EP1082296A1 - Stabilisation of organic polyisocyanates - Google Patents

Stabilisation of organic polyisocyanates

Info

Publication number
EP1082296A1
EP1082296A1 EP99913256A EP99913256A EP1082296A1 EP 1082296 A1 EP1082296 A1 EP 1082296A1 EP 99913256 A EP99913256 A EP 99913256A EP 99913256 A EP99913256 A EP 99913256A EP 1082296 A1 EP1082296 A1 EP 1082296A1
Authority
EP
European Patent Office
Prior art keywords
polyisocyanates
organic polyisocyanates
tert
butyl
stabilisation
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Withdrawn
Application number
EP99913256A
Other languages
German (de)
French (fr)
Inventor
Hansjürgen Rabe
Pramod 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
Application filed by Bayer AG filed Critical Bayer AG
Publication of EP1082296A1 publication Critical patent/EP1082296A1/en
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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

Definitions

  • the present invention relates to the use of 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid esters for the stabilization of polyisocyanates.
  • Organic isocyanates have become very important for the production of polyurethane plastics.
  • the organic polyisocyanates with polyols are used for foam, fiber, film, elastomer and paint production.
  • the organic polyisocyanates tend to discolor when stored, even at low temperatures. This property is particularly pronounced if storage must take place at higher temperatures, e.g. if the solid polyisocyanates are to be converted to urethanes for a homogeneous reaction with reactants such as polyether polyols, polyester polyols or glycols. Also in the prepolymer production, the NCO-OH reaction must be carried out at higher temperatures. It is observed that the isocyanates change color very quickly if no stabilization has been carried out.
  • stabilizers are e.g. sterically hindered phenols, dialkyldiphenylamines, phenothiazines, phosphites or mixtures of representatives from these classes of substances (see, for example, US Pat. No. 3,715,301, US Pat. No. 4,064,157, DT-OS 1,668,275,
  • BHT 2,6-di-tert-butyl-4-methylphenol
  • the present invention relates to the use of 3,5-di-tert-butyl-4-hydroxy-phenylpropionic acid esters as stabilizers for organic polyisocyanates, especially for aromatic polyisocyanates.
  • esters of the phenylpropionic acid mentioned: the methyl, ethyl, propyl and tert-butyl ester, in particular the methyl ester (BHPME).
  • Reactions with polyisocyanates require a balanced reactivity, which is also indicated by traces of other compounds, e.g. Antioxidants, should not be affected.
  • BHPME of e.g. is produced by base-catalyzed addition of acrylic acid methyl ester to 2,6-di-tert-butylphenol and is commercially available, is suitable for all common polyisocyanates, including aliphatic, aromatic and cycloaliphatic polyisocyanates.
  • Examples include: ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, 4,4'-methylene bis (cyclohexyl diisocyanate), m-phenylene diisocyanate, p-phenylene diisocyanate, toluene-2,4-diisocyanate, toluene-2,6 -diisocyanate, 4,4'-methylene-bis- (phenyl isocyanate), 2,3'-methylene-bis- (phenyl isocyanate), 2,3-methylene-bis- (phenyl isocyanate), toluene-
  • phenylpropionic acid esters according to the invention can also be used in combination with known isocyanate stabilizers.
  • the polyurethanes are used for foam, film, paint or elastomer production.
  • Isocyanate stabilizer (FZ) color number (ALPHA) * after 6, 15 and 21 days at 50 ° C
  • the isocyanate was heated 5 times to 60 ° C. and cooled again.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present invention relates to the use of 3.5-Di.tert.-butyl-4-hydroxy-phenyl propionic acid esters for stabilisation of organic polyisocyanates.

Description

Stabilisierung von organischen PolyisocyanatenStabilization of organic polyisocyanates
Die vorliegende Erfindung betrifft die Verwendung von 3,5-Di-tert.-butyl-4- hydroxyphenylpropionsäureestern zur Stabilisierung von Polyisocyanaten.The present invention relates to the use of 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid esters for the stabilization of polyisocyanates.
Die organischen Isocyanate haben ür 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.Organic isocyanates have become very important for the production of polyurethane plastics. For example, the organic polyisocyanates with polyols (polyether and polyester polyols) are used for foam, fiber, film, elastomer and paint production.
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 soll. Auch bei der Prepolymerherstellung 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 discolor when stored, even at low temperatures. This property is particularly pronounced if storage must take place at higher temperatures, e.g. if the solid polyisocyanates are to be converted to urethanes for a homogeneous reaction with reactants such as polyether polyols, polyester polyols or glycols. Also in the prepolymer production, the NCO-OH reaction must be carried out at higher temperatures. It is observed that the isocyanates change color very quickly if no stabilization has been carried out.
Es wurde bereits vorgeschlagen, verschiedene Stabilisatoren organischen Polyisocyanaten zuzusetzen, um die Verfarbungsneigung 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, DT-OS 1 668 275,It has already been proposed to add various stabilizers to organic polyisocyanates in order to reduce the tendency to discolour the organic polyisocyanates. Known stabilizers are e.g. sterically hindered phenols, dialkyldiphenylamines, phenothiazines, phosphites or mixtures of representatives from these classes of substances (see, for example, US Pat. No. 3,715,301, US Pat. No. 4,064,157, DT-OS 1,668,275,
DT-AS 1 618 845).DT-AS 1 618 845).
Am häufigsten findet 2,6-Di-tert.-butyl-4-methylphenol (BHT) allein oder in Kombination mit weiteren Verbindungen der angeführten Stabilisatorenklassen Verwendung zur Stabilisierung von organischen Polyisocyanaten. Nachteil von BHT ist die relativ hohe Flüchtigkeit und Migrationstendenz in Polyurethane umhüllende Substrate sowie die daraus resultierende starke Gelbfärbung der Substrate in NOx-belasteter Atmosphäre. Stabilisatoren ohne diese Nachteile sind daher von Interesse und es war Aufgabe der vorliegenden Erfindung, solche Materialien bereitzustellen.2,6-di-tert-butyl-4-methylphenol (BHT) is most frequently used alone or in combination with other compounds of the stabilizer classes mentioned for the stabilization of organic polyisocyanates. The disadvantage of BHT is the relatively high volatility and tendency to migrate into substrates enveloping polyurethanes, and the resulting strong yellow coloring of the substrates in an NO x -closed atmosphere. Stabilizers without these disadvantages are therefore of interest and it was 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 relates to the use of 3,5-di-tert-butyl-4-hydroxy-phenylpropionic acid esters as stabilizers for organic polyisocyanates, especially for aromatic polyisocyanates.
Als Ester der genannten Phenylpropionsäure kommen vor allem in Frage: der Methyl-, Ethyl-, Propyl- und Tert.-Butylester, insbesondere der Methylester (BHPME).The following are particularly suitable as esters of the phenylpropionic acid mentioned: the methyl, ethyl, propyl and tert-butyl ester, 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, which is also indicated by traces of other compounds, e.g. Antioxidants, should not be affected.
Überraschenderweise hat sich gezeigt, daß schon geringste Mengen von 3,5-Di-tert- butyl-4-hydroxyphenylpropionsäure-ester von 0,001 bis 0,1 Gew.-%, vorzugsweiseSurprisingly, it has been found that even the smallest amounts of 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid ester are preferably from 0.001 to 0.1% by weight
0,001 bis 0,003 Gew.-%, bezogen auf Polyisocyanat, wirksam sind.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- diisocyanat, Toluylen-2,6-diisocyanat, 4,4'-Methylen-bis-(phenylisocyanat), 2,3'-Methylen-bis-(phenylisocyanat), 2,3-Methylen-bis-(phenylisocyanat), Toluylen-BHPME of e.g. is produced by base-catalyzed addition of acrylic acid methyl ester to 2,6-di-tert-butylphenol and is commercially available, is suitable for all common polyisocyanates, including aliphatic, aromatic and cycloaliphatic polyisocyanates. Examples include: ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, 4,4'-methylene bis (cyclohexyl diisocyanate), m-phenylene diisocyanate, p-phenylene diisocyanate, toluene-2,4-diisocyanate, toluene-2,6 -diisocyanate, 4,4'-methylene-bis- (phenyl isocyanate), 2,3'-methylene-bis- (phenyl isocyanate), 2,3-methylene-bis- (phenyl isocyanate), toluene-
2,4,6-triisocyanat. Die erfindungsgemäßen Phenylpropionsäureester können auch in Kombination mit bekannten Isocyanatstabilisatoren eingesetzt werden.2,4,6-triisocyanate. The phenylpropionic acid esters according to the invention can also be used in combination with known isocyanate stabilizers.
Die so stabilisierten organischen Polyisocyanate zeigen eine sehr stark verminderteThe organic polyisocyanates stabilized in this way show a very greatly reduced
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.Tends to discolor when stored at elevated temperatures and can be used to advantage in the production of polyurethanes. The polyurethanes are 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 Temperaturangaben °C). The subject matter of the present invention will be explained in more detail with the aid of the following examples (percentages in each case mean% by weight and all temperature data ° C.).
Beispiel 1example 1
Isocyanat: Stabilisator (FZ) Farbzahl (ALPHA)* nach 6, 15 und 21 Tagen bei 50°CIsocyanate: stabilizer (FZ) color number (ALPHA) * after 6, 15 and 21 days at 50 ° C
Desmodur T 80® 10 - 50 - 1000Desmodur T 80® 10 - 50 - 1000
(Toluoldiisocyanat; 2,4 80 % 2,6 20 %)(Toluene diisocyanate; 2.4 80% 2.6 20%)
30 ppm BHT - 5 - 250 lOO ppm BHT - - 15030 ppm BHT - 5 - 250 lOO ppm BHT - - 150
30 ppm BHPME - - 50 10 ppm BHPME - - 10030 ppm BHPME - - 50 10 ppm BHPME - - 100
Aus dieser Zusammenstellung geht hervor, daß 10 ppm BHPME-Zusatz eine bessere Stabilisatorwirkung zeigt als 100 ppm Zusatz von BHTFrom this compilation it can be seen that 10 ppm addition of BHPME shows a better stabilizing effect than 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 2Example 2
Desmodur 44 M® (DiphenylmethandiisocyanatDesmodur 44 M ® (diphenylmethane diisocyanate
Probe A 44 M® 500 g + 50 mg BHT Probe B 44 M® 500 g + 50 mg BHPME Probe C 44 M® ohne ZusatzSample A 44 M ® 500 g + 50 mg BHT Sample B 44 M ® 500 g + 50 mg BHPME Sample C 44 M® without additives
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. FZ (APHA)The samples were subjected to a UV irradiation test to investigate the yellowing behavior. After exposure for 70 hours, color numbers of these samples were measured according to APHA. FZ (APHA)
Probe A 100Sample A 100
Probe B 40Sample B 40
Probe C 250 vor der Bestrahlung 0-5Sample C 250 before irradiation 0-5
Beispiel 3Example 3
Isocyanat Stabilisator Farbzahl (FZ) Reinheit (GC) (APHA)Isocyanate stabilizer Color number (FZ) Purity (GC) (APHA)
Desmodur T 80® 100 ppm BHT 5-10 99,9 % 30 ppm BHPME 5-10 99,9 %Desmodur T 80 ® 100 ppm BHT 5-10 99.9% 30 ppm BHPME 5-10 99.9%
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

- 6 -Patentansprüche - 6 patent claims
1. Verwendung von 3,5-Di-tert.-butyl-4-hydroxyphenylpropionsäureestern als Stabilisatoren für organische Polyisocyanate.1. Use of 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid esters 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) is used as a stabilizer for organic polyisocyanates.
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 esters are used 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 hydroxyphenylpropionic acid ester according to claim 1 in combination with known stabilizers for polyisocyanates.
EP99913256A 1998-03-25 1999-03-15 Stabilisation of organic polyisocyanates Withdrawn EP1082296A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19813136 1998-03-25
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

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EP1082296A1 true EP1082296A1 (en) 2001-03-14

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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)

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Publication number Priority date Publication date Assignee Title
JP6666459B2 (en) * 2016-10-14 2020-03-13 旭化成株式会社 Isocyanate composition, method for producing isocyanate composition, and method for producing isocyanate polymer
TW201829516A (en) 2016-10-14 2018-08-16 日商旭化成股份有限公司 Isocyanate composition and method for producing 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

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Publication number Priority date Publication date Assignee Title
GB1197437A (en) * 1966-09-23 1970-07-01 Ici Ltd Stabilisation of 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
EP0445608B1 (en) * 1990-03-07 1994-06-08 Bayer Ag Stabilisation of organic polyisocyanates
ES2212350T3 (en) * 1997-09-30 2004-07-16 Uniroyal Chemical Company, Inc. POLYETER STABILIZED POLYOL AND POLYURETHANE FOAM OBTAINED FROM THE SAME.

Non-Patent Citations (1)

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Title
See references of WO9948863A1 *

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CN1294575A (en) 2001-05-09
JP2002507594A (en) 2002-03-12
KR20010042135A (en) 2001-05-25
AU3145199A (en) 1999-10-18
TW461898B (en) 2001-11-01
DE19813136C1 (en) 1999-07-15
BR9909029A (en) 2000-12-05
CA2325034A1 (en) 1999-09-30
WO1999048863A1 (en) 1999-09-30

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