EP EP99913256A patent/EP1082296A1/en not_active Withdrawn
- 1999-03-15 AU AU31451/99A patent/AU3145199A/en not_active Abandoned
- 1999-03-15 WO PCT/EP1999/001689 patent/WO1999048863A1/en not_active Application Discontinuation
- 1999-03-15 CN CN99804416A patent/CN1294575A/en active Pending
- 1999-03-15 KR KR1020007010539A patent/KR20010042135A/en not_active Application Discontinuation
- 1999-03-15 CA CA002325034A patent/CA2325034A1/en not_active Abandoned
- 1999-03-15 JP JP2000537847A patent/JP2002507594A/en active Pending
- 1999-03-18 TW TW088104181A patent/TW461898B/en active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1618845B (en) * | Sumitomo Chemical Co. Ltd., Osaka (Japan) | Process for the production of storage-stable, liquid toluylene diisocyanate raw mixtures | ||
DE1668275A1 (en) * | 1966-09-23 | 1971-09-23 | Ici Ltd | Process for the stabilization of organic isocyanates |
US3715301A (en) * | 1971-06-30 | 1973-02-06 | Texaco Inc | Multi-hydrotorting of coal |
US4064157A (en) * | 1976-03-29 | 1977-12-20 | The Dow Chemical Company | Stabilization of polyisocyanates against discoloration |
Also Published As
Publication number | Publication date |
---|---|
TW461898B (en) | 2001-11-01 |
WO1999048863A1 (en) | 1999-09-30 |
AU3145199A (en) | 1999-10-18 |
BR9909029A (en) | 2000-12-05 |
JP2002507594A (en) | 2002-03-12 |
CA2325034A1 (en) | 1999-09-30 |
EP1082296A1 (en) | 2001-03-14 |
KR20010042135A (en) | 2001-05-25 |
CN1294575A (en) | 2001-05-09 |
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Legal Events
Date | Code | Title | Description |
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8100 | Publication of the examined application without publication of unexamined application | ||
D1 | Grant (no unexamined application published) patent law 81 | ||
8364 | No opposition during term of opposition | ||
8339 | Ceased/non-payment of the annual fee |