CA2325034A1 - Stabilisation of organic polyisocyanates - Google Patents
Stabilisation of organic polyisocyanates Download PDFInfo
- Publication number
- CA2325034A1 CA2325034A1 CA002325034A CA2325034A CA2325034A1 CA 2325034 A1 CA2325034 A1 CA 2325034A1 CA 002325034 A CA002325034 A CA 002325034A CA 2325034 A CA2325034 A CA 2325034A CA 2325034 A1 CA2325034 A1 CA 2325034A1
- Authority
- CA
- Canada
- Prior art keywords
- polyisocyanates
- organic polyisocyanates
- tert
- stabilisation
- butyl
- 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.)
- Abandoned
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
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
Le A 32 924-Foreign Bg/by/NT
Stabilisation of organic polJrisoc anates The present invention relates to the use of 3,5-di-tert.-butyl-4-hydroxyphenylpropionic esters for stabilising polyisocyanates.
The organic isocyanates have attained great importance in the production of polyurethane plastics. Thus, for example, the organic polyisocyanates together with polyols (polyether polyols and polyester polyols) are used for the production of foams, fibres, films, elastomers and coatings.
However, the organic polyisocyanates have a tendency to discolour during storage, even at low temperatures. This property is particularly marked when storage at elevated temperatures is necessary, for example, for a homogeneous reaction when the solid polyisocyanates together with co-reactants, such as polyether polyols, polyester 1 S polyols or glycols, are to be converted to urethanes. In the production of prepolymers, too, the NCO-OH reaction has to be carried out at elevated temperatures. In the course of this it is observed that the isocyanates discolour very rapidly if no stabilisation has been carned out.
The addition of various stabilisers to organic polyisocyanates in order to lessen the tendency of the organic polyisocyanates to discolour has already been proposed.
Known stabilisers are, for example, sterically hindered phenols, dilakyldiphenyl amines, phenothiazines, phosphites or mixtures of representatives from these classes of substances (cf., for example, US 3 71 S 301, US 4 064 157, DT-OS 1 668 275, DT-AS
1 618 845).
Stabilisation of organic polJrisoc anates The present invention relates to the use of 3,5-di-tert.-butyl-4-hydroxyphenylpropionic esters for stabilising polyisocyanates.
The organic isocyanates have attained great importance in the production of polyurethane plastics. Thus, for example, the organic polyisocyanates together with polyols (polyether polyols and polyester polyols) are used for the production of foams, fibres, films, elastomers and coatings.
However, the organic polyisocyanates have a tendency to discolour during storage, even at low temperatures. This property is particularly marked when storage at elevated temperatures is necessary, for example, for a homogeneous reaction when the solid polyisocyanates together with co-reactants, such as polyether polyols, polyester 1 S polyols or glycols, are to be converted to urethanes. In the production of prepolymers, too, the NCO-OH reaction has to be carried out at elevated temperatures. In the course of this it is observed that the isocyanates discolour very rapidly if no stabilisation has been carned out.
The addition of various stabilisers to organic polyisocyanates in order to lessen the tendency of the organic polyisocyanates to discolour has already been proposed.
Known stabilisers are, for example, sterically hindered phenols, dilakyldiphenyl amines, phenothiazines, phosphites or mixtures of representatives from these classes of substances (cf., for example, US 3 71 S 301, US 4 064 157, DT-OS 1 668 275, DT-AS
1 618 845).
2,6-di-tert.-butyl-4-methylphenol (BHT), alone or in combination with other compounds of the classes of stabilisers listed above, is most frequently used for stabilising organic polyisocyanates.
Le A 32 924-Foreign The disadvantage of BHT is the relatively high volatility and tendency to migrate into polyurethanes covering substrates as well as the resulting strong yellowing of the substrates in an atmosphere containing NOX. Stabilisers without these disadvantages are therefore of interest and it was the object of the present invention to provide such materials.
The present invention provides the use of 3,5-di-tert.-butyl-4-hydroxyphenylpropionic esters as stabilisers for organic polyisocyanates, in particular for aromatic polyisocyanates.
The most suitable esters of the above-mentioned phenylpropionic acid are: the methyl, ethyl, propyl and tert. butyl ester, in particular the methyl ester (BHPME).
Reactions with polyisocyanates demand a balanced reactivity, which should not be 1 S influenced either by traces of other compounds such as, for example, antioxidants.
Surprisingly, it has been found that even the smallest amounts of 3,5-di-tert.-butyl-4-hydroxyphenylpropionic esters, of from 0.001 to 0.1 wt.%, preferably from 0.001 to 0.003 wt.%, based on polyisocyanate, are effective.
BHPME, which is produced, for example, by base-catalysed addition of methyl acrylate to 2,6-di-tert.-butylphenol and is available commercially, is suitable for all commonly used polyisocyanates, including aliphatic, aromatic and cycloaliphatic polyisocyanates. Examples which may be mentioned are: ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, 4,4'-methylenebis(cyclohexyl diisocyanate), m-phenylene diisocyanate, p-phenylene diisocyanate, tolylene 2,4-diisocyanate, tolylene 2,6-diisocyanate, 4,4'-methylenebis(phenyl isocyanate), 2,3'-methylenebis(phenyl isocyanate), 2,3-methylenebis(phenyl isocyanate), tolylene 2,4,6-triisocyanate.
Le A 32 924-Foreien The phenylpropionic esters according to the invention may also be used in combination with known isocyanate stabilisers.
The organic polyisocyanates stabilised in this way exhibit a very greatly diminished S tendency to discolour when stored at elevated temperatures and can be used with advantage for the production of polyurethanes. The polyurethanes are, for their part, used for the production of foams, films, coatings or elastomers.
The subject matter of the present invention is explained in more detail with the aid of the following Examples (% data in each case denote wt.% and all temperature data denote °C).
Le A 32 924-Foreim Example 1 Isocyanate: Stabiliser Colour index (ALPHA)' after 6, 15 and 21 days at SO°C
Desmodur T 80~ 10 - 50 -(Toluene diisocyanate; 2,4 80% 2,6 20%) 30 ppm BHT - 5 - 250 100 ppm BHT - - 150 30 ppm BHPME - - 50 10 ppm BHPME - - 100 From this list it follows that addition of 10 ppm of BHPME exhibits a better stabilising 1 S action than does addition of 100 ppm of BHT.
Colour index in accordance with DIN 53 409 (July'67) or ISO (July 1988) Example 2 Desmodur 441VI~ (diphenylmethane diisocyanate) Sample A 44 M~ S00 g + 50 mg BHT
Sample B 44 M~ S00 g + SO mg BHPME
Sample C 44 M~ without additive The samples were subjected to a W irradiation test in order to investigate the yellowing behaviour. After exposure to light for 70 hours, colour indices of these samples were measured by the APHA method.
Le A 32 924-Foreign -S-Colour index (APHA) Sample A 100 Sample B 40 Sample C 250 Before irradiation 0 - 5 Example 3 Isocyanate Stabiliser Colour index pity (~) (APHA) Desmodur T 80~ 100 ppm BHT 5 - 10 99.9%
30 ppm BHPME 5 - 10 99.9%
1 S The isocyanate was heated to 60°C and cooled again S times.
Le A 32 924-Foreign The disadvantage of BHT is the relatively high volatility and tendency to migrate into polyurethanes covering substrates as well as the resulting strong yellowing of the substrates in an atmosphere containing NOX. Stabilisers without these disadvantages are therefore of interest and it was the object of the present invention to provide such materials.
The present invention provides the use of 3,5-di-tert.-butyl-4-hydroxyphenylpropionic esters as stabilisers for organic polyisocyanates, in particular for aromatic polyisocyanates.
The most suitable esters of the above-mentioned phenylpropionic acid are: the methyl, ethyl, propyl and tert. butyl ester, in particular the methyl ester (BHPME).
Reactions with polyisocyanates demand a balanced reactivity, which should not be 1 S influenced either by traces of other compounds such as, for example, antioxidants.
Surprisingly, it has been found that even the smallest amounts of 3,5-di-tert.-butyl-4-hydroxyphenylpropionic esters, of from 0.001 to 0.1 wt.%, preferably from 0.001 to 0.003 wt.%, based on polyisocyanate, are effective.
BHPME, which is produced, for example, by base-catalysed addition of methyl acrylate to 2,6-di-tert.-butylphenol and is available commercially, is suitable for all commonly used polyisocyanates, including aliphatic, aromatic and cycloaliphatic polyisocyanates. Examples which may be mentioned are: ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, 4,4'-methylenebis(cyclohexyl diisocyanate), m-phenylene diisocyanate, p-phenylene diisocyanate, tolylene 2,4-diisocyanate, tolylene 2,6-diisocyanate, 4,4'-methylenebis(phenyl isocyanate), 2,3'-methylenebis(phenyl isocyanate), 2,3-methylenebis(phenyl isocyanate), tolylene 2,4,6-triisocyanate.
Le A 32 924-Foreien The phenylpropionic esters according to the invention may also be used in combination with known isocyanate stabilisers.
The organic polyisocyanates stabilised in this way exhibit a very greatly diminished S tendency to discolour when stored at elevated temperatures and can be used with advantage for the production of polyurethanes. The polyurethanes are, for their part, used for the production of foams, films, coatings or elastomers.
The subject matter of the present invention is explained in more detail with the aid of the following Examples (% data in each case denote wt.% and all temperature data denote °C).
Le A 32 924-Foreim Example 1 Isocyanate: Stabiliser Colour index (ALPHA)' after 6, 15 and 21 days at SO°C
Desmodur T 80~ 10 - 50 -(Toluene diisocyanate; 2,4 80% 2,6 20%) 30 ppm BHT - 5 - 250 100 ppm BHT - - 150 30 ppm BHPME - - 50 10 ppm BHPME - - 100 From this list it follows that addition of 10 ppm of BHPME exhibits a better stabilising 1 S action than does addition of 100 ppm of BHT.
Colour index in accordance with DIN 53 409 (July'67) or ISO (July 1988) Example 2 Desmodur 441VI~ (diphenylmethane diisocyanate) Sample A 44 M~ S00 g + 50 mg BHT
Sample B 44 M~ S00 g + SO mg BHPME
Sample C 44 M~ without additive The samples were subjected to a W irradiation test in order to investigate the yellowing behaviour. After exposure to light for 70 hours, colour indices of these samples were measured by the APHA method.
Le A 32 924-Foreign -S-Colour index (APHA) Sample A 100 Sample B 40 Sample C 250 Before irradiation 0 - 5 Example 3 Isocyanate Stabiliser Colour index pity (~) (APHA) Desmodur T 80~ 100 ppm BHT 5 - 10 99.9%
30 ppm BHPME 5 - 10 99.9%
1 S The isocyanate was heated to 60°C and cooled again S times.
Claims (4)
1. Use of 3,5-di-tert.-butyl-4-hydroxyphenylpropionic esters as stabilisers for organic polyisocyanates.
2. Use according to claim 1, characterised in that methyl 3,5-di-tert.-butyl-4-hydroxyphenylpropionate (BHPME) is used as stabiliser for organic polyisocyanates.
3. Use according to claim 1, characterised in that the 3,5-di-tert.-butyl-4-hydroxyphenylpropionic esters are used in quantities of from 0.001 to 0.1 wt.%, based on the polyisocyanates.
4. Use of the hydroxyphenylpropionic esters according to claim 1 in combination with known per se stabilisers for polyisocyanates.
Applications Claiming Priority (3)
| 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 |
| DE19813136.4 | 1998-03-25 | ||
| PCT/EP1999/001689 WO1999048863A1 (en) | 1998-03-25 | 1999-03-15 | Stabilisation of organic polyisocyanates |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2325034A1 true CA2325034A1 (en) | 1999-09-30 |
Family
ID=7862279
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002325034A Abandoned CA2325034A1 (en) | 1998-03-25 | 1999-03-15 | Stabilisation of organic polyisocyanates |
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) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11118001B2 (en) | 2016-10-14 | 2021-09-14 | Asahi Kasei Kabushiki Kaisha | Isocyanate composition, method for producing isocyanate composition, and method for producing isocyanate polymer |
| US11548975B2 (en) | 2016-10-14 | 2023-01-10 | Asahi Kasei Kabushiki Kaisha | Isocyanate composition and method for producing isocyanate polymer |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Family Cites Families (5)
| 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 |
| DE59101819D1 (en) * | 1990-03-07 | 1994-07-14 | Bayer Ag | Stabilization of organic polyisocyanates. |
| DE69820285T2 (en) * | 1997-09-30 | 2004-10-14 | Uniroyal Chemical Co., Inc., Middlebury | STABILIZED POLYETHER AND POLYURETHANE FOAM MADE THEREOF |
-
1998
- 1998-03-25 DE DE19813136A patent/DE19813136C1/en not_active Expired - Fee Related
-
1999
- 1999-03-15 CA CA002325034A patent/CA2325034A1/en not_active Abandoned
- 1999-03-15 BR BR9909029-5A patent/BR9909029A/en not_active Application Discontinuation
- 1999-03-15 CN CN99804416A patent/CN1294575A/en active Pending
- 1999-03-15 WO PCT/EP1999/001689 patent/WO1999048863A1/en not_active Application Discontinuation
- 1999-03-15 JP JP2000537847A patent/JP2002507594A/en active Pending
- 1999-03-15 AU AU31451/99A patent/AU3145199A/en not_active Abandoned
- 1999-03-15 KR KR1020007010539A patent/KR20010042135A/en not_active Application Discontinuation
- 1999-03-15 EP EP99913256A patent/EP1082296A1/en not_active Withdrawn
- 1999-03-18 TW TW088104181A patent/TW461898B/en active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11118001B2 (en) | 2016-10-14 | 2021-09-14 | Asahi Kasei Kabushiki Kaisha | Isocyanate composition, method for producing isocyanate composition, and method for producing isocyanate polymer |
| US11548975B2 (en) | 2016-10-14 | 2023-01-10 | Asahi Kasei Kabushiki Kaisha | Isocyanate composition and method for producing isocyanate polymer |
Also Published As
| Publication number | Publication date |
|---|---|
| AU3145199A (en) | 1999-10-18 |
| WO1999048863A1 (en) | 1999-09-30 |
| DE19813136C1 (en) | 1999-07-15 |
| KR20010042135A (en) | 2001-05-25 |
| JP2002507594A (en) | 2002-03-12 |
| BR9909029A (en) | 2000-12-05 |
| EP1082296A1 (en) | 2001-03-14 |
| TW461898B (en) | 2001-11-01 |
| CN1294575A (en) | 2001-05-09 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Dead |