Classifications

• • 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
• • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
• • 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
• • 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
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/32—Phosphorus-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/15—Heterocyclic compounds having oxygen in the ring
  • C08K5/156—Heterocyclic compounds having oxygen in the ring having two oxygen atoms in the ring
  • C08K5/1565—Five-membered rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
  • C08K5/45—Heterocyclic compounds having sulfur in the ring
  • C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
• • 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

Definitions

• the present invention is directed to storage-stable advanced polymaleimde prepolymer compositions and products, such as prepreg products, produced therefrom.
• the storage-stable advanced polymaleimide prepolymer compositions include: (i) a polymaleimide prepolymer resulting from the advancement reaction of a polyimide and an alkenylphenol or alkenylphenol ether in the presence of an amine catalyst; and (ii) dioxolane.
• Bimaleimides may be used as raw materials for the manufacture of polyaddition and polymerization products.
• U.S. Pat. No. 3,658,764 discloses polyaddition products produced from unsaturated bismaleimides and amines
• U.S. Pat. No. 3,741,942 describes the manufacture of polyaddition products from bismaleimides and organic dithiols
• U.S. Pat. Nos. 4,038,251 and 4,065,433 describe the reaction of bismaleimides with polyhydric phenols and polyhydi ⁇ c alcohols in the presence of a catalyst to form the polyaddition products
• U.S. Pat. No. 4,100,140 describes polyaddition products prepared from bismaleimides and alkenylphenols or alkenylphenol ethers.
• polyaddition products produced from bismaleimides may be used in various prepreg applications.
• One such polyaddition product, supplied as a powder, is the reaction product of bismaleimidodiphenyl methane and methylene dianiline.
• the powder polyaddition product may then be dissolved in a high boiling solvent, such as N-methylpyt ⁇ olidone, for prepreg use.
• a high boiling solvent such as N-methylpyt ⁇ olidone
• U.S. Pat. No. 5,189,128 discloses a polyaddition product produced from the reaction of polymaleimide and alkenylphenol or alkenylphenol ether in the presence of specific molar amounts of basic catalyst for certain reaction times and at certain reaction temperatures.
• the resulting product exhibits improved solubility in the lower boiling solvent methyl ethyl ketone and improved storage stability as evidenced by an absence of precipitation.
• a further improvement in storage stability is described in U.S. Pat. No.
• the present invention relates to a storage- stable advanced polymaleimide prepolymer composition
• a storage- stable advanced polymaleimide prepolymer composition comprising: (a) a polymaleimide prepolymer resulting from the advancement reaction of a polyimide and an alkenylphenol, alkenylphenol ether or mixture thereof in the presence of an amine catalyst; and
• the storage-stable advanced polymaleimide prepolymer composition may be prepared by reacting at an elevated temperature a polyimide and an alkenylphenol, an alkenylphenol ether or mixture thereof, in the presence of an amine catalyst to form the polymaleimide prepolymer, substantially removing all of the amine catalyst; and subsequently adding dioxolane.
• a prepreg or laminate structure may be prepared by curing a fabric or fiber impregnated with the storage-stable advanced polymaleimide prepolymer composition of the present invention.
• FIG. 1 and FIG. 2 illustrate the stability of the advanced polymaleimide prepolymer composition over time at various storage temperatures.
• the storage-stable advanced polymaleimide prepolymer composition generally includes (i) a polymaleimide prepolymer resulting from the advancement reaction of a polyimide and an alkenylphenol, alkenylphenol ether or mixture thereof in the presence of an amine catalyst; and (ii) dioxolane. It has been surprisingly discovered that the addition of dioxolane to the polymaleimde prepolymer inhibits further advancement thereby eliminating or greatly reducing further polymerization, and thus, substantially improving the storage-stability of the prepolymer composition.
• the storage-stable advanced polymaleimide prepolymer composition of the present invention may be stored at room temperature, or temperatures even higher than room temperature, for a prolonged period of time without adverse effects to processing conditions, thus eliminating the need for storage at low temperatures, for example, refrigeration conditions.
• room temperature it is meant a temperature of about 20° C.
• dioxolane surprisingly improves other processing characteristics of the composition, for example, extending pot-life and reducing volatile content.
• Applicable polyimides contain at least two radicals of the formula
• R 1 is hydrogen or methyl
• the polyimide is a polymaleimide, preferably a bismaleimide of the formula
• R 2 and R 3 independently are chlorine, bromine, methyl, ethyl, or hydrogen and Z is a direct bond, methylene, 2,2- ⁇ ropylidene, -CO-, -0 ⁇ , -S-, -SO- or -SO 2 -,
• R 1 is methyl
• X is liexamethylene, trimethylhexamethylene, l,5,5-trimethyi-l,3- cyclohexylene or a group of the indicated formula (a) in which Z is methylene, 2,2- propylidene or -O- and R 2 and R 3 are hydrogen.
• polyimides include: N,N'-ethylene-bismaleimide, N,N'- hexamethylene-bismaieimide, N,N'-m-phenyiene-bismaleimide, N,N'-p ⁇ phenylene- bismaleimide, N 5 N l -4,4'-diphenylmethane-bismaleimide J N.N' ⁇ '-S.S'-dichloro- diphenylmethane-bismaleimide, N,N'-4,4'-(diphenylether)-bismaleimide, N,N'-4,4'-di- phenylsulphone-bismaleimide, N,N'-4,4'-dicyclohexylmethane-bismaleimide ; N,N'- ⁇ ,4,4'-dimethylenecyclohexane-bismaleimide, N,N'-m-xylene-bismaleimide, N,N p -p- xylene
• Applicable alkenylphenols and alkenylphenol ethers may include allylphenols, methallylphenols or ethers thereof.
• the alkenylphenol and alkenylphenol ether is a compound of the formulae (1) - (4):
• R is a direct bond, methylene, ispopropylidene, -0-, -S-, -SO- or -SO 2 -;
• R 4 , R 5 and R 6 are each independently hydrogen or a C 2 -C 1O alkenyl, preferably an ally! or propenyl, with the proviso that at least one of R 4 , R 5 or R 6 is a C 2 -Ci O alkenyl;
• R 4 , R 5 , R 6 and R 7 are each independently hydrogen or a C 2 -C 1 Q alkenyl, preferably an atlyl or alkenyl, with the proviso that at least one of R 4 , R 5 , R or R 7 is a C 2 -Ci O alkenyl and R is defined as in formula (1) and
• R 8 , R 9 , R 10 , R n , R 12 and R 13 are each independently hydrogen, Ci-C 4 alkyl, and C 2 -Ci O alkenyl, preferably allyl or propenyl, with the proviso that at least one of R 8 , R 9 , R 10 , R 11 , R 12 and R 13 is a C 2 -C 10 alkenyl and b is an integer from O to 10. It is also possible to use mixtures of compounds of the formulae (1) - (4).
• alkenylphenol and alkenylphenol ether compounds include: O 5 O'- diallyl-bisphenol A, 4 J 4'-dihydroxy-3,3'-diallyldiphenyl, bis(4-hydroxy-3- allylphenyl)methane, 2,2-bis(4-hydroxy-3,5-diallylphenyl)piOpane, O,O'-dimethallyl- bisphenol A, 4,4'-dihydiOxy-3,3'-dimethallyldiphenyl, bis(4-hydroxy-3- methallylphenytymethane ⁇ 2,2-bis(4-hydroxy-3,5-dimethaHylphenyl)-propane, 4- methallyl-2-methoxyphenol, 2,2-bis(4-methoxy-3-allyl ⁇ henyl) ⁇ ro ⁇ ane, 2,2-bis(4- methoxy-3 -methallylphenyl)propane, 4,4'-dimeth
• the alkenylphenolj alkenylphenol ether or mixture thereof may be employed in a range of between about 0.05 moles - 2.0 moles per mole of polyimide. In another embodiment, the alkenylphenol, alkenylphenol ether or mixture thereof may be employed in a range of between about 0.1 moles - 1.0 mole per mole of polyimide.
• Applicable amine catalysts include tertiary, secondary and primary amines or amines which contain several amino groups of different types and quaternary ammonium compounds.
• the amines may be either monoamines or polyamines and may include: diethylamine, tripropylamine, tributylamine, triethylamine, triamylamine, benzylamine, tetramethyl-diaminodiphenylmethane, N,N-d ⁇ sobutylaminoacetonitrile ; N 5 N- dibutylaminoacetoniti ⁇ le, heterocyclic bases, such as quinoline, N-methylpyrrolidine, imidazole, benzimidazole and their homologues, and also mercaptobenzothiazole.
• suitable quaternary ammonium compounds which may be mentioned are benzyltrimethylammonium hydroxide and benzyltrimethylammonium methoxide.
• Tripropylamine
• the amine catalyst may be employed in a range of between about 0.1% - 10% by weight of amine catalyst per total weight of the advancement reactants. In another embodiment, the amine catalyst present may be employed in a range of between about 0.2% - 5% by weight of amine catalyst per total weight of the advancement reactants.
• the method of preparation of the polymaleimide prepolymer includes blending the polyimide and the alkenylphenol, alkenylphenol ether or mixture thereof and heating the blend to a temperature of about 25 0 C - 15O 0 C until a clear melt is obtained.
• the amine catalyst may then be added and the reaction continued for an appropriate amount of time at a temperature of about 100 0 C - 140 0 C whereupon all of the amine catalyst is removed under vacuum.
• the degree of advancement may be monitored by measuring resin melt viscosity using a 0-100 poise scale at 125 0 C and may range from 20-85 poise for the advanced polymaleimide prepolymer.
• Gel time may also be used as an additional parameter and reflects the time to total gel formation as determined at a temperature of about 170°C-175°C and may range from 300 seconds-2000 seconds.
• the storage-stable advanced polymaleimide prepolymer composition further includes a dioxolane of the formula (5):
• the dioxolane may be employed in a range of between about 10%-50% by weight based on the total weight of the storage-stable advanced polymaleimide prepolymer composition. In another embodiment, the dioxolane may be employed in a range of between about 17.5%-40% by weight, preferably between about 20% ⁇ 30% by weight, based on the total weight of the storage-stable advanced polymaleimide prepolymer composition
• the storage-stable advanced polymaleimide prepolymer composition may be prepared by adding the dioxolane to the polymaleimide prepolymer at the conclusion of the advancement reaction.
• High solids, up to about 80% by weight, and low viscosity compositions of 50 centipoise or less are thereby formed which are stable for days at room temperature or temperatures higher than room temperature without precipitation or viscosity increase.
• the storage-stable advanced polymaleimide prepolymer composition may optionally be mixed at any stage before cure with one or more stabilizers, organic solvents, extenders, fillers, reinforcing agents, pigments, dyestuffs, plasticizers, tackifiers, rubbers, accelerators, diluents or any mixture thereof.
• Stabilizers which may be employed include: phenothiazine itself or C-substituted phenothiazines having 1 to 3 substituents or N-substituted phenothiazines having one substituent for example, 3-methyl-phenothiazine, 3-ethyl-phenothiazine, 10-methyl- phenothiazine; 3-phenyl-phenothiazine, 3,7-diphenyl-phenothiazine; 3- chlorophenothiazine, 2-chlorophenothiazine, 3-bromophenothiazine; 3- nitrophenothiazine, 3-aminophenothiazine ⁇ 3,7-diamino ⁇ henothiazine; 3-sulfonyl- phenothiazine, 3,7-disulfonyl-phenothiazine, 3,7-dithiocyanatophenthiazin; substituted quinines and catechols
• Organic solvents which may be added to the storage-stable advanced polymaleimide prepolymer composition include low boiling solvents (boiling points up to about 16O 0 C and preferably up to about 100 0 C) such as ketones, glycol ethers and glycol ether acetates, hydrocarbons, methoxy propanol, dimethylformamide and mixtures thereof.
• the organic solvents, when present, may be added to the storage-stable advanced polymaleimide prepolymer composition in amounts of up to about 30% by weight, preferably up to about 25% by weight, and most preferably up to about 20% by weight, based on the total weight of the advanced polymaleimide prepolymer composition.
• Extenders, reinforcing agents, fillers accelerators and pigments which can be employed include, for example: coal tar, bitumen, glass fibers, boron fibers, carbon fibers, cellulose, polyethylene powder, polypropylene powder, mica, asbestos, quartz powder, gypsum, antimony trioxide, bentones, silica aerogel ("aerosil"), lithopone, barite, titanium dioxide, eugenol, dicummyl peroxide, isoeugenol, carbon black, graphite, and iron powder.
• additives for example, flameproofing agents, flow control agents such as silicones, cellulose acetate butyrate, polyvinyl butyrate, waxes, stearates and the like (which are in part also used as mold release agents) to the advanced polymaleimide prepolymer composition,
• the storage-stable advanced polymaleimide prepolymer compositions described above are suitable in a broad range of end uses such as in prepregs, laminates of various thicknesses, printed circuit boards, castings, composites, moulded articles, adhesives and coatings.
• a prepreg may by obtained by impregnating or coating a base material with the storage-stable advanced polymaleimide prepolymer composition.
• the base material includes all base materials used for laminates. Examples thereof include various glass cloth such as E glass cloth, NE glass cloth and D glass cloth, natural inorganic fiber fabrics, woven fabrics and nonwoven fabrics obtained from liquid crystal fibers such as an aromatic polyamide fiber or an aromatic polyester fiber, woven fabrics and nonwoven fabrics obtained from synthetic fibers such as a polyvinyl alcohol fiber, a polyester fiber or an acrylic fiber, natural fiber nonwoven fabrics such as cotton fabric, linen fabric or felt, a carbon fiber fabric, natural cellulose type fabrics such as kraft paper, cotton paper or paper-glass combined paper, and porous PTFE.
• a polymer base material is impregnated or coated with the advanced polymaleimide prepolymer composition of the present invention.
• the polymer base material is not specially limited so long as it is a woven fabric, a nonwoven fabric, a sheet or a porous body each of which uses a polymer.
• liquid crystal polymers such as lyotropic liquid crystal polymers typified by aromatic polyamide, polyphenylene benzothiazole, thermotropic liquid crystal polymers typified by aromatic polyester, polyesteramide, a polyamide, an aramid resin, polyphenylene ether, polyphenylene sulfide, polyethylene, polypropylene, and a fluororesin.
• the polymer is properly selected depending upon an intended application or performance as required. These polymers may be used alone or in combination as required.
• the thickness of the base material is not specially limited. Generally, it is about 3 ⁇ m to 200 ⁇ m.
• the process for producing the prepreg is not specially limited so long as it can combine the storage-stable advanced polymaleimide prepolymer composition and a base material to produce the prepreg.
• a method is provided in which the above described advanced polymaleimide prepolymer composition is impregnated or applied to the base material and then heated, for example, in a dryer, at 80 0 C to 200 0 C for 1 to 90 minutes to B-stage the composition and thereby produce prepreg.
• the resin content of the prepreg may range from about 30%-90% by weight.
• a metal-clad laminate may also be obtained by stacking one prepreg or at least two prepregs, laminating metal foil(s), such as copper foil or aluminum foil, on upper and lower surfaces or one surface of the stacked prepreg(s) and heating and pressurizing the resultant set.
• metal foil(s) such as copper foil or aluminum foil
• General techniques of a laminate and a multilayer board for printed wiring boards may be applied for the molding conditions of the metal- clad laminate.
• a multiplaten press for example, generally, a multiplaten press, a multiplaten vacuum press, continuous molding, an autoclave molding machine or the like is used at a temperature of between about 100 0 C- 300 0 C and a pressure of between about 0,2 MPa-10 MPa, and at a heating time of about 0.1-5 hours, Further, it is also possible to produce a multilayer board by combining the prepreg of the present invention with an internal layer wiring board which is separately prepared and laminate-molding the resultant set.
• a prepreg or laminate structure comprises the cured product of a base material impregnated or coated with a storage-stable advanced polymaleimide prepolymer composition comprising (i) a polymaleimide prepolymer resulting from the advancement reaction of a polyimide and an alkenylphenol, alkenylphenol ether or mixture thereof in the presence of an amine catalyst; and (ii) dioxolane.
• Example 1 This example illustrates the preparation of a storage-stable advanced polymaleimide prepolymer composition of the present invention.
• Example 3 The storage stability of the advanced prepolymer composition prepared in Example 1 was compared against a prepolymer composition prepared in accordance with Example 1 with the exception being the replacement of dioxolane with methyl ethyl ketone. Samples of the comparative prepolymer composition were stored at 4 0 C and 5O 0 C for a period of time and the gel time (171 0 C) of the samples was measured at certain intervals. The results are presented in Table 3:
• the advanced prepolymer composition according to the present invention s when stored at 50 0 C over time, exhibited a much longer gel time as compared to the comparative prepolymer composition stored at 5O 0 C.
• Example 2 This example illustrates the preparation of a storage-stable advanced polymaleimide prepolymer composition of the present invention.
• the gel time (T 171 0 C) for the advanced polymaleimide prepolymer composition according to the present invention, when stored at room temperature and 50 0 C, was greater than 300 seconds over a period of at least 56 days.
• the advanced pofymaleimide prepolymer composition according to the present invention when stored at 50 0 C over time, exhibited a much longer gel time as compared to the comparative prepolymer composition stored at 5O 0 C.

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