WO1997033933A1 - Resines de bismaleinimide a teneur en diamine aromatique inferieure a 0,1 % en poids - Google Patents

Resines de bismaleinimide a teneur en diamine aromatique inferieure a 0,1 % en poids Download PDF

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Publication number
WO1997033933A1
WO1997033933A1 PCT/EP1997/001165 EP9701165W WO9733933A1 WO 1997033933 A1 WO1997033933 A1 WO 1997033933A1 EP 9701165 W EP9701165 W EP 9701165W WO 9733933 A1 WO9733933 A1 WO 9733933A1
Authority
WO
WIPO (PCT)
Prior art keywords
bismaleimide
aromatic diamine
aryl
radical
substituted
Prior art date
Application number
PCT/EP1997/001165
Other languages
German (de)
English (en)
Inventor
Heinrich Horacek
Erwin-Peter Sulzer
Original Assignee
Hos-Technik
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Hos-Technik filed Critical Hos-Technik
Priority to JP9532263A priority Critical patent/JP2000506213A/ja
Priority to EP97908198A priority patent/EP0886663A1/fr
Publication of WO1997033933A1 publication Critical patent/WO1997033933A1/fr

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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
    • C08G73/126—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
    • 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
    • C08G73/124—Unsaturated polyimide precursors the unsaturated precursors containing oxygen in the form of ether bonds 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
    • C08G73/125—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

Definitions

  • Bismaleimide resins belong to the leading class of thermosetting polyimides. They are used due to their excellent processability and balance between thermal and mechanical properties, for example in the electrical and electronics industry, as a prepreg for printed circuit boards or as a powder in reaction injection molding for molded articles.
  • Bismalein imide resins based on N, N'-aryl-bismaleimides, such as 4,4'-bismaleimide-phenylmethane (DPBM), and aromatic diamines such as 4,4'-diaminodiphenylmethane (MDA) are already on the Film, for example as Kerimid 601 from Ciba Geigy or bismaleimide resin B21 from Chemie Linz.
  • the object of the present invention was therefore bismaleimide resins based on N, N'-aryl-bismaleimides and aromatic diamines with a free aromatic diamines content of less than 0.1% by weight and a process for their preparation which reduces the content of below 0.1% by weight of free aromatic diamine guaranteed to be found.
  • This task was unexpectedly achieved by adding one or more acid anhydrides following the Michael addition.
  • the present invention therefore relates to bismaleimide resins based on aromatic diamines and N, N'-aryl-bismaleimides, which are characterized in that they have a free aromatic diamine content of less than 0.1% by weight.
  • the bismaleimide (BMI) resins according to the invention are composed of an aromatic diamine and an N, N'-aryl-bismaleimide.
  • Compounds of the formula I are preferably suitable as the N, N'-aryl-bismaleimide
  • R can be a radical -Ar- or -Ar-X-Ar, where Ar is a phenyl radical which is substituted or unsubstituted by (Cj-Cgl-alkyl) and X is a (Ci - Cglalkylene radical, -0-, -CO -, -S-, -SO2- or R-
  • -P O means, where Ri can be a substituted or unsubstituted phenyl or an alkyl radical.
  • Under (Ci -Cß) alkyl or alkylene are linear or branched radicals such as methyl, ethyl, i-propyl, n-propyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, methylene, ethylene to understand i-propylene, n-propylene, butylene or hexylene.
  • R are, for example, the residues 4,4'-diphenylmethane 3,3'-diphenylmethane, 2,4'-diphenylmethane, 4,4 * -o- or m-ditolylmethane, 3,3 ', 5,5'- Diethyl-4,4'-diphenylmethane, 3,5'-dimethyl-3 ', 5-diethyl-4,4'-diphenylmethane, 4,4'-diphenyl-dimethylmethane, 1, 4-phenylene, 1, 5-phenylene , 2,4-tolylene, 4,4'-diphenyl ether, 4,4'-diphenylene sulfone, 3,3'-diphenyl sulfone, 4,4'-diphenyl sulfide or benzophenone.
  • Compounds of the formula I are thus, for example, 4,4'-bismaleimide diphenyl methane (DPMB), 4,4'-bismaleimide diphenyl sulfone, 4,4'-bismaleimide diphenyl sulfide, 4,4'-bismaleimide diphenyl sulfide, 4,4'-bismaleimide phenylphosphine oxide and 3,3'-bismaleimide benzophenone.
  • DPMB 4,4'-bismaleimide diphenyl methane
  • DPMB 4,4'-bismaleimide diphenyl sulfone
  • 4,4'-bismaleimide diphenyl sulfide 4,4'-bismaleimide diphenyl sulfide
  • 4,4'-bismaleimide phenylphosphine oxide 4,4'-bismaleimide benzophenone.
  • bismaleimides such as 4,4'-bismaleimide diphenyl mercaptodiphenyl sulfone or 2,5-bis (4'-maleimide phenyl) thiadiazole.
  • 4,4'-bismaleimide diphenylmethane is particularly preferably used as N, N'-aryl-bismaiimine.
  • aromatic diamines examples include 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 1,4-diaminobenzene, 1,3-diaminobenzene, 2,4 -Diaminotoluene, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenylphosphine oxide.
  • aromatic diamines are amino-1- (4'-aminophenyl) 1, 3,3-trimethylindane and 2,6-diaminopyridine.
  • 4,4'-Diaminodiphenylmethane is particularly preferably used as the aromatic amine.
  • Another object of the present invention is a process for the preparation of bismaleimide resins with a free aromatic diamine content of less than 0.1 wt.%
  • Michael addition of an N, N'-aryl bismalein imide and an aromatic diamine the characterized in that one or more acid anhydrides are added to the reaction mixture following the Michael addition and free aromatic diamine is converted to the corresponding N, N'-aryl bisimide or amide.
  • an aromatic diamine and an N.N'-aryl-bismaleimide are condensed in the 1st step by Michael addition.
  • N, N'-Aryl-bismaleimides of the formula I and aromatic diamines of the formula II are preferably used.
  • N, N'-aryl-bismaleimides of the formula I defined above can also be prepared in situ from the corresponding diamines of the formula II.
  • the condensation can take place either in solution or in the melt. If the condensation is carried out in solution, the bismaleimide compound of the formula I is used in an aprotic diluent, such as dimethyl formamide (DMF), N-methylpyrrolidone (NMP), dimethylacetamide,
  • an aprotic diluent such as dimethyl formamide (DMF), N-methylpyrrolidone (NMP), dimethylacetamide
  • Glacial acetic acid or propionic acid can optionally also be used as the diluent.
  • an aprotic diluent is preferably used.
  • the reaction mixture is then heated to a temperature of 20-150 ° C., preferably 50-120 ° C., with stirring, and is kept at this temperature for 10 minutes to 10 hours, preferably for 30 minutes to 6 hours.
  • One or more anhydrides are then added to the solution thus obtained.
  • the acid anhydrides here are anhydrides of dicarboxylic acids, such as maleic anhydride (MA), succinic anhydride or anhydrides of two monocarboxylic acids, such as acetic anhydride, butanoic anhydride, heptanoic anhydride, phenylacetic acid anhydride,
  • Benzoic anhydride and phthalic anhydride, or propionic anhydride in question Only one of these anhydrides or a mixture of two or more of these anhydrides can be used.
  • a mixture of an anhydride of a dicarboxylic acid and an anhydride of two monocarboxylic acids is preferably used, particularly preferably a mixture of MA and acetic anhydride.
  • Other suitable acid anhydrides are, for example, mixed anhydrides of carboxylic acid and hydrochloric acid, such as benzoyl chloride, or else boric acid-carboxylic acid anhydrides or sulfonic acid-carboxylic acid anhydrides, such as acetic acid-methanesulfonic acid anhydride.
  • Phosphorus pentoxide or diacetyl sulfate can also be used.
  • the amount of anhydride is dependent on the free content of aromatic diamine, preferably a 5 to 20%, particularly preferably an 8 to 12% excess, based on the stoichiometric amount, of anhydride or anhydride mixture is added.
  • the molar ratio of the anhydrides in the mixture is between 1: 1 and 1: 6 or 6: 1.
  • a catalyst such as sodium, potassium or nickel acetate, is added.
  • the reaction mixture is stirred for a further 10 to 60 minutes at a temperature of 20 to 80 ° C., as a result of which free diamine is converted to the corresponding bismaleimide.
  • the desired end product is then isolated, for example, by precipitation in water or methanol. Then filtering, washing use water to remove residual thinner and dry. If the condensation or Michael addition takes place in the melt, the corresponding bismaleimide compound and the aromatic diamine are melted at a temperature between 100 and 300 ° C., preferably between 120 and 180 ° C., in the first step and for 1 to 20 minutes left at this temperature and condensed.
  • the condensation takes place, for example, in an extruder, each with a metering point for the reaction components of the Michael addition and for the anhydride or anhydride mixture, or in a heatable and stirrable static mixer.
  • the starting materials are preferably homogeneously ground before melting. If desired, the heating can also take place in several stages.
  • one or more anhydrides as described above and a catalyst are again added to the reaction mixture, and the temperature is allowed to remain for a further 0.1 to 10 minutes.
  • the product is then cooled to room temperature, for example by means of a cooling roll, and optionally ground.
  • a BMI resin is prepared from 4,4 * -bismaleinimiddiphenylmethane DPBM and MDA by means of a one-pot process, in which DPBM is obtained in situ from maleic anhydride (MSA) and MDA.
  • MSA is initially introduced (dissolved) in an aprotic diluent, such as DMF or NMP, and a solution of MDA in the same diluent is run in, the temperature by cooling to a value of up to max. 30 ° C is maintained.
  • the reaction mixture is then stirred for a further 1 to 5 hours at room temperature, heated to 90 to 120 ° C.
  • the bismaleimide resins according to the invention are therefore distinguished by the negligibly small content of free aromatic diamines classified as carcinogenic, such as MDA, and are suitable for use in the electrical and electronics industry as prepregs for printed circuit boards or as powders in reaction injection molding for moldings.
  • Example 2 225.5 kg / h DPBM and 49.5 kg / h MDA were mixed analogously to Example 2 in a static mixer for 2 minutes. Then 14 kg / h of acetic anhydride were fed in and a residence time of 1 minute was observed.
  • the product cooled on a chill roll had the following characteristics: Viscosity: 1 8 cSt 25 ° C / 40% in DMF

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  • 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

L'invention concerne des résines de bismaléinimide à base de diamines aromatiques et de N,N'-aryle-bismaléinimides à teneur en diamine aromatique libre inférieure à 0,1 % en poids. Les N,N'-aryle-bismaléinimides sont des composés de la formule (I) dans laquelle R peut être un reste -A- ou -Ar-X-Ar, Ar désignant un reste phényle substitué une fois ou plusieurs fois par alkyle C1-C6 ou non substitué, -O-, (a), -S-, -SO2- ou R1-P = O, R1 désignant un reste phényle ou alkyle substitué ou non.
PCT/EP1997/001165 1996-03-11 1997-03-07 Resines de bismaleinimide a teneur en diamine aromatique inferieure a 0,1 % en poids WO1997033933A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP9532263A JP2000506213A (ja) 1996-03-11 1997-03-07 ０．１重量％より少ない遊離芳香族ジアミンの含有量を有するビスマレインイミド樹脂
EP97908198A EP0886663A1 (fr) 1996-03-11 1997-03-07 Resines de bismaleinimide a teneur en diamine aromatique inferieure a 0,1 % en poids

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AT44996 1996-03-11
ATA449/96 1996-03-11

Publications (1)

Publication Number Publication Date
WO1997033933A1 true WO1997033933A1 (fr) 1997-09-18

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Application Number Title Priority Date Filing Date
PCT/EP1997/001165 WO1997033933A1 (fr) 1996-03-11 1997-03-07 Resines de bismaleinimide a teneur en diamine aromatique inferieure a 0,1 % en poids

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EP (1) EP0886663A1 (fr)
JP (1) JP2000506213A (fr)
WO (1) WO1997033933A1 (fr)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4395557A (en) * 1980-08-05 1983-07-26 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Phosphorus-containing imide resins
EP0334771A1 (fr) * 1988-03-03 1989-09-27 Ciba-Geigy Ag Polymères à groupements imides faits à partir de diamines encombrées et leurs procédés de préparation

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4395557A (en) * 1980-08-05 1983-07-26 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Phosphorus-containing imide resins
EP0334771A1 (fr) * 1988-03-03 1989-09-27 Ciba-Geigy Ag Polymères à groupements imides faits à partir de diamines encombrées et leurs procédés de préparation

Also Published As

Publication number Publication date
JP2000506213A (ja) 2000-05-23
EP0886663A1 (fr) 1998-12-30

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