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WO1992001014A1 - Polyimides et compositions utilisees pour leur preparation - Google Patents

Polyimides et compositions utilisees pour leur preparation Download PDF

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Publication number
WO1992001014A1
WO1992001014A1 PCT/GB1991/001022 GB9101022W WO9201014A1 WO 1992001014 A1 WO1992001014 A1 WO 1992001014A1 GB 9101022 W GB9101022 W GB 9101022W WO 9201014 A1 WO9201014 A1 WO 9201014A1
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WO
WIPO (PCT)
Prior art keywords
mixture
prepolymer
integer
general formula
component
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.)
Ceased
Application number
PCT/GB1991/001022
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English (en)
Inventor
Nigel David Hoyle
Nevin John Stewart
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BP PLC
Original Assignee
BP PLC
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Filing date
Publication date
Application filed by BP PLC filed Critical BP PLC
Publication of WO1992001014A1 publication Critical patent/WO1992001014A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • C08G73/121—Preparatory processes from unsaturated precursors and polyamines
    • 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
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C08G73/101—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents

Definitions

  • This invention relates to novel polyimides and compositions for their preparation.
  • PMR-15 is derived from a mixture of three materials:
  • US 4 203 922 and US 4 111 906 disclose a polyimide having an average molecular weight of at least 5000, consisting of recurring units of a diamine and the dianhydride of a tetracarboxylic acid, in which the diamine is 2, 2-bis[4-(4-aminophenoxy)phenyl]-hexafluoropropane.
  • These polyimides differ fundamentally from the PMR-15 type in that they contain no norbornene units, which in PMR-15 are present in an amount roughly equal to the amount of diamine. They are not significantly cross-linked.
  • EP-A-142149 discloses polyimides of a similar type to those of US 4 203 922 above, that is, long-chain molecules with recurring units of a diamine and the dianhydride of a tetracarboxylic acid. No norbornene units are present. The resulting polymers are stated to be useful as coating film material for semiconductors.
  • One of very many diamines used to prepare the polymers is 2,2-bis[4-(2-trifluoromethyl-4-aminophenoxy)phenyl]hexafluoropropane.
  • a characteristic of the invention is that the dianhydride component has a defined composition including four phenyl groups and a perfluoroalkylene linkage.
  • WO-84/04102 discloses polyimides very similar to those of
  • the polymers are long-chain molecules with recurring diamine and dianhydride units, and their stated utility is as various types of insulating films, particularly in electronics.
  • the present invention provides a mixture of:
  • R 1 is a C(1-4) alkyl group
  • each of R 2 and R 3 independently represents a C(1-4) alkyl group
  • each R f independently represent a C(1-4) perfluoroalkyl group, a is an integer from 1 to 4, b is 0 or an integer from 1 to 4, c is 0 or an integer from 1 to 4, and d is an integer from 1 to 4; components (b) and (c) being present in substantially stoicheiometric amounts, and the molar ratio of component (b) to component (a) being in the range of from 0.25 to 5.
  • R 1 represents a methyl group.
  • each of R 2 and R 3 represents a methyl group.
  • each R f represents a CF 3 group.
  • each of a and d is 1 or 2 and each of b and c is 0, 1 or 2.
  • a and d are 1 and c and d are 0, and in this case, preferably the R f groups are meta to the araine groups.
  • the compound of the general formula III is 2,2-bis-[4-(2-trifluoromethyl-4-aminophenoxy)phenyl]hexafluoropropane.
  • the mixture according to the invention contains components (b) and (c) in approximately stoicheiometric amounts - i.e. for each n moles of component (b), (n+1) moles of component (c) are present.
  • the molar ratio of component (b) to component (a) is in the range of from 0.25 to 5, especially 0.75 to 1.5.
  • the mixture according to the invention may be polymerised by the application of heat to produce a prepolymer.
  • the prepolymer can then be cross-linked to produce the cured polyimide by the application of further heat.
  • This reaction scheme is shown in Figure 1 of the drawings.
  • n represents the number of repeat units in the polymer.
  • the value of n for individual molecules can vary very widely indeed, but the average n is preferably from 0.5 to 10, especially 1.5 to 3.
  • the scheme of Figure 1 shows one possible structure IV of the prepolymer; it is likely, of course, that the prepolymer also contains other molecules due to the complex nature of the
  • the pre-polymer may begin to cross-link before all the diamine and tetracarboxylic acid derivative have reacted .
  • the polyimide has the structure (V) given in Figure 1.
  • the prepolymer IV and the polymer V are both novel, and both form further aspects of the present invention.
  • a mixture according to the invention is preferably in the form of a solution in an organic solvent.
  • Any suitable inert solvent for example an alcohol, ether, ester, hydrocarbon or chlorinated
  • hydrocarbon may be used.
  • an alcohol especially methanol, or a mixture of alcohols, is used.
  • the solution preferably contains up to 70% by weight of organic solvent, especially from 1 to 15% by weight.
  • a mixture according to the invention may be converted into a prepolymer by heating, preferably to a temperature in the range of from 100 to 500, especially from 175 to 220. It is preferred to heat under reduced pressure, especially from 100 to 200, in order to aid removal of volatiles from the mixture.
  • Subsequent curing of the prepolymer is carried out by heating, preferably to a temperature in the range of from 50 to 500, especially 200 to 300. This heating may be carried out under reduced,
  • the mixture according to the invention is to be used in the production of a fibre-reinforced composite, it is applied to the desired fibres before curing starts.
  • a typical process would involve applying the mixture, in the form of an organic solution, to the desired fibres and heating the resulting pre-preg to produce a prepolymer and remove voltiles. This may typically be performed in a vacuum oven, or in a mould or vacuum bag. In the latter two cases, the material may then be heated under pressure to produce the finished composite. In the case where the initial heating was performed in a vacuum oven, the material may be transferred to a vacuum bag or mould before heating under pressure to produce the finished composite.
  • the mixtures according to the invention may be used with any desired fibres, for example carbon, aramid, glass or ceramic fibres.
  • the resulting composites are strong, tough, and stable at high temperatures.
  • a fibre-reinforced component comprising reinforcing fibres, especially carbon, aramid, glass and/or ceramic fibres, in a matrix of a polyimide according to the invention.
  • hexafluoropropane (9.49 g, 14.5 mmol) was dissolved in ethyl acetate (232 ml) and charged with 5% palladium on activated carbon (0.51 g) to a rocking hydrogenator (capacity 500 ml).
  • the vessel was sealed and repeatedly evacuated and purged with hydrogen. Hydrogen pressure was increased to 320 psi and rocking and heating started. After 25 minutes the temperature reached 90oC. The reaction was held at 90oC for 21 ⁇ 4 hours and then allowed to cool to room temperature over 2 hours. Hydrogen was vented and the reaction mixture degassed.
  • Catalyst was recovered by filtration and the light orange solution concentrated at 33oC under reduced pressure on a rotary evaporator to give an orange-red viscous oil. This oil was further dried by stirring at 100oC (oil bath temperature) for 1.5 hours under high vacuum 0.1 mbar. On cooling an orange-red brittle glass identified as 2,2-bis[4-(2-trifluoromethyl-4-aminophenoxy)phenyl]hexafluoropropane was obtained (8.64 g, 99%, calculated solvent free weight).
  • HTA-76K, Trade Mark train using a commercial 12" California Graphite prepregging machine to produce a linear prepreg of approximately 60% by weight fibre and 40% by weight of resin. This prepreg was protected on each side by silicone release paper and stored at -18oC until required.
  • Prepreg as prepared above was cut into rectangular pieces and stacked.
  • the prepreg stack was placed inside the vacuum bag in an autoclave and subjected to temperature and pressure as depicted in Figure 2.
  • the resulting laminate was then heated to 300oC at 3oC/min the temperature increased to 350oC at 1°C/min and the temperature maintained at 350oC for 24 hours.
  • Prepreg as prepared above was cut into rectangular pieces and stacked.
  • the prepreg stack was placed inside the vacuum bag in an autoclave and subjected to temperature and pressure as depicted in Figure 3.
  • the resulting laminate was then heated to 290°C at 2oC/min, the temperature increased to 315oC at 1oC/min and the temperature maintained at 315oC, for 6 hours.
  • unidirectional fibre was measured as 633 J/m 2 .
  • the weight loss after 3000 hours at 300oC was 38%.
  • a sample of polyimide laminate was prepared essentially following the method of Example 2, using 239 g of 2,2'-bis(4-(2-trifluoromethyl-4-aminophenoxy)phenyl)hexafluoropropane and other materials in proportion.
  • the resulting laminate showed flex strength and
  • a sample of polyimide laminate was made according to Example 4, except that the diamine was replaced with an equimolar amount of 2,2'-bis(4-(4-aminophenoxy)phenyl)hexafluoropropane.
  • the amount of methanol in the mixture had to be increased by approximately 40% in order to maintain the necessary viscosity.
  • Autoclave curing took place simultaneously with the laminate sample of Example 4.
  • the resulting material showed flex strength and interlaminar shear strength (Crag standard test) of 1.67 GPa and 93.92 MPa respectively.
  • the fracture energy (G II c) was measured at 668.25Jm -2 .

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

De nouveaux matériaux de polyimide peuvent être produits par la polymérisation d'un mélange d'un dérivé de norbornène défini (a), d'un dérivé d'acide benzophénonetétracarboxylique défini (b), et d'une diamine (c) de la formule (III) où chaque Rf représente indépendamment un groupe perfluoroalkyle C(1-4), a est un nombre entier de 1 à 4, b est 0 ou un nombre entier de 1 à 4, c est 0 ou un nombre entier de 1 à 4; les constituants (b) et (c) sont présents en quantités sensiblement stoechiométriques, et le rapport molaire du constituant (b) et du constituant (a) se situe dans la plage de 0,25 à 5.
PCT/GB1991/001022 1990-07-04 1991-06-25 Polyimides et compositions utilisees pour leur preparation Ceased WO1992001014A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB909014846A GB9014846D0 (en) 1990-07-04 1990-07-04 Novel polyimides and compositions for their preparation
GB9014846.1 1990-07-04

Publications (1)

Publication Number Publication Date
WO1992001014A1 true WO1992001014A1 (fr) 1992-01-23

Family

ID=10678661

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1991/001022 Ceased WO1992001014A1 (fr) 1990-07-04 1991-06-25 Polyimides et compositions utilisees pour leur preparation

Country Status (2)

Country Link
GB (1) GB9014846D0 (fr)
WO (1) WO1992001014A1 (fr)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3745149A (en) * 1971-09-29 1973-07-10 Nasa Preparation of polyimides from mixtures of monomeric diamines and esters of polycarboxylic acids
US4455418A (en) * 1982-08-03 1984-06-19 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Chemical approach for controlling nadimide cure temperature and rate

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3745149A (en) * 1971-09-29 1973-07-10 Nasa Preparation of polyimides from mixtures of monomeric diamines and esters of polycarboxylic acids
US4455418A (en) * 1982-08-03 1984-06-19 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Chemical approach for controlling nadimide cure temperature and rate

Also Published As

Publication number Publication date
GB9014846D0 (en) 1990-08-22

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