CA2014380A1 - Curable bismaleimide adducts - Google Patents
Curable bismaleimide adductsInfo
- Publication number
- CA2014380A1 CA2014380A1 CA 2014380 CA2014380A CA2014380A1 CA 2014380 A1 CA2014380 A1 CA 2014380A1 CA 2014380 CA2014380 CA 2014380 CA 2014380 A CA2014380 A CA 2014380A CA 2014380 A1 CA2014380 A1 CA 2014380A1
- Authority
- CA
- Canada
- Prior art keywords
- adducts
- bismaleimide
- adduct
- temperature
- curable
- 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
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
- C07D207/34—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D207/36—Oxygen or sulfur atoms
- C07D207/40—2,5-Pyrrolidine-diones
- C07D207/416—2,5-Pyrrolidine-diones with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to other ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/12—Unsaturated polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/12—Unsaturated polyimide precursors
- C08G73/125—Unsaturated polyimide precursors the unsaturated precursors containing atoms other than carbon, hydrogen, oxygen or nitrogen in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/12—Unsaturated polyimide precursors
- C08G73/126—Unsaturated polyimide precursors the unsaturated precursors being wholly aromatic
- C08G73/127—Unsaturated polyimide precursors the unsaturated precursors being wholly aromatic containing oxygen in the form of ether bonds in the main chain
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
- C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09J179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (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)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Abstract of the Disclosure: An adduct of bismaleimide and 4-aminobenzocyclobutene can be used as an adhesive which on curing produces a temperature resistant bond.
Description
: ~ ~
O.Z. 0050~4 Curable bismaleimide adducts ~ he pre~ent invention relate~ to thermally curable bi maleLmide adducts which are particularly useful as adhe~ives for heat-~tressed structural com-ponents.
The customary adhesives for structural components which are exposed to elevated temperatures are epoxy resins. However, at above 150C bonds produced by these adhesives are no longer stable, and above 200C the shear strength drops off sharply. The same is true of adhesives based on simple bismaleimides.
US-A-4 675 370 and US-A-4 711 964 disclose adducts of the formulae R-C-C C~
~C~ ~Cl 0 and ll ll O O
which are said to be suitable for use as matrix resins for fiber composites and as temperature resistant adhe-sives.
However, such adhesives have a comparatively high polymerization/crosslinking onset temperature at which the viscosity of the adhesive is 80 low that it will run out from between the surfaces to be bonded together.
It is an ob~ect of the present invention to develop thermally curable compounds which are suitable for example for temperature resistant adhesive ~oints.
The adhesives should have in particular a relatively low onset temperature, and the adhesive ~oints should have constant high shear strength over a wide temperature range.
, . .
. ;:, ' ` ~ . ~ ~ ' ' `
.
:::
-:
. ~
~ - - 2 ~
O.Z. 0050~4 Curable bismaleimide adducts ~ he pre~ent invention relate~ to thermally curable bi maleLmide adducts which are particularly useful as adhe~ives for heat-~tressed structural com-ponents.
The customary adhesives for structural components which are exposed to elevated temperatures are epoxy resins. However, at above 150C bonds produced by these adhesives are no longer stable, and above 200C the shear strength drops off sharply. The same is true of adhesives based on simple bismaleimides.
US-A-4 675 370 and US-A-4 711 964 disclose adducts of the formulae R-C-C C~
~C~ ~Cl 0 and ll ll O O
which are said to be suitable for use as matrix resins for fiber composites and as temperature resistant adhe-sives.
However, such adhesives have a comparatively high polymerization/crosslinking onset temperature at which the viscosity of the adhesive is 80 low that it will run out from between the surfaces to be bonded together.
It is an ob~ect of the present invention to develop thermally curable compounds which are suitable for example for temperature resistant adhesive ~oints.
The adhesives should have in particular a relatively low onset temperature, and the adhesive ~oints should have constant high shear strength over a wide temperature range.
, . .
. ;:, ' ` ~ . ~ ~ ' ' `
.
:::
-:
. ~
~ - - 2 ~
- 2 - O.Z. ~050/40731 We have found that the~e ob~ects are achieved by the bismaleimide adducts according to the present in~en-tion.
The present invention accordingly provide~
thermally curable bi maleimide adducts of the general formula O o ,,~N--X--N~
O O
where X i8 a divalent aromatic or cycloaliphatic group with or without heteroatoms.
Examples of group~ X ares R ~ , where R can be a divalent group, egd SOl2, CO, O, S, CH2 or C(CH3)2, ~' ~ ' ,, ~ ' ' O O
Il 11 ~`c~C~3 o B
The adduct~ according to the present invention are prepared by Michael add$tion of about 2 molea of 4-~minobenzocyclobutene to 1 mole of bismaleimide of the formula - - 3 - O.Z. 0050/40731 o o ¢C~x~c3 2 ~1 ~ 3 3 D
Il 11 o o where X is as defined above.
If les3 than 2 moles of 4-aminobenzocyclobutene are u~ed, the imide protons of the adduct can be added to excess bi~male~mide, 80 that the reaction mixture may also contain molecule~ of the following ~tructures o o ~ ~o ~
\~N--X--N~3 O O
The adducts according to the present invention are highly viscou~ or solid substances at room tempera-ture, depending on the nature of the group X. In general they are soluble in polar solvents. They undergo curing at above 150-C, preferably at from 170 to 230-C, presum-ably by a pericyclic or free radical mechanism. The cured product~ are insoluble and infusible and they decompose at above 350 - 400-C.
lS The adducts according to the present invention are suitable for use a~ temperature resi~tant adhesive~, as matrix resins for fiber composites and as casting resins for fabricating electrical components.
They are particularly effective for the adhesive bonding of structural components which are to be exposed to high temperatures.
The structural components may consist of a variety of materials, for example metal, in particular .
- 4 - O.Z. 0050/40731 aluminum or steel, or plastic, preferably a fibQr~com~
posite.
The adducts are applied to the surfaces to be ~oined in a conventional manner, for example by brush, if appropriate at a somewhat elevated temperature, from solution or in the form of a film. The adhe~ive according to the preæent invention may contain customary additives, such as fillers, eg. CaCO3, SiOz or qlass, free radical polymerizable comonomers, eg. bismaleimides or triple bond compounds, and also plastics, for example tempera-ture resistant phosphazene rubbers or thermoplastics such as polysulfones or polyimides.
It i8 also possible, in principle, to apply the starting materials for the adducts according to the present invention, ie. bismaleimide and 4-aminobenzo-cyclobutene, to the surfaces to be ~oined together and to raise the temperature to form the bismaleimide adducts in situ and cure them in one operation.
EXAMPLES
1. 0.1 mol of 4,4'-diaminodiphenylmethane-bi~maleimide i~ stirred together with 0.2 mol of 4-amino-benzocyclobutene at 120C under nitrogen for 4 hours. The result is an adduct which is highly viscous at room temperature and which has a gel time of 2 minutes at 220-C. The adduct is applied to the smooth surfaces of steel ribbons by knife coating.
The surfaces are brought toqether under a slight pressure. This is followed by curing at 180C for 1 hour ~nd at 220-C for 5 hours. The shear strength i8 measured in line with German Standard Specifica-tion DIN 53 283. For the result see the table.
2. 0.1 mol of 4,4'-diaminodiphenylmethane-bismaleimide and 0.2 mol of 4-aminobenzocyclobutene are mixed at room temperature to form a viscous mass. Thi~ is applied to steel surfaces and then cured, both steps being carried out as described under 1. In the , , . - .
, ::
- 5 - O.Z. 0050/40731 process an adduct is formed in situ and crosslinked in the subsequent curing. 2 ~ ~ ~ 3 ~ ~
The present invention accordingly provide~
thermally curable bi maleimide adducts of the general formula O o ,,~N--X--N~
O O
where X i8 a divalent aromatic or cycloaliphatic group with or without heteroatoms.
Examples of group~ X ares R ~ , where R can be a divalent group, egd SOl2, CO, O, S, CH2 or C(CH3)2, ~' ~ ' ,, ~ ' ' O O
Il 11 ~`c~C~3 o B
The adduct~ according to the present invention are prepared by Michael add$tion of about 2 molea of 4-~minobenzocyclobutene to 1 mole of bismaleimide of the formula - - 3 - O.Z. 0050/40731 o o ¢C~x~c3 2 ~1 ~ 3 3 D
Il 11 o o where X is as defined above.
If les3 than 2 moles of 4-aminobenzocyclobutene are u~ed, the imide protons of the adduct can be added to excess bi~male~mide, 80 that the reaction mixture may also contain molecule~ of the following ~tructures o o ~ ~o ~
\~N--X--N~3 O O
The adducts according to the present invention are highly viscou~ or solid substances at room tempera-ture, depending on the nature of the group X. In general they are soluble in polar solvents. They undergo curing at above 150-C, preferably at from 170 to 230-C, presum-ably by a pericyclic or free radical mechanism. The cured product~ are insoluble and infusible and they decompose at above 350 - 400-C.
lS The adducts according to the present invention are suitable for use a~ temperature resi~tant adhesive~, as matrix resins for fiber composites and as casting resins for fabricating electrical components.
They are particularly effective for the adhesive bonding of structural components which are to be exposed to high temperatures.
The structural components may consist of a variety of materials, for example metal, in particular .
- 4 - O.Z. 0050/40731 aluminum or steel, or plastic, preferably a fibQr~com~
posite.
The adducts are applied to the surfaces to be ~oined in a conventional manner, for example by brush, if appropriate at a somewhat elevated temperature, from solution or in the form of a film. The adhe~ive according to the preæent invention may contain customary additives, such as fillers, eg. CaCO3, SiOz or qlass, free radical polymerizable comonomers, eg. bismaleimides or triple bond compounds, and also plastics, for example tempera-ture resistant phosphazene rubbers or thermoplastics such as polysulfones or polyimides.
It i8 also possible, in principle, to apply the starting materials for the adducts according to the present invention, ie. bismaleimide and 4-aminobenzo-cyclobutene, to the surfaces to be ~oined together and to raise the temperature to form the bismaleimide adducts in situ and cure them in one operation.
EXAMPLES
1. 0.1 mol of 4,4'-diaminodiphenylmethane-bi~maleimide i~ stirred together with 0.2 mol of 4-amino-benzocyclobutene at 120C under nitrogen for 4 hours. The result is an adduct which is highly viscous at room temperature and which has a gel time of 2 minutes at 220-C. The adduct is applied to the smooth surfaces of steel ribbons by knife coating.
The surfaces are brought toqether under a slight pressure. This is followed by curing at 180C for 1 hour ~nd at 220-C for 5 hours. The shear strength i8 measured in line with German Standard Specifica-tion DIN 53 283. For the result see the table.
2. 0.1 mol of 4,4'-diaminodiphenylmethane-bismaleimide and 0.2 mol of 4-aminobenzocyclobutene are mixed at room temperature to form a viscous mass. Thi~ is applied to steel surfaces and then cured, both steps being carried out as described under 1. In the , , . - .
, ::
- 5 - O.Z. 0050/40731 process an adduct is formed in situ and crosslinked in the subsequent curing. 2 ~ ~ ~ 3 ~ ~
3. For comparison, 4,4'-diaminodiphenylme~hane-bis-maleimide alone is applied to the steel surfaces and cured, aqain by a polymerization reaction.
Results Example Measurement Shear strength temperature -55-C 9 MPa 1 23C 9 NPa 220C 8 ~Pa -55C 9 MPa 2 23C 9 MPa 220C 7 MPa -55C 10 MPa 3 23C 10 NPa 220C 5 MPa ". ", . . , , , . . . . . , ~ . , .
Results Example Measurement Shear strength temperature -55-C 9 MPa 1 23C 9 NPa 220C 8 ~Pa -55C 9 MPa 2 23C 9 MPa 220C 7 MPa -55C 10 MPa 3 23C 10 NPa 220C 5 MPa ". ", . . , , , . . . . . , ~ . , .
Claims (3)
1. A thermally curable bismaleimide adduct of the general formula where X is a divalent aromatic or cycloaliphatic group with or without heteroatoms.
2. A bismaleimide adduct as claimed in claim 1, wherein X is a group where R is SO2, CO, O, S, CH2 or C(CH3)2.
3. A process for bonding structural components which are to be exposed to high temperatures by applying a bismaleimide adduct as claimed in claim 1 to the surfaces of said components, bringing the surfaces together and curing the adduct at above 150°C.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3912081.3 | 1989-04-13 | ||
| DE19893912081 DE3912081A1 (en) | 1989-04-13 | 1989-04-13 | TEMPERATURE BISMALEINIMID ADDUCTS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2014380A1 true CA2014380A1 (en) | 1990-10-13 |
Family
ID=6378560
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2014380 Abandoned CA2014380A1 (en) | 1989-04-13 | 1990-04-11 | Curable bismaleimide adducts |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0392354A1 (en) |
| CA (1) | CA2014380A1 (en) |
| DE (1) | DE3912081A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018124140A1 (en) * | 2016-12-27 | 2018-07-05 | 日産化学工業株式会社 | Novel polymer and diamine compound, liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5247037A (en) * | 1990-12-20 | 1993-09-21 | The Dow Chemical Company | Mono(cyclobutarene)/polymaleimide copolymers |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2925261C3 (en) * | 1979-06-22 | 1982-05-19 | Th. Goldschmidt Ag, 4300 Essen | Thermosetting adhesive |
| US4783514A (en) * | 1986-02-28 | 1988-11-08 | The Dow Chemical Company | Polymeric monoarylcyclobutane compositions |
| US4675370A (en) * | 1986-04-29 | 1987-06-23 | University Of Dayton | Resin systems derived from benzocyclobutene-alkyne imide monomers |
| US4711964A (en) * | 1986-05-08 | 1987-12-08 | University Of Dayton | Bisdiene from bis-benzocyclobutene compound |
| US4795827A (en) * | 1987-10-16 | 1989-01-03 | The Dow Chemical Company | Cyclobutarene ketoaniline monomeric and polymeric compositions |
-
1989
- 1989-04-13 DE DE19893912081 patent/DE3912081A1/en not_active Withdrawn
-
1990
- 1990-04-05 EP EP90106519A patent/EP0392354A1/en not_active Withdrawn
- 1990-04-11 CA CA 2014380 patent/CA2014380A1/en not_active Abandoned
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018124140A1 (en) * | 2016-12-27 | 2018-07-05 | 日産化学工業株式会社 | Novel polymer and diamine compound, liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element |
| JPWO2018124140A1 (en) * | 2016-12-27 | 2019-10-31 | 日産化学株式会社 | Novel polymer and diamine compound, liquid crystal aligning agent, liquid crystal aligning film and liquid crystal display element |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0392354A1 (en) | 1990-10-17 |
| DE3912081A1 (en) | 1990-10-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6620946B2 (en) | Low shrinkage thermosetting resin compositions and methods of use thereof | |
| US8193280B2 (en) | Ionic liquid epoxy resins | |
| EP1453087B1 (en) | Microelectronic assembly | |
| CA1258944A (en) | Stable imide-containing compositions | |
| US9441144B2 (en) | Benzoxazine-thiol adducts | |
| US7309724B2 (en) | Thermosetting resin compositions containing maleimide and/or vinyl compounds | |
| US9096503B2 (en) | Benzoxazine-thiol adducts | |
| US4661604A (en) | Monofunctional crosslinking imidophenols | |
| US5171822A (en) | Low toxicity high temperature pmr polyimide | |
| US4800125A (en) | Coupling agent compositions | |
| US4718944A (en) | Coupling agent compositions | |
| JPH0465831B2 (en) | ||
| US5242755A (en) | High temperature adhesive | |
| US6124035A (en) | High temperature transfer molding resins | |
| CA2014380A1 (en) | Curable bismaleimide adducts | |
| US20140275413A1 (en) | Heat and moisture resistant anaerobic adhesives and sealants | |
| US5350635A (en) | Cyanate resin adhesive for polyimide film | |
| US5708127A (en) | Polymerizable monomeric reactants (PMR) type resins | |
| US5093459A (en) | Bismaleimide resin containing unreacted monomer reactants | |
| JPH01256535A (en) | Imide group-containing polymer prepared from hindered diamine and production thereof | |
| US5464925A (en) | Benzocyclobutene-terminated polymides | |
| Alam et al. | Ethynyl-terminated imide oligomers | |
| KR0161802B1 (en) | Furniture adhesives | |
| JPS60210685A (en) | Heat-resistant adhesive composition | |
| CA2104726A1 (en) | Curable compositions |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Dead |