Patent US4100140A successfully refreshed from Google Patents.
US4100140A
Expired / Lapsed
US
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Process for the manufacture of crosslinked polymers which contain imide groups
Assignee: BASF Corp
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Filing: 1976-06-18
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Granted: 1978-07-11
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Expires: 1996-06-18
Abstract
Abstract The invention relates to the manufacture of crosslinked polymers which contain imide groups by reacting polymaleimides with alkenylphenols or alkenylphenol ethers, preferably at temperatures of 100° to 250° C. The reaction mixture optionally also contains polymerization catalysts. The manufacture of the polymers is as a rule carried out with simultaneous shaping. Shaped articles (for example castings), laminates, adhesive bonds and foams can be manufactured in this way. It is also possible to carry out the reaction in solution.
Inventors
- 👤 Abdul-Cader Zahir
- 👤 Alfred Renner
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-24 13:11
CPC Classifications
C; C08; C08F; C08F222/00; C08F222/36; C08F222/40; C08G; C08G73/00; C08G73/06; C08G73/10; C08G73/12; Y; Y10; Y10T; Y10T428/00; Y10T428/31504; Y10T428/31721
Claims Analysis
Total Claims: 36
Claim 1
Independent Claim
205 words
A process for the manufacture of a crosslinked polymer containing imide groups comprising reacting at a temperature of 20° to 250° C (a) a polyimide of the formula ##STR9## wherein R is hydrogen or methyl, and A is a divalent radical of the formula ##STR10## in which R 1 is selected from the group consisting of --CH 2 --; ##STR11## --SO 2 --, --SO--, --S-- and --O--, and n is 0 or 1; or a polyimide selected from the group consisting of the N,N'-bis-maleimide of 4,4'-diamino-triphenyl phosphate, the N,N'-bis-maleimide of 4,4'-diamino-triphenyl phosphate, the N,N',N"-tris-maleimide of tris-(4-aminophenyl) phosphate and the N,N',N"-tris-maleimide of tris-(4-aminophenyl) thiophosphate; or a mixture of said polyimides; with (b) an alkenylphenol selected from the group consisting of o,o'-diallyl-bisphenol A, 4,4'-dihydroxy-3,3'-diallyldiphenyl, bis-(4-hydroxy-3-allylphenyl)methane, 2,2-bis-(4-hydroxy-3,5-diallylphenyl)propane, eugenol, o,o'-dimethallyl-bisphenol A, 4,4'-dihydroxy-3,3'-dimethylallyldiphenyl, bis-(4-hydroxy-3-methallylphenyl)methane, 2,2-bis-(4-hydroxy-3,5-dimethallylphenyl)-propane and 4-methallyl-2-methoxyphenol; or an alkenylphenol ether selected from the group consisting of 2,2-bis(4-methoxy-3-allylphenyl)propane, 2,2-bis(4-methoxy-3-methallyphenyl)propane, 4,4'-dimethoxy-3,3'-diallyldiphenyl, 4,4'-dimethoxy-3,3'-dimethallyldiphenyl, bis(4-methoxy-3-allylphenyl)methane, bis(4-methoxy-3-methallylphenyl)methane, 2,2-bis(4-methoxy-3,5-diallylphenyl)propane, 2,2-bis-(4-methoxy-3,5-dimethallylphenyl)propane, 4-allylveratrole and 4-methallyl-veratrole; or a mixture of said alkenylphenols, a mixture of said alkenylphenol ethers or a mixture of said alkenylphenols and said alkenylphenol ethers; in such molar proportion that for each 1 equivalent of polyimide component (a) there is from 0.1 to 10 moles of alkenylphenol, alkenylphenol ether or mixture thereof as component (b).
Claim 2
Dependent Claim
205 words
A process for the manufacture of a crosslinked polymer containing imide groups comprising reacting at a temperature of 20° to 250° C (a) a polyimide of the formula ##STR9## wherein R is hydrogen or methyl, and A is a divalent radical of the formula ##STR10## in which R 1 is selected from the group consisting of --CH 2 --; ##STR11## --SO 2 --, --SO--, --S-- and --O--, and n is 0 or 1; or a polyimide selected from the group consisting of the N,N'-bis-maleimide of 4,4'-diamino-triphenyl phosphate, the N,N'-bis-maleimide of 4,4'-diamino-triphenyl phosphate, the N,N',N"-tris-maleimide of tris-(4-aminophenyl) phosphate and the N,N',N"-tris-maleimide of tris-(4-aminophenyl) thiophosphate; or a mixture of said polyimides; with (b) an alkenylphenol selected from the group consisting of o,o'-diallyl-bisphenol A, 4,4'-dihydroxy-3,3'-diallyldiphenyl, bis-(4-hydroxy-3-allylphenyl)methane, 2,2-bis-(4-hydroxy-3,5-diallylphenyl)propane, eugenol, o,o'-dimethallyl-bisphenol A, 4,4'-dihydroxy-3,3'-dimethylallyldiphenyl, bis-(4-hydroxy-3-methallylphenyl)methane, 2,2-bis-(4-hydroxy-3,5-dimethallylphenyl)-propane and 4-methallyl-2-methoxyphenol; or an alkenylphenol ether selected from the group consisting of 2,2-bis(4-methoxy-3-allylphenyl)propane, 2,2-bis(4-methoxy-3-methallyphenyl)propane, 4,4'-dimethoxy-3,3'-diallyldiphenyl, 4,4'-dimethoxy-3,3'-dimethallyldiphenyl, bis(4-methoxy-3-allylphenyl)methane, bis(4-methoxy-3-methallylphenyl)methane, 2,2-bis(4-methoxy-3,5-diallylphenyl)propane, 2,2-bis-(4-methoxy-3,5-dimethallylphenyl)propane, 4-allylveratrole and 4-methallyl-veratrole; or a mixture of said alkenylphenols, a mixture of said alkenylphenol ethers or a mixture of said alkenylphenols and said alkenylphenol ethers; in such molar proportion that for each 1 equivalent of polyimide component (a) there is from 0.1 to 10 moles of alkenylphenol, alkenylphenol ether or mixture thereof as component (b).
Claim 3
Dependent Claim
22 words
Process according to claim 1, characterised in that the reaction is allowed to proceed at a temperature of 100° to 250° C.
Claim 4
Dependent Claim
13 words
Process according to claim 1, characterised in that the polyimide employed is 4,4'-bis-maleimido-diphenylmethane.
Claim 5
Dependent Claim
20 words
Process according to claim 1, characterised in that the alkenylphenol or alkenylphenol ether employed is eugenol or eugenol methyl ether.
Claim 6
Dependent Claim
14 words
Process according to claim 1, characterised in that the alkenylphenol employed is o,o'-diallyl-bisphenol A.
Claim 7
Dependent Claim
15 words
Process according to claim 5, characterised in that a bis-maleimide is reacted with o,o'-diallyl-bisphenol A.
Claim 8
Dependent Claim
71 words
A process according to claim 1 wherein the reaction of the polyimide component (a) and the alkenylphenol, alkenylphenol ether or mixture thereof component (b) is carried out in the presence of a polymerization catalyst selected from the group consisting of an ionic catalyst, a free-radical polymerization catalyst and a transition metal acetylacetonate, said catalyst being in a concentration of 0.1 to 10% by weight, based on the total amount of reactants.
Claim 9
Dependent Claim
16 words
Process according to claim 7, characterised in that the polymerisation catalyst employed is an ionic catalyst.
Claim 10
Dependent Claim
25 words
Process according to claim 8, characterised in that the ionic catalyst employed is a tertiary, secondary or mixed tertiary/secondary amine or a quaternary ammonium compound.
Claim 11
Dependent Claim
17 words
Process according to claim 8, characterised in that the ionic catalyst employed is an alkali metal compound.
Claim 12
Dependent Claim
16 words
Process according to claim 7, characterised in that the polymerisation catalyst employed is a free-radical catalyst.
Claim 13
Dependent Claim
16 words
Process according to claim 11, characterised in that the free-radical catalyst employed is an organic peroxide.
Claim 14
Dependent Claim
14 words
Process according to claim 11, characterised in that the free-radical catalyst employed is azoisobutyronitrile.
Claim 15
Dependent Claim
15 words
Process according to claim 7, characterised in that the polymerisation catalyst employed is vanadium acetylacetonate.
Claim 16
Dependent Claim
30 words
Process according to claim 7, characterised in that a polymerisation catalyst is employed in a concentration of 0.1 to 5.0% by weight, based on the total amount of the reactants.
Claim 17
Dependent Claim
11 words
A crosslinked polymer manufactured by the process according to claim 1.
Claim 18
Dependent Claim
201 words
A mixture of which is stable on storage and can be cured by the action of heat which comprises (a) a polyimide of the formula ##STR12## wherein R is hydrogen or methyl, and A is a divalent radical of the formula ##STR13## in which R 1 is selected from the group consisting of --CH 2 --, ##STR14## --SO 2 --, --SO--, --S-- and --O--, and n is 0 or 1; or a polyimide selected from the group consisting of the N,N'-bis-maleimide of 4,4'-diamino-triphenyl phosphate, the N,N'-bis-maleimide of 4,4'-diamino-triphenyl phosphate, the N,N',N"-tris-maleimide of tris-(4-aminophenyl) phosphate and the N,N',N"-tris-maleimide of tris-(4-aminophenyl) thiophosphate; or a mixture of said polyimides; and (b) an alkenylphenol selected from the group consisting of o,o'-diallyl-bisphenol A, 4,4'-dihydroxy-3,3'-diallyldiphenyl, bis-(4-hydroxy-3-allylphenyl)methane, 2,2-bis-(4-hydroxy-3,5-diallylphenyl)propane, eugenol, o,o'-dimethallyl-bisphenol A, 4,4'-dihydroxy-3,3'-dimethallyldiphenyl, bis-(4-hydroxy-3-methallylphenyl)methane, 2,2-bis-(4-hydroxy-3,5-dimethallylphenyl)propane and 4-methallyl-2-methoxyphenol; or an alkenylphenol ether selected from the group consisting of 2,2-bis(4-methoxy-3-allylphenyl)propane, 2,2-bis(4-methoxy-3-methallyl-phenyl)propane, 4,4'-dimethoxy-3,3'-diallyldiphenyl,4,4'-dimethoxy-3,3'-dimethyallyldiphenyl, bis(4-methoxy-3-allyl-phenyl)methane, bis(4-methoxy-3-methallylphenyl)methane, 2,2-bis-(4-methoxy-3,5-diallylphenyl)propane, 2,2-bis-(4-methoxy-3,5-dimethallylphenyl)propane, 4-allylveratrole and 4-methallyl-veratrole; or a mixture of said alkenylphenols, a mixture of said alkenylphenol ethers or a mixture of said alkenylphenols and said alkenylphenol ethers; in such molar proportion that for each 1 equivalent of polyimide component (a) there is from 0.1 to 10 moles of alkenylphenol, alkenylphenol ether or mixture thereof as component (b).
Claim 19
Dependent Claim
201 words
A mixture of which is stable on storage and can be cured by the action of heat which comprises (a) a polyimide of the formula ##STR12## wherein R is hydrogen or methyl, and A is a divalent radical of the formula ##STR13## in which R 1 is selected from the group consisting of --CH 2 --, ##STR14## --SO 2 --, --SO--, --S-- and --O--, and n is 0 or 1; or a polyimide selected from the group consisting of the N,N'-bis-maleimide of 4,4'-diamino-triphenyl phosphate, the N,N'-bis-maleimide of 4,4'-diamino-triphenyl phosphate, the N,N',N"-tris-maleimide of tris-(4-aminophenyl) phosphate and the N,N',N"-tris-maleimide of tris-(4-aminophenyl) thiophosphate; or a mixture of said polyimides; and (b) an alkenylphenol selected from the group consisting of o,o'-diallyl-bisphenol A, 4,4'-dihydroxy-3,3'-diallyldiphenyl, bis-(4-hydroxy-3-allylphenyl)methane, 2,2-bis-(4-hydroxy-3,5-diallylphenyl)propane, eugenol, o,o'-dimethallyl-bisphenol A, 4,4'-dihydroxy-3,3'-dimethallyldiphenyl, bis-(4-hydroxy-3-methallylphenyl)methane, 2,2-bis-(4-hydroxy-3,5-dimethallylphenyl)propane and 4-methallyl-2-methoxyphenol; or an alkenylphenol ether selected from the group consisting of 2,2-bis(4-methoxy-3-allylphenyl)propane, 2,2-bis(4-methoxy-3-methallyl-phenyl)propane, 4,4'-dimethoxy-3,3'-diallyldiphenyl,4,4'-dimethoxy-3,3'-dimethyallyldiphenyl, bis(4-methoxy-3-allyl-phenyl)methane, bis(4-methoxy-3-methallylphenyl)methane, 2,2-bis-(4-methoxy-3,5-diallylphenyl)propane, 2,2-bis-(4-methoxy-3,5-dimethallylphenyl)propane, 4-allylveratrole and 4-methallyl-veratrole; or a mixture of said alkenylphenols, a mixture of said alkenylphenol ethers or a mixture of said alkenylphenols and said alkenylphenol ethers; in such molar proportion that for each 1 equivalent of polyimide component (a) there is from 0.1 to 10 moles of alkenylphenol, alkenylphenol ether or mixture thereof as component (b).
Claim 20
Dependent Claim
15 words
A mixture according to claim 17, characterised in that it contains, as the polyimide, 4,4'-bis-maleimido-diphenylmethane.
Claim 21
Dependent Claim
21 words
A mixture according to claim 17, characterised in that it contains, as the alkenylphenol or alkenylphenol-ether, eugenol or eugenol methyl ether.
Claim 22
Dependent Claim
16 words
A mixture according to claim 17, characterised in that it contains, as the alkenylphenol, o,o'-diallyl-bisphenol A.
Claim 23
Dependent Claim
16 words
A mixture according to claim 20, characterised in that it contains a bis-maleimide and o,o'-diallyl-bisphenol A.
Claim 24
Dependent Claim
47 words
A mixture according to claim 17 which additionally contains, in a concentration of 0.1 to 10% by weight, based on the total amount of the reactants, a polymerization catalyst selected from the group consisting of an ionic catalyst, a free-radical polymerization catalyst and a transition metal acetylacetonate.
Claim 25
Dependent Claim
18 words
A mixture according to claim 22, characterised in that it contains, as the polymerisation catalyst, an ionic catalyst.
Claim 26
Dependent Claim
27 words
A mixture according to claim 23, characterised in that it contains, as the ionic catalyst, a tertiary, secondary or mixed tertiary/secondary amine or a quaternary ammonium compound.
Claim 27
Dependent Claim
19 words
A mixture according to claim 23, characterised in that it contains, as the ionic catalyst, an alkali metal compound.
Claim 28
Dependent Claim
18 words
A mixture according to claim 22, characterised in that it contains, as the polymerisation catalyst, a free-radical catalyst.
Claim 29
Dependent Claim
18 words
A mixture according to claim 26, characterised in that it contains, as the free-radical catalyst, an organic peroxide.
Claim 30
Dependent Claim
16 words
A mixture according to claim 26, characterised in that it contains, as the free-radical catalyst, azoisobutyronitrile.
Claim 31
Dependent Claim
17 words
A mixture according to claim 22, characterised in that it contains, as the polymerisation catalyst, vanadium acetylacetonate.
Claim 32
Dependent Claim
31 words
A mixture according to claim 22, characterised in that it contains a polymerisation catalyst in a concentration of 0.1 to 5.0% by weight, based on the total amount of the reactants.
Claim 33
Dependent Claim
27 words
A mixture according to claim 17, characterised in that it contains the polyimide (a) and the alkenylphenol or alkenylphenol ether (b) in the form of the prepolymer.
Claim 34
Dependent Claim
15 words
A mixture according to claim 17, characterised in that it is a casting resin mixture.
Claim 35
Dependent Claim
32 words
A process according to claim 1 wherein for each 1 equivalent of polyimide component (a) there is from 0.25 to 1 mole of alkenylphenol, alkenylphenol ether or mixture thereof as component (b).
Claim 36
Dependent Claim
32 words
A mixture according to claim 17 wherein for each 1 equivalent of polyimide component (a) there is from 0.25 to 1 mole of alkenylphenol, alkenylphenol ether or mixture thereof as component (b).
References Cited (Backward Citations)
US3471458A
Cited
US4008186A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1981-07-10 | 1982-01-09 | 1982-07-11 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1985-07-10 | 1986-01-09 | 1986-07-11 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1989-07-10 | 1990-01-09 | 1990-07-11 | $7700.00 | Window Closed / Lapsed |