EP0708795A1 - Melanges et stratifies de polyimide thermoresistants - Google Patents

Melanges et stratifies de polyimide thermoresistants

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Publication number
EP0708795A1
EP0708795A1 EP94916533A EP94916533A EP0708795A1 EP 0708795 A1 EP0708795 A1 EP 0708795A1 EP 94916533 A EP94916533 A EP 94916533A EP 94916533 A EP94916533 A EP 94916533A EP 0708795 A1 EP0708795 A1 EP 0708795A1
Authority
EP
European Patent Office
Prior art keywords
group
solvent
radical
polyimide
formula
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.)
Withdrawn
Application number
EP94916533A
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German (de)
English (en)
Other versions
EP0708795A4 (fr
Inventor
Frank W. Harris
Hiroyuki Furutani
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University of Akron
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University of Akron
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Priority claimed from US08/092,225 external-priority patent/US5397847A/en
Application filed by University of Akron filed Critical University of Akron
Publication of EP0708795A1 publication Critical patent/EP0708795A1/fr
Publication of EP0708795A4 publication Critical patent/EP0708795A4/fr
Withdrawn legal-status Critical Current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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
    • C08J3/091—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of 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 C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/125—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyamides
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/24—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H19/30—Polyamides; Polyimides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of 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 C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/0346—Organic insulating material consisting of one material containing N

Definitions

  • the invention described herein pertains generally to novel heat-resistant polyimide blends which have excellent heat and moisture-resistance, are soluble in organic solvents, have excellent mechanical processibility, and are suited for laminating and molding.
  • the present invention relates to: new laminates made from blends of thermoplastic polyimides and thermosetting imide oligomers having improved thermal stability, high T g , and improved thermoplastic properties; and new high strength, low cost, fracture resistant, reinforced polyimide composites and laminates made from said blends where the composite is reinforced by fibrous materials such as carbon fibers, glass fibers, or Kevlar® and processes for their manufacture.
  • Polyimides are useful as components which require excellent thermal, electrical and/or mechanical properties.
  • polyimides preparation, characterization and applications see Polyimides, Synthesis, Characterization and Applications, K. L. Mittal, ed Plenum, NY 1984.
  • Polyimides based on pyromellitic dianhydride and various organic diamines are disclosed in U.S. Patent 4,485,140 to Gannett et al (E.I. DuPont de Nemours and Co.).
  • Polyimides based on diamines such as 2,2'-di-( -aminophenyloxy)diphenyl and various dianhydrides are disclosed in U.S. Patent 4,239,880 to Darms (Ciba-Geigy Corp.).
  • the polyimides taught in this reference are typically rod like polyimides and possess little if any thermoplastic properties.
  • polyimide resins when utilized for copper-clad lamination, are advantageous in that substantially no smear is generated during drill processing and that their heat resistance during processing is improved.
  • the prior art hardened polyimide resins have posed the following problems.
  • KerimidTM resins which are primarily composed of a combination of bismaleimide and 4,4'-diaminodiphenyl methane, have excellent lamination characteristics
  • 4,4'-diaminodiphenyl methane used in the synthesis is highly reactive, thus posing a shelf-life problem.
  • the varnish and prepreg using it can be used for only a short period of time.
  • 4,4'-diaminodiphenyl methane is toxic to the human body. Kerimid processing requires heating at high temperatures for long periods of time, which is a significant disadvantage.
  • polyester imides produced are usually lower in thermal softening points, than the polyimide alone, and additionally are inferior in their heat resistance when compared to the polyimide.
  • the polyester imides do however, have good fluidity.
  • Fig. 1 illustrates a prepreg drying cycle showing a heating ramp under vacuum followed by a one hour hold time at 250°C followed by a rapid cooling ramp still under vacuum.
  • Fig. 2 illustrates a compression molding cycle showing a heating ramp at
  • Fig. 3 illustrates the conditions for the preparation of a cast plate showing a heating ramp to 520°F, followed by a hold for 25 min, additional heating to 580°F, followed by a hold for an additional hour, with a rapid cooling ramp.
  • Fig. 4 illustrates the glass transition point (T g ) as a function of the weight percent of added thermid.
  • Fig. 5 illustrates the flexural strength as a function of the weight percent of added thermid.
  • Fig. 6 illustrates the flexural modulus as a function of the weight percent of added thermid.
  • Fig. 7 illustrates the fracture energy (G lc ) as a function of the weight percent of added thermid.
  • An object of this invention is to provide novel polyimide blends of thermoplastic polyimides and thermosetting imide oligomers.
  • thermoplastic polyimides and thermosetting imide oligomers which can be coated on a reinforcement material.
  • a further aspect of this invention is to provide a method of manufacturing the heat-resistant laminate by independently dissolving a thermoplastic polyimide and a thermosetting imide oligomer in an aprotic solvent, subsequently blending the two solutions to obtain a homogeneous blend solution, and precipitating the blend solution thereby obtaining the polyimide blend composition which can then be coated and impregnated on a reinforcement material.
  • the novel heat-resistant laminate blend material according to the invention comprises, as essential components: (1) a thermoplastic polyimide represented by the structure as shown in formula (I),
  • Z is a tetravalent organic radical selected from the group consisting of a carbocyclic aromatic containing radical and a heterocyclic aromatic containing radical where each anhydride group is located on an aromatic ring with the carbonyl units in an ortho orientation relative to one another
  • Q is divalent organic radical selected independently from the group consisting of a carbocyclic aliphatic radical, a carbocyclic aromatic containing radical, and a heterocyclic containing radical
  • carbocyclic aromatic containing radical and heterocyclic aromatic containing radical used to define Z is meant to include any radical which has the anhydride groups attached to one or more aromatic ring(s) and when describing Q has the amine groups attached to one or more aromatic ring(s), and wherein while the rings are usually unsubstituted, they may be substituted, particularly with halogens
  • Q and Z have the values previously defined, the groups Z being either the same or different, n being a positive integer of from 1 to 30, and X is a form of trivalent bond shown attached to group Z, which occupies two of the bonds, thereby leaving one additional bond for subsequent bonding to other components of the oligomer, and selected from the chemical formula group consisting of
  • thermoplastic polyimide represented by formula (I) represents the polycondensation reaction of at least one dianhydride of formula (IN)
  • a chain termination or limiting reagent can be added to the polymerization mixture to force termination of a growing polymer chain.
  • chain termination or limiting reagents are used to limit the molecular weight of the polymer and are well known in the art.
  • Amine termination reagents commonly employed include aniline or substituted anilines.
  • Common carboxy terminating reagents include phthalic anhydride and other similar aromatic anhydrides.
  • examples are for purposes of illustrating members of the type of dianhydrides of formula (IN) are selected from the representative and illustrative group consisting of: pyromellitic acid dianhydride, 3,6-diphenylpyromellitic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic acid dianhydride, 2,3,3 ',4'-benzophenonetetracarboxylic acid dianhydride, 2,2',3,3 '-benzophenonetetracarboxylic acid dianhydride,
  • 3,3',4,4'-biphenyltetracarboxylic acid dianhydride bis(2,3-dicarboxyphenyl)methane dianhydride, bis(2,5,6-trifluoro-3,4-dicarboxyphenyl)methane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, bis(3,4-dicarboxyphenyl) ether dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride, ⁇ , ⁇ -(3,4-dicarboxyphenyl)- ⁇ -methylamine dianhydride, bis(3 ,4-dicarboxyphenyl)diethylsilane dianhydride, 2,2-bis(3 ,4-dicarboxyphenyl)- 1,1,1,3,3,3 -hexafluoropropane dianhydride, 4,4'-[4,4'-isopropylidene-di
  • members of the diamine of formula (N) include: 2,6-diaminopyridine, 2,5-diaminopyridine, 2,4-diamino-6-hydroxypyrimidine, 2,4-diaminopyrimidine, 3,5-diamino-l ,2,4-triazole, 4-chloro-2,6-diaminopyrimidine, 2,4-diamino-s-triazine, 2-chloro-4,6-diaminotriazine, 6,6'-diamino-2,2 '-bipyridine, 1,4- diaminobenzene, 1,3-diaminobenzene, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, l,3-bis(3-aminophenoxy)benzene,
  • thermoplastic polyimide will have generic formula (NI),
  • the method of manufacturing the novel polyimide blend composition comprises the steps of: (1) independently dissolving the thermoplastic polyimide represented by formula (I), and the thermosetting imide oligomer represented by formula (II) in an organic solvent; (2) blending together the two separate solutions into a homogeneous blend solution; and (3) precipitating the polyimide blend composition in a coagulating solvent.
  • the weight ratio of component (I) / component (II) is selected in a range of 99:1 to 5:95.
  • the thermoplastic polyimide (I) has a number-average molecular weight of 10,000 or above.
  • the polyimide blend resins obtained are particularly good in bonding to other substrates and in their flexibility. In addition, moldings produced from these resins are less prone to the generation of voids and cracks. Thus, the resins are useful in flexible printed circuit boards and electric materials requiring excellent properties.
  • the solution of thermoplastic polyimide and thermosetting imide oligomer are stirred at from about 25- 150°C , preferably from about 50-120°C; for 2-24 hours, preferably 4-24 hours.
  • the homogeneous blend solution is typically coagulated by dropping the solution into an alcoholic solvent (e.g., methanol, ethanol, isopropanol, etc., or any solvent capable of producing the precipitate of the blend composition).
  • the coagulating solvent can even be water.
  • the obtained precipitate of the blend composition is filtered and collected.
  • the collected filtrate is solvent-exchanged with methanol or the like using a Soxhlet extractor to facilitate the subsequent drying under reduced pressure.
  • the resulting final blend product is a powder.
  • Effective organic solvents for the reaction leading to the formation of the blend composition are polar aprotic organic solvents which include: sulfoxide solvents, e.g., dimethyl sulfoxide, diethyl sulfoxide, etc.; formamide solvents, e.g., N,N'- dimethylformamide (DMF), N,N'-diethylformamide, etc.; acetamide solvents, e.g., N,N'-dimethylacetamide (DMAc), N,N' -diethylacetamide, etc.; N-methylpyrrolidinone (NMP); and phenol solvents, e.g., o-cresol, -cresol, p-c ⁇ eso ⁇ , 4-t-butylphenol, etc.
  • sulfoxide solvents e.g., dimethyl sulfoxide, diethyl sulfoxide, etc.
  • formamide solvents e.g., N,N'-
  • solvents can be used alone or as a mixture of two or more solvents.
  • these polar solvents may be used in mixtures with polyimide non- solvents, e.g., methanol, ethanol, isopropanol, benzenemethylcellosolve, etc.
  • One method of manufacturing a novel thermoplastic polyimide of formula (VI) comprises dissolving an organic diamine represented by formula (Nil)
  • R 1 and R 2 are as previously defined, the groups R 1 and R 2 being the same or different, in an inert gas atmosphere (e.g. argon, nitrogen, etc.), and an organic tetracarboxylic acid moiety or derivative thereof of chemical formula represented by formula (HI)
  • a viscous polyamic acid solution is obtained.
  • the reaction temperature is from about -15 to 120°C, preferably -15 to 100°C, and more preferably, -5 to 50°C.
  • the reaction time is from about 1-5 hours.
  • an azeotriping agent may be added and the polyamic acid is converted into a polyimide under refluxing azeotropic conditions.
  • the azeotroping agent may be xylene, toluene, and similar aromatic hydrocarbons, and more preferredly, is toluene.
  • azeotropic water is removed using a Dean-Stark trap.
  • Thermal imidization may also be carried out without an azeotroping agent in a refluxing solvent, which optionally contains isoquinoline.
  • the polyimide solution is subsequently poured into water or an alcoholic solvent while vigorously stirring the system to effect the precipitation of the polyimide polymer as a powder.
  • the powder is filtered, preferably solvent-exchanged with methanol using a Soxhlet extractor to facilitate the drying. The drying is completed under reduced pressure to obtain the thermoplastic polyimide powder.
  • dehydrating imidization agent examples include organic carboxylic acid anhydrides, N,N'-dialkyl carbodiimide, lower fatty acid halides, lower halo-fatty acid anhydrides, alkylsulfonic acid dihalides and thionyl halides as well as mixtures of these compounds.
  • Acetic acid anhydride is a preferred embodiment.
  • Other preferred reagents would include ketene and benzoic acid anhydride.
  • Examples of the catalysts which may be used to assist the reaction would include pyridine, quinoline and tertiary amines. Specifically, 3,4-lutidine, 3,5-lutidine, 4-methylpyridine, 4-isopropylpyridine, N-dimethylbenzylamine, 4-benzylpyridine and 4-dimethyldodecylamine.
  • the number-average degree of polymerization (DP; P.J. Flory, Principles of Polymer Chemistry: Cornell University Press: Ithaca, NY, p. 91, 1953) of the thermosetting imide oligomer, one of the constituent components according to the invention, is suitably 1 to 30, preferably 1 to 15, more preferably 1 to 10. If the degree of polymerization is excessive, the solubility in organic solvents is reduced. If the degree of polymerization is insufficient, on the other hand, problems are posed in connection with the mechanical strength.
  • the molecular weight is not particularly limited.
  • the number-average molecular weight is suitably 10,000 or above, preferably 20,000 or above, more preferably 30,000 or above, particularly preferably 40,000 or above. It is often difficult to directly measure the molecular weight of polyimide polymers. In such cases, the measurement is made indirectly by estimation. For example, where a polyimide copolymer is synthesized from polyamic acid, a value corresponding to the molecular weight of the polyamic acid may be thought to be the molecular weight of polyimide.
  • the dianhydride component comprises, as its essential component, an organic dianhydride represented by formula (IV), but it is possible to copolymerize with a dianhydride wherein Z in formula (IN) is replaced by Z', but being selected however, from the same Markush group as that previously designated for Z.
  • Z in formula (IN) is replaced by Z'
  • Z' is replaced by Z'
  • Z' is replaced by Z'
  • examples representative of the Markush groups Z and Z' would include:
  • organic tetracarboxylic acid dianhydrides may be used alone, or in combinations of two or more of them.
  • the novel polyimide blend composition has particularly high heat-resistance and excellent mechanical properties. Without being held to any particular theory, it is thought that these properties are attributable not only to the attainment of a simple polymer blend or semi-IPN structure (i.e., mutually introducing polymer mesh structure), but rather due to the effective contribution of the blend composition as a polymer alloy system.
  • thermoplastic polyimide or thermosetting imide oligomer has a peak maxima of mechanical properties exceeding those of the sole thermoplastic polyimide or thermosetting imide oligomer, as evidenced by Figures 5 to 7.
  • Further characterization of the polyimide blends produced by the synthetic routes detailed in this invention indicates that the blends can maintain semi-crystallinity even after the blend composition is produced. Additionally, the melt viscosity of the blend composition is low.
  • composition described comprises as its essential elements, the polyimide resins, it is possible to use in combination, if necessary, well-known epoxy resins, epoxy resin hardening agents, hardening promoters, fillers, incombustible agents, reinforcing agents, surface treatment agents, pigments and various elastomers.
  • a well-known epoxy resin is a compound having two or more epoxy (or glycidyl) groups in its molecule.
  • it may be at least one member of the group consisting of polyglycidylether compounds derived from divalent and higher valence phenols, e.g., bisphenol A, bisphenol F, hydroquinone, resorcinol, furylglycine, tris-(4-bisphenol F, hydroquinone, resorcinol, furylglycine, tris-(4- hydroxyphenyl)methane, 1,1,2,2-tetrakis (4-hydroxyphenyl)ethane, etc., from tetrabromobisphenol A and other brominated polyphenols, and from novolak and other halo-polyphenols, novolak epoxy resins as products of reaction between phenols, e.g., phenol, o-cresol, etc., and formaldehyde, amine epoxy resins derived from aniline,
  • -oxybenzoic acid, terephthalic acid, isophthalic acid, etc. indane epoxy resins derived from 5,5- dimethyl indane etc.
  • alicyclic epoxy resins e.g., 2,2-bis(3,4- epoxycyclohexyl)propane, 2,2-bis [4-(2,3-epoxypropyl)cyclohexyl] propane, 2,2-bis[4- (2,3-epoxypropyl)cyclohexyl]propane, vinylcyclohexane dioxide, 3,4-epoxycyclohexane carboxylate, etc., and further triglycidyl isocyanulate and 2,4,6-triglycidoxy-s-triadine, etc.
  • These resins may be used alone or in combinations of two or more of them.
  • Examples of well-known epoxy hardening agents are phenolic hardening agents, e.g., phenol novolak, cresol novolak, etc., and hydrazide compounds.
  • Examples of the hardening promoters are amines, e.g., benzyldimethyl amine, 2,4,6-tris (dimethylaminomethyl) phenol, 1,8-diazabicycloundecene, etc., imidazole compounds, e.g., 2-ethyl-4-methyl imidazole, and boron trifluoride amine complexes.
  • amines e.g., benzyldimethyl amine, 2,4,6-tris (dimethylaminomethyl) phenol, 1,8-diazabicycloundecene, etc.
  • imidazole compounds e.g., 2-ethyl-4-methyl imidazole
  • boron trifluoride amine complexes boron tri
  • Incombustible agents and inorganic fillers may be suitably added.
  • Inorganic fillers may be used which are water-insoluble and insulating.
  • examples of such inorganic fillers are metal oxides, such as silica, alumina, zirconia, titanium dioxide and zinc flower, metal hydroxides such as magnesium hydroxide and aluminum hydroxide, natural minerals such as talc, kaolin, mica, waltherite and clay minerals, and insoluble salts such as calcium carbonate, magnesium carbonate, barium sulfate and calcium phosphate.
  • reinforcement material examples include woven fabric, non- woven fabric, mat, paper and combinations of these materials, and continuous fibers such as carbon fibers, glass fibers, aramide fibers, liquid crystal polyester fibers, poly(p-phenylenebenzobisthiazole) (PBT) and poly(p-phenylenebenzobisoxazole) (PBO) fibers, alumina fibers and so forth.
  • PBT poly(p-phenylenebenzobisthiazole)
  • PBO poly(p-phenylenebenzobisoxazole)
  • BNPDMP dinitro compound
  • BAPDMP diamine
  • the blend mixture was coated on glass cloth (available with a product number "RST57PA-535CS" from Nittobo Co., Ltd.) to impregnate the same by using a prepregger, i.e., a "Model 130 Prepregger” manufactured by Research Tool Co., Ltd.
  • a prepregger i.e., a "Model 130 Prepregger” manufactured by Research Tool Co., Ltd.
  • a unidirectional reinforced prepreg was produced with two rollers. This reinforced prepreg was cut to a predetermined standard size and then dried under the drying condition shown in Figure 1.
  • Table 1 shows the results of the observations.
  • Example # 4 (Sample #2) Preparation of BT A Thermid Blend (70/30)
  • a blend solution was obtained in the same manner as shown in Example 3 except for using 40.0686 g (0.1248 mol) of benzophenone tetracarboxylic acid dianhydride (hereinafter referred to as BTDA), 34.7545 g (0.1249 mol) of BAPDMP and 19 g of "Thermid IP-600".
  • BTDA benzophenone tetracarboxylic acid dianhydride
  • BAPDMP tetracarboxylic acid dianhydride
  • the resin viscosity of the obtained resin solution was obtained and found to be 21 poise.
  • Example #5 (Sample #3) Preparation of PMDA/BTDA/Thermid Blend (14/56/30)
  • a blend solution was obtained in the manner as shown in Example 3 except for using 9.2031 g (0.0422 mol) of pyromellitic acid dianhydride (hereinafter referred to as PMDA), 20.3560 g (0.06 mol) of BTDA, 29.3297 g (0.10539 mol) of BAPDMP and 20 g of "Thermid IP-600".
  • PMDA pyromellitic acid dianhydride
  • BTDA pyromellitic acid dianhydride
  • BAPDMP 29.3297 g (0.10539 mol) of BAPDMP
  • Thermid IP-600 The resin viscosity of the resin solution thus obtained was measured and found to be 16 poise.
  • Example 3 Using the blend solution thus obtained, a heat-resistant laminate material with a thickness of 3.42 mm was obtained in the manner as shown in Example 3. Of the heat-resistant laminate material thus produced, the various physical property values were measured in the manner as shown in Example 3, and also the moisture resistance was examined. The results of the evaluation are shown in Table 1.
  • Example #6 (Sample #4) Preparation of PMDA/ODPA Thermid Blend (28/42/30) A blend solution was obtained in the manner as shown in Example 3 except for using 20.8816 g (0.09574 mol) of PMDA, 44.5310 g (0.14356 mol) of ODPA, 66.4659 g (0.23883 mol) of BAPDMP and 57 g of "Thermid IP-600". The resin viscosity of the obtained resin solution was measured and found to be 28 poise.
  • Comparative Example #7 (Sample #5) 95 g of "Kerimid 601 " (purchased from Nippon Polyimide Co., Ltd.) was dissolved in 120 g of DMF (resin concentration: 45 wt. %DMF). The resin solution thus obtained was coated on glass fibers to impregnate the cloth in the same manner as shown in Example 1, followed by drying in a hot air circulation furnace at 120°C, or 85 minutes to produce a prepreg with a resin concentration of 40.2% by weight and a residual solvent concentration of 6.4%. Eight prepregs thus formed were laminated at 220°C for 2 hours at 25 kg/cm 2 using a press with heater to obtain a laminate with a thickness of 3.7 mm.
  • Comparative Example #8 (Sample #6) 165 g of imide oligomer, i.e., "Thermid MC-600" (purchased from Kanebo NSC Co., Ltd.), was dissolved in 2,000 g of DMF (resin concentration: 45 wt.%). The obtained resin solution was coated on glass fibers to impregnate the same as shown in Example 4, followed by drying in a hot air re-circulation furnace at 120 °C for 35 minutes to obtain a prepreg with a resin concentration of 31.2 % by weight and a residual solvent concentration of 9.4%.
  • PCT pressure cooker test
  • Example #9 Comparative Sample 1 A polyimide preparation by chemical imidization and thermal imidization processes will now be described.
  • Chemical Imidization To a dried 500 ml, 3-necked round bottom flask were attached a bubbler, a N 2 bubbler, and a mechanical stirrer. The flask was flushed with nitrogen and 11.7811 g (42.330 mmol) of BAPDMP dissolved in 100 ml of NMP and 13.1310 g (42.330 mmol) of oxydiphthalic acid dianhydride (hereinafter ODPA) dissolved in 30 ml of N- methyl-2-pyrrolidinone. The solution was dropped into the nitrogen purged reaction vessel at room temperature and allowed to react for 24 hours. A blend solution containing 5 ml (62.00 mmol) of pyridine and 6 ml (62.0 mmol) of acetic anhydride was added and the resultant system allowed to further react for 24 hours.
  • ODPA oxydiphthalic acid
  • thermoplastic polyimide After the reaction, a fiber-like polymer was precipitated in 2,000 ml of ethanol.
  • the polymer was pulverized using a mortar and solvent exchanged for 12-18 hours under reflux using a Soxhlet extractor using methanol as the solvent.
  • the polymer was subsequently dried under reduced pressure at 180°C to obtain 2.4 g (yield 95.8%) of thermoplastic polyimide.
  • the reaction was allowed to proceed under nitrogen at room temperature for 2 hours, then heated to 150°C for 2 hours, then allowed to react for an additional 19 hours under imidization conditions After the reaction, a fiber-like polymer was precipitated in 2,000 ml of ethanol.
  • the polymer was pulverized using a mortar and solvent exchanged for 12-18 hours under reflux using a Soxhlet extractor using methanol as the solvent.
  • the polymer was subsequently dried under reduced pressure at 180°C to obtain 59.57 g (yield 98.3%) of thermoplastic polyimide.
  • Example 2 The physical properties are summarized in Table 2 (Example 1 '). To determine the mechanical properties, a cast plate was produced under the conditions of 585°F and 3000 psi. All tests were conducted on a cut cast plate with a length of 50.0 mm, 32.0 width, and a thickness of 2.8 mm. Flexural strength and flexural modulus tests were conducted on conformity with ASTM D790M-86 and at 23°C. The fracture energy (G lc ) was measured according with ASTM E399-83. The glass transition point (T g ) was measured using a DMS200 manufactured by
  • Example #10 Comparative Sample 2' A polyimide was synthesized according to the steps outlined above for the thermal imidization process in Example #9, except that 18.4707g (66.3697 mol) of BAPDMP, and 21.3845 g (66.3702 mol) of benzophenone tetracarboxylic acid dianhydride (hereinafter BTDA), and 350 ml w-cresol were used thus obtaining 37.2 g (yield 92.3%) of polyimide.
  • BTDA benzophenone tetracarboxylic acid dianhydride
  • Example #11 Comparative Sample 3 ' A polyimide was prepared according to the steps outlined above for the thermal imidization process in Example #9, except that 16.8863 g (60.6766 mol) of BAPDMP, 15.6648 g (48.6182 mol) of BTDA, 2.6508 g of pyromellitic acid dianhydride (hereinafter PMDA), and 300 ml of w-cresol were used thus obtaining 31.0 g (yield 95.6%) of polyimide.
  • a polyimide was prepared according to the steps outlined above for the thermal imidization process in Example #9, except that 16.9641 g (60.9561 mol) of BAPDMP, 5.3232 g (24.4049 mol) of PMDA, 11.3451 g (36.5735 mol) of ODPA and 280 ml of w-cresol were used thus obtaining 31.3 g (yield 92.9%) of polyimide.
  • thermoplastic polyimide prepared from ODPA and BAPDMP with thermosetting imide oligomer (Thermid IP-600) in a ratio of 4/1.
  • thermoplastic polyimide powder comprising ODPA and BAPDMP, synthesized according to the thermal imidization process detailed in Example #9, and 11.2 g of "Thermid IP-600" (Kanebo NSC) dissolved in 200 ml of w-cresol.
  • the system was stirred at 120°C for 18 hours to obtain a homogeneous solution which was processed according to the procedure outlined for the polymer solution in Example #9, thereby obtaining 28.29 g (yield 55.8%) of the blended powder.
  • thermoplastic polyimide prepared from ODPA and BAPDMP, and thermosetting imide oligomer "Thermid IP- 600" in a ratio of 2/1. Under the same conditions used in Example #13, except for using 9.00 g of thermoplastic polyimide powder synthesized by the thermal imidization process of Example #9, 4.50 g of "Thermid IP-600” and 300 ml of w-cresol yielded 9.97 g (55.8%) of the blend composition.
  • Example #15 Sample C A blend composition was synthesized by charging thermoplastic polyimide, prepared from ODPA and BAPDMP, and thermosetting imide oligomer "Thermid IP- 600" in a ratio of 1/1.
  • Example #13 Under the same conditions used in Example #13, except for using 9.16 g of thermoplastic polyimide powder synthesized by the thermal imidization process of Example #9, 9.12 g of "Thermid IP-600" and 300 ml of w-cresol yielded 7.68 g (99.0%) of the blend composition.
  • Example #16 Sample D A blend composition was synthesized by charging thermoplastic polyimide, prepared from ODPA and BAPDMP, and thermosetting imide oligomer "Thermid IP- 600" in a ratio of 1/2.
  • thermoplastic polyimide prepared from BDTA and BAPDMP
  • thermosetting imide oligomer " ⁇ hermid IP- 600" in a ratio of 1/1.
  • Example #13 Under the same conditions used in Example #13, except for using 8.45 g of thermoplastic polyimide powder synthesized by the thermal imidization process of Example #10, 8.25 g of "Thermid IP-600" and 200 ml of w-cresol yielded 9.31 g (56.9%) of the blend composition.
  • Example #18 Sample F A blend composition was synthesized by charging thermoplastic polyimide, prepared from BDTA and BAPDMP, and thermosetting imide oligomer "Thermid IP- 600" in a ratio of 2/1.
  • Example 13 Under the same conditions used in Example 13, except for using 10.45 g of thermoplastic polyimide powder synthesized by the thermal imidization process of Example #10, 5.05 g of "Thermid IP-600" and 200 ml of w-cresol yielded 7.36 g (56.1%) of the blend composition.
  • Example #20 Sample H A blend composition was synthesized by charging thermoplastic polyimide, prepared from BDTA and BAPDMP, and thermosetting imide oligomer "Thermid IP- 600" in a ratio of 1/2.
  • Example #13 Under the same conditions used in Example #13, except for using 5.04 g of thermoplastic polyimide powder synthesized by the thermal imidization process of Example #10, 10.25 g of "Thermid IP-600" and 200 ml of w-cresol yielded 12.08 g (73.5%) of the blend composition.
  • Example #21 Sample I A blend composition was synthesized by charging thermoplastic polyimide, prepared from BDTA, PMDA and BAPDMP, and thermosetting imide oligomer "Thermid IP-600" in a ratio of 1/1. Under the same conditions used in Example #13, except for using 8.15 g of thermoplastic polyimide powder synthesized by the thermal imidization process of Example #11, 8.45 g of "Thermid IP-600” and 200 ml of w-cresol yielded 15.12 g (91.1%) of the blend composition.
  • thermoplastic polyimide prepared from BDTA, PMDA and BAPDMP
  • thermosetting imide oligomer "Thermid IP-600” in a ratio of 1/2.
  • Example #13 Under the same conditions used in Example #13, except for using 4.45 g of thermoplastic polyimide powder synthesized by the thermal imidization process of Example #11, 9.67 g of "Thermid IP-600" and 200 ml of w-cresol yielded 12.79 g (90.6%) of the blend composition.
  • Example #23 Sample K A blend composition was synthesized by charging thermoplastic polyimide, prepared from BDTA, PMDA and BAPDMP, and thermosetting imide oligomer "Thermid IP-600" in a ratio of 3/1.
  • Example #13 Under the same conditions used in Example #13, except for using 9.24 g of thermoplastic polyimide powder synthesized by the thermal imidization process of Example #11, 3.56 g of "Thermid IP-600" and 250 ml of w-cresol yielded 12.50 g (93.2%) of the blend composition.
  • thermoplastic polyimide prepared from ODPA, PMDA and BAPDMP, and thermosetting imide oligomer "Thermid IP-600" in a ratio of 1/2. Under the same conditions used in Example #13, except for using 5.06 g of thermoplastic polyimide powder synthesized by the thermal imidization process of Comparative Example 4', 10.01 g of "Thermid IP-600” and 150 ml of w-cresol yielded 10.50 g (69.7%) of the blend composition.
  • Example #26 Sample N A blend composition was synthesized by charging thermoplastic polyimide, prepared from ODPA, PMDA and BAPDMP, and thermosetting imide oligomer "Thermid IP-600" in a ratio of 3/1.
  • Example 1 Under the same conditions used in Example 1, except for using 18.89 g of thermoplastic polyimide powder synthesized by the thermal imidization process of Example #12, 6.41 g of "Thermid IP-600" and 350 ml of w-cresol yielded 22.26 g (88.0%) of the blend composition.
  • Example #26 Comparative Sample 5' 12.56 g of powdered "Thermid IP-600” was fused in a vacuum oven at 190°C at 3 torr for 2 hours. The solidified resin was powdered, and 8.56 g was used to produce a cast plate under conditions used in Example #9.
  • Example #27 Comparative Sample 6 The following example illustrates the preparation of a 4:1 blend of a commercial thermoplastic polyimide (Ultem®1000, available from General Electric Plastics) and "Thermid IP-600".
  • the blend powder was compression molded at 280°C under a pressure of 1,000 psi for 20 minutes, the resins underwent considerable flow under these conditions to afford a well consolidated plaque.

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Abstract

Cette invention concerne des mélanges de polyimide thermorésistants et des éléments moulés réalisés avec ceux-ci. Ces mélanges ont une excellente résistance à la chaleur et à l'humidité, ils sont relativement solubles dans les solvants organiques, et ils se prêtent facilement aux transformations telles que la formation de stratifiés et le moulage. Les mélanges contiennent un composant polyimide thermoplastique et un oligomère d'imide thermodurcissant. Le rapport pondéral entre le composant thermoplastique et le composant thermodurcissant est choisi dans la plage 99/1 à 5/95. Le composant polyimide thermoplastique a une masse moléculaire moyenne au nombre de 10.000 ou plus.
EP94916533A 1993-07-15 1994-04-15 Melanges et stratifies de polyimide thermoresistants Withdrawn EP0708795A4 (fr)

Applications Claiming Priority (5)

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US92226 1987-09-02
US9222693A 1993-07-15 1993-07-15
US08/092,225 US5397847A (en) 1992-10-20 1993-07-15 Heat-resistant laminate materials and preparation thereof
PCT/US1994/004147 WO1995002627A1 (fr) 1993-07-15 1994-04-15 Melanges et stratifies de polyimide thermoresistants
US92225 1998-06-05

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JPH10279799A (ja) * 1997-04-04 1998-10-20 Nitto Denko Corp 熱硬化性樹脂組成物
JP4553648B2 (ja) * 2004-07-02 2010-09-29 日本化薬株式会社 エポキシ樹脂組成物及びその硬化物
JP2009511297A (ja) * 2005-10-11 2009-03-19 シーアールシー フォー アドバンスト コンポジット ストラクチャーズ リミテッド 乾燥強化繊維の結合方法
RU2532514C1 (ru) * 2013-09-19 2014-11-10 Закрытое акционерное общество "Институт новых углеродных материалов и технологий" (ЗАО "ИНУМиТ") Связующее, способ его изготовления и препрег на его основе
WO2015069966A1 (fr) * 2013-11-07 2015-05-14 Georgia-Pacific Chemicals Llc Adhésifs de crêpage et leurs procédés de fabrication et d'utilisation
US9416229B2 (en) 2014-05-28 2016-08-16 Industrial Technology Research Institute Dianhydride and polyimide
CN105398136B (zh) * 2015-12-29 2018-03-09 广东生益科技股份有限公司 一种二层法双面挠性覆铜板
CN113172959B (zh) * 2021-04-23 2022-12-16 中国科学院化学研究所 一种高韧性、耐高温聚酰亚胺复合材料及其制备方法

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JPH02222451A (ja) * 1989-02-23 1990-09-05 Toray Ind Inc 芳香族ポリイミド樹脂組成物

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US4996101A (en) * 1988-08-08 1991-02-26 Lockheed Corporation Processible polyimide blends
US5175242A (en) * 1989-02-24 1992-12-29 The University Of Akron Phenylated polyimides prepared from 3,6-diarylpyromellitic dianhydride and aromatic diamines
US5059273A (en) * 1989-10-26 1991-10-22 E. I. Du Pont De Nemours And Company Process for preparing polyimide composites
US5155179A (en) * 1990-04-25 1992-10-13 Hoechst Celanese Corp. Miscible blends of polyimide polymers
US5391183A (en) * 1990-09-21 1995-02-21 Datascope Investment Corp Device and method sealing puncture wounds

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See also references of WO9502627A1 *

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