CA2097797A1 - Method to make matrix composites in which the matrix contains polybenzoxazole or polybenzothiazole - Google Patents
Method to make matrix composites in which the matrix contains polybenzoxazole or polybenzothiazoleInfo
- Publication number
- CA2097797A1 CA2097797A1 CA002097797A CA2097797A CA2097797A1 CA 2097797 A1 CA2097797 A1 CA 2097797A1 CA 002097797 A CA002097797 A CA 002097797A CA 2097797 A CA2097797 A CA 2097797A CA 2097797 A1 CA2097797 A1 CA 2097797A1
- Authority
- CA
- Canada
- Prior art keywords
- polymer
- copolymer
- fiber
- polybenzoxazole
- polybenzothiazole
- 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.)
- Abandoned
Links
- 239000011159 matrix material Substances 0.000 title claims abstract description 46
- 239000002131 composite material Substances 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 39
- 229920002577 polybenzoxazole Polymers 0.000 title claims abstract description 36
- 229920000642 polymer Polymers 0.000 claims abstract description 80
- 239000000835 fiber Substances 0.000 claims abstract description 76
- 229920001577 copolymer Polymers 0.000 claims abstract description 44
- 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 22
- 239000004416 thermosoftening plastic Substances 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- -1 poly(aromatic ether) Polymers 0.000 claims description 11
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 229920001400 block copolymer Polymers 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 239000004693 Polybenzimidazole Substances 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 238000005345 coagulation Methods 0.000 claims description 6
- 230000015271 coagulation Effects 0.000 claims description 6
- 239000004760 aramid Substances 0.000 claims description 5
- 229940098779 methanesulfonic acid Drugs 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
- 229920000137 polyphosphoric acid Polymers 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
- 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
- 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
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- 239000007864 aqueous solution Substances 0.000 claims 1
- 229910052796 boron Inorganic materials 0.000 claims 1
- 229920006376 polybenzimidazole fiber Polymers 0.000 claims 1
- 239000012783 reinforcing fiber Substances 0.000 claims 1
- 239000002253 acid Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 239000000178 monomer Substances 0.000 description 10
- 229920000049 Carbon (fiber) Polymers 0.000 description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 239000004917 carbon fiber Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000004744 fabric Substances 0.000 description 7
- 229920002480 polybenzimidazole Polymers 0.000 description 6
- 239000004809 Teflon Substances 0.000 description 5
- 229920006362 Teflon® Polymers 0.000 description 5
- 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
- 239000000126 substance Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000002787 reinforcement Effects 0.000 description 3
- 239000000779 smoke Substances 0.000 description 3
- OGNVQLDIPUXYDH-ZPKKHLQPSA-N (2R,3R,4S)-3-(2-methylpropanoylamino)-4-(4-phenyltriazol-1-yl)-2-[(1R,2R)-1,2,3-trihydroxypropyl]-3,4-dihydro-2H-pyran-6-carboxylic acid Chemical compound CC(C)C(=O)N[C@H]1[C@H]([C@H](O)[C@H](O)CO)OC(C(O)=O)=C[C@@H]1N1N=NC(C=2C=CC=CC=2)=C1 OGNVQLDIPUXYDH-ZPKKHLQPSA-N 0.000 description 2
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 2
- 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
- 101100156763 Schizosaccharomyces pombe (strain 972 / ATCC 24843) wos2 gene Proteins 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
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003733 fiber-reinforced composite Substances 0.000 description 2
- 229920002313 fluoropolymer Polymers 0.000 description 2
- 239000004811 fluoropolymer Substances 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
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 1
- CDZMWAHBQLPCHD-UHFFFAOYSA-N 3-(4-carboxyphenyl)-1,1,3-trimethyl-2h-indene-5-carboxylic acid Chemical compound C12=CC(C(O)=O)=CC=C2C(C)(C)CC1(C)C1=CC=C(C(O)=O)C=C1 CDZMWAHBQLPCHD-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
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-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
- 229920000271 Kevlar® Polymers 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004642 Polyimide Substances 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
- 150000008365 aromatic ketones Chemical class 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
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 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
- 125000000623 heterocyclic group Chemical group 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
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 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
- 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
Abstract
This application claims a method for using a dope solution that contains polybenzoxazole or polybenzothiazole polymer or copolymer. Fibers are prepregged with the dope, and the prepreg is be contacted with water or another coagulant to coagulate the polymer and form a matrix composite.
Description
wos2~1os36 PCT/US91/09t27 ~C~ 97 .
i, METHOD TO MAKE MATRIX CO~POSITES IN WHICH THE MATRIX
CONTAINS POLYBENZOXAZOLE OR POLYBENZOTHIAZOLE
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). Typicnlly, the fibers give s~rength and~or stiffness to the composite, and the matrix maintains fiber alignment and transfers load around broken ~ibers.
Matrix compos~tes are described in detail in numerous references, suoh a~ Kirk-Othmer Ency. Chem., Tech. -Supp., ComPosites. Hi~h Performance, at 260-281 (J. ~iley & Sons 1984).
.
A number of fibers are available for use in matrix composites, each having diP~erent combinations of tensile and compre~ive strength and modulus, tempera-ture stability, creep, cost, and other properties.
Suitable fibers may contain, ~or example, aramid (~uch as Kevlars~ fibers), boro~, glass, carbon, gel-~pun polyethylenes (~uch as SpectraT~ fiber) 9 polybenz-ox~zole, polybenzothiazole, or polybenzimidazole.
- . . . . ~ . . . , . -W~92/~0536 ~ 9~7 PCT/~S91/0~227 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 & Sons 1978); Kirk-Othmer Ency.
Chem., Tech. - Supp., ComPosites. ~ erformance, at 261-263; 11 Ency. Poly. Sci. & Eng., Polybenzothiazoles and Polybenzoxazoles, 601 (J. Wiley & Sons 1988) and W.
W. Adams et al~, The Materials Science and Engineerin~
of Ri~id-Rod Pol~mers, at 245--312 (Materials Research Society 1989).
A number of matrix materials are also available for use in matrix composites. Examples of 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.
There is a need for improved matrix materials in advanced matrix composites. For example, the flame resistance, chemical resistance, solvent resistance and thermal stability of many polymer matrix materials is much poorer than the same properties of the Piber reinforcement. Stronger polymer matrloes could yield stronger composite~ uYing the same amount Or Piber.
Metal matrix materials are heavier than polymer3.
Ceramic and carbon matrix materials are expensive and brittle. An objective of the present invention is to provide a Piber-reinPorced composite having new polymer matrix materials that show improvement over existing thermoset or thermoplastic matrix resins in at least one . ., ' ~ ~ . .,': - ' . , , :.
:... , ....- ..:. -. . , .: ...
.. ~ . : .
WO9~ 536 ~C~ 97 ~- PCT/USsl/09Z27 of the following propertie~: 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 polybenzoxazale 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:
(1) prepregging a plurality of rein~orcing fibers with the dope solution; and (2) contacting the dope ~olution with a liquid that causes the polymer or copolymer to coagulate, in a quantity su~ficient to cause the polymer or copolymer to coagulate with the fibers embedded therein.
The method of the present invention can be used to synbhesize 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 toprovide any one o~ 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 o~ those properties. Composite3 o~ the pre3ent invention and shaped articles containing them are use~ul ~or ~tructural materials and parts.
~,... . . .
: : . . , - -., . . , , . ~ - . . .
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- , .. .. .
,: ., . . . ' . .' :
WO92/1~536 ~ C ~ 9~ PCTtUS~1/09227 The present invention uaeq fibers, such as those previously described. The ~ibers 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, polybenzoxazole or polybenzothiazole. It is most preferably carbon or polybenzoxazole. Polybenæoxazole and polybenzothiazole fibers are preferably heat treated. The tensile strength of the fiber is preferably at least 2.5 GPa, more preferably at least 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 lea~t 270 GPa.
The fibers may have dimenqions that are usual ~or reinPorcing materialq in matrix compoqites. Their average diameter i3 preferably between 1 ~ and 100 ~.
It is more preferably no more than 40 ~ and most preferably no more than 20 ~. The fiber may be, for instance, in the form of a cloth or in the ~orm of long strands or in the form of a short ~iber or fiber pulp suitable for making random fiber composites. A mixture of fibers may be used. For instance, the fibers may contain a mixture o~ at least one fiber having high tensile properties, such as aramid or polybenzazole, and another fiber having high compressive properties, such as quartz.
3 The present invention al~o u es matrix materials containing polybenzoxazole (PB0) or poly-benzothiazole (PBT) or copolymers thereo~. Those matr`ix materials are di~301ved in a dope solution with a suitable solvent, - ., , , ., ~ . . , ,, :
' : . ' . , , : . - , :, . . ~ . . . '-' ' : :
... . . ...
, . . . . .
- .-- - . - , . ... :;. :.:, . : :: .: , .
-: . ~ , . . . . . .. .. . . . . . . . . .
WO9~/10536 PCT/US9l/09227 ~C~'^J'~9~7 PBO, PBT and random, sequential and block copolymers of PBO and PBT are de~cribed in references such as Wolfe et al., ~iquid Crvstalline Polvmer ComDositions. Proces~ and P _ ducts, U.S. Patent 4,703,103 (October 27, 1987); Wolfe et al., Liquid 5 Cr~stalline PolYmer ComPositions. Process and Products, U.SO 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, Linuid 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 Makin~ Heteroc~clic Block Copol~mer, U.S.
Patent 4,578,432 (March 25, 1986); 11 Ency. Poly. Sci.
& Eng., Pol~enzothiazoles ar!d Polxbenzoxazoles, 601 (J. Wiley & Sonq 1988) and W. W. Adams et al., The Materials Science and Engineerin~ of Ri~id-Rod Polymers (Materials Research Society 1989). Other block copolymers of PBO and PBT are de~cribed 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 3 Them, EPO Application 90104963.5 (~iled March 16, 1990), EPO Publication 0 388 803 (published September 26, 19~0).
- , , :. .
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i, METHOD TO MAKE MATRIX CO~POSITES IN WHICH THE MATRIX
CONTAINS POLYBENZOXAZOLE OR POLYBENZOTHIAZOLE
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). Typicnlly, the fibers give s~rength and~or stiffness to the composite, and the matrix maintains fiber alignment and transfers load around broken ~ibers.
Matrix compos~tes are described in detail in numerous references, suoh a~ Kirk-Othmer Ency. Chem., Tech. -Supp., ComPosites. Hi~h Performance, at 260-281 (J. ~iley & Sons 1984).
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A number of fibers are available for use in matrix composites, each having diP~erent combinations of tensile and compre~ive strength and modulus, tempera-ture stability, creep, cost, and other properties.
Suitable fibers may contain, ~or example, aramid (~uch as Kevlars~ fibers), boro~, glass, carbon, gel-~pun polyethylenes (~uch as SpectraT~ fiber) 9 polybenz-ox~zole, polybenzothiazole, or polybenzimidazole.
- . . . . ~ . . . , . -W~92/~0536 ~ 9~7 PCT/~S91/0~227 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 & Sons 1978); Kirk-Othmer Ency.
Chem., Tech. - Supp., ComPosites. ~ erformance, at 261-263; 11 Ency. Poly. Sci. & Eng., Polybenzothiazoles and Polybenzoxazoles, 601 (J. Wiley & Sons 1988) and W.
W. Adams et al~, The Materials Science and Engineerin~
of Ri~id-Rod Pol~mers, at 245--312 (Materials Research Society 1989).
A number of matrix materials are also available for use in matrix composites. Examples of 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.
There is a need for improved matrix materials in advanced matrix composites. For example, the flame resistance, chemical resistance, solvent resistance and thermal stability of many polymer matrix materials is much poorer than the same properties of the Piber reinforcement. Stronger polymer matrloes could yield stronger composite~ uYing the same amount Or Piber.
Metal matrix materials are heavier than polymer3.
Ceramic and carbon matrix materials are expensive and brittle. An objective of the present invention is to provide a Piber-reinPorced composite having new polymer matrix materials that show improvement over existing thermoset or thermoplastic matrix resins in at least one . ., ' ~ ~ . .,': - ' . , , :.
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WO9~ 536 ~C~ 97 ~- PCT/USsl/09Z27 of the following propertie~: 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 polybenzoxazale 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:
(1) prepregging a plurality of rein~orcing fibers with the dope solution; and (2) contacting the dope ~olution with a liquid that causes the polymer or copolymer to coagulate, in a quantity su~ficient to cause the polymer or copolymer to coagulate with the fibers embedded therein.
The method of the present invention can be used to synbhesize 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 toprovide any one o~ 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 o~ those properties. Composite3 o~ the pre3ent invention and shaped articles containing them are use~ul ~or ~tructural materials and parts.
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WO92/1~536 ~ C ~ 9~ PCTtUS~1/09227 The present invention uaeq fibers, such as those previously described. The ~ibers 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, polybenzoxazole or polybenzothiazole. It is most preferably carbon or polybenzoxazole. Polybenæoxazole and polybenzothiazole fibers are preferably heat treated. The tensile strength of the fiber is preferably at least 2.5 GPa, more preferably at least 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 lea~t 270 GPa.
The fibers may have dimenqions that are usual ~or reinPorcing materialq in matrix compoqites. Their average diameter i3 preferably between 1 ~ and 100 ~.
It is more preferably no more than 40 ~ and most preferably no more than 20 ~. The fiber may be, for instance, in the form of a cloth or in the ~orm of long strands or in the form of a short ~iber or fiber pulp suitable for making random fiber composites. A mixture of fibers may be used. For instance, the fibers may contain a mixture o~ at least one fiber having high tensile properties, such as aramid or polybenzazole, and another fiber having high compressive properties, such as quartz.
3 The present invention al~o u es matrix materials containing polybenzoxazole (PB0) or poly-benzothiazole (PBT) or copolymers thereo~. Those matr`ix materials are di~301ved in a dope solution with a suitable solvent, - ., , , ., ~ . . , ,, :
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WO9~/10536 PCT/US9l/09227 ~C~'^J'~9~7 PBO, PBT and random, sequential and block copolymers of PBO and PBT are de~cribed in references such as Wolfe et al., ~iquid Crvstalline Polvmer ComDositions. Proces~ and P _ ducts, U.S. Patent 4,703,103 (October 27, 1987); Wolfe et al., Liquid 5 Cr~stalline PolYmer ComPositions. Process and Products, U.SO 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, Linuid 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 Makin~ Heteroc~clic Block Copol~mer, U.S.
Patent 4,578,432 (March 25, 1986); 11 Ency. Poly. Sci.
& Eng., Pol~enzothiazoles ar!d Polxbenzoxazoles, 601 (J. Wiley & Sonq 1988) and W. W. Adams et al., The Materials Science and Engineerin~ of Ri~id-Rod Polymers (Materials Research Society 1989). Other block copolymers of PBO and PBT are de~cribed 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 3 Them, EPO Application 90104963.5 (~iled March 16, 1990), EPO Publication 0 388 803 (published September 26, 19~0).
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6 ~( q~ PCT/US91/09227 The polymer or copolymer contains any one of A9-mer units, as repre en~ed in Formula l(a), and/or AA/BB-mer units, as repre~ented in Formula 1(b) ~r < ~
z 1(a) AB
~/ Ar < 9~DM
1(b) AA/BB
wherein :
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 sy~tem, but is preferably a single six-membered ring. Size is not critical, but the aromatlc group preferably contains no more than 3 18 carbon atoms, more pre~erably no more than 12 carbon atoms and most preferably no more than 6 carbon atoms. Examples o~ suitable aromatic groups include phenylene moietie-~7 tolylene moieties, biphenylene moieties and bis-phenylene ether moieties. Ar in AA/BB-mer units is preferably a .. , , . ., , . : .
WO92/10s36 ~ 7~ PCT/US91/09227 1,2,4,5-phe~ylene moiety or an analog thereof. Ar in AB-mer units is preferably a 193,4-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 previou~ly deseribed. It is mo~t preferably a l,4-phenylene moiety or an analog thereof.
The nitrogen atom and the Z moiety in each azole ring are bonded to adjacent carbon atoms in the aromatic group, uch that a five-membered azole ring fused with the aromatic group is formed.
The 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.
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The polymer or copolymer preferably consists essentially of either AB-PBZ mer unit~ or AA/BB-PBZ mer units, and more preferably consi~ts es~entially of AA/BB-PBZ mer units. The polybenzazole polymer may be rigid rod, emi-rigid rod or flexible coil. It is pre~erably rigid rod in the case of an AA/BB-PBZ polymer 3 or semi-rigid in the ca~e of an AB-PBZ polymer. Azole rings within the polymer are preferably oxazole rings (Z ~ 0), so that the polymer is a polybenzoxazole polymer. Preferred mer units are any one illustrated in Formulae 2 (a)-th). The polymer more preferably -; ~ , , , , ~
WV 92/10536 ;~ 3'~ 7 PCl/US91/092~7 , ,~ I
consists essentially of any oP the mer units illustrated in 2(a)-(h), and most preferably consists essentially of any of the mer units illu trated in 2(a)-(c).
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W092/10536 ; PCT/US91/09227 3~7 _9_ S ~ ~
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The polybenzoxazole or polybenzothiazole polymer or copolymer may also be a blo¢k copolymer in which the previously described repeating unit~ are bonded to blocks of thermoplastic polymer. For example 9 the thermoplastic block may contain a thermoplastic polyamide, polyimid~, poly(aromatic ketone~, poly(aromatic sulfone), poly(aromatic ether), or random or sequential copol~mer of those polymer~ with each other or with polybenzazole. The thermoplastic block may also contain a thermoplastic polybenzazole polymer, such as the polymers deqcribed in Harris et al., Thermoplastic Compo3ition~ Containing Polybenzoxazole 9 Polybenzothiazole and Polybenzimidazole Moieties and Proce~s for Making Shaped Articles from Them, EP0 Application 90104963.5 (~iled March 16, 1990), EP0 Publication 0 388 803 (published September 26, 1990) and . . ~ . , . . - , , . : . . .. .
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wo 92/10536 ;~ 7~;~q~ PCr/U~91/09227 in K . -U . Buhler, Spezialplaste 838-866 ( Akademie-Verlag 1978). The thermoplastic block preferably contains any one of:
( a ) a thermoplastic polyamide;
(b) a thermoplastic poly(aromatic ether);
(c) a thermoplastic polybenzazole-poly(aromatic ether) copolymer;
(d) a jointed polybenzazole are more preferably represented by Formula 5(a) .
(a) ~ / ~ Ar--X--Ar ~ Ar-X'-A~--(e) an aliphatic polybenzazole represented by Formula 5 ( b ) (b) ~ / > Ar < ~ R1 _ wherein each X and X' iS independently any o~ an oxygen atom, a carbonyl group, a sulfonyl group~ an alkyl group 3 or a perfluoroalkyl group; each Ar i9 independently an aromatiC group as previously described; and R1 is a substituted or unsubstituted alkyl group that contains at least three carbon atoms 9 in whioh the illu~trated bonds are not to khe same or adjacent carbon atoms .
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W092/1~36 ~ 137 PCT/USsl/09227 _ 1 1 _ Each polybenzoxazole or polybenzothiazole polymer or copolymer preferably containq on average at least 25 mer unit~, more preferably at least 50 mer units and most preferably at leaqt 100 mer units. The intrinsic viscosity of rigid AA/BB-PBZ polymers in methanesulfonic acid at 25C 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 visco~ity oP 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~ The intrin~ic visc03ity of semi--rigid AB-PBZ polymers is preferably at least 5 dL/g, more preferably at least 10 dL/g and most preferably at least 1~ 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 decompo~ition temperature. The homopolymer is preferably essentially insoluble in common organic solvents such as halogenated hydrocarbons, alkanes, benzene or toluene. The homopolymer iq preferably insoluble in non-acidic aqueous solvents.
The polymer or copolymer is di~solved in a solvent to form a solution or dope. Some polybenz-oxazole and polybenzothiazole polymers are soluble in 3 cresol, but the solvent is preferably an acid capable of di~solving the polymer. The acid is preferably non~
-oxidizing. Examples of suitable acids include polyphosphoric acid, methanesulfonic acid and sulfuric acid and mixtures of those acids. The acid is prefer-- : , ,, - , , . . . , , "" -' '.., ' ' ' . ~ . '~ ' ' ~ ' , , .
., . . .. '. . .
W092/10536 ~C ~ 7 ~97 PCT/US91/09227 -l2 ably polypho~phoric acid and/or methanesul~onic acid, and is more preferably polyphosphoric acid. The fiber Qhould be cho~en 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. The concentration of polymer in the dope is usually at least 0.5 weight percent, prefer-ably at least l percent and more preferably at least two percent. The maximum concentration is limited primarily by practical factors, such as polymer solubility and dope viscosity. The concentration o~ 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.
When the polymer is rigid or semi-rigid, then 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 wei~ht percent, more pref~rably at least 10 weight percent and most preferably at least 14 weight percent.
On the other hand, a block copolymer that contains rigid or ~smirigid polybenzazols blocks and thermopla~tic polymer blocks i3 preferably in a lower concentration, so that the dope solution is not liquid 3 crystalline. The total weight percent o~ rigid or semirigid blocks in the ~olution is preferably no more than 4 weight percent. Coagulation of the block oopolymer ~rom isotropic dopes yields a substantially .: : .: - -. . . , : . . - :. . :: . .,. : - .
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W092/10536 PCTt~'S91/09~7 '7'~9 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 (August 6, 1985); Sybert et al., U.S. Patent 4,772,678 (September 20, 1988); Harris, U.S. Patent 4,847,350 (July 11, 1989); Ledbetter et al., "An Integrated Laboratory Process for Preparing Rigid Rod Fibers from the Monomers~" The Materials Science and En~ineering of Ri~id-Rod Polymers at 253-64 (Materials Res. Soc. 1989);
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 Harris et al., Thermopla~tic Compositions Containing Polybenzoxazole, Polybenzothiazo~e 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).
, In summary, to make polybenzoxazole or polybenzothiazole homopolymer or random or sequential copolymer, suitable monomers (AA-monomer~ and BB--monomers or AB-monomers) are reacted in a ~olution of non-oxidizing and dehydrating acid under non-oxidizing atmosphere with vigorou3 mixing and high shear at a 3 temperature that is increa~ed -in step-wise or ramped fa~hion from no more than 120C to at least 190C.
Examples of suitable AA-monomers include terephthalic acid and analog~ thereof. Examples of suitable BB-- -monomers include 4,6-diaminoresorcinol, 2 9 5-.. .. . .
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WO92~10536 PCr/USgl/Og227 9~ _ -diaminohydroquinone, 2,5-diamino-1,4-dithiobenzene and analogs thereof, typically stored as acid salts.
Examples of 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.
To make a block copolymer, the polybenzoxazole or polybenzothiazole oligomer or polymer may be reacted with~ a thermoplastic polymer; or (2) monomers that polymeri~e 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-~is-(benzoic aci~) 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 re ins. Likewi~e, 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 oross-head die.
Such processes ordinarily form a prepregged 3 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 ~ingle direction to form a unidirectional composite, having .
great strength in one direction but poorer properties in ' :
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Wo92/10536 PCT/US~l/0~27 '~'~ 797 ~ i other directions. The fiberq may be laid out in layers directed at di~ferent angles with re3pect to each other to form a multidirectional composite. The prepreg may be laid out flat or ~ilament 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 film~ 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 pres~ed together to form a composite having several layers of fiber. The fibers pressed into the dope may have unidirectional or multidirectional orientation as previously de~cribed.
They may be part of a cloth or a non-woven mat. The dope ~ilm may be thicker to form a "resin-rich"
composite or thinner to ~orm a "resin-starved"
composite. The dope film i~ pre~erably on average at least 25 ~m thick. The temperature should be high enough ~or the ~ibers to embed in the dope and ~or the dope sheet~ to consolidate.
The film may be uniaxially ~tretched to provide best properties in a ~ingle direction, but it is prefer-ably biaxially ~tretched to provide good properties in at least two direotions. The extru~ion of dopes to form films is de~cribed in numerous references, such as in Chenevey, U.S. Patent 4,487,735 (D~cember 11, 1984);
3 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. Patent 4,966,806 , ....... , . . . ~ . - - :
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wos2/los36 P~T/US~1/09227 (October 30, 1990), For in~tance, the dope may be extruded from a ~lit die, after which it is preferably mechanically ~tretched before coagula~ion to impart biaxial orientation, Alternatively, the dope may be extruded in a tubular ~ilm that i~ preferably stretched biaxially by a bubble proces~ to impart biaxial orientation.
The fibers may be short fibers or fiber pulps that are immer3ed in the dope to form a random fiber composite, Rimilar to those described in U.S. Patents 4,426,470 and 4,550,131.
After prepregging is accomplished and the prepregs are laid up in the desired shape and configuration, the composite i9 hardened by contacting the dope with a liquid that causes the polymer or copolymer to coagulate. Ordinarily, the liquid is a nonsolvent for the polymer or copolymer that dilut~s the solvent. Many non~olvent liquids have been studied and their effects on polybenzazole coagulation reported.
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 aqueou~, and more preferably consists esqentially of water, at least at the commencement of the coagulation. When the ~olvent is volatile or contains a volatile component, suoh as methanesulfonic acid, then the volatile 3 component can be at least partially removed by evapora-tion to ooncentrate the polymer before coagulation.
The coagulated polymer is pre~erably washed for a period of time suf~icient to remove substantially all . .
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- -, " - . :~ , ; , : , ;~c~t79~7 of the remaining solvent. The composite may be dried.
It is preferably restrained from shrinking as it is dried. After drying, the compo~ite may be heat treated.
Heat treatment is preferably carried out under pressure.
The finished composi~e 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 eomposite. 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 compo~ite`preferably contains at least Z0 volume percent fiber, more preferably at least 40 volume percent fiber and most preferably at least 50 volu~e percent fiber. It preferably contains at least 20 volume percent matrix and more preferably at least 35 volume percent matrix.
Several variations on the basic composite are possible. For in tance, the fiber may recelve surface treatment or be coated with an adhesive to improve the adhe~ion of the fiber to the matrixO The matrix may contain a mixture of more than one polymer, such as 3 -qeveral polybenzazole polymers or a mixture of the polybenzazole fiber and a non-polybenzazole polymer, as de~cribed in Uy,'U.S. Patent 4,810,735 (March 7, 1989).
The matrix preferably contains only a ~ingle polymer or . . , . ~ . ~. :, .: . .'', ': ' .' - '. ''' ' '' .
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WO92/10536 PCT/US91/092~7 2 ~ ~'7~ ~ _ copolymer. The fiber may be wrapped with another fiber to improve compresqive strength (filed August 8, 1990).
The pre~erred polybenzoxazole and polybenzo-thiazole matrix resins have one or more of the following 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. The composite may be fabricated into structural parts for many known uses.
Illustrative Examples The following examples are given to illustrate the invention and should not be interpreted as limiting the Specification or the Claims. Unless stated otherwise, all parts and percentages are given by weight.
ExamDle 1 - Com~osite Containing Carbon Fiber and Polybenzoxazole Matrix.
A dope containing 14 weight percent cis-poly-benzoxazole (consis~ing essen~ially of mer units illustrated in Formula 2(a) - intrinsic viscosity of 25 dL/g to 45 dL/g in methanesulfonic acid at 25C) in polyphoqphoric acid is extruded ~rom a slit die as a 15 mil thick sheet between two sheets of 2 mil thick Teflon'U fluoropolymer. Two 3 inch by 3 inch squareq of the dope film are cut, and the Teflon~ sheet is stripped off of one side of each sheet.
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, W092/10536 PCT/US91/092~7 '7'7~7 _,9 A 3 inch by 3 inch piece of Panex'~ PWB-6 carbon fiber cloth, available from Stackpole Fibers Inc., is placed between the two dope film samples, with the dope sides against the carbon fiber cloth. The article is pressed at 150C under 5 tons of pressure for one minute to form a prepreg.
The prepreg is cooled to room temperature, and the Teflon~ 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 ~he water for ~wo days, removed from the frame and dried in air at ambient temperature. A
composite having carbon fiber rein~oroement and a cis--polybenzoxazole matrix results.
The oom?osite is cut in half. One half is placed in a heated press at 150C and 5000 lbs. pressure, for one minute. It i golden yellow in color. One half is placed in a heated pres~ at 300C and 5000 lbs.
pressure for one hour. It is darker yellow with a purple tinge. Both have smooth surfaces with no visible hole~. The polybenzoxazole in both adheres firmly to the cloth.
Example 2 - comPosite Containin~ Carbon Fiber and 3 Nonri~id Matrix.
The procedure of Example 1 is followed, except that:
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WO92/10536 ~ C ~'~'7~7 P~T/US91/092'7 Instead of 14 weight peroent 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; and Only one sample is pressed after coagulation at 300C for 90 minutes under 5000 lbs. pressure. It turns black and stick~ to the pre3s.
Example 3 - ComPosite Containin~ Pol~benzoxazole Fiber t~
'' and Polvbenzoxazole Matrix.
The procedure of Example 1 is followed, except that:
The cloth consists essentially of polybenz-oxazole fiber and has dimension~ of 5 inches by 5 inches;
The dope film~Q have dimensions of 5 inches by 5 incheq;
The sample is coagulated in 2 gallons of water.
The resulting composite appears similar to the composite o~ Example 1.
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WO92~10536 PCT/US91/09227 Example 4 - Com~o~ite Containin~ Two La~ers of Carbon Fiber and Pol~benzoxazole Matrix.
The procedure o~ Example 1 is followed, except that:
The cloth and dope film are laid up so that there is from top to bottom: a layer of Teflon~Y
film, a layer of polybenzoxazole dope, a layer of carbon fabric, a layer of polybenzoxazole dope, a layer of carbon ~abric, a layer of polybenzoxazole dope, and a layer of Teflon~U film;
The prepregging is carried out at 150C and 5000 lbs. pressure for 3 minutes;
The finished composite i~ pressed under 5000 lbs pressure at a temperature ramped from room temperature to 300C over 90 minutes and held at 300~C for 30 minutes.
The resulting structures are much stiffer than the structures prepared in Example 1.
Example ~ - Composite Containin~ Carbon Fiber and Polvbenzoxazole/PEEK-PB0 Block Co~olymer Matrix ~5 A compo~ite is fabricated by the following procedure using (1) a graphite fiber and (2) a dope containing a mixture of methanesul~onic acid and poly-phosphoric acid and about 3 weight percent of a block copolymer having rigid rod ci~-polybenzoxazole blocks and blocks of thermoplastic cis-PB0/PEEK copolymer. The block copolymer contain~ about`38 weight percent rigid rod block and about 62 weight percent thermoplastic : : . , : -, : .
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. .
w092/10536 ,~ 3,.~"~¢3.7 PcT/Uss1~0s2~7 block. Its average structure iq represented by the Formula:
~5 ~ 0 ~ ~ O ~ C~
({~ O ~ O--~o~o~N~
((~0 ~ C {~--0 ~--0 ~
wherein "a", "b" and ~c~i are each a number of mer units suitable to provide the desired proportion~ of polymer.
The fiber is passed through a 400C oven at a rate of 140 inches/min. in order to remove the sizing on the fiber. The fiber pa ses through several idler rollers and through a resin bath that contains the dope at room temperature. The impregnated fiber pas~es 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 3o drum such that each wrap is immediately adjacent to the previous wrap without oYerlappingD The prepreg is cut into Qeven 7 inch x 7 inch panels, which are stacked to form a ~even-ply unidirectional laminate. The laminate is placed in a porous Terlon~ fluoropolymer bag, ., ' ~ " ~ ,' ' ' ' -'. ~.
WC) 92/10;36 PCT/ US9 1/09227 clamped between perforated aluminum plates and immersed in running water at room temperature for 24 hours.
The resulting wet composite is pressed at 80C
and 100 psi for 4-1/2 hours and is placed in a vacuum oven at 90C for 24 hours to dry. It is then compressed for 6 minutes at 400C and 50 psi, for 15 minutes at 400C and 1000 psi, and for a time sufficiënt to cool at 1000 psi to consolidate. The resulting composite is rigid with individual plies bonded firmly together.
Example 6 - Composite Containin~ Carbon Fiber and Polybenzothiazol~ Matrix The procedure of Example 1 is repeated, except that the dope solution contains trans-polybenzothiazole polymer. Similar results will be obtained.
/
- . ,.. . . . , , . .. . .. - .: .. .. . .;, . :
- , .. . . , .... . - . . ,... : . : . -:: , . . - ; - . :
z 1(a) AB
~/ Ar < 9~DM
1(b) AA/BB
wherein :
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 sy~tem, but is preferably a single six-membered ring. Size is not critical, but the aromatlc group preferably contains no more than 3 18 carbon atoms, more pre~erably no more than 12 carbon atoms and most preferably no more than 6 carbon atoms. Examples o~ suitable aromatic groups include phenylene moietie-~7 tolylene moieties, biphenylene moieties and bis-phenylene ether moieties. Ar in AA/BB-mer units is preferably a .. , , . ., , . : .
WO92/10s36 ~ 7~ PCT/US91/09227 1,2,4,5-phe~ylene moiety or an analog thereof. Ar in AB-mer units is preferably a 193,4-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 previou~ly deseribed. It is mo~t preferably a l,4-phenylene moiety or an analog thereof.
The nitrogen atom and the Z moiety in each azole ring are bonded to adjacent carbon atoms in the aromatic group, uch that a five-membered azole ring fused with the aromatic group is formed.
The 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 unit~ or AA/BB-PBZ mer units, and more preferably consi~ts es~entially of AA/BB-PBZ mer units. The polybenzazole polymer may be rigid rod, emi-rigid rod or flexible coil. It is pre~erably rigid rod in the case of an AA/BB-PBZ polymer 3 or semi-rigid in the ca~e of an AB-PBZ polymer. Azole rings within the polymer are preferably oxazole rings (Z ~ 0), so that the polymer is a polybenzoxazole polymer. Preferred mer units are any one illustrated in Formulae 2 (a)-th). The polymer more preferably -; ~ , , , , ~
WV 92/10536 ;~ 3'~ 7 PCl/US91/092~7 , ,~ I
consists essentially of any oP the mer units illustrated in 2(a)-(h), and most preferably consists essentially of any of the mer units illu trated in 2(a)-(c).
) ~ ~ 0 (b) ~o ~ /~
.. :
(c) ~5 ~N>{~
(d) (e) .
. . . .
~, - , ., , ' , . . , ' .
W092/10536 ; PCT/US91/09227 3~7 _9_ S ~ ~
1O (g) f~s~ , and (h) ~
The polybenzoxazole or polybenzothiazole polymer or copolymer may also be a blo¢k copolymer in which the previously described repeating unit~ are bonded to blocks of thermoplastic polymer. For example 9 the thermoplastic block may contain a thermoplastic polyamide, polyimid~, poly(aromatic ketone~, poly(aromatic sulfone), poly(aromatic ether), or random or sequential copol~mer of those polymer~ with each other or with polybenzazole. The thermoplastic block may also contain a thermoplastic polybenzazole polymer, such as the polymers deqcribed in Harris et al., Thermoplastic Compo3ition~ Containing Polybenzoxazole 9 Polybenzothiazole and Polybenzimidazole Moieties and Proce~s for Making Shaped Articles from Them, EP0 Application 90104963.5 (~iled March 16, 1990), EP0 Publication 0 388 803 (published September 26, 1990) and . . ~ . , . . - , , . : . . .. .
. .
wo 92/10536 ;~ 7~;~q~ PCr/U~91/09227 in K . -U . Buhler, Spezialplaste 838-866 ( Akademie-Verlag 1978). The thermoplastic block preferably contains any one of:
( a ) a thermoplastic polyamide;
(b) a thermoplastic poly(aromatic ether);
(c) a thermoplastic polybenzazole-poly(aromatic ether) copolymer;
(d) a jointed polybenzazole are more preferably represented by Formula 5(a) .
(a) ~ / ~ Ar--X--Ar ~ Ar-X'-A~--(e) an aliphatic polybenzazole represented by Formula 5 ( b ) (b) ~ / > Ar < ~ R1 _ wherein each X and X' iS independently any o~ an oxygen atom, a carbonyl group, a sulfonyl group~ an alkyl group 3 or a perfluoroalkyl group; each Ar i9 independently an aromatiC group as previously described; and R1 is a substituted or unsubstituted alkyl group that contains at least three carbon atoms 9 in whioh the illu~trated bonds are not to khe same or adjacent carbon atoms .
... - . . ~ ~ . .. . .
. ' ,, 1, . .. . .
- . , ~ , . ~ -. : , . : . :
- , . : : . ' , , . . . -: : .
.. . . . . .. .. .
W092/1~36 ~ 137 PCT/USsl/09227 _ 1 1 _ Each polybenzoxazole or polybenzothiazole polymer or copolymer preferably containq on average at least 25 mer unit~, more preferably at least 50 mer units and most preferably at leaqt 100 mer units. The intrinsic viscosity of rigid AA/BB-PBZ polymers in methanesulfonic acid at 25C 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 visco~ity oP 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~ The intrin~ic visc03ity of semi--rigid AB-PBZ polymers is preferably at least 5 dL/g, more preferably at least 10 dL/g and most preferably at least 1~ 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 decompo~ition temperature. The homopolymer is preferably essentially insoluble in common organic solvents such as halogenated hydrocarbons, alkanes, benzene or toluene. The homopolymer iq preferably insoluble in non-acidic aqueous solvents.
The polymer or copolymer is di~solved in a solvent to form a solution or dope. Some polybenz-oxazole and polybenzothiazole polymers are soluble in 3 cresol, but the solvent is preferably an acid capable of di~solving the polymer. The acid is preferably non~
-oxidizing. Examples of suitable acids include polyphosphoric acid, methanesulfonic acid and sulfuric acid and mixtures of those acids. The acid is prefer-- : , ,, - , , . . . , , "" -' '.., ' ' ' . ~ . '~ ' ' ~ ' , , .
., . . .. '. . .
W092/10536 ~C ~ 7 ~97 PCT/US91/09227 -l2 ably polypho~phoric acid and/or methanesul~onic acid, and is more preferably polyphosphoric acid. The fiber Qhould be cho~en 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. The concentration of polymer in the dope is usually at least 0.5 weight percent, prefer-ably at least l percent and more preferably at least two percent. The maximum concentration is limited primarily by practical factors, such as polymer solubility and dope viscosity. The concentration o~ 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.
When the polymer is rigid or semi-rigid, then 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 wei~ht percent, more pref~rably at least 10 weight percent and most preferably at least 14 weight percent.
On the other hand, a block copolymer that contains rigid or ~smirigid polybenzazols blocks and thermopla~tic polymer blocks i3 preferably in a lower concentration, so that the dope solution is not liquid 3 crystalline. The total weight percent o~ rigid or semirigid blocks in the ~olution is preferably no more than 4 weight percent. Coagulation of the block oopolymer ~rom isotropic dopes yields a substantially .: : .: - -. . . , : . . - :. . :: . .,. : - .
., . , ~
: ,,,, : . . , .. :
W092/10536 PCTt~'S91/09~7 '7'~9 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 (August 6, 1985); Sybert et al., U.S. Patent 4,772,678 (September 20, 1988); Harris, U.S. Patent 4,847,350 (July 11, 1989); Ledbetter et al., "An Integrated Laboratory Process for Preparing Rigid Rod Fibers from the Monomers~" The Materials Science and En~ineering of Ri~id-Rod Polymers at 253-64 (Materials Res. Soc. 1989);
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 Harris et al., Thermopla~tic Compositions Containing Polybenzoxazole, Polybenzothiazo~e 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).
, In summary, to make polybenzoxazole or polybenzothiazole homopolymer or random or sequential copolymer, suitable monomers (AA-monomer~ and BB--monomers or AB-monomers) are reacted in a ~olution of non-oxidizing and dehydrating acid under non-oxidizing atmosphere with vigorou3 mixing and high shear at a 3 temperature that is increa~ed -in step-wise or ramped fa~hion from no more than 120C to at least 190C.
Examples of suitable AA-monomers include terephthalic acid and analog~ thereof. Examples of suitable BB-- -monomers include 4,6-diaminoresorcinol, 2 9 5-.. .. . .
- . . . . . . . . .
. .
., . ., .. . , . , .,~ . , - .
. . . : :, ~ ~ . . , . :,: ~., : , . -:
.: ' ' :- . . . : . , ~ ' .
.,:~, , . . . ~ : . .. . . . . .
. .. . .
WO92~10536 PCr/USgl/Og227 9~ _ -diaminohydroquinone, 2,5-diamino-1,4-dithiobenzene and analogs thereof, typically stored as acid salts.
Examples of 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.
To make a block copolymer, the polybenzoxazole or polybenzothiazole oligomer or polymer may be reacted with~ a thermoplastic polymer; or (2) monomers that polymeri~e 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-~is-(benzoic aci~) 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 re ins. Likewi~e, 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 oross-head die.
Such processes ordinarily form a prepregged 3 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 ~ingle direction to form a unidirectional composite, having .
great strength in one direction but poorer properties in ' :
-, . ... . , . . :
.
... ,, , ,, :
' . . . . . . . .
Wo92/10536 PCT/US~l/0~27 '~'~ 797 ~ i other directions. The fiberq may be laid out in layers directed at di~ferent angles with re3pect to each other to form a multidirectional composite. The prepreg may be laid out flat or ~ilament 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 film~ 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 pres~ed together to form a composite having several layers of fiber. The fibers pressed into the dope may have unidirectional or multidirectional orientation as previously de~cribed.
They may be part of a cloth or a non-woven mat. The dope ~ilm may be thicker to form a "resin-rich"
composite or thinner to ~orm a "resin-starved"
composite. The dope film i~ pre~erably on average at least 25 ~m thick. The temperature should be high enough ~or the ~ibers to embed in the dope and ~or the dope sheet~ to consolidate.
The film may be uniaxially ~tretched to provide best properties in a ~ingle direction, but it is prefer-ably biaxially ~tretched to provide good properties in at least two direotions. The extru~ion of dopes to form films is de~cribed in numerous references, such as in Chenevey, U.S. Patent 4,487,735 (D~cember 11, 1984);
3 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. Patent 4,966,806 , ....... , . . . ~ . - - :
,- :. .. . . .
- . ,: .:. . . .
wos2/los36 P~T/US~1/09227 (October 30, 1990), For in~tance, the dope may be extruded from a ~lit die, after which it is preferably mechanically ~tretched before coagula~ion to impart biaxial orientation, Alternatively, the dope may be extruded in a tubular ~ilm that i~ preferably stretched biaxially by a bubble proces~ to impart biaxial orientation.
The fibers may be short fibers or fiber pulps that are immer3ed in the dope to form a random fiber composite, Rimilar to those described in U.S. Patents 4,426,470 and 4,550,131.
After prepregging is accomplished and the prepregs are laid up in the desired shape and configuration, the composite i9 hardened by contacting the dope with a liquid that causes the polymer or copolymer to coagulate. Ordinarily, the liquid is a nonsolvent for the polymer or copolymer that dilut~s the solvent. Many non~olvent liquids have been studied and their effects on polybenzazole coagulation reported.
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 aqueou~, and more preferably consists esqentially of water, at least at the commencement of the coagulation. When the ~olvent is volatile or contains a volatile component, suoh as methanesulfonic acid, then the volatile 3 component can be at least partially removed by evapora-tion to ooncentrate the polymer before coagulation.
The coagulated polymer is pre~erably washed for a period of time suf~icient to remove substantially all . .
: . . ' :
,. . . . ,.:;
~ , . . .
- -, " - . :~ , ; , : , ;~c~t79~7 of the remaining solvent. The composite may be dried.
It is preferably restrained from shrinking as it is dried. After drying, the compo~ite may be heat treated.
Heat treatment is preferably carried out under pressure.
The finished composi~e 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 eomposite. 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 compo~ite`preferably contains at least Z0 volume percent fiber, more preferably at least 40 volume percent fiber and most preferably at least 50 volu~e percent fiber. It preferably contains at least 20 volume percent matrix and more preferably at least 35 volume percent matrix.
Several variations on the basic composite are possible. For in tance, the fiber may recelve surface treatment or be coated with an adhesive to improve the adhe~ion of the fiber to the matrixO The matrix may contain a mixture of more than one polymer, such as 3 -qeveral polybenzazole polymers or a mixture of the polybenzazole fiber and a non-polybenzazole polymer, as de~cribed in Uy,'U.S. Patent 4,810,735 (March 7, 1989).
The matrix preferably contains only a ~ingle polymer or . . , . ~ . ~. :, .: . .'', ': ' .' - '. ''' ' '' .
: ~ , . . .
.. . . .
WO92/10536 PCT/US91/092~7 2 ~ ~'7~ ~ _ copolymer. The fiber may be wrapped with another fiber to improve compresqive strength (filed August 8, 1990).
The pre~erred polybenzoxazole and polybenzo-thiazole matrix resins have one or more of the following 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. The composite may be fabricated into structural parts for many known uses.
Illustrative Examples The following examples are given to illustrate the invention and should not be interpreted as limiting the Specification or the Claims. Unless stated otherwise, all parts and percentages are given by weight.
ExamDle 1 - Com~osite Containing Carbon Fiber and Polybenzoxazole Matrix.
A dope containing 14 weight percent cis-poly-benzoxazole (consis~ing essen~ially of mer units illustrated in Formula 2(a) - intrinsic viscosity of 25 dL/g to 45 dL/g in methanesulfonic acid at 25C) in polyphoqphoric acid is extruded ~rom a slit die as a 15 mil thick sheet between two sheets of 2 mil thick Teflon'U fluoropolymer. Two 3 inch by 3 inch squareq of the dope film are cut, and the Teflon~ sheet is stripped off of one side of each sheet.
. ~ , . .
,:
, W092/10536 PCT/US91/092~7 '7'7~7 _,9 A 3 inch by 3 inch piece of Panex'~ PWB-6 carbon fiber cloth, available from Stackpole Fibers Inc., is placed between the two dope film samples, with the dope sides against the carbon fiber cloth. The article is pressed at 150C under 5 tons of pressure for one minute to form a prepreg.
The prepreg is cooled to room temperature, and the Teflon~ 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 ~he water for ~wo days, removed from the frame and dried in air at ambient temperature. A
composite having carbon fiber rein~oroement and a cis--polybenzoxazole matrix results.
The oom?osite is cut in half. One half is placed in a heated press at 150C and 5000 lbs. pressure, for one minute. It i golden yellow in color. One half is placed in a heated pres~ at 300C and 5000 lbs.
pressure for one hour. It is darker yellow with a purple tinge. Both have smooth surfaces with no visible hole~. The polybenzoxazole in both adheres firmly to the cloth.
Example 2 - comPosite Containin~ Carbon Fiber and 3 Nonri~id Matrix.
The procedure of Example 1 is followed, except that:
.. . . ~ , . . .
WO92/10536 ~ C ~'~'7~7 P~T/US91/092'7 Instead of 14 weight peroent 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; and Only one sample is pressed after coagulation at 300C for 90 minutes under 5000 lbs. pressure. It turns black and stick~ to the pre3s.
Example 3 - ComPosite Containin~ Pol~benzoxazole Fiber t~
'' and Polvbenzoxazole Matrix.
The procedure of Example 1 is followed, except that:
The cloth consists essentially of polybenz-oxazole fiber and has dimension~ of 5 inches by 5 inches;
The dope film~Q have dimensions of 5 inches by 5 incheq;
The sample is coagulated in 2 gallons of water.
The resulting composite appears similar to the composite o~ Example 1.
...
,, ~ ,. '; . ,, . , ........ ~ . ~', , '' . .
, ~ , .
WO92~10536 PCT/US91/09227 Example 4 - Com~o~ite Containin~ Two La~ers of Carbon Fiber and Pol~benzoxazole Matrix.
The procedure o~ Example 1 is followed, except that:
The cloth and dope film are laid up so that there is from top to bottom: a layer of Teflon~Y
film, a layer of polybenzoxazole dope, a layer of carbon fabric, a layer of polybenzoxazole dope, a layer of carbon ~abric, a layer of polybenzoxazole dope, and a layer of Teflon~U film;
The prepregging is carried out at 150C and 5000 lbs. pressure for 3 minutes;
The finished composite i~ pressed under 5000 lbs pressure at a temperature ramped from room temperature to 300C over 90 minutes and held at 300~C for 30 minutes.
The resulting structures are much stiffer than the structures prepared in Example 1.
Example ~ - Composite Containin~ Carbon Fiber and Polvbenzoxazole/PEEK-PB0 Block Co~olymer Matrix ~5 A compo~ite is fabricated by the following procedure using (1) a graphite fiber and (2) a dope containing a mixture of methanesul~onic acid and poly-phosphoric acid and about 3 weight percent of a block copolymer having rigid rod ci~-polybenzoxazole blocks and blocks of thermoplastic cis-PB0/PEEK copolymer. The block copolymer contain~ about`38 weight percent rigid rod block and about 62 weight percent thermoplastic : : . , : -, : .
.: , . . ....................................... : .
. .
w092/10536 ,~ 3,.~"~¢3.7 PcT/Uss1~0s2~7 block. Its average structure iq represented by the Formula:
~5 ~ 0 ~ ~ O ~ C~
({~ O ~ O--~o~o~N~
((~0 ~ C {~--0 ~--0 ~
wherein "a", "b" and ~c~i are each a number of mer units suitable to provide the desired proportion~ of polymer.
The fiber is passed through a 400C oven at a rate of 140 inches/min. in order to remove the sizing on the fiber. The fiber pa ses through several idler rollers and through a resin bath that contains the dope at room temperature. The impregnated fiber pas~es 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 3o drum such that each wrap is immediately adjacent to the previous wrap without oYerlappingD The prepreg is cut into Qeven 7 inch x 7 inch panels, which are stacked to form a ~even-ply unidirectional laminate. The laminate is placed in a porous Terlon~ fluoropolymer bag, ., ' ~ " ~ ,' ' ' ' -'. ~.
WC) 92/10;36 PCT/ US9 1/09227 clamped between perforated aluminum plates and immersed in running water at room temperature for 24 hours.
The resulting wet composite is pressed at 80C
and 100 psi for 4-1/2 hours and is placed in a vacuum oven at 90C for 24 hours to dry. It is then compressed for 6 minutes at 400C and 50 psi, for 15 minutes at 400C and 1000 psi, and for a time sufficiënt to cool at 1000 psi to consolidate. The resulting composite is rigid with individual plies bonded firmly together.
Example 6 - Composite Containin~ Carbon Fiber and Polybenzothiazol~ Matrix The procedure of Example 1 is repeated, except that the dope solution contains trans-polybenzothiazole polymer. Similar results will be obtained.
/
- . ,.. . . . , , . .. . .. - .: .. .. . .;, . :
- , .. . . , .... . - . . ,... : . : . -:: , . . - ; - . :
Claims (15)
1. A method of using a dope solution that contains: (i) a polybenzoxazole polymer or copolymer and/or a polybenzothiazole polymer or copolymer, and (ii) a solvent for the polymer or copolymer, said method being characterized the steps of:
(1) prepregging a plurality of reinforcing fibers with a the 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; and (2) contacting the dope solution with a liquid coagulant that causes the polymer or copolymer to coagulate, in a quantity sufficient to cause the polymer or copolymer to coagulate with the fibers embedded therein.
(1) prepregging a plurality of reinforcing fibers with a the 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; and (2) contacting the dope solution with a liquid coagulant that causes the polymer or copolymer to coagulate, in a quantity sufficient to cause the polymer or copolymer to coagulate with the fibers embedded therein.
2. A method as described in Claim 1 wherein the polymer or copolymer i not thermoplastic and contains repeating units that are each individually represented by any of the following Formulae:
1(a) AB
1(b) AA/BB
wherein:
Each Ar represents an aromatic group that contains no more than 18 carbon atoms.
Each Z is independently an oxygen or a sulfur atom.
Each DM is independently a bond or an aromatic group as previously described.
1(a) AB
1(b) AA/BB
wherein:
Each Ar represents an aromatic group that contains no more than 18 carbon atoms.
Each Z is independently an oxygen or a sulfur atom.
Each DM is independently a bond or an aromatic group as previously described.
3. A method as described in any of the preceding Claims wherein the polymer or copolymer contains repeating units that are represented by any of the following Formulae:
(a) , (b) , (c) , (d) , (e) , (f) , (g) , and (h) ,
(a) , (b) , (c) , (d) , (e) , (f) , (g) , and (h) ,
4. A method as described in any of the preceding Claims wherein the dope solution contains 7 to 20 weight percent polymer or copolymer.
5. A method as described in Claim 1 wherein the polymer or copolymer is a block copolymer that contain blocks of polybenzoxazole or polybenzothiazole polymer and blocks of thermoplastic polymer.
6. A method as described in any one of Claims 1, 3 or 5 wherein the polymer or copolymer is a block copolymer containing blocks of any of the following thermoplastic polymers:
(a) a thermoplastic polyamide;
(b) a thermoplastic poly(aromatic ether);
(c) a thermoplastic polybenzazole-polytaromatic ether) copolymer;
(d) a jointed polybenzazole represented by the Formula:
(a) (e) an aliphatic polybenzazole represented by the Formula:
(b) wherein each X and X' is independently any of an oxygen atom, a carbonyl group, a sulfonyl group, an alkyl group or a perfluoroalkyl group; each Ar is independently an aromatic group as previously described; and R1 is a substituted or unsubsubsituted alkyl group that contains at least three carbon atoms, in which the illustrated bonds are not to the same or adjacent carbon atoms.
(a) a thermoplastic polyamide;
(b) a thermoplastic poly(aromatic ether);
(c) a thermoplastic polybenzazole-polytaromatic ether) copolymer;
(d) a jointed polybenzazole represented by the Formula:
(a) (e) an aliphatic polybenzazole represented by the Formula:
(b) wherein each X and X' is independently any of an oxygen atom, a carbonyl group, a sulfonyl group, an alkyl group or a perfluoroalkyl group; each Ar is independently an aromatic group as previously described; and R1 is a substituted or unsubsubsituted alkyl group that contains at least three carbon atoms, in which the illustrated bonds are not to the same or adjacent carbon atoms.
7. A method as-described in any one of Claims 1, 3, 5 or 6 wherein the dope solution contains from 1 to 4 weight percent polymer or copolymer.
8. A method as described in any of the preceding Claims wherein the solvent in the dope solution is polyphosphoric acid or methanesulfonic acid.
9. A method as described in any of the preceding Claims wherein the fiber is an aramid, boron, glass, carbon, gel-spun polyethylene, polybenzoxazole, polybenzothiazole, or polybenzimidazole fiber.
10. A method as described in any of the preceding Claims wherein the fiber is prepregged with sufficient dope solution to make a composite containing at least 20 weight percent fiber and at least 20 weight percent matrix polymer.
11. A method as described in any of the preceding Claims wherein the prepregged fibers are continuous fibers that are laid up as any one of:
(a) a unidirectional composite; or (b) a multidirectional composite, before the polymer or copolymer is coagulated.
(a) a unidirectional composite; or (b) a multidirectional composite, before the polymer or copolymer is coagulated.
12. A method as described in any of Claims 1 through 10 wherein the prepregged fibers are short fibers or fiber pulps that are mixed with the dope solution to form a random fiber composite on coagulation.
13. A method as described in any of the preceding Claims wherein the coagulant liquid is water or an aqueous solution.
14. A method as described in any of the preceding Claims wherein the polymer or copolymer is a polybenzoxazole polymer or copolymer.
15. A method as described in any of Claims 1 through 14 wherein the polymer or copolymer is a polybenzothiazole polymer or copolymer.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/624,164 US5196259A (en) | 1990-12-07 | 1990-12-07 | Matrix composites in which the matrix contains polybenzoxazole or polybenzothiazole |
| US07/624,164 | 1990-12-07 | ||
| US07/668,532 | 1991-03-13 | ||
| US07/668,532 US5248721A (en) | 1991-03-13 | 1991-03-13 | Prepregs containing a fiber and a thermoplastic polybenzazole copolymer matrix |
| PCT/US1991/009227 WO1992010536A1 (en) | 1990-12-07 | 1991-12-06 | Method to make matrix composites in which the matrix contains polybenzoxazole or polybenzothiazole |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2097797A1 true CA2097797A1 (en) | 1992-06-08 |
Family
ID=27089622
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002097797A Abandoned CA2097797A1 (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 |
|---|---|
| EP (1) | EP0560897A1 (en) |
| JP (1) | JPH06503597A (en) |
| KR (1) | KR930703387A (en) |
| CA (1) | CA2097797A1 (en) |
| IE (1) | IE914252A1 (en) |
| WO (1) | WO1992010536A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0643738A1 (en) * | 1992-06-04 | 1995-03-22 | 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 |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| JPH1115935A (en) * | 1997-06-19 | 1999-01-22 | Paloma Ind Ltd | Data rewriting device |
-
1991
- 1991-12-06 IE IE425291A patent/IE914252A1/en not_active Application Discontinuation
- 1991-12-06 EP EP92901707A patent/EP0560897A1/en not_active Withdrawn
- 1991-12-06 JP JP4502394A patent/JPH06503597A/en active Pending
- 1991-12-06 CA CA002097797A patent/CA2097797A1/en not_active Abandoned
- 1991-12-06 WO PCT/US1991/009227 patent/WO1992010536A1/en not_active Application Discontinuation
-
1993
- 1993-06-04 KR KR1019930701675A patent/KR930703387A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| EP0560897A1 (en) | 1993-09-22 |
| IE914252A1 (en) | 1992-06-17 |
| WO1992010536A1 (en) | 1992-06-25 |
| JPH06503597A (en) | 1994-04-21 |
| KR930703387A (en) | 1993-11-29 |
| EP0560897A4 (en) | 1994-02-23 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |