TW201527286A - 多官能苯并化物及內含該化物之複合材料 - Google Patents
多官能苯并化物及內含該化物之複合材料 Download PDFInfo
- Publication number
- TW201527286A TW201527286A TW103144636A TW103144636A TW201527286A TW 201527286 A TW201527286 A TW 201527286A TW 103144636 A TW103144636 A TW 103144636A TW 103144636 A TW103144636 A TW 103144636A TW 201527286 A TW201527286 A TW 201527286A
- Authority
- TW
- Taiwan
- Prior art keywords
- benzo
- group
- resin composition
- component
- curable resin
- Prior art date
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 16
- 150000005130 benzoxazines Chemical class 0.000 title abstract 2
- 239000000203 mixture Substances 0.000 claims abstract description 70
- 229920005989 resin Polymers 0.000 claims abstract description 33
- 239000011347 resin Substances 0.000 claims abstract description 33
- 239000011342 resin composition Substances 0.000 claims abstract description 23
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 125000005605 benzo group Chemical group 0.000 claims description 110
- 125000003118 aryl group Chemical group 0.000 claims description 30
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 27
- 125000000217 alkyl group Chemical group 0.000 claims description 26
- 150000001875 compounds Chemical class 0.000 claims description 23
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 18
- 125000001424 substituent group Chemical group 0.000 claims description 17
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 14
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims description 13
- -1 cyanic acids Ester Chemical class 0.000 claims description 11
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 claims description 10
- 239000000835 fiber Substances 0.000 claims description 9
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- 150000002367 halogens Chemical class 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000010521 absorption reaction Methods 0.000 claims description 7
- 235000010233 benzoic acid Nutrition 0.000 claims description 7
- 239000007795 chemical reaction product Substances 0.000 claims description 7
- 150000002118 epoxides Chemical class 0.000 claims description 7
- 125000000623 heterocyclic group Chemical group 0.000 claims description 7
- 239000012783 reinforcing fiber Substances 0.000 claims description 7
- 239000005711 Benzoic acid Substances 0.000 claims description 6
- 229920001568 phenolic resin Polymers 0.000 claims description 6
- 229920001187 thermosetting polymer Polymers 0.000 claims description 6
- HXDOZKJGKXYMEW-UHFFFAOYSA-N 4-ethylphenol Chemical compound CCC1=CC=C(O)C=C1 HXDOZKJGKXYMEW-UHFFFAOYSA-N 0.000 claims description 5
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methyl-N-phenylamine Natural products CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 claims description 5
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 5
- 125000003277 amino group Chemical group 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 229920002866 paraformaldehyde Polymers 0.000 claims description 5
- WSNMPAVSZJSIMT-UHFFFAOYSA-N COc1c(C)c2COC(=O)c2c(O)c1CC(O)C1(C)CCC(=O)O1 Chemical compound COc1c(C)c2COC(=O)c2c(O)c1CC(O)C1(C)CCC(=O)O1 WSNMPAVSZJSIMT-UHFFFAOYSA-N 0.000 claims description 4
- 150000004982 aromatic amines Chemical class 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 229920000768 polyamine Polymers 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims 3
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 claims 2
- 239000004744 fabric Substances 0.000 claims 2
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 claims 2
- 229920003192 poly(bis maleimide) Polymers 0.000 claims 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims 1
- 239000004917 carbon fiber Substances 0.000 claims 1
- 239000003365 glass fiber Substances 0.000 claims 1
- 125000001188 haloalkyl group Chemical group 0.000 claims 1
- 238000006467 substitution reaction Methods 0.000 claims 1
- 239000011159 matrix material Substances 0.000 abstract description 8
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 abstract 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 87
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 8
- 239000012745 toughening agent Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 5
- 239000013538 functional additive Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003063 flame retardant Substances 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 4
- 239000005060 rubber Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 125000006705 (C5-C7) cycloalkyl group Chemical group 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N Bisphenol A Natural products C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 244000028419 Styrax benzoin Species 0.000 description 3
- 235000000126 Styrax benzoin Nutrition 0.000 description 3
- 235000008411 Sumatra benzointree Nutrition 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 3
- 229960002130 benzoin Drugs 0.000 description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 3
- 239000012965 benzophenone Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 235000019382 gum benzoic Nutrition 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229920001169 thermoplastic Polymers 0.000 description 3
- 239000004416 thermosoftening plastic Substances 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- ICKWICRCANNIBI-UHFFFAOYSA-N 2,4-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C(C(C)(C)C)=C1 ICKWICRCANNIBI-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229940106691 bisphenol a Drugs 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 239000002482 conductive additive Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000001739 density measurement Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000000518 rheometry Methods 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- PXKLMJQFEQBVLD-UHFFFAOYSA-N Bisphenol F Natural products C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 229940049706 benzodiazepine Drugs 0.000 description 1
- 150000001559 benzoic acids Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000004643 cyanate ester Substances 0.000 description 1
- 150000001913 cyanates Chemical class 0.000 description 1
- HBEHVMJHLMWTGV-UHFFFAOYSA-N diphenylmethanone;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 HBEHVMJHLMWTGV-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003733 fiber-reinforced composite Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- RSAZYXZUJROYKR-UHFFFAOYSA-N indophenol Chemical compound C1=CC(O)=CC=C1N=C1C=CC(=O)C=C1 RSAZYXZUJROYKR-UHFFFAOYSA-N 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- VUQUOGPMUUJORT-UHFFFAOYSA-N methyl 4-methylbenzenesulfonate Chemical compound COS(=O)(=O)C1=CC=C(C)C=C1 VUQUOGPMUUJORT-UHFFFAOYSA-N 0.000 description 1
- NFFIWVVINABMKP-UHFFFAOYSA-N methylidynetantalum Chemical compound [Ta]#C NFFIWVVINABMKP-UHFFFAOYSA-N 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000001485 positron annihilation lifetime spectroscopy Methods 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910003468 tantalcarbide Inorganic materials 0.000 description 1
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
- 239000004634 thermosetting polymer Substances 0.000 description 1
- 230000004580 weight loss Effects 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
- C08G73/02—Polyamines
- C08G73/0233—Polyamines derived from (poly)oxazolines, (poly)oxazines or having pendant acyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
- C07D265/04—1,3-Oxazines; Hydrogenated 1,3-oxazines
- C07D265/12—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems
- C07D265/14—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems condensed with one six-membered ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
- C07D265/04—1,3-Oxazines; Hydrogenated 1,3-oxazines
- C07D265/12—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems
- C07D265/14—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems condensed with one six-membered ring
- C07D265/16—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems condensed with one six-membered ring with only hydrogen or carbon atoms directly attached in positions 2 and 4
-
- 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
-
- 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
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/35—Heterocyclic compounds having nitrogen in the ring having also oxygen in the ring
- C08K5/357—Six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
- C08K5/375—Thiols containing six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/61—Polyamines polyimines
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
本發明係關於含有多官能苯并□化物之摻合物之可固化樹脂組合物及源自該等摻合物之複合材料。該苯并□化物摻合物含有(A)二官能苯并□化物組份及(B)官能度大於2之多官能苯并□化物組份之組合。與不含組份(B)之相同固化基質樹脂及複合材料相比,含有該苯并□化物摻合物之固化基質樹脂及固化複合材料展現有機溶劑吸取速率之顯著阻滯。
Description
使用苯并(BOX)與其他熱固性樹脂相比提供多個優點,包括相對較長之儲放壽命、分子設計靈活性、低成本、高玻璃轉換溫度(Tg)、高模數、相對較低之黏度、良好的阻燃特性、低吸濕性、在固化期間無副產物釋放及固化後之極低收縮率。此外,苯并在加熱後能夠自固化;即無需額外固化劑。此特性組合意味著苯并可能對航空應用中之使用具有吸引力。
純苯并基質於高效複合物中之商業應用目前尚未充分建立。可利用苯并雜合系統之若干商業系統(通常苯并-環氧化物),但環氧化物會消除苯并所帶來之一些益處。僅苯并系統之韌化限於使用橡膠、經修飾苯并單體及低性能熱塑性塑膠,但該等物質亦減少苯并之有益特性、最顯著地撓曲及拉伸模數。
本文揭示多官能苯并之摻合物、含有該等摻合物之可固化組合物、源自該等摻合物之固化基質樹脂及含有該等摻合物之複合材料。摻合物及可固化組合物係基於二官能苯并組份及官能度大於2之多官能苯并組份、具體而言平均官能度為2.1至3之苯并的組合。
含有二官能及多官能苯并之摻合物之固化基質樹脂及固化
複合材料展現有機溶劑吸取速率之顯著阻滯。
圖1展示多官能苯并摻合物及Bis-A苯并之回流MEK中之MEK吸取。
圖2展示即使在1%多官能苯并下MEK吸取速率仍降低,且由於摻合物中多官能苯并之量增加,MEK吸取甚至進一步減慢。
圖3展示比率為80:20之Bis-A苯并:多官能苯并之摻合物的比較,其中多官能苯并係經由途徑A或途徑B合成。
圖4展示使用置換技術之多官能苯并:Bis-A苯并摻合物之密度量測。
已知苯并樹脂對水吸取具有極高抗性,通常在飽和時吸取<2%。此益處容許在其(較高)乾態Tg與(較低)濕態Tg之間具有較小差別,此意味著其使用溫度可高於例如具有相當乾態Tg之環氧樹脂或苯并-環氧化物雜合物。
已知苯并具有極其良好的溶劑抗性,且報導在7個月MEK浸潤後室溫下之MEK吸取<0.2%。MEK抗性測試至關重要,此乃因大多數航空複合物製造商將其用作其設計標準之部分。令人驚訝的是,已發現,在沸騰MEK中,純淨苯并在剛好16hr內之吸取可>23%。苯并-環氧化物雜合系統並非如此,其在190hr後吸收約2.5%。
儘管苯并-環氧化物雜合系統具有良好的特性平衡,但其不具純淨苯并系統(即100%苯并)之極高撓曲模數。此發現提供因減輕可能的樹脂失效而將純淨苯并樹脂系統用於航空複合物中之可能性。解決此失效之替代性策略可係將更親水之組份調配成調配物。然而,水吸收將存在損害性吸取之風險。所採用方式之主要益處反映於以下事實中:對該等純淨苯并中之水吸取存在極輕微效
應。吸取量在添加30%多官能苯并時增加,但在平衡時仍保持在1.6%以下。
已發現,當樹脂組合物含有(A)二官能苯并組份及(B)平均官能度>2之多官能苯并組份、具體而言平均官能度為約2.1至約3之苯并之摻合物時,對於基於苯并之固化樹脂可達成減少的溶劑吸取。已發現溶劑(例如MEK)吸取之阻滯與不含組份(B)之相同固化苯并樹脂相比較為顯著。
在苯并摻合物中,多官能苯并組份係以基於苯并摻合物之總重量至多30重量%之量存在。根據一個實施例,多官能苯并組份(B)對二官能苯并組份(A)之重量比可介於1:99至30:70範圍內。
如本文所揭示,多官能苯并(或聚苯并)係指在化合物中具有至少兩個部分之可聚合苯并化合物,此使得能夠形成交聯。更特定而言,二官能苯并含有兩個部分,且三官能苯并含有三個部分。由於合成期間之不完全反應或整數個功能分子之環開口或經由摻和具有整數個官能基之分子,可形成具有非整數個平均官能度(例如2.1、2.2、2.3、2.4、2.5等)之苯并之摻合物。舉例而言,具有兩個部分之分子及具有三個部分之分子的組合將產生具有介於2與3之間之平均官能度的苯并組份。摻合物中之多官能苯并化合物包括可藉由固化聚合形成熱固性樹脂之多官能單體及寡聚物。
固化後,多官能苯并化合物容易地經由環開口聚合來聚合。該聚合通常係以陽離子方式(使用陽離子起始劑)或熱方式來起始。
源自二官能苯并及平均官能度大於2(或>2)之多官能苯并 的固化摻合物之固化基質樹脂展現有機溶劑、例如甲基乙基酮
(MEK)吸取速率之阻滯。
在溶劑吸取背景下之溶劑包括諸如MEK等有機溶劑。預期在苯并雜合系統(例如苯并-環氧化物系統)中將或多或少地觀察到此效應。此上下文中之純淨或純(100%)苯并系統係指不含任何其他可固化/熱固性樹脂(例如環氧化物、氰酸酯、BMI及酚醛/酚-甲醛樹脂)、但可包括觸媒/起始劑、韌化劑或功能性添加劑之基於苯并 之組合物。該等功能性添加劑之實例包括(但不限於)填充劑、顏料、流變控制劑、增黏劑、導電添加劑、阻燃劑、紫外(UV)保護劑及諸如此類。該等添加劑可呈各種幾何形式,包括(但不限於)粒子、薄片、棒及諸如此類。
當摻和一或多種平均官能度>2之多官能苯并與二官能苯并(例如雙酚-A苯并)時,減少MEK吸取之效應應使其可以基於樹脂調配物之重量低至1wt%之量來使用。在平均官能度為2.5之多官能苯并之情形下,其納入會使達到3% MEK吸取所用之時間自約9小時(對於純雙酚-A苯并)增加至49小時(對於99:1 Bis-A苯并 :多官能苯并之摻合物)。預期該低納入量並不展示固化樹脂之顯著機械特性差異或劣化。
上文所論述之多官能苯并組份包括一或多種官能度>2之多官能苯并,包括由以下一般結構I表示之三官能苯并:
其中R1、R2及R3係獨立地選自烷基(較佳C1-8烷基)、環烷基(較佳C5-7環烷基,尤其C6環烷基)及芳基,其中環烷基及芳基視情況經例如C1-8烷基、鹵素及胺基團、且較佳經C1-8烷基取代,且在取代時,在每一環烷基及芳基上可存在一或多個取代基(較佳一個取代基);R4係選自氫、鹵素、烷基及烯基。
根據較佳實施例,三官能苯并係由以下結構II表示:
其中R1、R2及R3係獨立地選自烷基(較佳C1-8烷基)。
適宜三官能苯并之特定實例係:
官能度>2之多官能苯并組份可係三元酚(或叁酚)、芳香族胺及甲醛之反應產物。尤其適宜之叁酚係1,1,1-叁(4-羥基苯基)乙烷。根據一特定實施例,多官能苯并組份係1,1,1-叁(4-羥基苯基)乙烷、對甲苯胺及多聚甲醛之反應產物。
官能度>2之苯并之另一實例係上述三官能結構I、II或III及僅具有兩個完全閉合之部分之類似結構的摻合物,最終酚係未反應、與甲醛部分反應或環開口的。
二官能苯并組份可包括一或多種由以下結構IV表示之苯并:
其中Z1係選自直接鍵、-C(R3)(R4)-、-C(R3)(芳基)-、-C(O)-、-S-、-O-、-S(O)-、-S(O)2-、二價雜環及-[C(R3)(R4)]x-伸芳基-[C(R5)(R6)]y-,或苯并部分之兩個苄基環可稠合;且
R1及R2係獨立地選自烷基(較佳C1-8烷基)、環烷基(較佳C5-7環烷基,較佳C6環烷基)及芳基,其中環烷基及芳基視情況經例如C1-8烷基、鹵素及胺基團、且較佳經C1-8烷基取代,且在取代時,在每一環烷基及芳基上可存在一或多個取代基(較佳一個取代基);在一個實施例中,Z1係選自直接鍵、-C(R3)(R4)-、-C(R3)(芳基)-、-C(O)-、-S-、-O-、二價雜環及-[C(R3)(R4)]x-伸芳基-[C(R5)(R6)]y-,或苯并部分之兩個苄基環可稠合;R3、R4、R5及R6係獨立地選自H、C1-8烷基(較佳C1-4烷基,且較佳甲基)及鹵化烷基(其中鹵素通常係氯或氟(較佳氟),且其中鹵化烷基較佳係CF3);且x及y獨立地係0或1;其中Z1係選自二價雜環,其較佳係3,3-異苯并呋喃-1(3h)-酮,即其中式(III)化合物係源自酚酞;其中Z1係選自-[C(R3)(R4)]x-伸芳基-[C(R5)(R6)]y-,則連接兩個苯并基團之鏈可進一步包含一或多個伸芳基及/或一或多個-C(R7)(R8)-基團,其中R7及R8係獨立地選自上文針對R3定義之基團。
在較佳實施例中,伸芳基係伸苯基。在一個實施例中,附接至伸苯基之基團可相對於彼此以對位或間位構形。在較佳實施例中,芳基係苯基。
基團Z1可為直鏈或非直鏈,且通常為直鏈。基團Z1較佳鍵結至每一苯并部分之相對於苯并部分之氧原子對位處的苄基,如式(I)中所展示,且此係較佳異構構形。然而,基團Z1亦可附接至雙-苯并化合物之一或兩個苄基之間位或鄰位。因此,基團Z1可以對/對、對/間、對/鄰、間/間或鄰/間構形附接至苄基環。在一個實施例中,二官能苯并樹脂組份包含異構物之混合物,較佳地其中混合物之主要部分係結構IV中所展示之對/對異構物,且較佳地此係以佔
總異構混合物之至少75mol%、較佳至少90mol%、且較佳至少99mol%存在。
在較佳實施例中,二官能苯并係選自其中Z1係選自-C(CH3)2-、-CH2-及3,3-異苯并呋喃-1(3H)-酮之化合物,即雙酚A、雙酚F及酚酞之苯并衍生物。
在另一實施例中,二官能苯并係選自其中R1及R2係獨立地選自芳基、較佳苯基之化合物。在一個實施例中,芳基可經取代,較佳地其中取代基係選自C1-8烷基,且較佳地其中在至少一個芳基上存在單一取代基。C1-8烷基包括直鏈及具支鏈烷基鏈。較佳地,R1及R2係獨立地選自未經取代之芳基、較佳未經取代之苯基。
本文所定義二官能苯并化合物之每一苯并基團之苄基環可在每一環之三個可用位置中之任一者處獨立地經取代,且任一可選取代基通常存在於Z1基團之附接位置之鄰位。然而,較佳地,苄基環保持未經取代。
二官能苯并之替代性結構V表示於下文中:
其中Z1係選自直接鍵、-C(R3)(R4)-、-C(R3)(芳基)-、-C(O)-、-S-、-O-、-S(O)-、-S(O)2-、二價雜環及-[C(R3)(R4)]x-伸芳基-[C(R5)(R6)]y-,或兩個苄基環可稠合;且R1及R2係獨立地選自氫、烷基(較佳C1-8烷基)、環烷基(較佳C5-7環烷基,較佳C6環烷基)及芳基,其中環烷基及芳基視情況經例如C1-8烷基、鹵素及胺基團、且較佳經C1-8烷基取代,且在取代時,在每一環烷基及芳基上可存在一或多個取代基(較佳一個取代基);
在一個實施例中,Z1係選自直接鍵、-C(R3)(R4)-、-C(R3)(芳基)-、-C(O)-、-S-、-O-、二價雜環及-[C(R3)(R4)]x-伸芳基-[C(R5)(R6)]y-,或兩個苄基環可稠合;R3、R4、R5及R6係獨立地選自H、C1-8烷基(較佳C1-4烷基,且較佳甲基)及鹵化烷基(其中鹵素通常係氯或氟(較佳氟),且其中鹵化烷基較佳係CF3);且x及y獨立地係0或1;其中Z1係選自二價雜環,其較佳係3,3-異苯并呋喃-1(3h)-酮,即其中式(I)化合物係源自酚酞;其中Z1係選自-[C(R3)(R4)]x-伸芳基-[C(R5)(R6)]y-,則連接兩個苯并基團之鏈可進一步包含一或多個伸芳基及/或一或多個-C(R7)(R8)-基團,其中R7及R8係獨立地選自上文針對R3定義之基團,前提係該或每一經取代或未經取代之亞甲基不與另一經取代或未經取代之亞甲基毗鄰。
在較佳實施例中,伸芳基係伸苯基。在一個實施例中,附接至伸苯基之基團可相對於彼此以對位或間位構形。在較佳實施例中,芳基係苯基。
基團Z1可為直鏈或非直鏈,且通常為直鏈。基團Z1可附接至雙-苯并化合物之一或兩個苄基之間位、對位或鄰位。因此,基團Z1可以對/對、對/間、對/鄰、間/間或鄰/間構形附接至苄基環。在一個實施例中,熱固性苯并樹脂組份(A)包含異構物之混合物,較佳地其中混合物之主要部分係結構IV中所展示之對/對異構物,且較佳地此係以佔總異構混合物之至少75mol%、較佳至少90mol%、且較佳至少99mol%存在。
在較佳實施例中,二官能苯并係選自其中Z1係選自-C(CH3)2-、-CH2-及3,3-異苯并呋喃-1(3H)-酮之化合物。
在另一實施例中,二官能苯并係選自其中R1及R2係獨立地選
自芳基、較佳苯基之化合物。在一個實施例中,芳基可經取代,較佳地其中取代基係選自C1-8烷基,且較佳地其中在至少一個芳基上存在單一取代基。C1-8烷基包括直鏈及具支鏈烷基鏈。較佳地,R1及R2係獨立地選自未經取代之芳基、較佳未經取代之苯基。
本文所定義二官能苯并化合物之苄基環可在每一環之三個可用位置中之任一者處獨立地經取代,且任一可選取代基通常存在於Z1基團附接位置之鄰位。然而,較佳地,苄基環保持未經取代。
上文所論述之苯并摻合物可與其他組份(例如觸媒及韌化劑)組合以形成適於製造樹脂膜(例如黏著膜、貼面膜)或纖維強化複合物(例如預浸體)之可固化組合物。可固化組合物為純或不含任何其他可固化/熱固性樹脂(例如環氧化物、氰酸酯、BMI及酚醛/酚-甲醛樹脂)之100%苯并系統。可固化組合物中所有可聚合苯并化合物之總量基於可固化組合物之總重量較佳大於80重量%、較佳85重量%。
如本文所使用,「可固化組合物」係指固化前之組合物,且「固化基質樹脂」係指自固化可固化組合物製造之固化樹脂。
可視情況添加觸媒,但用此可增加固化速率及/或降低固化溫度。適用於基於苯并之組合物之觸媒包括(但不限於)路易斯酸(Lewis acid,例如酚及其衍生物)、強酸(例如鏈烯酸)、甲苯磺酸甲酯、氰酸酯、對甲苯磺酸、2-乙基-4-甲基咪唑(EMI)、2,4-二-第三丁基酚、BF3O(Et)2、己二酸、有機酸、五氯化磷(PCl5)。
可添加韌化劑(Toughening agent)(或韌化劑(toughener))以製造適用於高強度複合物之韌化基質樹脂,例如用於航空應用中之彼等。適宜韌化劑包括(但不限於)熱塑性韌化劑,例如聚醚碸(PES)、PES及聚醚醚碸(PEES)之共聚物、彈性物(包括具有反應性基團之液體橡膠);
微粒韌化劑,例如熱塑性粒子、玻璃珠、橡膠粒子及核殼橡膠粒子。
在可固化組合物中亦可包括功能性添加劑,以影響固化或未固化樹脂組合物之機械、流變、電、光學、化學、阻燃性及/或熱特性中之一或多者。該等功能性添加劑之實例包括(但不限於)填充劑、顏料、流變控制劑、增黏劑、導電添加劑、阻燃劑、紫外(UV)保護劑及諸如此類。該等添加劑可呈各種幾何形式,包括(但不限於)粒子、薄片、棒及諸如此類。
若存在,其他添加劑(包括觸媒、韌化劑)及功能性添加劑之總量基於組合物之總重量至多15重量%。
如上文所論述之可固化組合物可與強化纖維組合形成複合材料或結構。強化纖維可呈以下形式:鬚晶、短纖維、連續纖維、長絲、絲束、束、片、層片及其組合。連續纖維可進一步採用單向、多維、非織造、織造、針織、縫合、捲繞及編織構形以及捲曲氈墊、毛氈及短切纖維氈結構中之任一者。可改變纖維之組成以達成最終複合結構所需之特性。實例性纖維材料可包括(但不限於)玻璃、碳、石墨、聚芳醯胺、石英、聚乙烯、聚酯、聚-對伸苯基-苯并二唑(PBO)、硼、聚醯胺、石墨、碳化矽、氮化矽及其組合。
為形成複合材料,使用習用處理技術(例如(但不限於)預浸及樹脂浸沒)用可固化組合物浸漬或浸沒強化纖維。樹脂浸漬/浸沒後,可在至多230℃、較佳介於160℃至230℃範圍內、更佳在約170℃-230℃之升高溫度下且使用升高壓力、適宜地在至多10巴、較佳介於3巴至7巴範圍內之絕對壓力下實施固化,以限制逸出氣體之變形效應或限制孔隙形成。可藉由以至多5℃/min、例如2℃/min至3℃/min加熱達到固化溫度,且維持至多9小時、較佳至多6小時、例如3小時至4小時之所需時段。徹底釋放壓力並藉由以至多5℃/min.(例如至多3℃/min)冷卻來降溫。可在介於190℃至230℃範圍內之溫度下在大氣壓力下使用適
宜加熱速率實施後固化以改良產物之玻璃轉換溫度(Tg)。
本文闡述由以下化學結構表示之基於1,1,1-叁(4-羥基苯基)乙烷之苯并之合成程序:
將1,1,1-叁(4-羥基苯基)乙烷(60.00g,0.20mol)、多聚甲醛(36.04g,1.2mol)及對甲苯胺(64.29g,0.60mol)於罐中與DMSO(150cm3)合併,且置於配備有頂部攪拌之85℃油浴中。1小時後,將溫度升高至130℃並再保持3小時。然後將粗熔融物直接傾倒至冷IPA(600cm3,-78.5℃)中且攪拌30分鐘,然後過濾並研磨。然後於水(600cm3)中將粉末洗滌30分鐘,過濾並研磨,然後於冷IPA中再洗滌。隨後在70℃下用NaOH(250cm3,0.10mol dm-3)洗滌20分鐘。然後用溫水(3.5dm3)中之Silverson L5M將固體軟化40分鐘,且經過濾器乾燥。將此軟化重複三次。在真空中在40℃下乾燥最終產物。產率為約120g(0.17mol)、88%。
此合成程序給出平均苯并官能度為約2.5(官能度定義為每個分子中苯并環之平均數量)之分子摻合物。
將1,1,1-叁(4-羥基苯基)乙烷(60.00g,0.20mol)、多聚甲醛(37.2g,1.24mol)及對甲苯胺(66.00g,0.616mol)合併於罐中,且置於油浴
中。為罐配備頂部攪拌且將油浴加熱至85℃。在此溫度附近發生放熱反應。將油浴溫度升高至110℃並保持30分鐘。然後將溫度設定為130℃,且在樹脂之內部溫度達到110℃後,立即開始30分鐘定時。經過30分鐘後,將熔融混合物傾倒至離型紙上且容許冷卻。然後將固體壓碎成精細粉末。在70℃下於NaOH溶液(700cm3,1mol dm-3)中將粉末洗滌兩次。在70℃下用700cm3蒸餾水逐份洗滌固體直至水為pH 7為止。然後將固體過濾且在真空中在40℃下乾燥。產率為約120g(0.17mol)、88%。此合成程序給出平均苯并官能度為約3之分子。
將Bis-A苯并(84g)添加至多官能苯并(36g)中,然後置於140℃油浴中。經由頂部空氣攪拌器攪拌苯并。熔融後,立即將樹脂攪拌30分鐘。摻和後,將10-12g材料置於60mm直徑鋁盤中及/或將85-90g置於6"×4"鋼模具中(以製造用於機械及撓曲模數測試之飾板)。在120℃下在Thermo-Scientific真空烘箱中脫氣約3小時,此端視系統之黏度及真空強度而定。
使用Huntsman所推薦固化週期之修改形式固化所有苯并樣品:若樹脂係自冷固化則起始溫度為25℃,或若固化與脫氣同一天完成則起始溫度為100℃。起始溫度為-180℃,1℃ min-1,保持2hr;180℃至200℃,1℃ min-1,保持2hr;200℃至25℃,2℃ min-1。
根據表1中所展示之重量%製備多種不同的苯并摻合物。
圖1展示多官能苯并摻合物及Bis-A苯并之回流MEK中之MEK吸取。除非另外陳述,否則所有溶劑吸取及密度數據皆來自利用經由方法A製造之多官能苯并之摻合物。本文所揭示表及圖中之術語「BOX」係苯并之縮寫。
用於MEK吸取測試之樹脂樣本為約40mm長、4mm深及1.6mm厚。在當天在MEK溶劑中將樣本回流,冷卻至環境溫度且在環境溫度下保持過夜及週末。每天早上將樣本移除、空氣乾燥且稱重,然後返回至MEK中且回流當天剩下的時間。圖1中之圖表展示X軸上回流時間量之平方根對Y軸上之MEK吸取(%)。應注意,在圖1中,含有多官能苯并之摻合物之吸取速率顯著降低。
Bis-A苯并之痕跡展示與其他樣品相比之快速MEK獲取,但隨後在約36h後展示樣本之重量損失,此歸因於樣品降解以及材料之裂解及剝落。
為進行比較,固化多官能Bis-A苯并摻合物中3% MEK吸取之時間展示於表2中。
應注意,即使添加僅5%多官能苯并MEK獲取速率仍顯著降
低。
因此授權其他溶劑吸取研究以檢查1%-5%多官能BOX添加之效應。數據展示於圖2中。
圖2明確展示即使在1%多官能苯并下MEK吸取速率仍降低,且由於摻合物中多官能苯并之量增加,MEK吸取甚至進一步減慢。
比率為80:20之Bis-A苯并:多官能苯并之摻合物的比較展示於圖3中,其中多官能苯并係經由途徑A或途徑B合成。自圖3可見,平均官能度為3之多官能苯并比平均官能度為2之多官能苯并甚至更有效地阻滯MEK吸取速率。
使用置換技術之多官能苯并:Bis-A苯并摻合物之密度量測展示於圖4中。如圖可見,多官能苯并之量越大,材料越不緻密。「自由體積」之正電子消減壽命光譜(PALS)量測往往隨多官能苯并之增加而增加(參見表3)。令人驚訝的是MEK吸取減少。此表明多官能苯并發揮功能之可能機制係阻滯MEK對樹脂之溶脹。該溶脹有助於MEK進入。
表3展示苯并摻合物之樣品之正電子消減光譜之結果。所展示比率為重量比。將樣品夾入密封於阻擋5%-10%正電子之薄Kapton片中的弱22Na正電子源。光譜儀之γ檢測器檢測消減事件,此量測正電子素之壽命及正電子素消減之強度。此容許計算總自由體積、孔徑自由體積及平均孔直徑。此給出密度及分子堆積之量測。
表4展示藉由峰值Tan δ量測之Tg。應注意,Tg在30%多官能苯并下增加高達11℃。
Claims (21)
- 一種可固化樹脂組合物,其包含大於80重量%之苯并化物摻合物,其中該苯并化物摻合物包含:(A)二官能苯并化物組份;及(B)平均官能度大於2之多官能苯并化物組份,其中組份(B)包含由以下結構I表示之三官能苯并化物化合物:
- 如請求項1之可固化樹脂組合物,其中在該樹脂組合物固化形成固化樹脂後,該固化樹脂展現為相對於不含組份(B)之相同固化樹脂之5倍慢的有機溶劑吸取速率。
- 如請求項1之可固化樹脂組合物,其中組份(B)包含由以下結構II表示之三官能苯并化物化合物:
- 如請求項3之可固化樹脂組合物,其中結構II之R1、R2及R3係獨立地選自C1-8烷基。
- 如請求項4之可固化樹脂組合物,其中組份(B)包含由以下結構III表示之三官能苯并化物:
- 如請求項1之可固化樹脂組合物,其中多官能苯并化物組份(B)對二官能苯并化物組份(A)之重量比介於1:99至30:70範圍內。
- 如請求項1之可固化樹脂組合物,其中組份(B)係三元酚、芳香族胺及甲醛之反應產物,且包含結構I及僅具有兩個完全閉合之 部分之類似結構的摻合物。
- 如請求項3之可固化樹脂組合物,其中組份(B)係三元酚、芳香族胺及甲醛之反應產物,且包含結構II及僅具有兩個完全閉合之 部分之類似結構的摻合物。
- 如請求項5之可固化樹脂組合物,其中組份(B)係1,1,1-叁(4-羥基苯基)乙烷、對甲苯胺及多聚甲醛之反應產物。
- 如請求項9之可固化樹脂組合物,其中組份(B)包含結構III及僅具有兩個完全閉合之部分之類似結構的摻合物。
- 如請求項1之可固化樹脂組合物,其中該二官能苯并化物係由以下結構(IV)來表示:
- 如請求項1之可固化樹脂組合物,其中該二官能苯并化物係由以下結構V來表示:
- 如請求項1之可固化樹脂組合物,其中該可固化組合物不含或含有基於該組合物之總重量小於5重量%之選自以下各項之任一熱固性樹脂:環氧化物、氰酸酯、雙馬來醯亞胺及酚-甲醛。
- 一種可固化樹脂組合物,其包含大於80重量%之苯并化物摻合物,其中該苯并化物摻合物包含:(A)二官能苯并化物組份;及(B)平均官能度大於2且至多為3之多官能苯并化物組份,其中組份(B)係三元酚、芳香族胺及甲醛之反應產物,且該三元酚係由以下結構來表示:
- 如請求項14之可固化樹脂組合物,其中組份(B)係1,1,1-叁(4-羥基苯基)乙烷、對甲苯胺及多聚甲醛之反應產物。
- 如請求項14之可固化樹脂組合物,其中組份(B)對組份(A)之重量比介於1:99至30:70範圍內。
- 如請求項14之可固化樹脂組合物,其中該可固化組合物不含或含有基於該組合物之總重量小於5重量%之選自以下各項之任一熱固性樹脂:環氧化物、氰酸酯、雙馬來醯亞胺及酚-甲醛。
- 一種複合材料,其包含使用如請求項1之可固化樹脂組合物浸漬或浸沒之強化纖維。
- 如請求項18之複合材料,其中該等強化纖維係選自碳纖維、玻璃纖維及聚芳醯胺纖維。
- 如請求項18之複合材料,其中該等強化纖維呈單向纖維、織物或包含多層纖維或織物層片之預成型體形式。
- 一種固化複合部件,其係自包含以下步驟之方法製造:(i)使用如請求項1之可固化樹脂組合物浸漬或浸沒強化纖維;及(ii)固化該等經浸漬或浸沒之纖維。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GBGB1322758.2A GB201322758D0 (en) | 2013-12-20 | 2013-12-20 | Multifunctional benzoxazines and composite materials incorporating then same |
??1322758.2 | 2013-12-20 |
Publications (2)
Publication Number | Publication Date |
---|---|
TW201527286A true TW201527286A (zh) | 2015-07-16 |
TWI616441B TWI616441B (zh) | 2018-03-01 |
Family
ID=50071289
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW103144636A TWI616441B (zh) | 2013-12-20 | 2014-12-19 | 多官能苯并化物及內含該化物之複合材料 |
Country Status (15)
Country | Link |
---|---|
US (1) | US9822219B2 (zh) |
EP (1) | EP3083760B1 (zh) |
JP (1) | JP6434031B2 (zh) |
KR (1) | KR102253344B1 (zh) |
CN (1) | CN106062036B (zh) |
AU (1) | AU2014367002B2 (zh) |
BR (1) | BR112016012719B1 (zh) |
CA (1) | CA2934450C (zh) |
ES (1) | ES2651495T3 (zh) |
GB (1) | GB201322758D0 (zh) |
MX (1) | MX365486B (zh) |
MY (1) | MY181399A (zh) |
RU (1) | RU2646605C2 (zh) |
TW (1) | TWI616441B (zh) |
WO (1) | WO2015094635A1 (zh) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BR112017013909B1 (pt) * | 2014-12-29 | 2021-08-24 | Cytec Industries Inc | Monômero de benzoxazina trifuncional meta-substituído, composições de resina e curável, material compósito, prepreg, e, estrutura compósita |
CN107108827B (zh) * | 2014-12-29 | 2020-09-04 | 塞特工业公司 | 苯并噁嗪及含有苯并噁嗪的组合物 |
CN107743508B (zh) * | 2015-06-12 | 2020-07-03 | 塞特工业公司 | 含有苯并噁嗪环氧共混物的可固化组合物及其用途 |
CN106967002A (zh) * | 2017-04-07 | 2017-07-21 | 常州焱晶科技有限公司 | 一种三元苯并噁嗪中间体、制备方法及其聚合物 |
CN106967001B (zh) * | 2017-04-07 | 2019-06-18 | 杭州中一科技有限公司 | 一种三元苯并噁嗪-邻苯二甲腈中间体、制备方法及其聚合物 |
CN110713691B (zh) * | 2019-09-19 | 2022-10-21 | 航天科工(长沙)新材料研究院有限公司 | 一种苯并噁嗪及其制备方法 |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2004217941A (ja) * | 1997-01-20 | 2004-08-05 | Hitachi Chem Co Ltd | 熱硬化性組成物及びその硬化物 |
JPH11217416A (ja) * | 1998-02-02 | 1999-08-10 | Showa Highpolymer Co Ltd | 熱硬化性組成物 |
EP2218748B1 (en) * | 2005-09-03 | 2012-10-10 | Samsung SDI Co., Ltd. | Polybenzoxazine-based compound, electrolyte membrane including the same, and fuel cell employing the electrolyte membrane |
KR100754374B1 (ko) * | 2006-02-07 | 2007-08-31 | 삼성에스디아이 주식회사 | 폴리벤조옥사진계 화합물을 이용한 전해질막 및 그제조방법 |
KR100818255B1 (ko) | 2006-05-29 | 2008-04-02 | 삼성에스디아이 주식회사 | 폴리벤조옥사진계 화합물, 이를 포함한 전해질막 및 이를채용한 연료전지 |
TWI295288B (en) * | 2006-08-17 | 2008-04-01 | Univ Nat Chunghsing | New route for the synthesis of benzoxazine |
EP2086949A4 (en) | 2006-11-29 | 2011-07-27 | Henkel Corp | PROCESS FOR THE PREPARATION OF BENZOXAZINES |
KR100893523B1 (ko) * | 2006-12-15 | 2009-04-17 | 삼성에스디아이 주식회사 | 연료전지용 전극, 그 제조방법 및 이를 채용한 연료전지 |
KR20100038372A (ko) * | 2007-06-18 | 2010-04-14 | 헨켈 코포레이션 | 벤족사진 함유 물질 조성물 및 그것으로 만든 경화성 조성물 |
CA2737833C (en) * | 2008-09-19 | 2016-08-09 | Henkel Ag & Co. Kgaa | Benzoxazine-based compositions containing isocyanate-based tougheners |
TWI400292B (zh) * | 2010-06-14 | 2013-07-01 | Nanya Plastics Corp | Used in glass fiber laminates high glass transition temperature resin varnish composition |
JP5750004B2 (ja) * | 2010-10-26 | 2015-07-15 | Jfeケミカル株式会社 | 熱硬化性組成物、そのワニスおよびその熱硬化物 |
GB201101302D0 (en) * | 2011-01-25 | 2011-03-09 | Cytec Tech Corp | Benzoxazine resins |
GB201205574D0 (en) * | 2012-03-29 | 2012-05-16 | Cytec Tech Corp | Benzoxazines and compositions containing the same |
-
2013
- 2013-12-20 GB GBGB1322758.2A patent/GB201322758D0/en not_active Ceased
-
2014
- 2014-12-02 ES ES14816039.3T patent/ES2651495T3/es active Active
- 2014-12-02 BR BR112016012719-6A patent/BR112016012719B1/pt active IP Right Grant
- 2014-12-02 EP EP14816039.3A patent/EP3083760B1/en active Active
- 2014-12-02 MX MX2016007198A patent/MX365486B/es active IP Right Grant
- 2014-12-02 CA CA2934450A patent/CA2934450C/en active Active
- 2014-12-02 MY MYPI2016000877A patent/MY181399A/en unknown
- 2014-12-02 RU RU2016129468A patent/RU2646605C2/ru active
- 2014-12-02 WO PCT/US2014/068068 patent/WO2015094635A1/en active Application Filing
- 2014-12-02 AU AU2014367002A patent/AU2014367002B2/en active Active
- 2014-12-02 CN CN201480069939.1A patent/CN106062036B/zh active Active
- 2014-12-02 KR KR1020167014952A patent/KR102253344B1/ko active IP Right Grant
- 2014-12-02 JP JP2016541033A patent/JP6434031B2/ja active Active
- 2014-12-08 US US14/562,799 patent/US9822219B2/en active Active
- 2014-12-19 TW TW103144636A patent/TWI616441B/zh not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
CA2934450A1 (en) | 2015-06-25 |
GB201322758D0 (en) | 2014-02-05 |
RU2646605C2 (ru) | 2018-03-06 |
ES2651495T3 (es) | 2018-01-26 |
KR102253344B1 (ko) | 2021-05-18 |
BR112016012719A2 (zh) | 2017-08-08 |
CN106062036B (zh) | 2018-02-27 |
MX2016007198A (es) | 2016-07-21 |
JP6434031B2 (ja) | 2018-12-05 |
TWI616441B (zh) | 2018-03-01 |
MX365486B (es) | 2019-06-05 |
KR20160102402A (ko) | 2016-08-30 |
BR112016012719B1 (pt) | 2022-01-04 |
US20150175746A1 (en) | 2015-06-25 |
US9822219B2 (en) | 2017-11-21 |
RU2016129468A (ru) | 2018-01-25 |
JP2017502135A (ja) | 2017-01-19 |
WO2015094635A1 (en) | 2015-06-25 |
CA2934450C (en) | 2021-02-23 |
MY181399A (en) | 2020-12-21 |
AU2014367002A1 (en) | 2016-06-02 |
CN106062036A (zh) | 2016-10-26 |
EP3083760B1 (en) | 2017-09-13 |
AU2014367002B2 (en) | 2017-10-26 |
EP3083760A1 (en) | 2016-10-26 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
TWI616441B (zh) | 多官能苯并化物及內含該化物之複合材料 | |
CA2868786C (en) | Benzoxazines and compositions containing the same | |
US20200291179A1 (en) | Composite materials containing benzoxazines and method for making the same | |
JP6550136B2 (ja) | 三官能性ベンゾオキサジン並びに硬化性樹脂組成物及び複合材料におけるその使用 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
MM4A | Annulment or lapse of patent due to non-payment of fees |