← Back to Patent Explorer
US4426463A Expired / Lapsed US ⏱️ 0.0 years remaining

Modified polyimide foams and methods of making same

Assignee: IMI-TECH Corp ELK GROVE ILL A CORP OF
•
Filing: 1983-04-15
•
Granted: 1984-01-17
•
Expires: 2003-04-15
📄 Original PDF 🌐 Google Patents 🔄 Sync Now

Abstract

Abstract Methods of making modified polyimide/polyimide-amide foams having selected compressive resistance and density characteristics and the resulting compositions. An N-substituted aliphatic imide is prepared by reacting a suitable aromatic dianhydride with a suitable oxoimine. Within the mole ratio range of oxoimine to dianhydride of about 0.5:1 to about 0.05:1 the compressive resistance of the final foam can be selected in accordance with the intended end use of the foam. Density and compressive resistance varies inversely with the oxoimine quantity in the ratio, being greatest with the 0.5:1 ratio and lowest with the 0.05:1 ratio. A polyimide forming material is prepared by dissolving the N-substituted aliphatic imide in an esterifying solvent, then adding a suitable aromatic diamine. This material is dried to a powder or film. A foam is produced by heating the mateial to reaction temperature for a period sufficient to produce a stable foam. The material melts, then spontaneously expands into a foam which becomes self supporting and cures to a resilient flexible foam. Depending upon heating conditions, a polyimide, polyimide-amide or mixture thereof may be produced, resulting in foams having varying physical properties.

Inventors

  • 👤 John Gagliani
  • 👤 John V. Long

Bibliographic Details

Application Number —
Jurisdiction US
Data Source google_patents
Last Synchronized 2026-10-29 18:04
CPC Classifications
C; C08; C08J; C08J9/00; C08J9/02; C08J2379/00; C08J2379/04; C08J2379/08; Y; Y10; Y10S; Y10S264/00; Y10S264/05

Claims Analysis

Total Claims: 25
Claim 1
Independent Claim 145 words
The method of making a resilient, flame resistant modified polyimide foam having a selected compressive resistance which comprises the steps of: reacting an aromatic dianhydride with an oximine having the general formula: CH.sub.2 --(CH.sub.2).sub.x --NHCO wherein "X" is an integer from 2 to 4, in a selected mole ratio of oxoimine to dianhydride between about 0.5:1 and about 0.05:1 to produce an N-substituted aliphatic imide; dissolving said imide in a reactive solvent esterifying agent to exterify said imide; adding thereto a diamine; drying the resulting solution; and heating the dry material to a selected foaming temperature of from about 120° C. to about 320° C. for a period of from about 10 to about 60 minutes; whereby a resilient foam having a selected compressive resistance in accordance with the selected oxoimine to dianhydride mole ratio, the compressive resistance being inversely proportional to the oxoimine quantity.
Claim 2
Independent Claim 145 words
The method of making a resilient, flame resistant modified polyimide foam having a selected compressive resistance which comprises the steps of: reacting an aromatic dianhydride with an oximine having the general formula: CH.sub.2 --(CH.sub.2).sub.x --NHCO wherein "X" is an integer from 2 to 4, in a selected mole ratio of oxoimine to dianhydride between about 0.5:1 and about 0.05:1 to produce an N-substituted aliphatic imide; dissolving said imide in a reactive solvent esterifying agent to exterify said imide; adding thereto a diamine; drying the resulting solution; and heating the dry material to a selected foaming temperature of from about 120° C. to about 320° C. for a period of from about 10 to about 60 minutes; whereby a resilient foam having a selected compressive resistance in accordance with the selected oxoimine to dianhydride mole ratio, the compressive resistance being inversely proportional to the oxoimine quantity.
Claim 3
Dependent Claim 29 words
The method according to claim 1 wherein the mole ratio of oxoimine to dianhydride is about 0.05:1, whereby the resulting foam has a high density and high compressive resistance.
Claim 4
Dependent Claim 29 words
The method according to claim 1 wherein the mole ratio of oxoimine to dianhydride is about 0.5:1, whereby the resulting foam has a low density and low compressive resistance.
Claim 5
Dependent Claim 31 words
The method according to claim 1 wherein said foaming temperature is in the range of from about 230° C. and about 320° C. and the resulting foam comprises primarily a polyimide.
Claim 6
Dependent Claim 31 words
The method according to claim 1 wherein said foaming temperature is in the range of from about 120° C. and about 220° C. and the resulting foam is primarily a polyimide-amide.
Claim 7
Dependent Claim 20 words
The method according to claim 1 wherein said aromatic dianhydride is pyromellitic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic acid dianhydride or mixtures thereof.
Claim 8
Dependent Claim 11 words
The method according to claim 1 wherein said oxoimine is caprolactam.
Claim 9
Dependent Claim 13 words
The method according to claim 1 wherein said reactive solvent is methyl alcohol.
Claim 10
Dependent Claim 12 words
The method according to claim 1 wherein said diamine is 4,4'-diaminophenyl methane.
Claim 11
Dependent Claim 24 words
The method according to claim 1 wherein said diamine comprises at least two different diamines, at least one of which is an aromatic diamine.
Claim 12
Dependent Claim 29 words
The method according to claim 1 further including the step of adding from about 0.01 to about 2 wt. % of a surfactant to the solution prior to drying.
Claim 13
Dependent Claim 22 words
The method according to claim 1 further including the step of adding fillers or reinforcing materials to the solution prior to drying.
Claim 14
Independent Claim 317 words
The method of making a modified polyimide foam having a selected compressive resistance comprising a mixture of polyimide and polyimide-amide resins with the polyimide-amide predominating which comprises the steps of: mixing together an aromatic dianhydride selected from pyromellitic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic acid dianhydride and mixtures thereof and an oxoimine having the general formula: ##STR8## wherein "x" is an integer from 2 to 4, the mole ratio of oxoimine to dianhydride being selected within the range of from about 0.5:1 to about 0.05:1 in accordance with the final foam compressive resistance desired; heating the mixture to a temperature of from about 150° C. to about 200° C. for from about 5 to about 90 minutes to react said dianhydride with said oxoimine to produce an N-substituted aliphatic imide; cooling the mixture to a temperature of from about 40° C. to about 70° C.; dissolving said imide in a reactive solvent esterifying agent to esterify said imide; heating the imide solution to reflux at a temperature of from about 70° C. to about 80° C. for a period of from about 60 to about 90 minutes to esterify said imide; adding thereto about 1.0 M 4,4'-diaminodiphenyl methane per 1.0 M of dianhydride; heating the resulting solution to reflux at a temperature of from about 70° C. to about 80° C. for a period of about 2 to about 30 minutes; drying the solution at a temperature of from about 60° C. to about 70° C. for a period of about 60 to about 240 minutes to produce a dry material; and foaming said dry material by heating to a temperature of about 120° C. to about 220° C. in a pre-heated oven for from about 10 to about 40 minutes; whereby a resilient foam having a selected compressive resistance in accordance with the selected oxoimine to dianhydride mole ratio, the compressive resistance being inversely proportional to the oxoimine quantity.
Claim 15
Independent Claim 317 words
The method of making a modified polyimide foam having a selected compressive resistance comprising a mixture of polyimide and polyimide-amide resins with the polyimide-amide predominating which comprises the steps of: mixing together an aromatic dianhydride selected from pyromellitic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic acid dianhydride and mixtures thereof and an oxoimine having the general formula: ##STR8## wherein "x" is an integer from 2 to 4, the mole ratio of oxoimine to dianhydride being selected within the range of from about 0.5:1 to about 0.05:1 in accordance with the final foam compressive resistance desired; heating the mixture to a temperature of from about 150° C. to about 200° C. for from about 5 to about 90 minutes to react said dianhydride with said oxoimine to produce an N-substituted aliphatic imide; cooling the mixture to a temperature of from about 40° C. to about 70° C.; dissolving said imide in a reactive solvent esterifying agent to esterify said imide; heating the imide solution to reflux at a temperature of from about 70° C. to about 80° C. for a period of from about 60 to about 90 minutes to esterify said imide; adding thereto about 1.0 M 4,4'-diaminodiphenyl methane per 1.0 M of dianhydride; heating the resulting solution to reflux at a temperature of from about 70° C. to about 80° C. for a period of about 2 to about 30 minutes; drying the solution at a temperature of from about 60° C. to about 70° C. for a period of about 60 to about 240 minutes to produce a dry material; and foaming said dry material by heating to a temperature of about 120° C. to about 220° C. in a pre-heated oven for from about 10 to about 40 minutes; whereby a resilient foam having a selected compressive resistance in accordance with the selected oxoimine to dianhydride mole ratio, the compressive resistance being inversely proportional to the oxoimine quantity.
Claim 16
Dependent Claim 29 words
The method according to claim 13 wherein the mole ratio of oxoimine to dianhydride is about 0.05:1, whereby the resulting foam has a high density and high compressive resistance.
Claim 17
Dependent Claim 29 words
The method according to claim 13 wherein the mole ratio of oxoimine to dianhydride is about 0.5:1, whereby the resulting foam has a low density and low compressive resistance.
Claim 18
Independent Claim 317 words
The method of making a modified polyimide foam having a selected compressive resistance comprising a mixture of polyimide and polyimide-amide with the polyimide predominating which comprises the steps of: mixing together an aromatic dianhydride selected from pyromellitic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic acid dianhydride and mixtures thereof and an oxoimine having the general formula: ##STR9## wherein "x" is an integer from 2 to 4, the mole ratio of oxoimine to dianhydride being selected within the range of from about 0.5:1 to about 0.05:1 in accordance with the desired final foam compressive resistance, said compressive resistance being inversely proportional to the oxoimine quantity; heating the mixture to a temperature of from about 150° C. to about 200° C. for from about 5 to about 90 minutes to react said dianhydride with said oxoimine to produce an N-substituted aliphatic imide; cooling the mixture to a temperature of from about 40° C. to about 70° C.; dissolving said imide in a reacting solvent esterifying agent to esterify said imide; heating the imide solution to reflux at a temperature of from about 70° C. to about 80° C. for a period of from about 60 to about 90 minutes to esterify said imide; adding thereto about 1.0 M 4,4'-diaminodiphenyl methane per about 1.0 M of dianhydride; heating the resulting solution of reflux at a temperature of from about 70° C. to about 80° C. for a period of about 2 to about 30 minutes; drying the solution at a temperature of from about 60° C. to about 70° C. for a period of about 60 to about 240 minutes to produce a dry material; and foaming said dry material by heating to a temperature of about 230° C. to about 320° C. in a pre-heated oven for about 30 to about 60 minutes; whereby a resilient flame resistant modified polyimide foam having selected compressive resistance characteristics is produced, consisting primarily of polyimide resin.
Claim 19
Independent Claim 317 words
The method of making a modified polyimide foam having a selected compressive resistance comprising a mixture of polyimide and polyimide-amide with the polyimide predominating which comprises the steps of: mixing together an aromatic dianhydride selected from pyromellitic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic acid dianhydride and mixtures thereof and an oxoimine having the general formula: ##STR9## wherein "x" is an integer from 2 to 4, the mole ratio of oxoimine to dianhydride being selected within the range of from about 0.5:1 to about 0.05:1 in accordance with the desired final foam compressive resistance, said compressive resistance being inversely proportional to the oxoimine quantity; heating the mixture to a temperature of from about 150° C. to about 200° C. for from about 5 to about 90 minutes to react said dianhydride with said oxoimine to produce an N-substituted aliphatic imide; cooling the mixture to a temperature of from about 40° C. to about 70° C.; dissolving said imide in a reacting solvent esterifying agent to esterify said imide; heating the imide solution to reflux at a temperature of from about 70° C. to about 80° C. for a period of from about 60 to about 90 minutes to esterify said imide; adding thereto about 1.0 M 4,4'-diaminodiphenyl methane per about 1.0 M of dianhydride; heating the resulting solution of reflux at a temperature of from about 70° C. to about 80° C. for a period of about 2 to about 30 minutes; drying the solution at a temperature of from about 60° C. to about 70° C. for a period of about 60 to about 240 minutes to produce a dry material; and foaming said dry material by heating to a temperature of about 230° C. to about 320° C. in a pre-heated oven for about 30 to about 60 minutes; whereby a resilient flame resistant modified polyimide foam having selected compressive resistance characteristics is produced, consisting primarily of polyimide resin.
Claim 20
Dependent Claim 29 words
The method according to claim 16 wherein the mole ratio of oxoimine to dianhydride is about 0.05:1, whereby the resulting foam has a high density and high compressive resistance.
Claim 21
Dependent Claim 29 words
The method according to claim 16 wherein the mole ratio of oxoimine to dianhydride is about 0.5:1, whereby the resulting foam has a low density and low compressive resistance.
Claim 22
Independent Claim 325 words
The method of making a modified polyimide foam having a selected compressive resistance comprising a mixture of polyimide and polyimide-amide with significant portions of both polyimide and polyimide-amide which comprises the steps of: mixing together an aromatic dianhydride selected from pyromellitic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic acid dianhydride and mixtures thereof and an oxoimine having the general formula: ##STR10## wherein "x" is an integer from 2 to 4, the mole ratio of oxoimine to dianhydride being selected within the range of from about 1.5:1 to about 0.05:1 in accordance with the desired final foam compressive resistance, said compressive resistance being inversely proportional to the oxoimine quantity; heating the mixture to a temperature of from about 150° C. to about 200° C. for from about 5 to about 90 minutes to react said dianhydride with said oxoimine to produce an N-substituted aliphatic imide; cooling the mixture to a temperature of from about 40° C. to about 70° C.; dissolving said imide in a reactive solvent esterifying agent to esterify said imide; heating the imide solution to reflux at a temperature of from about 70° C. to about 80° C. for a period of from about 60 to about 90 minutes to esterify said imide; adding thereto about 1.0 M 4,4'-diaminodiphenyl methane per about 1.0 M of dianhydride; heating the resulting solution to reflux at a temperature of from about 70° C. to about 80° C. for a period of about 2 to about 30 minutes; drying the solution at a temperature of from about 60° C. to about 70° C. for a period of about 60 to about 240 minutes to produce a dry material; and foaming said dry material by heating to a temperature of from about 210° C. to about 250° C. for a period of about 30 to about 45 minutes; whereby a resilient flame resistant modified polyimide foam having selected compressive resistance characteristics is produced containing significant portions of both polyimide and polyimide-amide resins.
Claim 23
Independent Claim 325 words
The method of making a modified polyimide foam having a selected compressive resistance comprising a mixture of polyimide and polyimide-amide with significant portions of both polyimide and polyimide-amide which comprises the steps of: mixing together an aromatic dianhydride selected from pyromellitic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic acid dianhydride and mixtures thereof and an oxoimine having the general formula: ##STR10## wherein "x" is an integer from 2 to 4, the mole ratio of oxoimine to dianhydride being selected within the range of from about 1.5:1 to about 0.05:1 in accordance with the desired final foam compressive resistance, said compressive resistance being inversely proportional to the oxoimine quantity; heating the mixture to a temperature of from about 150° C. to about 200° C. for from about 5 to about 90 minutes to react said dianhydride with said oxoimine to produce an N-substituted aliphatic imide; cooling the mixture to a temperature of from about 40° C. to about 70° C.; dissolving said imide in a reactive solvent esterifying agent to esterify said imide; heating the imide solution to reflux at a temperature of from about 70° C. to about 80° C. for a period of from about 60 to about 90 minutes to esterify said imide; adding thereto about 1.0 M 4,4'-diaminodiphenyl methane per about 1.0 M of dianhydride; heating the resulting solution to reflux at a temperature of from about 70° C. to about 80° C. for a period of about 2 to about 30 minutes; drying the solution at a temperature of from about 60° C. to about 70° C. for a period of about 60 to about 240 minutes to produce a dry material; and foaming said dry material by heating to a temperature of from about 210° C. to about 250° C. for a period of about 30 to about 45 minutes; whereby a resilient flame resistant modified polyimide foam having selected compressive resistance characteristics is produced containing significant portions of both polyimide and polyimide-amide resins.
Claim 24
Dependent Claim 29 words
The method according to claim 19, wherein the mole ratio of oxoimine to dianhydride is about 0.05:1, whereby the resulting foam has a high density and high compressive resistance.
Claim 25
Dependent Claim 29 words
The method according to claim 19 wherein the mole ratio of oxoimine to dianhydride is about 0.5:1, whereby the resulting foam has a low density and low compressive resistance.

References Cited (Backward Citations)

US4335120A Cited
US4361453A Cited
US4360604A Cited

USPTO Annuity & Maintenance Windows

Annuity Stage Window Opens Payment Deadline Surcharge Period Until Estimated Fee Status
3.5 Years (Year 4) 1987-01-16 1987-07-18 1988-01-17 $2000.00 Window Closed / Lapsed
7.5 Years (Year 8) 1991-01-16 1991-07-18 1992-01-17 $3760.00 Window Closed / Lapsed
11.5 Years (Year 12) 1995-01-16 1995-07-18 1996-01-17 $7700.00 Window Closed / Lapsed

Assigned Categories & Tags

No categories assigned to this patent yet.

Assign Category Tag