DE19813136C1 - 3,5-Di-tert-butyl-4-hydroxyphenylpropionic acid esters - Google Patents

3,5-Di-tert-butyl-4-hydroxyphenylpropionic acid esters

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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
Application number
DE19813136A
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German (de)
Inventor
Hansjuergen Dr Rabe
Pramod Dr Gupta
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Original Assignee
Bayer AG
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Filing date
Publication date
Priority to DE19813136A priority Critical patent/DE19813136C1/en
Application filed by Bayer AG filed Critical Bayer AG
Priority to KR1020007010539A priority patent/KR20010042135A/en
Priority to PCT/EP1999/001689 priority patent/WO1999048863A1/en
Priority to EP99913256A priority patent/EP1082296A1/en
Priority to CN99804416A priority patent/CN1294575A/en
Priority to BR9909029-5A priority patent/BR9909029A/en
Priority to AU31451/99A priority patent/AU3145199A/en
Priority to CA002325034A priority patent/CA2325034A1/en
Priority to JP2000537847A priority patent/JP2002507594A/en
Priority to TW088104181A priority patent/TW461898B/en
Application granted granted Critical
Publication of DE19813136C1 publication Critical patent/DE19813136C1/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C263/00Preparation of derivatives of isocyanic acid
    • C07C263/18Separation; Purification; Stabilisation; Use of additives

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  • 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

The use of 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid esters (I) as stabilizers for organic polyisocyanates is claimed.

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).  

Beispiel 1 example 1

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)

Beispiel 2 Example 2

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.  

FZ (APHA)FC (APHA) Probe ASample A 100100 Probe BSample B 4040 Probe CSample C 250250 vor der Bestrahlungbefore the irradiation 0-50-5

Beispiel 3 Example 3

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)

1. Verwendung von 3,5-Di-tert.-butyl-4-hydroxyphenylpropionsäureestern als Stabilisatoren für organische Polyisocyanate.1. Use of 3,5-di-tert-butyl-4-hydroxyphenylpropionsäureestern as Stabilizers for organic polyisocyanates. 2. Verwendung nach Anspruch 1, dadurch gekennzeichnet, daß der 3,5-Di-tert.- butyl-4-hydroxy-phenylpropionsäuremethylester (BHPME) als Stabilisator für organische Polyisocyanate eingesetzt wird.2. Use according to claim 1, characterized in that the 3,5-di-tert.- Butyl-4-hydroxy-phenylpropionic acid methyl ester (BHPME) as a stabilizer for organic polyisocyanates is used. 3. Verwendung nach Anspruch 1, dadurch gekennzeichnet, daß die 3,5-Di-tert.- butyl-4-hydroxy-phenylpropionsäureester in Mengen von 0,001 bis 0,1 Gew.-%, bezogen auf die Polyisocyanate, eingesetzt werden.3. Use according to claim 1, characterized in that the 3,5-di-tert.- butyl-4-hydroxy-phenylpropionic acid ester in amounts of 0.001 to 0.1 % By weight, based on the polyisocyanates. 4. Verwendung der Hydroxyphenylpropionsäureester nach Anspruch 1 in Kombination mit an sich bekannten Stabilisatoren für Polyisocyanate.4. Use of the Hydroxyphenylpropionsäureester according to claim 1 in Combination with known stabilizers for polyisocyanates.
DE19813136A 1998-03-25 1998-03-25 3,5-Di-tert-butyl-4-hydroxyphenylpropionic acid esters Expired - Fee Related DE19813136C1 (en)

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

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DE19813136C1 true DE19813136C1 (en) 1999-07-15

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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)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
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

Patent Citations (4)

* Cited by examiner, † Cited by third party
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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