CN116178194B - Polybenzoxazine oligomer, high-thermal-conductivity aromatic ester crosslinked liquid crystal polybenzoxazine and preparation method thereof - Google Patents
Polybenzoxazine oligomer, high-thermal-conductivity aromatic ester crosslinked liquid crystal polybenzoxazine and preparation method thereof Download PDFInfo
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- CN116178194B CN116178194B CN202310156959.3A CN202310156959A CN116178194B CN 116178194 B CN116178194 B CN 116178194B CN 202310156959 A CN202310156959 A CN 202310156959A CN 116178194 B CN116178194 B CN 116178194B
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- Prior art keywords
- polybenzoxazine
- liquid crystal
- oligomer
- obz
- aromatic ester
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 57
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title abstract description 7
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000178 monomer Substances 0.000 claims abstract description 31
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- -1 amine compounds Chemical class 0.000 claims abstract description 20
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims abstract description 20
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 claims abstract description 15
- 229930040373 Paraformaldehyde Natural products 0.000 claims abstract description 13
- 229920002866 paraformaldehyde Polymers 0.000 claims abstract description 13
- 238000010992 reflux Methods 0.000 claims description 31
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical group CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 27
- 238000001723 curing Methods 0.000 claims description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 238000004132 cross linking Methods 0.000 claims description 22
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical group CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 19
- 239000012298 atmosphere Substances 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000003999 initiator Substances 0.000 claims description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 11
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 claims description 10
- 239000012043 crude product Substances 0.000 claims description 10
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 8
- 238000005917 acylation reaction Methods 0.000 claims description 8
- CYYZDBDROVLTJU-UHFFFAOYSA-N 4-n-Butylphenol Chemical compound CCCCC1=CC=C(O)C=C1 CYYZDBDROVLTJU-UHFFFAOYSA-N 0.000 claims description 7
- 150000008064 anhydrides Chemical class 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 239000003377 acid catalyst Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2,2'-azo-bis-isobutyronitrile Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 4
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- 239000012295 chemical reaction liquid Substances 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 claims description 3
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical group [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims description 2
- 239000001639 calcium acetate Substances 0.000 claims description 2
- 235000011092 calcium acetate Nutrition 0.000 claims description 2
- 229960005147 calcium acetate Drugs 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 229960004249 sodium acetate Drugs 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- 229960000314 zinc acetate Drugs 0.000 claims description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims 4
- 229910052786 argon Inorganic materials 0.000 claims 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 35
- 238000003786 synthesis reaction Methods 0.000 abstract description 27
- 239000000463 material Substances 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- 238000006640 acetylation reaction Methods 0.000 abstract description 4
- 238000006683 Mannich reaction Methods 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 43
- 239000000203 mixture Substances 0.000 description 28
- 239000000047 product Substances 0.000 description 23
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 16
- 229910052782 aluminium Inorganic materials 0.000 description 16
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 14
- 239000002244 precipitate Substances 0.000 description 12
- 125000003118 aryl group Chemical group 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 8
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 238000010907 mechanical stirring Methods 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 238000003760 magnetic stirring Methods 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 5
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 5
- 238000005886 esterification reaction Methods 0.000 description 5
- 238000010998 test method Methods 0.000 description 4
- VVJKKWFAADXIJK-UHFFFAOYSA-N allylamine Natural products NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 229920006324 polyoxymethylene Polymers 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical group N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 2
- 239000012346 acetyl chloride Substances 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 150000007860 aryl ester derivatives Chemical group 0.000 description 2
- 150000005130 benzoxazines Chemical class 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- RZWZRACFZGVKFM-UHFFFAOYSA-N propanoyl chloride Chemical compound CCC(Cl)=O RZWZRACFZGVKFM-UHFFFAOYSA-N 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000000235 small-angle X-ray scattering Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000001757 thermogravimetry curve Methods 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- WLPATYNQCGVFFH-UHFFFAOYSA-N 2-phenylbenzonitrile Chemical group N#CC1=CC=CC=C1C1=CC=CC=C1 WLPATYNQCGVFFH-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 1
- 239000004990 Smectic liquid crystal Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000011825 aerospace material Substances 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
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- 230000007547 defect Effects 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical compound CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000011363 dried mixture Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
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- 230000002349 favourable effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000002425 furfuryl group Chemical group C(C1=CC=CO1)* 0.000 description 1
- DDRPCXLAQZKBJP-UHFFFAOYSA-N furfurylamine Chemical compound NCC1=CC=CO1 DDRPCXLAQZKBJP-UHFFFAOYSA-N 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000001424 substituent group Chemical group 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
- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
- C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
- C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
- C07C227/18—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions involving amino or carboxyl groups, e.g. hydrolysis of esters or amides, by formation of halides, salts or esters
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C229/38—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino groups bound to acyclic carbon atoms and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
-
- 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
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/52—Radicals substituted by nitrogen atoms not forming part of a nitro radical
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
- C07D413/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/38—Polymers
- C09K19/3804—Polymers with mesogenic groups in the main chain
- C09K19/3823—Polymers with mesogenic groups in the main chain containing heterocycles having at least one nitrogen as ring hetero atom
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/14—Solid materials, e.g. powdery or granular
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
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Abstract
The invention provides a polybenzoxazine oligomer, high-thermal-conductivity aromatic ester crosslinked liquid crystal polybenzoxazine and a preparation method thereof. The invention takes p-hydroxybenzoic acid, amine compounds and paraformaldehyde as raw materials, synthesizes benzoxazine monomers through Mannich reaction, and then obtains the polybenzoxazine oligomer through ring-opening polymerization and hydroxyl acetylation reaction. The polybenzoxazine oligomer is self-crosslinked to produce the crosslinked product polybenzoxazine containing aromatic ester bond with liquid crystal structure and high heat conductivity for the first time. The invention has simple synthesis process, mild reaction condition, high yield and low equipment requirement, and is suitable for large-scale production. The polybenzoxazine obtained by the invention has a liquid crystal structure, high heat conduction and heat resistance, and is a material with important functions, which can be used in the fields of integrated circuits, light-emitting diodes and the like.
Description
Technical Field
The invention relates to a polybenzoxazine oligomer, high-thermal-conductivity aromatic ester crosslinked liquid crystal polybenzoxazine and a preparation method thereof, and belongs to the technical field of high polymer materials.
Background
Electronic devices in integrated circuits are currently moving towards higher power and lighter, thinner, smaller size. The reduction in size and improvement in performance of electronic devices can result in the generation of large amounts of heat, which can lead to a number of potential problems such as failure, reduced durability, and even explosion of equipment. In recent years, heat dissipation has become a critical issue limiting integrated circuit development and Light Emitting Diode (LED) development. Therefore, a polymer material having excellent Thermal Conductivity (TC) and high heat resistance is demanded to effectively dissipate heat.
However, most polymeric materials have an ultra-low thermal conductivity and are considered insulators. Traditionally, there are two approaches to improving the thermal conductivity of polymers: first, highly thermally conductive inorganic particles such as Boron Nitride (BN), aluminum oxide (Al 2O3) and Carbon Nanotubes (CNTs) are added to a polymer matrix. Although a very high thermal conductivity is obtained, a very large amount (> 30 vol%) of filler is required, which greatly reduces the mechanical and processing properties of the polymer composite. Another most efficient approach is to incorporate crystalline or liquid crystal structures in the polymer
Recently, a new type of thermosetting resin called benzoxazine resin has emerged internationally. It has high heat resistance, high solvent resistance, low dielectric constant and low cost. It also shows excellent dimensional stability and ring-opening polymerization is performed in curing without releasing any by-products. It is actively developed into high potential electronic materials, adhesives, precision mechanical parts, carbon fiber reinforced composites, and aerospace materials. However, polybenzoxazines are similar to other resins and have very low thermal conductivity.
In order to improve the intrinsic thermal conductivity of benzoxazine resins, many chemists have explored liquid crystalline benzoxazines. For example, ishida et al first synthesized Liquid Crystal (LC) benzoxazines containing cyanobiphenyl intermediates and reported their phase behavior. Kawauchi et al synthesized LC benzoxazine monomers. Ito et al report increasing the temperature range of LC by introducing more rigid biphenyl groups. The above reports, although successful, often lose liquid crystalline behavior after polymerization of LC benzoxazine monomers.
Therefore, there is a need to develop a polybenzoxazine having a liquid crystal structure, high heat conductivity and heat resistance.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides a polybenzoxazine oligomer, high-thermal-conductivity aromatic ester crosslinked liquid crystal polybenzoxazine and a preparation method thereof. The invention takes p-hydroxybenzoic acid, amine compounds and paraformaldehyde as raw materials, synthesizes benzoxazine monomers through Mannich reaction, and then obtains the polybenzoxazine oligomer through ring-opening polymerization and hydroxyl acetylation reaction. The polybenzoxazine oligomer is self-crosslinked to produce the crosslinked product polybenzoxazine containing aromatic ester bond with liquid crystal structure and high heat conductivity for the first time. The invention has simple synthesis process, mild reaction condition, high yield and low equipment requirement, and is suitable for large-scale production. The polybenzoxazine obtained by the invention has a liquid crystal structure, high heat conduction and heat resistance, and is a material with important functions, which can be used in the fields of integrated circuits, light-emitting diodes and the like.
The invention is realized by the following technical scheme:
a polybenzoxazine oligomer having the structure of formula I:
wherein R 1 is selected from one of the following ：-CH3,-(CH2)11CH3,-CH2CH2OH,-CH2-CH＝CH2,
R 2 is selected from one of the following: -CH 2CH3,-CH3;
n is 3-6.
The preparation method of the polybenzoxazine oligomer comprises the following steps:
(1) Dissolving p-hydroxybenzoic acid, amine compounds and paraformaldehyde in a low-polarity solvent, and carrying out reflux reaction to obtain benzoxazine monomers;
Wherein R 1 and R 1 in the compound of formula I have the same meaning;
(2) Dissolving benzoxazine monomer and initiator in solvent, and performing ring-opening polymerization reaction to obtain oligomeric benzoxazine; then adding anhydride, acid catalyst and solvent, fully mixing and dispersing uniformly, and obtaining the polybenzoxazine oligomer (I) through acylation reaction and drying.
According to a preferred embodiment of the present invention, in the step (1), the amine compound has a structural formula of R 1-NH2; wherein R 1 and R 1 in the compound of formula I have the same meaning.
According to the invention, in the step (1), the molar ratio of the parahydroxybenzoic acid, the amine compound and the paraformaldehyde is preferably 1:2:1 to 1:2:6.
According to the present invention, preferably, in the step (1), the low polarity solvent is one or a combination of two or more of toluene, xylene, ethanol or dioxane; the volume ratio of the molar quantity of the parahydroxybenzoic acid to the low-polarity solvent is 1:1-1:20 mol/L.
According to the present invention, in the step (1), the reflux reaction temperature is 80 to 110℃and the reflux reaction time is 10 to 24 hours.
According to the present invention, in the step (1), the post-treatment method of the reaction liquid obtained by the reflux reaction comprises the steps of: deionized water is added into the reaction liquid, and then the benzoxazine monomer is obtained through filtration, washing and drying.
Preferably, in step (2) according to the present invention, the solvent is tetrahydrofuran or toluene; the volume ratio of the mass of the benzoxazine monomer to the solvent is 0.1-1 g/mL.
According to a preferred embodiment of the invention, in step (2), the initiator is Benzoyl Peroxide (BPO), 2' -Azobisisobutyronitrile (AIBN) or tert-butylphenol (TBP). The addition amount of the initiator is 0.1-15% of the mass of the benzoxazine monomer.
According to the invention, in the step (2), the ring-opening polymerization reaction temperature is 130-200 ℃ and the reaction time is 2-5 h. The polymerization temperature depends on the kind of amine compound used, and the use of an amine compound having a long hydrocarbon chain can lower the polymerization temperature.
According to the present invention, preferably, in the step (2), the post-treatment method of the crude product obtained by the ring-opening polymerization reaction comprises the steps of: the crude product is cooled to room temperature, then is dissolved in normal hexane, is added dropwise into methanol for precipitation, and is filtered and dried to obtain the oligobenzoxazine.
Preferably, in step (2) according to the present invention, the anhydride is acetic anhydride, propionic anhydride, acetyl chloride or propionyl chloride; the molar ratio of the anhydride to the oligobenzoxazine is 1:1-2:1. The anhydride is preferably acetic anhydride or propionic anhydride; if acetyl chloride or propionyl chloride is used, hydrogen chloride is formed as a by-product.
Preferably, in step (2) according to the present invention, the acidic catalyst is an aqueous solution of an acid, which is sulfuric acid, sulfonic acid or hydrochloric acid; the concentration of the aqueous solution of the acid is 0.005-0.05 mol/L; the molar ratio of the acid catalyst to the oligobenzoxazine is 1:500-1:820.
Preferably, in step (2) according to the present invention, the solvent is dimethylacetamide; the ratio of the molar amount of the oligobenzoxazine to the volume of the solvent is 0.2-1 mol/L.
According to the present invention, in the step (2), the acylation reaction temperature is 100 to 150 ℃, the acylation reaction time is 2 to 6 hours, and the acylation reaction is performed in an inert atmosphere under stirring. Preferably, the inert atmosphere is a nitrogen or argon atmosphere.
According to the invention, in the step (2), the drying is vacuum drying, the drying temperature is 60-130 ℃, and the drying time is 20-30 hours.
A high thermal conductivity aromatic ester crosslinked liquid crystal polybenzoxazine has a structure shown in the following formula II:
Wherein R 1 and R 1 in the compound of formula I have the same meaning.
The preparation method of the high-thermal-conductivity aromatic ester crosslinked liquid crystal polybenzoxazine comprises the following steps: and (3) dissolving the polybenzoxazine oligomer (I) and a catalyst in an organic solvent, and heating, crosslinking and curing to obtain the high-thermal-conductivity aromatic ester crosslinked liquid crystal polybenzoxazine.
According to the invention, the catalyst is preferably calcium acetate, sodium acetate, manganese acetate or zinc acetate; the mass ratio of the catalyst to the polybenzoxazine oligomer (I) is 0.01:1-0.05:1.
According to the invention, the organic solvent is preferably dimethylacetamide, N-dimethylformamide or N-methylpyrrolidone; the ratio of the molar amount of the polybenzoxazine oligomer (I) to the volume of the organic solvent is 0.5 to 1mol/L.
According to the invention, the method further comprises the steps of reflux stirring and drying before the heating crosslinking curing. The purpose of reflux stirring is to allow better mixing of the raw materials, to heat the solution without loss of the raw materials, and to increase the yield. If the solution is heated without reflux stirring, there may be a loss of material. The drying is to remove impurities such as by-products.
Preferably, the reflux stirring temperature is 110-180 ℃, the reflux stirring time is 2-6 h, and the reflux stirring is carried out in inert atmosphere under stirring conditions; further preferably, the inert atmosphere is a nitrogen or argon atmosphere.
Preferably, the drying is vacuum drying, the drying temperature is 60-100 ℃, and the drying time is 20-30 h.
According to the present invention, preferably, the heat crosslinking curing is performed in air; the heating crosslinking curing method comprises the following steps: heating to 160-273 ℃ at a heating rate of 8-12 ℃/min, and then preserving heat for 0-2 h; or the heat crosslinking curing method comprises the following steps: directly preserving the temperature at 160-273 ℃ for 6 min-2 h.
The synthetic route of the polybenzoxazine oligomer and the high-thermal-conductivity aromatic ester crosslinked liquid crystal polybenzoxazine is as follows.
Wherein R 1 is selected from one of the following ：-CH3,-(CH2)11CH3,-CH2CH2OH,-CH2-CH＝CH2,
R 2 is selected from one of the following: -CH 2CH3,-CH3;
n is 3-6.
The invention has the technical characteristics and beneficial effects that:
1. the invention adopts commercial raw materials and has low cost; the synthesis route is simple, the working procedure is not inflammable and explosive, the production is safe, the reaction condition is mild, the equipment requirement is low, the yield is high, and the method is favorable for industrial production.
2. The invention takes p-hydroxybenzoic acid, amine compounds and paraformaldehyde as raw materials, synthesizes benzoxazine monomers through Mannich reaction, and then obtains the polybenzoxazine oligomer through ring-opening polymerization and hydroxyl acetylation reaction. The polybenzoxazine oligomer is self-crosslinked to obtain the crosslinked product polybenzoxazine. The liquid crystal structure is formed by introducing the rigid aromatic ester bond, wherein the rigid aromatic ester bond forms an ordered structure within the temperature range of 160-273 ℃. The synthesized polybenzoxazine can maintain a liquid crystal structure during polymerization, and a common liquid crystal benzoxazine monomer usually loses the liquid crystal structure during polymerization.
3. The ordered arrangement of the polybenzoxazine liquid crystal structure improves the thermal conductivity of the material. In the present invention, the thermal conductivity of the aromatic ester-crosslinked liquid crystalline polybenzoxazine is 21% and 16% higher than that of the oligobenzoxazines and polybenzoxazine oligomers, respectively.
4. The invention synthesizes aromatic ester bond crosslinked polybenzoxazine products which are formed as a result of self-crosslinking. The results show that heat resistance is improved while the crosslink density is improved. The glass transition temperature tg=269 ℃ of the product synthesized according to the invention is much higher than that of other resins.
5. The variety of the amine compound influences the ring-opening polymerization reaction temperature, and has certain influence on the liquid crystal structure, the thermal performance and the like of the finally obtained polybenzoxazine. The acid anhydride type used in the invention affects the acetylation reaction and has a certain influence on the crosslinking effect of the esterification reaction and the formation of a liquid crystal structure. In the self-crosslinking process of the polybenzoxazine oligomer, the crosslinking curing temperature and time have important influence on the formation of a liquid crystal structure; meanwhile, all groups are combined to prepare the aromatic ester crosslinked liquid crystal polybenzoxazine with a liquid crystal structure and high heat conduction and heat resistance.
Drawings
FIG. 1 is a SEC chromatogram of BZ-COOH, OBZ-COOH prepared in example 1.
FIG. 2 shows the 1H-NMR spectra of (A) BZ-COOH, (B) OBZ-COOH, and (C) OBZ-AC prepared in example 1.
FIG. 3 is an image of POM at various temperatures during the OBZ-AC thermal crosslinking curing process in example 1.
FIG. 4 is a DSC profile of OBZ-AC prepared in example 1.
FIG. 5 is a SAXS curve of OBZ-PES (b) obtained after crosslinking curing at 273℃for 60min for OBZ-AC (a) prepared in example 1 and example 2.
FIG. 6 is an isothermal curing graph of example 1 in which OBZ-AC was heated at 273℃for (a) 1min (b) 3min (c) 6min (d) 17min (e) 30min (f) 60 min.
FIG. 7 is the FT-IR spectra of (a) BZ-COOH, (b) OBZ-COOH, (c) OBZ-AC prepared in example 1 and (d) OBZ-PES prepared in example 2.
FIG. 8 is a FTIR spectrum of OBZ-AC prepared in example 1 after curing at different temperatures for 2 hours.
FIG. 9 is a solid 13 CNMR of OBZ-PES prepared in example 2.
FIG. 10 is a graph of the Thermal Conductivity (TC) of OBZ-COOH, OBZ-AC prepared in example 1 and OBZ-PES prepared in example 2.
FIG. 11 is a DMA curve of the OBZ-PES prepared in example 2.
FIG. 12 is a TGA curve of OBZ-COOH prepared in example 1, OBZ-AC, and OBZ-PES prepared in example 2.
Detailed Description
The invention will be further illustrated with reference to specific examples. But is not limited thereto.
Meanwhile, the experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents, materials, and devices are commercially available unless otherwise specified.
Example 1
Synthesis of benzoxazine monomer (BZ-COOH, wherein R 1 is- (CH 2)11CH3)
In a 100mL flask, 4-hydroxybenzoic acid (5 mmol,0.69 g), dodecylamine (5 mmol,0.945 g) and paraformaldehyde (12.5 mmol,0.3877 g) were mixed in 10mL dioxane and heated to reflux at 90℃for 24h (magnetic stirring). The mixture was then allowed to cool at room temperature, and then 100mL of deionized water was poured into the above mixture in a 500 mL beaker to give a pale yellow precipitate. After the product is filtered, the product is further washed by deionized water for 3 times, and is dried at 60 ℃ to obtain the benzoxazine monomer. The yield thereof was found to be 90%.
Synthesis of Oligobenzoxazines (OBZ-COOH, wherein R 1 is- (CH 2)11CH3)
BZ-COOH (0.90 g), t-butylphenol (0.10 g) and tetrahydrofuran (5 mL, dried in advance in an oven at about 60 ℃ C. For 12 hours) were added to a 100mL flask. And ring-opening polymerization is carried out by taking p-n-butylphenol as an initiator. The mixture was then poured into an aluminum mold, which was placed in an air circulation oven and polymerized at 150℃for 3h. The crude product was cooled to room temperature, dissolved in n-hexane, and precipitated by dropping in methanol. The precipitate was filtered and dried overnight in vacuo to give the orange product in 77% yield.
FIG. 1 is a SEC chromatogram of BZ-COOH and OBZ-COOH. In comparison with BZ-COOH, the GPC trace of OBZ-COOH shifted to the high molecular weight region, indicating that ring opening polymerization of the benzoxazine monomer occurred, forming a benzoxazine oligomer. In addition, it represents a bimodal curve. The average molecular weight (Mn) of the OBZ-COOH was 1200g/mol, and the polydispersity index (PDI) was 1.40.
Synthesis of polybenzoxazine oligomer, dodecylamino acetoxy polybenzoxazine (OBZ-AC)
OBZ-COOH (4 mmol), acetic anhydride (0.47 g,4.7 mmol), aqueous H 2SO4 (0.49 mL,0.005 mmol) and dimethylacetamide DMAC (5 mL) were mixed thoroughly and dispersed uniformly, and refluxed at 110℃for 2 hours (under mechanical stirring, nitrogen atmosphere). And then dried in a vacuum oven at 80℃for 24 hours to give dodecylamino acetoxy polybenzoxazine (OBZ-AC).
The yield was 90% calculated using OBZ-COOH as starting material.
FIG. 2 shows the 1H NMR spectra of (A) BZ-COOH, (B) OBZ-COOH and (C) OBZ-AC prepared in this example.
In FIG. 2A, the characteristic formants of Ar-CH 2 -N (a) and O-CH 2 -N (b) appear at 3.99ppm and 4.91ppm, respectively, indicating oxazine ring formation. The peak at 0.84ppm (d) is attributed to the proton of-CH 3 in n-dodecylamine, the integral ratio is 1.97:1.98:3.09, consistent with the theoretical value of 2:2:3. This means a successful synthesis of BZ-COOH benzoxazine monomers. Peaks from 6.77ppm (f) to 7.66ppm (g) belong to aromatic protons. After the ring-opening polymerization, the peak at 4.91ppm (B) of O-CH 2 -N completely disappeared, and the peak at 3.99ppm (a) was broadened and shifted to 3.55ppm, as shown in FIG. 2B, indicating that the BZ-COOH ring-opening polymerization was successful.
In FIG. 2C, the new peak at 2.01ppm (j) is due to the methyl proton of the acetoxy group. Based on the integrated values of the 2.01ppm peak and the 7.98ppm peak, the percent conversion of OBZ-COOH to OBZ-AC was calculated as:
Wherein P is the integral value of the peak value of methyl protons at 2.01ppm, respectively, and R is the integral value of the peak value of phenol hydroxyl protons at 7.98ppm, respectively. The calculated conversion of OBZ-COOH was 84.5%.
In fig. 2B and C, the substituent R is dodecyl.
FIG. 3 is a POM image at various temperatures during the OBZ-AC thermal crosslinking curing process of this example. The test method is as follows: the dodecylamine acetoxy polybenzoxazine (OBZ-AC) (4 mmol), zn (CH 3COO)2 (0.04 mmol) and dimethylacetamide DMAC (5 mL) prepared in this example were thoroughly mixed and dispersed uniformly, and refluxed for 3h under an inert atmosphere of nitrogen at 140 ℃ after which the mixture was poured into an aluminum mold and dried at 80 ℃ for 24h in a vacuum oven, placed on a polarizing microscope hot stand at a heating rate of 10 ℃ per minute, and the POM image of the resulting product was tested when the temperature was raised from room temperature to 160, 180, 200, 220, 240, 260, 273 or 280 ℃, observed that no liquid crystal structure was observed when heated at low temperature, and that lamellar structure appeared when heated at 160 ℃, indicating the initiation of copolymerization.
FIG. 4 is a DSC thermogram of OBZ-AC prepared in this example. The Tonset and Tmax of the exothermic peaks were 151 ℃ and 239 ℃, respectively. The exothermic temperature is in the range of 151-340 c due to the occurrence of the esterification crosslinking reaction.
FIG. 6 is an isothermal curing graph of the OBZ-AC of this example heated at 273 ℃ (a) 1min (b) 3min (c) 6min (d) 17min (e) 30min (f) 60 min. The test method is as follows: dodecylamine acetoxy polybenzoxazine (OBZ-AC) (4 mmol), zn (CH 3COO)2 (0.04 mmol) and dimethylacetamide DMAC (5 mL) prepared in this example were thoroughly mixed and dispersed uniformly, and mechanically stirred under an inert atmosphere of nitrogen at 140℃for reflux for 3h, then the mixture was poured into an aluminum mold and dried in a vacuum oven at 80℃for 24 h.a polarizing microscope was heated from room temperature to 273℃at a heating rate of 10℃per minute, the above-mentioned dried mixture was directly placed on the hot stage of a polarizing microscope at 273℃for different times (a) 1min (b) 3min (c) 6min (d) 17min (e) 30min (f) 60min, and an isothermal curing pattern was tested at the initial stage after curing 1min (a) and 3min (b) without the appearance of bright birefringent images, indicating isotropic phase, but when the reaction proceeded to 6min, a clear birefringent image (c) indicating the formation of a liquid crystal structure was observed.
FIG. 8 is a FTIR spectrum of the OBZ-AC of this example after curing at different temperatures for 2 hours. The test method is as follows: dodecylamine acetoxy polybenzoxazine (OBZ-AC) (4 mmol), zn (CH 3COO)2 (0.04 mmol) and dimethylacetamide DMAC (5 mL) prepared in this example were thoroughly mixed and dispersed well, and refluxed under nitrogen under an inert atmosphere at 140℃for 3h after which the mixture was poured into an aluminum mould and dried in a vacuum oven at 80℃for 24h after which it was placed in an air circulation oven at a heating rate of 10℃per minute and warmed up to different temperatures (120, 140, 160, 180, 200 or 220 ℃) from room temperature and then incubated for 2h after cooling to room temperature, the FTIR spectrum of the test sample was reduced in peak intensity at 1775cm -1 for acetoxyC=O with increasing temperature while, due to the action of the ester group C=O, a new peak was developed and added at 1749cm -1, these changes indicated that the esterification reaction was taking place, the peak at 1775cm -1 was almost disappeared after the sample was cured at 200℃for 2h, indicating that the esterification reaction of OBZ-AC was completed.
Example 2
Synthesis of highly thermally conductive aromatic ester-crosslinked liquid crystalline polybenzoxazines, namely aromatic ester-based polybenzoxazines [1] (OBZ-PES)
Dodecylamine acetoxy polybenzoxazine (OBZ-AC) (4 mmol) prepared in example 1, zn (CH 3COO)2 (0.04 mmol) and dimethylacetamide DMAC (5 mL) were thoroughly mixed and dispersed uniformly, and mechanically stirred under reflux for 3h under an inert atmosphere of nitrogen at 140 ℃ then the mixture was poured into an aluminum mold, dried for 24h at 80 ℃ in a vacuum oven then placed in an air circulation program oven at a heating rate of 10 ℃/min from room temperature to 273 ℃ and then incubated for 1h to give OBZ-PES.
FIG. 5 shows SAXS spectra of OBZ-AC (a) of the present example and OBZ-PES (b) prepared in the present example. In the spectrum 5a, no clear peak could be observed due to its amorphous nature. After curing, both types of peaks can be seen in fig. 5 b. The broad peak at q1=0.9 nm -1、q3＝12.36nm-1、q4＝14.22nm-1 is a short-range ordered lamellar arrangement. The peak at q2=6.7 nm -1 corresponds to a long range ordered lamellar arrangement of the smectic C phase structure. The interlayer spacing was calculated to be 2.3nm according to the bragg equation (d=2pi/q). Curing and crosslinking for 60min at 273 ℃ to form a liquid crystal structure.
FIG. 7 (a) is an FTIR spectrum of a benzoxazine monomer prepared in example 1, wherein the peak at 925cm -1 corresponds to the oxazine ring. The FTIR spectrum of the oligobenzoxazine prepared in example 1 is shown in FIG. 7 (b), the peak intensity at 1465cm -1 corresponding to the tetra-substituted benzene ring increases, and the new peak at 3545cm -1 corresponds to the phenolic hydroxyl group. The FTIR spectrum of the polybenzoxazine oligomer prepared in example 1 is shown in FIG. 7 (c), and the success of the substitution of hydroxyl group with acetoxy group is shown by the appearance of a new peak at 1759cm -1 and the disappearance of the peak at 3545cm -1. The FTIR spectrum of the OBZ-PES prepared in this example is shown in FIG. 7 (d), and the crosslinking reaction of OBZ-AC is represented by the peak at 1759cm -1 which disappeared due to the acetate carbonyl group and the new peak at 1749cm -1 which formed due to the polyester carbonyl group.
The solid phase 13 CNMR spectrum of OBZ-PES confirmed the formation of aromatic ester bonds (FIG. 9). The new peak at 194.82ppm (f) was due to carbon resonance of the aromatic ester linkage, indicating successful esterification.
FIG. 10 shows the Thermal Conductivity (TC) of OBZ-COOH, OBZ-AC prepared in example 1 and OBZ-PES prepared in this example. TC of the OBZ-PES was as high as 0.284W/mK, 21% and 16% higher than OBZ-COOH and OBZ-AC, respectively. The high thermal conductivity of the OBZ-PES is due to its liquid crystal structure. This ordered structure facilitates its thermal conductivity. The low TC of OBZ-COOH and OBZ-AC is due to the lack of ordered arrangement and the amorphous nature of the molecular chains.
The DMA curve of the OBZ-PES prepared in this example is shown in FIG. 11. From the ratio peaks of the G ', G' and tan delta curves, the glass transition temperatures were 248 ℃, 269 ℃ and 290 ℃, respectively. In general, the stiffness and crosslink density of the polymer chains can significantly affect the Tg value of the thermoset polymer. The high crosslink density and the presence of rigid aryl ester units of the polymers of the present invention result in a high Tg.
FIG. 12 shows the TGA curves of OBZ-COOH prepared in example 1, OBZ-AC and OBZ-PES prepared in this example. Compared to OBZ-COOH, OBZ-AC has better thermal stability, while cross-linked OBZ-PES has the highest thermal stability. The 5% weight loss temperature (Td 5) and 10% weight loss temperature (Td 10) of the OBZ-PES were up to 383℃and 410℃respectively. This is due to its high crosslink density and high aromatic ester bond energy. In addition, the coke rate of OBZ-PES was 49%, which was far higher than 16% of OBZ-COOH and 17% of OBZ-AC. A significant enhancement of thermal properties by aryl ester cross-linking can clearly be observed.
Example 3
Synthesis of benzoxazine monomer (BZ-COOH 2 in which R 1 is-CH 3)
In a 100mL flask, 4-hydroxybenzoic acid (5 mmol,0.69 g), methylamine (5 mmol,0.155 g) and paraformaldehyde (12.5 mmol,0.3877 g) were mixed in 10mL dioxane and heated to reflux at 90℃for 24h (magnetic stirring). The mixture was then allowed to cool at room temperature, and then 100mL of deionized water was poured into the above mixture in a 500 mL beaker to give a pale yellow precipitate. After the product is filtered, the product is further washed by deionized water for 3 times, and is dried at 60 ℃ to obtain the benzoxazine monomer. The yield thereof was found to be 87%.
Synthesis of Oligobenzoxazines (wherein R 1 is-CH 3, abbreviated as OBZ-COOH 2)
BZ-COOH (0.90 g), t-butylphenol (0.10 g) and tetrahydrofuran (5 mL, dried in advance in an oven at about 60 ℃ C. For 12 hours) were added to a 100mL flask. And ring-opening polymerization is carried out by taking p-n-butylphenol as an initiator. The mixture was then poured into an aluminum mold, which was placed in an air circulation oven and polymerized at 180℃for 3h. The crude product was cooled to room temperature, dissolved in n-hexane, and precipitated by dropping in methanol. The precipitate was filtered and dried overnight in vacuo to give the orange product in 75% yield.
Synthesis of polybenzoxazine oligomer, i.e., methylamino acetoxy polybenzoxazine (OBZ-AC 2)
OBZ-COOH2 (4 mmol), acetic anhydride (0.47 g,4.7 mmol), aqueous H 2SO4 (0.58 mL, 0.006mmol) and dimethylacetamide DMAC (5 mL) prepared above were taken, thoroughly mixed and dispersed uniformly, and refluxed at 130℃for 3 hours (mechanical stirring, nitrogen atmosphere). Then dried in a vacuum oven at 100deg.C for 24h to give methylamino acetoxy polybenzoxazine (OBZ-AC 2).
Example 4
Synthesis of highly thermally conductive aromatic ester-crosslinked liquid crystalline polybenzoxazines, namely aromatic ester-based polybenzoxazines [2] (OBZ-PES 2)
The methylamino acetoxy polybenzoxazine (OBZ-AC 2) (4 mmol) prepared in example 3, zn (CH 3COO)2 (0.04 mmol) and dimethylacetamide DMAC (5 mL) were thoroughly mixed and dispersed uniformly, and mechanically stirred under reflux for 3h under an inert atmosphere of nitrogen at 140 ℃ then the mixture was poured into an aluminum mold and dried in a vacuum oven at 80 ℃ for 24h then placed in an air circulation program oven at a heating rate of 10 ℃/min to 220 ℃ and then incubated for 1h to give OBZ-PES2.
Example 5
Synthesis of benzoxazine monomer (BZ-COOH 3, wherein R 1 is-CH 2CH2 OH)
In a 100mL flask, 4-hydroxybenzoic acid (5 mmol,0.69 g), ethanolamine (5 mmol,0.305 g) and paraformaldehyde (12.5 mmol,0.3877 g) were mixed in 10mL dioxane and heated to reflux at 90℃for 24h (magnetic stirring). The mixture was then allowed to cool at room temperature, and then 100mL of deionized water was poured into the above mixture in a 500mL beaker to give a pale yellow precipitate. After the product is filtered, the product is further washed by deionized water for 3 times, and is dried at 60 ℃ to obtain the benzoxazine monomer. The yield thereof was found to be 83%.
Synthesis of Oligobenzoxazines (wherein R 1 is-CH 2CH2 OH, abbreviated as OBZ-COOH 3)
BZ-COOH (0.90 g), t-butylphenol (0.10 g) and tetrahydrofuran (5 mL, dried in advance in an oven at about 60 ℃ C. For 12 hours) were added to a 100mL flask. And ring-opening polymerization is carried out by taking p-n-butylphenol as an initiator. The mixture was then poured into an aluminum mold, which was placed in an air circulation oven and polymerized at 200℃for 4h. The crude product was cooled to room temperature, dissolved in n-hexane, and precipitated by dropping in methanol. The precipitate was filtered and dried overnight in vacuo to give the orange product in 70% yield.
Synthesis of polybenzoxazine oligomer, 2-aminoethanol acetoxy polybenzoxazine (OBZ-AC 3)
The ethanol group-containing OBZ-COOH3 (4 mmol), acetic anhydride (0.47 g,4.7 mmol), aqueous H 2SO4 (0.68 mL, 0.0075 mmol) and dimethylacetamide DMAC (5 mL) prepared above were taken, thoroughly mixed and dispersed uniformly, and refluxed at 130℃for 3 hours (mechanical stirring, nitrogen atmosphere). Then dried in a vacuum oven at 100deg.C for 24h to give 2-aminoethoxy acetoxy polybenzoxazine (OBZ-AC 3).
Example 6
Synthesis of highly thermally conductive aromatic ester-crosslinked liquid crystalline polybenzoxazines, namely aromatic ester-based polybenzoxazines [3] (OBZ-PES 3)
The 2-aminoethanol-based acetoxy polybenzoxazine (OBZ-AC 3) (4 mmol) prepared in example 5, zn (CH 3COO)2 (0.04 mmol) and N, N-dimethylformamide DMF (5 mL) were thoroughly mixed and dispersed uniformly, and mechanically stirred under reflux for 3 hours under nitrogen in an inert atmosphere at 140 ℃ then the mixture was poured into an aluminum mold and dried for 24 hours at 80 ℃ in a vacuum oven then placed in an air circulation program oven at a heating rate of 10 ℃ C./min and heated to 240 ℃ C., followed by heat preservation for 1 hour to obtain OBZ-PES3.
Example 7
Synthesis of benzoxazine monomer (BZ-COOH 4, wherein R 1 is-CH 2-CH＝CH2)
In a 100mL flask, 4-hydroxybenzoic acid (5 mmol,0.69 g), acrylamide (5 mmol, 0.284 g) and paraformaldehyde (12.5 mmol,0.3877 g) were mixed in 10mL dioxane and heated to reflux at 90℃for 24h (magnetic stirring). The mixture was then allowed to cool at room temperature, and then 100mL of deionized water was poured into the above mixture in a 500 mL beaker to give a pale yellow precipitate. After the product is filtered, the product is further washed by deionized water for 3 times, and is dried at 60 ℃ to obtain the benzoxazine monomer. The yield thereof was found to be 87%.
Oligobenzoxazines (wherein R 1 is-CH 2-CH＝CH2, OBZ-COOH4 for short)
BZ-COOH (0.90 g), t-butylphenol (0.10 g) and toluene (5 mL, dried in an oven at about 80℃for 12 hours in advance) were added to a 100mL flask. And ring-opening polymerization is carried out by taking p-n-butylphenol as an initiator. The mixture was then poured into aluminum molds. The mold was placed in an air circulation oven and polymerized for 3 hours at 175 ℃. The crude product was cooled to room temperature, dissolved in n-hexane, and precipitated by dropping in methanol. The precipitate was filtered and dried overnight in vacuo to give the orange product in 65% yield.
Synthesis of allylamine acetoxy polybenzoxazine (OBZ-AC 4)
The allyl-containing OBZ-COOH4 (4 mmol), acetic anhydride (0.47 g,4.7 mmol), aqueous H 2SO4 (0.68 mL, 0.0071 mmol) and dimethylacetamide DMAC (5 mL) prepared above were thoroughly mixed and dispersed uniformly, and refluxed at 145℃for 5 hours (mechanical stirring, nitrogen atmosphere). Then dried in a vacuum oven at 120deg.C for 24h to give allylamine-based acetoxy polybenzoxazine (OBZ-AC 4).
Example 8
Synthesis of highly thermally conductive aromatic ester-crosslinked liquid crystalline polybenzoxazines, namely aromatic ester-based polybenzoxazines [4] (OBZ-PES 4)
Allylacetoxy polybenzoxazine (OBZ-AC 4) (4 mmol) prepared in example 7, zn (CH 3COO)2 (0.04 mmol) and N-methylpyrrolidone NMP (5 mL) were thoroughly mixed and dispersed uniformly, mechanically stirred under nitrogen at 140℃for reflux for 3h, then the mixture was poured into an aluminum mold, dried at 80℃for 24h in a vacuum oven, then placed in an air circulation program oven at a heating rate of 10℃per minute, heated to 233℃and then kept for 1h to obtain OBZ-PES4.
Example 9
Synthesis of benzoxazine monomer (BZ-COOH 5, wherein R 1 is furfuryl)
In a 100mL flask, 4-hydroxybenzoic acid (5 mmol,0.69 g), furfuryl amine (5 mmol,0.406 g) and paraformaldehyde (12.5 mmol,0.3877 g) were mixed in 10mL dioxane and heated to reflux at 90℃for 24h (magnetic stirring). The mixture was then allowed to cool at room temperature, and then 100mL of deionized water was poured into the above mixture in a 500 mL beaker to give a pale yellow precipitate. After the product is filtered, the product is further washed by deionized water for 3 times, and is dried at 60 ℃ to obtain the benzoxazine monomer. The yield thereof was found to be 79%.
Synthesis of Oligobenzoxazines (wherein R1 is furfuryl, OBZ-COOH5 for short):
BZ-COOH (0.90 g), t-butylphenol (0.10 g) and tetrahydrofuran (5 mL, dried in advance in an oven at about 80℃for 12 hours) were added to a 100mL flask. And ring-opening polymerization is carried out by taking p-n-butylphenol as an initiator. The mixture was then poured into aluminum molds, which were placed in an air circulation oven and polymerized for 5 hours at 193 ℃. The crude product was cooled to room temperature, dissolved in n-hexane, and precipitated by dropping in methanol. The precipitate was filtered and dried overnight in vacuo to give the orange product in 72% yield.
Synthesis of furfuryl-amino-acetoxy-polybenzoxazine (OBZ-AC 5)
The furfuryl group-containing OBZ-COOH5 (4 mmol), acetic anhydride (0.47 g,4.7 mmol), aqueous H 2SO4 (0.70 mL,0.0072 mmol) and dimethylacetamide DMAC (8 mL) prepared above were taken, thoroughly mixed and dispersed uniformly, and refluxed at 150℃for 5 hours (mechanical stirring, nitrogen atmosphere). Then dried in a vacuum oven at 120℃for 24 hours to give furfuryl-amino-acetoxy-polybenzoxazine (OBZ-AC 5).
Example 10
Synthesis of highly thermally conductive aromatic ester-crosslinked liquid crystalline polybenzoxazines, namely aromatic ester-based polybenzoxazines [5] (OBZ-PES 5)
The furfuryl acetoxy polybenzoxazine (OBZ-AC 5) (4 mmol) prepared in example 9, zn (CH 3COO)2 (0.04 mmol) and dimethylacetamide DMAC (5 mL) were thoroughly mixed and dispersed uniformly, and mechanically stirred under reflux for 3h under nitrogen in an inert atmosphere at 140 ℃ then the mixture was poured into an aluminum mold and dried in a vacuum oven at 80 ℃ for 24h then placed in an air circulation program oven at a heating rate of 10 ℃/min to 206 ℃ and then incubated for 1h to give OBZ-PES5.
Example 11
Synthesis of benzoxazine monomer (BZ-COOH 6 for short, wherein R 1 is phenyl)
In a 100mL flask, 4-hydroxybenzoic acid (5 mmol,0.69 g), aniline (5 mmol, 0.4636 g) and paraformaldehyde (12.5 mmol,0.3877 g) were mixed in 10mL dioxane and heated to reflux at 90℃for 24h (magnetic stirring). The mixture was then allowed to cool at room temperature, and then 100mL of deionized water was poured into the above mixture in a 500mL beaker to give a pale yellow precipitate. After the product is filtered, the product is further washed by deionized water for 3 times, and is dried at 60 ℃ to obtain the benzoxazine monomer. The yield thereof was found to be 84%.
Synthesis of Oligobenzoxazines (wherein R1 is phenyl, abbreviated as OBZ-COOH 6)
BZ-COOH (0.90 g), t-butylphenol (0.10 g) and tetrahydrofuran (5 mL, dried in advance in an oven at about 80℃for 12 hours) were added to a 100mL flask. And ring-opening polymerization is carried out by taking p-n-butylphenol as an initiator. The mixture was then poured into an aluminum mold, which was placed in an air circulation oven and polymerized at 190℃for 3h. The crude product was cooled to room temperature, dissolved in n-hexane, and precipitated by dropping in methanol. The precipitate was filtered and dried overnight in vacuo to give the orange product in 71.5% yield.
Synthesis of anilinoacetoxy polybenzoxazine (OBZ-AC 6)
The anilino group-containing OBZ-COOH6 (4 mmol), acetic anhydride (0.47 g,4.7 mmol), aqueous H 2SO4 (0.78 mL,0.008 mmol) and dimethylacetamide DMAC (10 mL) prepared above were taken, thoroughly mixed and dispersed uniformly, and refluxed at 150℃for 5 hours (mechanical stirring, nitrogen atmosphere). Then dried in a vacuum oven at 130℃for 24 hours to give anilinoacetoxypolybenzoxazine (OBZ-AC 6).
Example 12
Synthesis of highly thermally conductive aromatic ester-crosslinked liquid crystalline polybenzoxazines, namely aromatic ester-based polybenzoxazines [6] (OBZ-PES 6)
Anilinoacetoxy polybenzoxazine (OBZ-AC 6) (4 mmol) prepared in example 11, zn (CH 3COO)2 (0.04 mmol) and dimethylacetamide DMAC (5 mL) were thoroughly mixed and dispersed uniformly, and mechanically stirred under reflux for 3h under an inert atmosphere of nitrogen at 140 ℃ then the mixture was poured into an aluminum mold and dried in a vacuum oven at 80 ℃ for 24h then placed in an air circulation program oven at a heating rate of 10 ℃/min to 245 ℃ and then incubated for 1h to obtain OBZ-PES6.
Test examples
The temperature range of formation of the liquid crystal structure during curing of the polybenzoxazine oligomer of the examples, and the TC, tg, T d5、Td10, scorch rate of the oligomeric polybenzoxazine, polybenzoxazine oligomer, aromatic ester-crosslinked liquid crystal polybenzoxazine prepared in the examples were tested.
The temperature range in which the liquid crystal structure is formed means: the temperature at which the formation of the liquid crystal structure starts to be carried out to a temperature at which the liquid crystal structure is no longer changed.
The test method of the temperature range of the liquid crystal structure formation is as follows: the polybenzoxazine oligomer sample (4 mmol), zn (CH 3COO)2 (0.04 mmol) and dimethylacetamide DMAC (5 mL) were thoroughly mixed and dispersed uniformly, and refluxed under mechanical stirring under nitrogen at 140℃for 3 hours, then the mixture was poured into an aluminum mold, dried in a vacuum oven at 80℃for 24 hours, the sample was heated on a hot stage of a polarizing microscope at a heating rate of 10℃per minute, and the formation of liquid crystal structures at different temperatures was examined from room temperature to different temperatures, thereby obtaining a temperature range in which the liquid crystal structures were formed.
The results are shown in Table 1.
TABLE 1 Performance data for different samples
As can be seen from Table 1, the temperature range at which the liquid crystal is present during curing of the polybenzoxazine oligomer prepared in example 1 is 160℃to 273 ℃. The liquid crystal structure is an ordered structure formed by self-crosslinking to form an aromatic ester bond. The liquid crystal of the present invention exists in a temperature range exceeding that of a conventional liquid crystal, which means that the polymer of the present invention does not lose a liquid crystal structure upon polymerization like a conventional polymer, and has a higher thermal conductivity than a conventional liquid crystal polymer. The glass transition temperature (Tg is more than or equal to 260 ℃) is far higher than that of the common liquid crystal copolymer. Therefore, the heat resistance of the thermosetting resin designed and synthesized by the invention is superior to that of common resin, and the requirement of high heat resistance can be met.
The above-described embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above-described embodiments. Other changes, modifications, substitutions, and simplifications without departing from the spirit and principles of the invention are equivalent substitution methods, and belong to the scope of the invention.
The liquid crystal polybenzoxazines synthesized according to the invention are useful in integrated circuits, electronics, LED lighting and liquid crystal displays.
Claims (11)
1. A polybenzoxazine oligomer having the structure of formula I:
wherein R 1 is selected from one of the following ：-CH3,-(CH2)11CH3,-CH2CH2OH,-CH2-CH＝CH2,
R 2 is selected from one of the following: -CH 2CH3,-CH3;
n is 3-6.
2. The method for preparing the polybenzoxazine oligomer according to claim 1, comprising the steps of:
(1) Dissolving p-hydroxybenzoic acid, amine compounds and paraformaldehyde in a low-polarity solvent, and carrying out reflux reaction to obtain benzoxazine monomers;
Wherein R 1 and R 1 in the compound of formula I have the same meaning;
the low-polarity solvent is one or more of toluene, xylene, ethanol or dioxane;
(2) Dissolving benzoxazine monomer and initiator in solvent, and performing ring-opening polymerization reaction to obtain oligomeric benzoxazine; then adding anhydride, acid catalyst and solvent, fully mixing and dispersing uniformly, and obtaining the polybenzoxazine oligomer (I) through acylation reaction and drying.
3. The method of preparing a polybenzoxazine oligomer according to claim 2, wherein in step (1) one or more of the following conditions are included:
i. The structural formula of the amine compound is R 1-NH2; wherein R 1 and R 1 in the compound of formula I have the same meaning;
ii. The molar ratio of the parahydroxybenzoic acid to the amine compound to the paraformaldehyde is 1:2:1-1:2:6;
iii, the volume ratio of the molar quantity of the parahydroxybenzoic acid to the low-polarity solvent is 1:1-1:20 mol/L;
iv, the reflux reaction temperature is 80-110 ℃, and the reflux reaction time is 10-24 hours;
v, the post-treatment method of the reaction liquid obtained by the reflux reaction comprises the following steps: deionized water is added into the reaction liquid, and then the benzoxazine monomer is obtained through filtration, washing and drying.
4. The method of preparing a polybenzoxazine oligomer according to claim 2, wherein in step (2) one or more of the following conditions are included:
i. the solvent is tetrahydrofuran or toluene; the volume ratio of the mass of the benzoxazine monomer to the solvent is 0.1-1 g/mL;
ii. The initiator is Benzoyl Peroxide (BPO), 2' -Azobisisobutyronitrile (AIBN), tert-butylphenol (TBP) or p-n-butylphenol; the addition amount of the initiator is 0.1-15% of the mass of the benzoxazine monomer;
iii, the ring-opening polymerization reaction temperature is 130-200 ℃ and the reaction time is 2-5 h;
The post-treatment method of the crude product obtained by ring-opening polymerization reaction comprises the following steps: the crude product is cooled to room temperature, then is dissolved in normal hexane, is added dropwise into methanol for precipitation, and is filtered and dried to obtain the oligobenzoxazine.
5. The method of preparing a polybenzoxazine oligomer according to claim 2, wherein in step (2) one or more of the following conditions are included:
i. The anhydride is acetic anhydride or propionic anhydride; the molar ratio of the anhydride to the oligobenzoxazine is 1:1-2:1;
ii. The acid catalyst is an aqueous solution of an acid, wherein the acid is sulfuric acid, sulfonic acid or hydrochloric acid; the concentration of the aqueous solution of the acid is 0.005-0.05 mol/L; the molar ratio of the acid catalyst to the oligobenzoxazine is 1:500-1:820;
iii, the solvent is dimethylacetamide; the volume ratio of the molar quantity of the oligobenzoxazine to the solvent is 0.2-1 mol/L;
iv, the acylation reaction temperature is 100-150 ℃, the acylation reaction time is 2-6 h, and the acylation reaction is carried out in inert atmosphere under stirring condition; the inert atmosphere is nitrogen or argon;
v, drying is vacuum drying, the drying temperature is 60-130 ℃, and the drying time is 20-30 h.
6. The high-thermal-conductivity aromatic ester crosslinked liquid crystal polybenzoxazine is characterized by having a structure shown in the following formula II:
wherein R 1 is selected from one of the following ：-CH3,-(CH2)11CH3,-CH2CH2OH,-CH2-CH＝CH2,
7. The method for preparing a high thermal conductivity aromatic ester crosslinked liquid crystal polybenzoxazine according to claim 6, comprising the steps of: dissolving the polybenzoxazine oligomer (I) and a catalyst in an organic solvent, and heating, crosslinking and curing to obtain high-thermal-conductivity aromatic ester crosslinked liquid crystal polybenzoxazine;
wherein R 1 is selected from one of the following ：-CH3,-(CH2)11CH3,-CH2CH2OH,-CH2-CH＝CH2,
R 2 is selected from one of the following: -CH 2CH3,-CH3;
n is 3-6.
8. The method for preparing a high thermal conductivity aromatic ester crosslinked liquid crystal polybenzoxazine according to claim 7, including one or more of the following conditions:
i. the catalyst is calcium acetate, sodium acetate, manganese acetate or zinc acetate; the mass ratio of the catalyst to the polybenzoxazine oligomer (I) is 0.01:1-0.05:1;
ii. The organic solvent is dimethylacetamide, N-dimethylformamide or N-methylpyrrolidone; the ratio of the molar amount of the polybenzoxazine oligomer (I) to the volume of the organic solvent is 0.5 to 1mol/L.
9. The method for preparing a high thermal conductivity aromatic ester crosslinked liquid crystal polybenzoxazine according to claim 7, further comprising the steps of reflux stirring and drying before the heat crosslinking curing.
10. The method for preparing high thermal conductivity aromatic ester crosslinked liquid crystal polybenzoxazine according to claim 9, wherein the reflux stirring temperature is 110-180 ℃, the reflux stirring time is 2-6 h, and the reflux stirring is performed in inert atmosphere under stirring conditions; the inert atmosphere is nitrogen or argon; the drying is vacuum drying, the drying temperature is 60-100 ℃, and the drying time is 20-30 h.
11. The method for preparing a high thermal conductivity aromatic ester crosslinked liquid crystal polybenzoxazine according to claim 7, wherein the heat crosslinking curing is performed in air; the heating crosslinking curing method comprises the following steps: heating to 160-273 ℃ at a heating rate of 8-12 ℃/min, and then preserving heat for 0-2 h; or the heat crosslinking curing method comprises the following steps: directly preserving the temperature at 160-273 ℃ for 6 min-2 h.
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| Carboxylic acid-containing benzoxazines as efficient catalysts in the thermal polymerization of benzoxazines;Andreu, R.，et al.;《 Journal of Polymer Science, Part A: Polymer Chemistry》;20081231;第46卷(第18期);6091-6101 * |
| 高性能聚苯并噁嗪树脂;门薇薇，等;《化学进展》;20070531;第19卷(第5期);779-786 * |
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