EP0560897A4 - - Google Patents
Info
- Publication number
- EP0560897A4 EP0560897A4 EP19920901707 EP92901707A EP0560897A4 EP 0560897 A4 EP0560897 A4 EP 0560897A4 EP 19920901707 EP19920901707 EP 19920901707 EP 92901707 A EP92901707 A EP 92901707A EP 0560897 A4 EP0560897 A4 EP 0560897A4
- Authority
- EP
- European Patent Office
- Prior art keywords
- polymer
- copolymer
- fiber
- fibers
- polybenzoxazole
- 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- Withdrawn
Links
- 239000000835 fiber Substances 0.000 claims abstract description 82
- 229920000642 polymer Polymers 0.000 claims abstract description 75
- 239000002131 composite material Substances 0.000 claims abstract description 53
- 239000011159 matrix material Substances 0.000 claims abstract description 46
- 229920001577 copolymer Polymers 0.000 claims abstract description 43
- 229920002577 polybenzoxazole Polymers 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000701 coagulant Substances 0.000 claims abstract 3
- 229920001169 thermoplastic Polymers 0.000 claims description 24
- 239000004416 thermosoftening plastic Substances 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 15
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 14
- 229920001400 block copolymer Polymers 0.000 claims description 13
- 125000003118 aryl group Chemical group 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- -1 poly(aromatic ether) Polymers 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 239000004693 Polybenzimidazole Substances 0.000 claims description 7
- 238000005345 coagulation Methods 0.000 claims description 7
- 230000015271 coagulation Effects 0.000 claims description 7
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 239000004760 aramid Substances 0.000 claims description 5
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 229920003235 aromatic polyamide Polymers 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 229920006345 thermoplastic polyamide Polymers 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 239000012783 reinforcing fiber Substances 0.000 claims description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 125000004434 sulfur atom Chemical group 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims 8
- 239000007864 aqueous solution Substances 0.000 claims 1
- 229920006376 polybenzimidazole fiber Polymers 0.000 claims 1
- 239000000203 mixture Substances 0.000 description 13
- 229920000049 Carbon (fiber) Polymers 0.000 description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 10
- 239000000178 monomer Substances 0.000 description 10
- 229920005989 resin Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- 239000004917 carbon fiber Substances 0.000 description 8
- 239000004744 fabric Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 229920002480 polybenzimidazole Polymers 0.000 description 6
- 229920001519 homopolymer Polymers 0.000 description 5
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical group NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 4
- 230000002787 reinforcement Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229920000106 Liquid crystal polymer Polymers 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003733 fiber-reinforced composite Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920003252 rigid-rod polymer Polymers 0.000 description 3
- 239000000779 smoke Substances 0.000 description 3
- DPYROBMRMXHROQ-UHFFFAOYSA-N 4,6-diaminobenzene-1,3-diol Chemical compound NC1=CC(N)=C(O)C=C1O DPYROBMRMXHROQ-UHFFFAOYSA-N 0.000 description 2
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229920002313 fluoropolymer Polymers 0.000 description 2
- 239000004811 fluoropolymer Substances 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229920002530 polyetherether ketone Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical group C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 1
- RLXBOUUYEFOFSW-UHFFFAOYSA-N 2,5-diaminobenzene-1,4-diol Chemical compound NC1=CC(O)=C(N)C=C1O RLXBOUUYEFOFSW-UHFFFAOYSA-N 0.000 description 1
- UOFDVLCOMURSTA-UHFFFAOYSA-N 2-(2-carboxyphenoxy)benzoic acid Chemical compound OC(=O)C1=CC=CC=C1OC1=CC=CC=C1C(O)=O UOFDVLCOMURSTA-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- NFPYJDZQOKCYIE-UHFFFAOYSA-N 4-amino-3-hydroxybenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1O NFPYJDZQOKCYIE-UHFFFAOYSA-N 0.000 description 1
- BWKDAAFSXYPQOS-UHFFFAOYSA-N Benzaldehyde glyceryl acetal Chemical compound O1CC(O)COC1C1=CC=CC=C1 BWKDAAFSXYPQOS-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229960004050 aminobenzoic acid Drugs 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 description 1
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 1
- 125000002837 carbocyclic group Chemical group 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011153 ceramic matrix composite Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011156 metal matrix composite Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000904 poly(2,6-benzothiazole) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 125000005551 pyridylene group Chemical group 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000005628 tolylene group Chemical group 0.000 description 1
- 230000017105 transposition Effects 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
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
- C08G73/22—Polybenzoxazoles
-
- 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
- C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
- C08J5/243—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using carbon fibres
-
- 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
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/32—Polythiazoles; Polythiadiazoles
-
- 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
- C08J5/247—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using fibres of at least two types
-
- 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
- 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
-
- 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
- C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
Definitions
- This invention relates to matrix composites and processes for making them.
- a fiber-reinforced composite, or matrix composite is an article comprising a plurality of fibers (the reinforcement) embedded in a plastic (the matrix). Typically, the fibers give strength and/or stiffness to the composite, and the matrix maintains fiber alignment and transfers load around broken fibers. Matrix composites are described in detail in numerous references, such as Kirk-Othmer Ency. Chem., Tech. - Supp., Composites, High Performance, at 260-281 (J. Wiley & Sons 1984).
- Suitable fibers are available for use in matrix composites, each having different combinations of tensile and compressive strength and modulus, tempera ⁇ ture stability, creep, cost, and other properties.
- Suitable fibers may contain, for example, aramid (such as KevlarTM fibers), boron, glass, carbon, gel-spun polyethylenes (such as SpectraTM fiber), polybenz- oxazole, polybenzothiazole, or polybenzimidazole.
- aramid such as KevlarTM fibers
- boron such as KevlarTM fibers
- SpectraTM fiber such as SpectraTM fiber
- polybenz- oxazole polybenzothiazole
- polybenzimidazole polybenzimidazole.
- Suitable fibers and processes for their fabrication are described in numerous references, such as U.S. Patent 4,533,693; 3 Kirk-Othmer Ency. Chem. Tech., Aramid Fibers, 213 (J. Wiley & Son
- a number of matrix materials are also available for use in matrix composites.
- polymer matrix materials include polyesters, epoxy resins, polycyanates, polybutadienes, vinyl ester resins and polyimides.
- Thermoplastic polymers such as poly(ether ether ketone), are also used as matrix materials in some composites.
- Some carbon matrix composites have been made.
- Metal and ceramic matrix composites are also known.
- An objective of the present invention is to provide a fiber-reinforced composite having new polymer matrix materials that show improvement over existing thermoset or thermoplastic matrix resins in at least one of the following properties: flame resistance, smoke from exposure to flame, chemical resistance, solvent resistance, thermal stability, tensile strength or tensile modulus.
- the present invention is a method of using a dope solution that contains: (i) a polybenzoxazole polymer or copolymer or a polybenzothiazole polymer or copolymer, and (ii) a solvent for the polymer or copolymer, said method being characterized by the steps of:
- the method of the present invention can be used to synthesize fiber-reinforced composites in which the matrix resin is a polybenzoxazole or polybenzothiazole polymer or copolymer.
- the polybenzoxazole or poly- benzothiazole matrix in the composite can be selected to provide any one of the properties of low flammability, low smoke generation, high temperature stability, high chemical resistance, high solvent resistance, high strength and/or modulus or a combination of those properties.
- Composites of the present invention and shaped articles containing them are useful for structural materials and parts.
- the present invention uses fibers, such as those previously described.
- the fibers should be a type whose properties are not substantially degraded by contact with the solution of polymer or copolymer and its solvent.
- the fiber is preferably aramid, carbon, c - polybenzoxazole or polybenzothiazole. It is most preferably carbon or polybenzoxazole.
- Polybenzoxazole and polybenzothiazole fibers are preferably heat treated.
- the tensile strength of the fiber is preferably at least 2.5 GPa, more preferably at least 10 3.0 GPa and most preferably at least 3.5 GPa.
- the tensile modulus of the fiber is preferably at least 135 GPa, more preferably at least 200 GPa and most preferably at least 270 GPa.
- the fibers may have dimensions that are usual for reinforcing materials in matrix composites. Their average diameter is preferably between 1 ⁇ and 100 ⁇ .
- the fiber may be, for instance, in the form of a cloth or in the form of long strands or in the form of a short fiber or fiber pulp suitable for making random fiber composites.
- a mixture of fibers may be used.
- the fibers may 5 contain a mixture of at least one fiber having high tensile properties, such as aramid or polybenzazole, and another fiber having high compressive properties, such as quartz.
- the present invention also uses matrix materials containing polybenzoxazole (PB0) or poly ⁇ benzothiazole (PBT) or copolymers thereof. Those matrix materials are dissolved in a dope solution with a suitable solvent.
- PBO, PBT and random, sequential and block copolymers of PBO and PBT are described in references such as Wolfe et al., Liquid Crystalline Polymer Compositions, Process and Products, U.S. Patent 4,703,103 (October 27, 1987); Wolfe et al., Liquid Crystalline Polymer Compositions, Process and Products, U.S.
- Patent 4,533,692 (August 6, 1985); Wolfe et al., Liquid Crystalline Poly(2,6-Benzothiazole) Compositions, Process and Products, U.S. Patent 4,533,724 (August 6, 1985); Wolfe, Liquid Crystalline Polymer Compositions, Process and Products, U.S. Patent 4,533,693 (August 6, 1985); Evers, Thermoxadatively Stable Articulated p-Benzobisoxazole and p-Benzobisthiazole Polymers, U.S. Patent 4,359,567 (November 16, 1982); Tsai et al., Method for Making Heterocyclic Block Copolymer, U.S.
- Patent 4,578,432 (March 25, 1986); 11 Ency. Poly. Sci. & Eng., Polybenzothiazoles and Polybenzoxazoles, 601 (J. Wiley & Sons 1988) and W. W. Adams et al., The Materials Science and Engineering of Rigid-Rod Polymers (Materials Research Society 1989).
- Other block copolymers of PBO and PBT are described in detail in Harris et al., Copolymers Containing Polybenzoxazole, Polybenzothiazole and Polybenzimidazole Moieties, International Application No. PCT/US89/04464 (filed October 6, 1989), International Publication No.
- WO 90/03995 (published April 19, 1990) and in Harris et al., Thermoplastic Compositions Containing Polybenzoxazole, Polybenzothiazole and Polybenzimidazole Moieties and Process for Making Shaped Articles from Them, EPO Application 90104963-5 (filed March 16, 1990), EP0 Publication 0 388 803 (published September 26, 1990).
- the polymer or copolymer contains any one of AB-mer units, as represented in Formula 1(a), and/or AA/BB-mer units, as represented in Formula Kb)
- Each Ar represents an aromatic group.
- the aromatic group may be heterocyclic, such as a pyridinylene group, but it is preferably carbocyclic.
- the aromatic group may be a fused or unfused polycyclic system, but is preferably a single six-membered ring. Size is not critical, but the aromatic group preferably contains no more than 18 carbon atoms, more preferably no more than 12 carbon atoms and most preferably no more than 6 carbon atoms. Examples of suitable aromatic groups include phenylene moieties, tolylene moieties, biphenylene moieties and bis-phenylene ether moieties.
- Ar in AA/BB-mer units is preferably a 1 ,2,4,5-phenylene moiety or an analog thereof.
- Ar in AB-mer units is preferably a 1,3,4-phenylene moiety or an analog thereof.
- Each Z is independently an oxygen or a sulfur atom.
- Each DM is independently a bond or a divalent organic moiety that does not interfere with the synthesis, fabrication or use of the polymer.
- the divalent organic moiety may contain an aliphatic group, which preferably has no more than 12 carbon atoms, but the divalent organic moiety is preferably an aromatic group (Ar) as previously described. It is most preferably a 1 ,4-phenylene moiety or an analog thereof.
- each azole ring is bonded to adjacent carbon atoms in the aromatic group, such that a five-membered azole ring fused with the aromatic group is formed.
- azole rings in AA/BB-mer units may be in cis- or trans-position with respect to each other, as illustrated in 11 Ency. Poly. Sci. & Eng., supra, at 602.
- the polymer or copolymer preferably consists essentially of either AB-PBZ mer units or AA/BB-PBZ mer units, and more preferably consists essentially of AA/BB-PBZ mer units.
- the polybenzazole polymer may be rigid rod, semi-rigid rod or flexible coil. It is preferably rigid rod in the case of an AA/BB-PBZ polymer or semi-rigid in the case of an AB-PBZ polymer.
- Preferred mer units are any one illustrated in Formulae 2 (a)-(h).
- the polymer more preferably consists essentially of any of the mer units illustrated in 2(a)-(h), and most preferably consists essentially of any of the mer units illustrated in 2(a)-(c).
- the polybenzoxazole or polybenzothiazole polymer or copolymer may also be a block copolymer in which the previously described repeating units are bonded to blocks of thermoplastic polymer.
- the thermoplastic block may contain a thermoplastic polyamide, polyimide, poly(aromatic ketone), poly(aromatic sulfone), poly(aromatic ether), or random or sequential copolymer of those polymers with each other or with polybenzazole.
- the thermoplastic block may also contain a thermoplastic polybenzazole polymer, such as the polymers described in Harris et al., Thermoplastic Compositions Containing Polybenzoxazole, Polybenzothiazole and Polybenzimidazole Moieties and Process for Making Shaped Articles from Them, EPO Application 90104963.5 (filed March 16, 1990), EPO Publication 0 388 803 (published September 26, 1990) and in K.-U. B ⁇ hler, Spezialplaste 838-866 (Akademie-Verlag 1978).
- the thermoplastic block preferably contains any one of:
- thermoplastic polyamide (a) a thermoplastic polyamide; (b) a thermoplastic poly(aromatic ether);
- thermoplastic polybenzazole-poly(aromatic ether) copolymer (c) a thermoplastic polybenzazole-poly(aromatic ether) copolymer
- Each polybenzoxazole or polybenzothiazole polymer or copolymer preferably contains on average at least 25 mer units, more preferably at least 50 mer units and most preferably at least 100 mer units.
- the intrinsic viscosity of rigid AA/BB-PBZ polymers in methanesulfonic acid at 25°C is preferably at least 10 dL/g, more preferably at least 15 dL/g and most preferably at least 20 dL/g. For some purposes, an intrinsic viscosity of at least 25 dL/g or 30 dL/g may be best. Intrinsic viscosity of 60 dL/g or higher is possible, but the intrinsic viscosity is preferably no more than 40 dL/g.
- -rigid AB-PBZ polymers is preferably at least 5 dL/g, more preferably at least 10 dL/g and most preferably at least 15 dL/g.
- the polybenzoxazole or polybenzothiazole polymer or copolymer is a preferably a homopolymer.
- the homopolymer preferably is not thermoplastic - i.e., it does not become flowable or moldable at any temperature below its decomposition temperature.
- the homopolymer is preferably essentially insoluble in common organic solvents such as halogenated hydrocarbons, alkanes, benzene or toluene.
- the homopolymer is preferably insoluble in non-acidic aqueous solvents.
- the polymer or copolymer is dissolved in a solvent to form a solution or dope.
- a solvent is preferably an acid capable of dissolving the polymer.
- the acid is preferably non- -oxidizing.
- suitable acids include polyphosphoric acid, methanesulfonic acid and sulfuric acid and mixtures of those acids.
- the acid is prefer- ably polyphosphoric acid and/or methanesulfonic acid, and is more preferably polyphosphoric acid.
- the fiber should be chosen so that its properties do not degrade upon contact with the acid.
- the dope should contain a high enough concentration of polymer for the polymer to coagulate to form a solid article.
- concentration of polymer in the dope is usually at least 0.5 weight percent, prefer ⁇ ably at least 1 percent and more preferably at least two percent.
- the maximum concentration is limited primarily by practical factors, such as polymer solubility and dope viscosity.
- concentration of polymer is seldom more than 30 weight percent, and usually no more than about 20 weight percent. The best concentration within that range varies, depending upon the polymer in the dope.
- the concentration of polymer in the dope is preferably high enough to provide a liquid crystalline dope.
- the concentration of the polymer is preferably at least 7 weight percent, more preferably at least 10 weight percent and most preferably at least 14 weight percent.
- a block copolymer that contains rigid or semirigid polybenzazole blocks and thermoplastic polymer blocks is preferably in a lower concentration, so that the dope solution is not liquid crystalline.
- the total weight percent of rigid or semirigid blocks in the solution is preferably no more than 4 weight percent. Coagulation of the block copolymer from isotropic dopes yields a substantially non-phase-separated matrix that can be thermoformed without phase separation.
- Suitable polymers or copolymers and dopes can be synthesized by known procedures, such as those described in Wolfe et al., U.S. Patent 4,533,693
- suitable monomers AA-monomers and BB- -monomers or AB-monomers
- suitable AA-monomers include terephthalic acid and analogs thereof.
- BB- -monomers examples include 4,6-diaminoresorcinol, 2,5- -diaminohydroquinone, 2,5-diamino-1 ,4-dithiobenzene and analogs thereof, typically stored as acid salts.
- suitable AB-monomers include 3-amino-4- -hydroxybenzoic acid, 3-hydroxy-4-aminobenzoic acid, 3-amino-4-thiobenzoic acid, 3-thio-4-aminobenzoic acid and analogs thereof, typically stored as acid salts.
- the polybenzoxazole or polybenzothiazole oligomer or polymer may be reacted with: (1) a thermoplastic polymer; or (2) monomers that polymerize to form a thermoplastic polymer.
- the polybenzoxazole or polybenzothiazole may be end-capped with a reactive group, such as by end-capping with an oxy-bis-(benzoic acid) monomer, to facilitate formation of the block copolymer.
- the fiber is prepregged with the dope solution.
- the optimum procedure for prepregging the fiber in the dope will vary depending upon the fiber, the dope and the desired composite.
- a less viscous dope, whose viscosity is similar to that of other uncured matrix resins, may be prepregged according to processes used for known matrix resins.
- a fiber or fiber tow or a group of tows may be prepregged with a viscous dope by known means for putting viscous coatings on fibers or wires, such as by extruding the dope on the fiber using a cross-head die.
- Such processes ordinarily form a prepregged tape that can be laid up in a desired orientation and shape.
- Many different fiber configurations are known and may be used.
- the fibers may run in a single direction to form a unidirectional composite, having great strength in one direction but poorer properties in other directions.
- the fibers may be laid out in layers directed at different angles with respect to each other to form a multidirectional composite.
- the prepreg may be laid out flat or filament wound to form a shaped article.
- a group of fibers or tows may be prepregged with a dope that is viscous enough to form a film, by forming one or more dope films and either pressing the fibers into a single film of dope or pressing the fibers between two films of dope.
- Several alternating layers of fiber and dope film may be pressed together to form a composite having several layers of fiber.
- the fibers pressed into the dope may have unidirectional or multidirectional orientation as previously described.
- the dope film may be thicker to form a "resin-rich” composite or thinner to form a "resin-starved” composite.
- the dope film is preferably on average at least 25 ⁇ m thick. The temperature should be high enough for the fibers to embed in the dope and for the dope sheets to consolidate.
- the film may be uniaxially stretched to provide best properties in a single direction, but it is prefer ⁇ ably biaxially stretched to provide good properties in at least two directions.
- the extrusion of dopes to form films is described in numerous references, such as in Chenevey, U.S. Patent 4,487,735 (December 11, 1984); Lusignea et al., U.S. Patent 4,871,595 (October 3, 1989); Chenevey, U.S. Patent 4,898,924 (February 6, 1990); Harvey et al., U.S. Patent 4,939,235 (July 3, 1990); Harvey et al., U.S. Patent 4,963,428 (October 16, 1990); and Lusignea et al., U.S.
- the dope may be extruded from a slit die, after which it is preferably mechanically stretched before coagulation to impart biaxial orientation.
- the dope may be extruded in a tubular film that is preferably stretched biaxially by a bubble process to impart biaxial orientation.
- the fibers may be short fibers or fiber pulps that are immersed in the dope to form a random fiber composite, similar to those described in U.S. Patents 4,426,470 and 4,550,131.
- the composite is hardened by contacting the dope with a liquid that causes the polymer or copolymer to coagulate.
- the liquid is a nonsolvent for the polymer or copolymer that dilutes the solvent.
- the nonsolvent liquid is preferably volatile.
- the nonsolvent liquid may be an organic compound, such as an alcohol or a ketone containing no more than 4 carbon atoms.
- the nonsolvent liquid is preferably aqueous, and more preferably consists essentially of water, at least at the commencement of the coagulation.
- the solvent is volatile or contains a volatile component, such as methanesulfonic acid, then the volatile component can be at least partially removed by evapora ⁇ tion to concentrate the polymer before coagulation.
- the coagulated polymer is preferably washed for a period of time sufficient to remove substantially all of the remaining solvent.
- the composite may be dried. It is preferably restrained from shrinking as it is dried. After drying, the composite may be heat treated. Heat treatment is preferably carried out under pressure. The finished composite may be machined into a desired final shape.
- the resulting composite has fibers as previously described embedded in a matrix resin containing a polybenzoxazole or polybenzothiazole polymer or copolymer as previously described.
- the composite should contain a sufficient number of fibers to provide reinforcement for the composite. It should contain a sufficient quantity of matrix material to hold the fibers together and maintain fiber alignment, and preferably to transfer loads around broken fibers.
- the composite preferably contains at least 20 volume percent fiber, more preferably at least 40 volume percent fiber and most preferably at least 50 volume percent fiber. It preferably contains at least 20 volume percent matrix and more preferably at least 35 volume percent matrix.
- the fiber may receive surface treatment or be coated with an adhesive to improve the adhesion of the fiber to the matrix.
- the matrix may contain a mixture of more than one polymer, such as several polybenzazole polymers or a mixture of the polybenzazole fiber and a non-polybenzazole polymer, as described in Uy, U.S. Patent 4,810,735 (March 7, 1989).
- the matrix preferably contains only a single polymer or copolymer.
- the fiber may be wrapped with another fiber to improve compressive strength (filed August 8, 1990).
- the preferred polybenzoxazole and polybenzo ⁇ thiazole matrix resins have one or more of the following c- advantages over current corresponding thermoset or thermoplastic matrix resins: better flame resistance, lower smoke, good solvent resistance, good chemical resistance, high continuous use temperatures, higher tensile strength and higher tensile modulus.
- Example 1 Composite Containing Carbon Fiber and t - Polybenzoxazole Matrix.
- a dope containing 14 weight percent cis-poly- benzoxazole (consisting essentially of mer units illustrated in Formula 2(a) - intrinsic viscosity of 25 0 dL/g to 45 dL/g in methanesulfonic acid at 25°C) in polyphosphoric acid is extruded from a slit die as a 15 mil thick sheet between two sheets of 2 mil thick TeflonTM fluoropolymer. Two 3 inch by 3 inch squares of the dope film are cut, and the TeflonTM sheet is stripped off of one side of each sheet.
- the prepreg is cooled to room temperature, and the TeflonTM sheet is stripped off of each side of the prepreg.
- the prepreg is placed in a "picture frame" holder to prevent shrinkage along the length and width of the sample but allow shrinkage in the thickness of the sample.
- the framed prepreg is placed in two liters of water, left in the water for two days, removed from the frame and dried in air at ambient temperature. A composite having carbon fiber reinforcement and a cis- -polybenzoxazole matrix results.
- the composite is cut in half. One half is placed in a heated press at 150°C and 5000 lbs. pressure for one minute. It is golden yellow in color. One half is placed in a heated press at 300°C and 5000 lbs. pressure for one hour. It is darker yellow with a purple tinge. Both have smooth surfaces with no visible holes.
- Example 2 Composite Containing Carbon Fiber and Nonrigid Matrix.
- Example 1 The procedure of Example 1 is followed, except that: Instead of 14 weight percent cis-polybenz- oxazole, the dope contains 12 weight percent of a polymer formed by the reaction of 4,6-diamino- resorcinol bis(hydrogen chloride) and 1,1,3-tri- methyl-3-phenylindan-4' ,5-dicarboxylic acid in poly- phosphoric acid, such as is described in Summers et al., Ser. No. 513,316 (filed April 20, 1990);
- the sheets pressed together are 2 inches by 3 inches;
- Example 3 Composite Containing Polybenzoxazole Fiber and Polybenzoxazole Matrix.
- the cloth consists essentially of polybenz ⁇ oxazole fiber and has dimensions of 5 inches by 5 inches;
- the dope films have dimensions of 5 inches by 5 inches; The sample is coagulated in 2 gallons of water.
- Example 4 Composite Containing Two Layers of Carbon Fiber and Polybenzoxazole Matrix.
- the cloth and dope film are laid up so that there is from top to bottom: a layer of TeflonTM film, a layer of polybenzoxazole dope, a layer of carbon fabric, a layer of polybenzoxazole dope, a layer of carbon fabric, a layer of polybenzoxazole dope, and a layer of TeflonTM film;
- the prepregging is carried out at 150°C and 5000 lbs. pressure for 3 minutes;
- the finished composite is pressed under 5000 lbs pressure at a temperature ramped from room temperature to 300°C over 90 minutes and held at 300°C for 30 minutes.
- Example 5 Composite Containing Carbon Fiber
- a composite is fabricated by the following procedure using (1) a graphite fiber and (2) a dope containing a mixture of methanesulfonic acid and poly ⁇ phosphoric acid and about 3 weight percent of a block copolymer having rigid rod cis-polybenzoxazole blocks and blocks of thermoplastic cis-PBO/PEEK copolymer.
- the block copolymer contains about 38 weight percent rigid rod block and about 62 weight percent thermoplastic block. Its average structure is represented by the Formula:
- the fiber is passed through a 400°C oven at a rate of 140 inches/min. in order to remove the sizing on the fiber.
- the fiber passes through several idler rollers and through a resin bath that contains the dope at room temperature.
- the impregnated fiber passes through a rectangular die 0.120 in. x 0.008 in. to clean off excess dope.
- the prepreg is wound around a rotating 70 inch drum such that each wrap is immediately adjacent to the previous wrap without overlapping.
- the prepreg is cut into seven 7 inch x 7 inch panels, which are stacked to form a seven-ply unidirectional laminate.
- the laminate is placed in a porous TeflonTM fluoropolymer bag, clamped between perforated aluminum plates and immersed in running water at room temperature for 24 hours.
- the resulting wet composite is pressed at 80°C and 100 psi for 4-1/2 hours and is placed in a vacuum oven at 90°C for 24 hours to dry. It is then compressed for 6 minutes at 400°C and 50 psi, for 15 minutes at 400°C and 1000 psi, and for a time sufficient to cool at 1000 psi to consolidate.
- the resulting composite is rigid with individual plies bonded firmly together.
- Example 1 The procedure of Example 1 is repeated, except that the dope solution contains trans-polybenzothiazole polymer. Similar results will be obtained.
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Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US624164 | 1984-06-24 | ||
US07/624,164 US5196259A (en) | 1990-12-07 | 1990-12-07 | Matrix composites in which the matrix contains polybenzoxazole or polybenzothiazole |
US668532 | 1991-03-13 | ||
US07/668,532 US5248721A (en) | 1991-03-13 | 1991-03-13 | Prepregs containing a fiber and a thermoplastic polybenzazole copolymer matrix |
Publications (2)
Publication Number | Publication Date |
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EP0560897A1 EP0560897A1 (en) | 1993-09-22 |
EP0560897A4 true EP0560897A4 (ja) | 1994-02-23 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP92901707A Withdrawn EP0560897A1 (en) | 1990-12-07 | 1991-12-06 | Method to make matrix composites in which the matrix contains polybenzoxazole or polybenzothiazole |
Country Status (6)
Country | Link |
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EP (1) | EP0560897A1 (ja) |
JP (1) | JPH06503597A (ja) |
KR (1) | KR930703387A (ja) |
CA (1) | CA2097797A1 (ja) |
IE (1) | IE914252A1 (ja) |
WO (1) | WO1992010536A1 (ja) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
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WO1993024558A1 (en) * | 1992-06-04 | 1993-12-09 | The Dow Chemical Company | Method to synthesize carbon-carbon composites |
EP0594145B1 (en) * | 1992-10-22 | 2000-01-26 | Toyobo Co., Ltd. | Block copolymers containing blocks of polybenzazole polymer and blocks of polybenzoxazinone polymer or polyoxadiazole polymer |
Citations (1)
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JPH1115935A (ja) * | 1997-06-19 | 1999-01-22 | Paloma Ind Ltd | データ書換装置 |
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US4533693A (en) * | 1982-09-17 | 1985-08-06 | Sri International | Liquid crystalline polymer compositions, process, and products |
US4533692A (en) * | 1982-09-17 | 1985-08-06 | Sri International | Liquid crystalline polymer compositions, process, and products |
US4996281A (en) * | 1989-09-29 | 1991-02-26 | The Dow Chemical Company | Polymers containing amide moieties and a process for their preparation |
-
1991
- 1991-12-06 EP EP92901707A patent/EP0560897A1/en not_active Withdrawn
- 1991-12-06 WO PCT/US1991/009227 patent/WO1992010536A1/en not_active Application Discontinuation
- 1991-12-06 CA CA002097797A patent/CA2097797A1/en not_active Abandoned
- 1991-12-06 JP JP4502394A patent/JPH06503597A/ja active Pending
- 1991-12-06 IE IE425291A patent/IE914252A1/en not_active Application Discontinuation
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1993
- 1993-06-04 KR KR1019930701675A patent/KR930703387A/ko not_active Application Discontinuation
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
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JPH1115935A (ja) * | 1997-06-19 | 1999-01-22 | Paloma Ind Ltd | データ書換装置 |
Non-Patent Citations (3)
Title |
---|
PATENT ABSTRACTS OF JAPAN vol. 13, no. 339 (C - 624)<3687> 31 July 1989 (1989-07-31) * |
SANDOR R. ET AL.: "Polybenzimidazole (PBI) Prepreg with improved Autoclave Processability", COMPOSITE POLYMERS, vol. 4, no. 5, 1991, SHREWSBURY GB, pages 331 - 340 * |
See also references of WO9210536A1 * |
Also Published As
Publication number | Publication date |
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EP0560897A1 (en) | 1993-09-22 |
WO1992010536A1 (en) | 1992-06-25 |
IE914252A1 (en) | 1992-06-17 |
CA2097797A1 (en) | 1992-06-08 |
JPH06503597A (ja) | 1994-04-21 |
KR930703387A (ko) | 1993-11-29 |
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