WO1992003418A1 - Hindered phenolic norbornene dicarboximide - Google Patents
Hindered phenolic norbornene dicarboximide Download PDFInfo
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- WO1992003418A1 WO1992003418A1 PCT/US1991/005608 US9105608W WO9203418A1 WO 1992003418 A1 WO1992003418 A1 WO 1992003418A1 US 9105608 W US9105608 W US 9105608W WO 9203418 A1 WO9203418 A1 WO 9203418A1
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- Prior art keywords
- polymer
- hydroxy
- norbornene dicarboximide
- dicarboximide
- butyl
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/58—[b]- or [c]-condensed
- C07D209/72—4,7-Endo-alkylene-iso-indoles
- C07D209/76—4,7-Endo-alkylene-iso-indoles with oxygen atoms in positions 1 and 3
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F22/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
- C08F22/36—Amides or imides
- C08F22/40—Imides, e.g. cyclic imides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3415—Five-membered rings
- C08K5/3417—Five-membered rings condensed with carbocyclic rings
Definitions
- novel antioxidant compounds are hindered phenolic norbornene dicarboximides, oligomers, polymers and copolymers of such antioxidant compounds and polymeric compositions stabilized by such antioxidant compounds, oligomers, polymers and copolymers.
- polymeric compositions are generally combined with stabilizing agents to prolong their useful life in hostile environments, e.g. the presence of oxidizing agents or ultraviolet light.
- stabilizing agents are physically combined with the polymer thereby prolonging its useful life.
- Stabilizing agents are commonly monomeric or oligomeric compounds which are free to migrate, albeit slowly, within the polymeric composition and to the surface thereof. This often presents a problem manifested by a bloom of powder on the surface or extraction of the stabilizer into a fluid which not only reduced environmental stability but also detracts from the aesthetic appearance of a polymeric article.
- some stabilizers have a sufficiently low molecular weight that they may be vaporized, or otherwise become ineffective, at elevated service temperatures especially in high performance thermoplastics.
- Antioxidants derived from cyclic olefins have been proposed. For instance. Layer discloses in U.S. Patent 4,484,010 hindered hydroxybenzylcyclo- pentadiene antioxidants prepared by reacting cyclo- pentadiene, an alkali metal, and a hindered para methylphenol having attached to the methyl group a displaceable group, e.g. dimethylamino group, for up to a couple of days at 60"C in a non-protic solvent. Because conjugated dienes like cyclopentadiene are easily oxidized. Layer's antioxidants are preferably hydrogenated and thus not amenable to incorporated into polymeric compounds or grafted to polymers.
- Another object is to provide cyclic olefinic antioxidants which can be incorporated into polymeric compounds or grafted to polymers, especially unsaturated polymers or metathesis ring-opening polymerized polymers and copolymers, so as to provide a polymeric compounds with inherent and enhanced antioxidant character.
- another object of this invention is to provide polymeric compounds which are inherently antioxidant and which can be blended with other polymers to provide oxidation resistant polymer compositions.
- This invention provides hindered phenolic norbornene dicarboximides which are useful for inhibiting oxidation of polymer compositions.
- This invention also provides polymeric compounds, e.g. homopolymers, of such hindered phenolic norbornene dicarboximides which are useful both in low molecular weight oligomeric species and in higher molecular weight polymeric species as polymeric oxidation inhibitors.
- Another aspect of this invention provides polymeric compounds, e.g. copolymers having such hindered phenolic norbornene dicarboximide incorporated therein or grafted thereto.
- Useful oxidation inhibitors can also comprise a mixture of monomeric and polymeric species.
- both the grafted monomer and residual free monomer can be effective in inhibiting oxidation.
- the hindered phenolic group of the norbornene dicarboximide antioxidant of this invention is preferably a 3,5-dialkyl-4-hydroxy-phenyl group, where preferred alkyl is t-butyl.
- preferred embodiments of this invention include, as a monomeric antioxidant, N-(3,5-di-t-butyl-4-hydroxy)phenyl norbornene dicarboximide; as a polymeric antioxidant, poly(N-(3,5-di-t-butyl-4--hydroxy)phenyl norbornene dicarboximide) and copolymers having N-(3,5-di-t- butyl-4-hydroxy)phenyl norbornene dicarboximide incorporated therein or grafted thereto.
- a useful embodiment of this invention comprises copolymers of N-(3,5-di-t-butyl-4- hydroxy)phenyl norbornene dicarboximide and other cyclic olefins, e.g. a norbornene or norbornene derivative.
- the oxidation inhibitor as a high temperature resistant copolymer, e.g. of a norbornene dicarboximide.
- Oxidation inhibitor copolymer according to this invention can be prepared having a glass transition temperature greater than 200 ⁇ C.
- Homopolymer oxidation inhibitors can be prepared having a glass transition temperature of about 235 ⁇ C.
- EXAMPLE 1 This example illustrates methods of preparating the oxidation inhibitor N-(3,5-di-t-butyl- 4-hydroxy) phenyl norbornene dicarboximide.
- a mixture of 253 g of 2,6-di-t-butyl-4- nitrophenol, 1 liter of tetrahydrofuran (THF) and 2.57 g 5% palladium on carbon catalyst was maintained in a pressurized reactor for 2 hours at 70 ⁇ C under hydrogen pressurized to 5.3 atm.
- the reactor contents were cooled and transferred to a flask containing about 165 g of exo-5-norbornene-2,3-dicarboxylic anhydride which was stirred overnight.
- This example illustrates the preparation of copolymer oxidation inhibitors.
- EXAMPLE 4 This example illustrates the preparation of polybutadiene grafted with N-(3,5-di-t-butyl-4- hydroxy)phenyl norbornene dicarboximide.
- About 0.1 ml of t-butylperoctoate was added to solution of 5 g of polybutadiene and 0.5 g of N-(3,5- di-t-butyl-4-hydroxy)phenyl norbornene dicarboximide dissolved in 200 ml of toluene.
- the solution was mixed at about 80"C for 2 hours with an increase in viscosity indicating some crosslinking.
- the reaction product was diluted with chloroform and oxidation stabilized polybutadiene was recovered in methanol.
- EXAMPLE 5 This example illustrates the stabilization of polybutadiene by addition of monomeric N-(3,5-di- t-butyl-4-hydroxy)phenyl norbornene dicarboximide.
- Antioxidant was removed from polybutadiene (PB, as received) by dissolving polybutadiene in toluene and recovering in methanol.
- Purified polybutadiene (PB, purified) and N-(3,5-di-t-butyl-4-hydrox )phenyl norbornene dicarboximide (at 2% and 5%) were dissolved in ethylene chloride; after mixing the solvent was allowed to evaporate.
- the thermoxidative stability of the stabilized polybutadiene compositions were evaluated by measuring the exotherm temperature exhibited by the polymer heated in an oxygen atmosphere in a differential scanning calorimeter. TABLE 2
- EXAMPLE 6 This example illustrates the preparation of a copolymer oxidation inhibitor. Using the catalysts and procedures of
- Example 2 but using 100 parts by weight of N- cyclohexyl norbornene dicarboximide (I) and about 10 parts by weight N-(3,5-di-t-butyl-4-hydroxy)phenyl norbornene dicarboximide (II) , an oxidatively stable cyclic olefin copolymer was prepared.
- the thermoxidative stability of the copolymer was evaluated by measuring the exotherm temperature exhibited by finely ground polymer heated in an oxygen atmosphere in a differential scanning calorimeter.
- Table 3 illustrate the effectiveness of providing oxidative stability to a cyclic olefin polymer by incorporating therein a minor amount, e.g. about 10%, of a cyclic olefin oxidation inhibitor.
- MONOMER I MONOMER II Exotherm (°C) 100 0 204
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Organic Insulating Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
N-(3,5-di-alkyl-4-hydroxy)phenyl norbornene dicarboximides useful for inhibiting oxidation of polymeric compositions. Such oxidation inhibitor can be provided as a monomer, oligomer or homopolymer or incorporated into copolymers or grafted onto polymers. Preferred oxidation inhibitors are based on N-(3,5-di-t-butyl-4-hydroxy)phenyl norbornene dicarboximide. Especially useful are cyclic olefin copolymers, e.g. of antioxidant monomer and norbornene dicarboximides.
Description
HINDERED PHENOLIC NORBORNENE DICARBOXIMIDE
Disclosed herein as novel antioxidant compounds are hindered phenolic norbornene dicarboximides, oligomers, polymers and copolymers of such antioxidant compounds and polymeric compositions stabilized by such antioxidant compounds, oligomers, polymers and copolymers.
BACKGROUND OF THE INVENTION Except in the cases where environmental degradation is desired, polymeric compositions are generally combined with stabilizing agents to prolong their useful life in hostile environments, e.g. the presence of oxidizing agents or ultraviolet light. The art of stabilizing polymeric materials is both complex and unpredictable. Ordinarily stabilizing agents are physically combined with the polymer thereby prolonging its useful life. Stabilizing agents are commonly monomeric or oligomeric compounds which are free to migrate, albeit slowly, within the polymeric composition and to the surface thereof. This often presents a problem manifested by a bloom of powder on the surface or extraction of the stabilizer into a fluid which not only reduced environmental stability but also detracts from the aesthetic appearance of a polymeric article. Furthermore, some stabilizers have a sufficiently low molecular weight that they may be vaporized, or otherwise become ineffective, at elevated service temperatures especially in high performance thermoplastics.
Antioxidants derived from cyclic olefins have been proposed. For instance. Layer discloses in U.S. Patent 4,484,010 hindered hydroxybenzylcyclo- pentadiene antioxidants prepared by reacting cyclo- pentadiene, an alkali metal, and a hindered para methylphenol having attached to the methyl group a displaceable group, e.g. dimethylamino group, for up
to a couple of days at 60"C in a non-protic solvent. Because conjugated dienes like cyclopentadiene are easily oxidized. Layer's antioxidants are preferably hydrogenated and thus not amenable to incorporated into polymeric compounds or grafted to polymers.
In U.S. Patents 4,045,404 and 3,896,147 Stephen discloses hindered phenolic stabilizers derived from alkylthionorbornane dicarboximides. Due to their preparation by free radical addition of a mercaptan to 5-norbornene-endo-2,3-dicarboximide, these stabilizers are not amenable to be incorporated into polymeric compounds or grafted to polymers.
It is an object of this invention to provide antioxidants which can stabilize polymer compositions without adverse consequences of leaching, vaporization or other deficiency which commonly occur at elevated temperatures.
Another object is to provide cyclic olefinic antioxidants which can be incorporated into polymeric compounds or grafted to polymers, especially unsaturated polymers or metathesis ring-opening polymerized polymers and copolymers, so as to provide a polymeric compounds with inherent and enhanced antioxidant character. Thus, another object of this invention is to provide polymeric compounds which are inherently antioxidant and which can be blended with other polymers to provide oxidation resistant polymer compositions. SUMMARY OF THE INVENTION
This invention provides hindered phenolic norbornene dicarboximides which are useful for inhibiting oxidation of polymer compositions. This invention also provides polymeric compounds, e.g. homopolymers, of such hindered phenolic norbornene dicarboximides which are useful both in low molecular weight oligomeric species and in higher molecular
weight polymeric species as polymeric oxidation inhibitors. Another aspect of this invention provides polymeric compounds, e.g. copolymers having such hindered phenolic norbornene dicarboximide incorporated therein or grafted thereto. Useful oxidation inhibitors can also comprise a mixture of monomeric and polymeric species. For instance, where monomeric hindered phenolic norbornene dicarboximide is grafted to a polymer, e.g. a polymer having terminal alpha olefin groups such as polybutadiene, both the grafted monomer and residual free monomer can be effective in inhibiting oxidation.
The hindered phenolic group of the norbornene dicarboximide antioxidant of this invention is preferably a 3,5-dialkyl-4-hydroxy-phenyl group, where preferred alkyl is t-butyl. Thus, preferred embodiments of this invention include, as a monomeric antioxidant, N-(3,5-di-t-butyl-4-hydroxy)phenyl norbornene dicarboximide; as a polymeric antioxidant, poly(N-(3,5-di-t-butyl-4--hydroxy)phenyl norbornene dicarboximide) and copolymers having N-(3,5-di-t- butyl-4-hydroxy)phenyl norbornene dicarboximide incorporated therein or grafted thereto.
A useful embodiment of this invention comprises copolymers of N-(3,5-di-t-butyl-4- hydroxy)phenyl norbornene dicarboximide and other cyclic olefins, e.g. a norbornene or norbornene derivative. To avoid lowering the temperature resistance of polymeric compositions, it is advantageous to provide the oxidation inhibitor as a high temperature resistant copolymer, e.g. of a norbornene dicarboximide. Oxidation inhibitor copolymer according to this invention can be prepared having a glass transition temperature greater than 200βC. Homopolymer oxidation inhibitors can be prepared having a glass transition temperature of about 235βC.
EXAMPLE 1 This example illustrates methods of preparating the oxidation inhibitor N-(3,5-di-t-butyl- 4-hydroxy) phenyl norbornene dicarboximide. A mixture of 253 g of 2,6-di-t-butyl-4- nitrophenol, 1 liter of tetrahydrofuran (THF) and 2.57 g 5% palladium on carbon catalyst was maintained in a pressurized reactor for 2 hours at 70βC under hydrogen pressurized to 5.3 atm. The reactor contents were cooled and transferred to a flask containing about 165 g of exo-5-norbornene-2,3-dicarboxylic anhydride which was stirred overnight. After the THF was removed by rotary evaporation, about 560 g anhydrous sodium acetate and about 1090 g of acetic anhydride were added to the mixture which was refluxed for 24 hours. Excess acetic anhydride was evaporated. The residual brown solid was dissolved in acetone and treated with concentrated hydrochloric acid. The resulting solid was recrystallized in methanol, yielding substantially pure N-(3,5-di-t-butyl-4-hydroxy)phenyl norbornene dicarboximide.
In an alternative method of preparing N-(3,5-di-t-butyl-4- hydroxy) phenyl norbornene dicarboximide, a mixture of 700 grams of 2,6-di-t-butyl-4-nitrophenol, 1 liter of THF and 7.1 grams of 5% palladium on carbon catalyst was pressurized with hydrogen to about 5.3 atm at 70βC. When the hydrogen takeup stopped, the product was cooled, separated from the catalyst by filtration and added to a flask containing 457 grams of exo-5- norbornene-2,3- dicarboxylic anhydride. After four hours the THF was replaced with 1300 ml of xylene and the contents heated to reflux with water of cyclization removed with xylene by azeotropic
distillation. Crystalline N-(3,5-di-t-butyl- 4-hydroxy)phenyl norbornene dicarboximide recovered at below room temperature was purified by recystalization from xylene. EXAMPLE 2
This example illustrates the preparation of a polymeric oxidation inhibitor by the polymerization of N-(3,5-di-t-butyl-4-hydroxy)phenyl norbornene dicarboximide. Polymerization catalyst comprising about 0.9 ml of 0.5 M tungsten hexachloride solution in toluene and 0.14 ml of 2.05 M diethyl aluminum chloride in heptane were sequentially added to about 2 g of N- (3,5-di-t-butyl-4-hydroxy)phenyl norbornene dicarboximide dissolved in 6 ml of dichloroethane. The mixture was maintained at about 65"C overnight. Poly(N-(3,5-di-t-butyl-4-hydroxy)phenyl norbornene dicarboximide) was recovered in methanol and vacuum dried. EXAMPLE 3
This example illustrates the preparation of copolymer oxidation inhibitors.
Using the catalysts and procedures of Example 2, but using the monomers in the weight ratio identified in Table 1, copolymers of N-methyl norbornene dicarboximide (I) and N-(3,5-di-t-butyl-4- hydroxy)phenyl norbornene dicarboximide (II) were prepared. The thermoxidative stability of the copolymers was evaluated by measuring the exotherm temperature exhibited by finely ground polymer heated in an oxygen atmosphere in a differential scanning calorimeter. The results reported in Table 1 illustrate the effectiveness of providing oxidative stability to a cyclic olefin polymer by incorporating therein a minor amount, e.g. about 5 %, of a cyclic olefin oxidation inhibitor. The results also
illustrate the high temperature oxidation stability afforded by copolymers comprising higher levels, e.g. 10 to 33%, of cyclic olefin oxidation inhibitor.
TABLE 1
EXAMPLE 4 This example illustrates the preparation of polybutadiene grafted with N-(3,5-di-t-butyl-4- hydroxy)phenyl norbornene dicarboximide. About 0.1 ml of t-butylperoctoate was added to solution of 5 g of polybutadiene and 0.5 g of N-(3,5- di-t-butyl-4-hydroxy)phenyl norbornene dicarboximide dissolved in 200 ml of toluene. The solution was mixed at about 80"C for 2 hours with an increase in viscosity indicating some crosslinking. The reaction product was diluted with chloroform and oxidation stabilized polybutadiene was recovered in methanol.
EXAMPLE 5 This example illustrates the stabilization of polybutadiene by addition of monomeric N-(3,5-di- t-butyl-4-hydroxy)phenyl norbornene dicarboximide. Antioxidant was removed from polybutadiene (PB, as received) by dissolving polybutadiene in toluene and recovering in methanol. Purified polybutadiene (PB, purified) and N-(3,5-di-t-butyl-4-hydrox )phenyl norbornene dicarboximide (at 2% and 5%) were dissolved in ethylene chloride; after mixing the solvent was allowed to evaporate. The thermoxidative stability of
the stabilized polybutadiene compositions were evaluated by measuring the exotherm temperature exhibited by the polymer heated in an oxygen atmosphere in a differential scanning calorimeter. TABLE 2
COMPOSITION Exotherm (βC)
PB, as received 206
PB, purified 195
PB + 2% 212 PB + 5% 238
EXAMPLE 6 This example illustrates the preparation of a copolymer oxidation inhibitor. Using the catalysts and procedures of
Example 2, but using 100 parts by weight of N- cyclohexyl norbornene dicarboximide (I) and about 10 parts by weight N-(3,5-di-t-butyl-4-hydroxy)phenyl norbornene dicarboximide (II) , an oxidatively stable cyclic olefin copolymer was prepared. The thermoxidative stability of the copolymer was evaluated by measuring the exotherm temperature exhibited by finely ground polymer heated in an oxygen atmosphere in a differential scanning calorimeter. The results reported in Table 3 illustrate the effectiveness of providing oxidative stability to a cyclic olefin polymer by incorporating therein a minor amount, e.g. about 10%, of a cyclic olefin oxidation inhibitor. TABLE 3
MONOMER I MONOMER II Exotherm (°C) 100 0 204
90 10 268
While specific embodiments of the invention have been described, it should be apparent to those skilled in the art that various modifications thereof
can be made without departing from the true spirit and scope of the invention. Accordingly, it is intended that the following claims cover all such modifications within the full inventive concept.
Claims
1. N-(3,5-di-alkyl-4-hydroxy)phenyl norbornene dicarboximide.
2. Norbornene dicarboximide according to claim 1 consisting of N-(3,5-di-t-butyl-4- hydroxy)phenyl norbornene dicarboximide.
3. Poly(N-(3,5-di-alkyl-4-hydroxy)phenyl norbornene dicarboximide) .
4. A polymer according to claim 3 consisting of poly(N-(3,5-di-t-butyl-4-hydroxy)phenyl norbornene dicarboximide) .
5. A polymer having N-(3,5-di-alkyl-4- hydroxy)phenyl norbornene dicarboximide incorporated therein or grafted thereto.
6. A polymer according to claim 5 having N-
(3,5-di-t-butyl-4-hydroxy)phenyl norbornene dicarboximide incorporated therein or grafted thereto.
7. An oxidation inhibitor comprising at least one of N-(3,5-di-alkyl-4-hydroxy)phenyl norbornene dicarboximide, a polymer having N-(3,5-di- alkyl-4-hydroxy) phenyl norbornene dicarboximide incorporated therein or grafted thereto or poly(N- (3,5-di-alkyl-4-hydroxy) phenyl norbornene dicarboximide) or a mixture thereof.
8. An oxidation inhibitor according to claim 7 comprising at least one of N-(3,5-di-t-butyl- 4-hydroxy)phenyl norbornene dicarboximide, a polymer having N-(3,5-di-t-butyl-4-hydroxy) phenyl norbornene dicarboximide incorporated therein or grafted thereto or poly(N-(3,5-di-t-butyl-4-hydroxy) phenyl norbornene dicarboximide) or a mixture thereof.
9. Oxidation-inhibited polymer composition comprising a major amount of at least one polymer and an oxidation inhibiting amount of a polymer oxidation inhibitor according to claim 7.
10. Oxidation-inhibited polymer composition comprising a major amount of at least one polymer and -lo¬ an oxidation inhibiting amount of a polymer oxidation inhibitor according to claim 8.
11. A composition according to claim 9 wherein said at least one polymer is a cyclic olefin polymer.
12. A composition according to claim 11 wherein said cyclic olefin polymer is essentially a norbornene or norbornene derivative polymer.
13. A composition according to claim 12 wherein said polymer is essentially a norbornene dicarboximide polymer.
14. A composition according to claim 13 wherein said polymer oxidation inhibitor is incorporated into said norbornene dicarboximide polymer.
15. A composition according to claim 9 wherein said at least one polymer is characterized as having alpha olefin terminal groups.
16. A composition according to claim 15 wherein said at least one polymer is polybutadiene.
17. A composition according to claim 16 wherein said polymer oxidation inhibitor is grafted to said polybutadiene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019930700490A KR930701400A (en) | 1990-08-23 | 1991-08-07 | Hindered Phenolnorbornene Dicarboxymid |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US57220690A | 1990-08-23 | 1990-08-23 | |
| US572,206 | 1990-08-23 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1992003418A1 true WO1992003418A1 (en) | 1992-03-05 |
Family
ID=24286819
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US1991/005608 WO1992003418A1 (en) | 1990-08-23 | 1991-08-07 | Hindered phenolic norbornene dicarboximide |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0544843A1 (en) |
| JP (1) | JPH06500351A (en) |
| KR (1) | KR930701400A (en) |
| AU (1) | AU8441491A (en) |
| CA (1) | CA2088143A1 (en) |
| WO (1) | WO1992003418A1 (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3896147A (en) * | 1973-12-28 | 1975-07-22 | Ciba Geigy Corp | Hindered phenolic norbornane-2,3-dicarboximides |
| US3906002A (en) * | 1973-12-28 | 1975-09-16 | John F Stephen | Hindered phenolic norbornane-2,3-dicarboximides |
| US3941746A (en) * | 1973-12-28 | 1976-03-02 | Ciba-Geigy Corporation | Containing hindered phenolic norbornane-2,3-dicarboximides stabilized compositions |
| US4045404A (en) * | 1973-12-28 | 1977-08-30 | Ciba-Geigy Corporation | Hindered phenolic norbornane-2,3-dicarboximides and stabilized compositions |
| EP0067976A1 (en) * | 1981-06-16 | 1982-12-29 | The Boeing Company | Method for the preparation of cross-linkable polymers |
-
1991
- 1991-08-07 JP JP3514508A patent/JPH06500351A/en active Pending
- 1991-08-07 WO PCT/US1991/005608 patent/WO1992003418A1/en not_active Application Discontinuation
- 1991-08-07 AU AU84414/91A patent/AU8441491A/en not_active Abandoned
- 1991-08-07 CA CA002088143A patent/CA2088143A1/en not_active Abandoned
- 1991-08-07 KR KR1019930700490A patent/KR930701400A/en not_active Application Discontinuation
- 1991-08-07 EP EP92904677A patent/EP0544843A1/en not_active Withdrawn
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3896147A (en) * | 1973-12-28 | 1975-07-22 | Ciba Geigy Corp | Hindered phenolic norbornane-2,3-dicarboximides |
| US3906002A (en) * | 1973-12-28 | 1975-09-16 | John F Stephen | Hindered phenolic norbornane-2,3-dicarboximides |
| US3941746A (en) * | 1973-12-28 | 1976-03-02 | Ciba-Geigy Corporation | Containing hindered phenolic norbornane-2,3-dicarboximides stabilized compositions |
| US4045404A (en) * | 1973-12-28 | 1977-08-30 | Ciba-Geigy Corporation | Hindered phenolic norbornane-2,3-dicarboximides and stabilized compositions |
| EP0067976A1 (en) * | 1981-06-16 | 1982-12-29 | The Boeing Company | Method for the preparation of cross-linkable polymers |
Non-Patent Citations (1)
| Title |
|---|
| J. Polym. Sci., Part A: Polymer Chemistry, vol. 27, no. 4, March 1989, A Renner et al: "Allylnadic-Imides: A New Class of Heat-Resistant Thermosets", pages 1301-1323, see especially page 1306 formula 14 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2088143A1 (en) | 1992-02-24 |
| EP0544843A1 (en) | 1993-06-09 |
| KR930701400A (en) | 1993-06-11 |
| AU8441491A (en) | 1992-03-17 |
| JPH06500351A (en) | 1994-01-13 |
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