CN109456571A - A kind of heat molten type boron bakelite resin and preparation method thereof - Google Patents
A kind of heat molten type boron bakelite resin and preparation method thereof Download PDFInfo
- Publication number
- CN109456571A CN109456571A CN201811193668.7A CN201811193668A CN109456571A CN 109456571 A CN109456571 A CN 109456571A CN 201811193668 A CN201811193668 A CN 201811193668A CN 109456571 A CN109456571 A CN 109456571A
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- CN
- China
- Prior art keywords
- phenol
- boric acid
- molten type
- resin
- heat molten
- Prior art date
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- 229910052796 boron Inorganic materials 0.000 title claims abstract description 109
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 229920005989 resin Polymers 0.000 title claims abstract description 108
- 239000011347 resin Substances 0.000 title claims abstract description 108
- 229920001342 Bakelite® Polymers 0.000 title claims abstract description 74
- 239000004637 bakelite Substances 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 97
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 65
- 239000012745 toughening agent Substances 0.000 claims abstract description 61
- 150000001875 compounds Chemical class 0.000 claims abstract description 31
- 150000001299 aldehydes Chemical class 0.000 claims description 39
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 229920001971 elastomer Polymers 0.000 claims description 24
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 23
- 239000013067 intermediate product Substances 0.000 claims description 22
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 19
- 239000004327 boric acid Substances 0.000 claims description 19
- 229910052810 boron oxide Inorganic materials 0.000 claims description 16
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 16
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 claims description 16
- MIHINWMALJZIBX-UHFFFAOYSA-N cyclohexa-2,4-dien-1-ol Chemical compound OC1CC=CC=C1 MIHINWMALJZIBX-UHFFFAOYSA-N 0.000 claims description 14
- 239000005060 rubber Substances 0.000 claims description 13
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims description 12
- 238000009835 boiling Methods 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 150000001642 boronic acid derivatives Chemical class 0.000 claims description 11
- 239000000806 elastomer Substances 0.000 claims description 11
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 claims description 10
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims description 10
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 10
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 9
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 8
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- 229920005992 thermoplastic resin Polymers 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 7
- 230000006837 decompression Effects 0.000 claims description 7
- 230000018044 dehydration Effects 0.000 claims description 7
- 238000006297 dehydration reaction Methods 0.000 claims description 7
- 229920002866 paraformaldehyde Polymers 0.000 claims description 7
- 229920001187 thermosetting polymer Polymers 0.000 claims description 7
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 6
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 6
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 6
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 239000003822 epoxy resin Substances 0.000 claims description 6
- 229910021389 graphene Inorganic materials 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 229920000647 polyepoxide Polymers 0.000 claims description 6
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 claims description 5
- -1 Boratex Chemical compound 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 5
- 229940106691 bisphenol a Drugs 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 5
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 5
- 239000010445 mica Substances 0.000 claims description 5
- 229910052618 mica group Inorganic materials 0.000 claims description 5
- SQYNKIJPMDEDEG-UHFFFAOYSA-N paraldehyde Chemical compound CC1OC(C)OC(C)O1 SQYNKIJPMDEDEG-UHFFFAOYSA-N 0.000 claims description 5
- 229960003868 paraldehyde Drugs 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052582 BN Inorganic materials 0.000 claims description 4
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 4
- 239000004695 Polyether sulfone Substances 0.000 claims description 4
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims description 4
- 229950011260 betanaphthol Drugs 0.000 claims description 4
- BRTALTYTFFNPAC-UHFFFAOYSA-N boroxin Chemical compound B1OBOBO1 BRTALTYTFFNPAC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 4
- 239000004927 clay Substances 0.000 claims description 4
- VIGVRXYWWFPORY-UHFFFAOYSA-N diphenylborinic acid Chemical class C=1C=CC=CC=1B(O)C1=CC=CC=C1 VIGVRXYWWFPORY-UHFFFAOYSA-N 0.000 claims description 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 4
- LBBMOAOCCQOIAQ-UHFFFAOYSA-N methoxy(phenyl)borinic acid Chemical compound COB(O)C1=CC=CC=C1 LBBMOAOCCQOIAQ-UHFFFAOYSA-N 0.000 claims description 4
- 229920006393 polyether sulfone Polymers 0.000 claims description 4
- CQRYARSYNCAZFO-UHFFFAOYSA-N salicyl alcohol Chemical compound OCC1=CC=CC=C1O CQRYARSYNCAZFO-UHFFFAOYSA-N 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims description 4
- 239000010456 wollastonite Substances 0.000 claims description 4
- 229910052882 wollastonite Inorganic materials 0.000 claims description 4
- SXFRDDSPNXCCNE-UHFFFAOYSA-N (2,3-dichlorophenoxy)boronic acid Chemical compound OB(O)OC1=CC=CC(Cl)=C1Cl SXFRDDSPNXCCNE-UHFFFAOYSA-N 0.000 claims description 3
- ZYYANAWVBDFAHY-UHFFFAOYSA-N (2,3-dimethylphenyl)boronic acid Chemical compound CC1=CC=CC(B(O)O)=C1C ZYYANAWVBDFAHY-UHFFFAOYSA-N 0.000 claims description 3
- AWNLRKYJYJWIMZ-UHFFFAOYSA-N (2-butylphenoxy)boronic acid Chemical compound CCCCC1=CC=CC=C1OB(O)O AWNLRKYJYJWIMZ-UHFFFAOYSA-N 0.000 claims description 3
- QOCQQHJSBRCCRA-UHFFFAOYSA-N (2-ethylphenoxy)boronic acid Chemical compound CCC1=CC=CC=C1OB(O)O QOCQQHJSBRCCRA-UHFFFAOYSA-N 0.000 claims description 3
- SCWWDULYYDFWQV-UHFFFAOYSA-N (2-hydroxyphenoxy)boronic acid Chemical compound OB(O)OC1=CC=CC=C1O SCWWDULYYDFWQV-UHFFFAOYSA-N 0.000 claims description 3
- MCAIDINWZOCYQK-UHFFFAOYSA-N (2-phenylmethoxyphenyl)boronic acid Chemical compound OB(O)C1=CC=CC=C1OCC1=CC=CC=C1 MCAIDINWZOCYQK-UHFFFAOYSA-N 0.000 claims description 3
- KTZUVUWIBZMHMC-UHFFFAOYSA-N (2-propan-2-ylphenyl)boronic acid Chemical compound CC(C)C1=CC=CC=C1B(O)O KTZUVUWIBZMHMC-UHFFFAOYSA-N 0.000 claims description 3
- CVISDVLTGPAQGC-UHFFFAOYSA-N (3-hydroxyphenoxy)boronic acid Chemical compound OB(O)OC1=CC=CC(O)=C1 CVISDVLTGPAQGC-UHFFFAOYSA-N 0.000 claims description 3
- SIZFXIGLFOAOAD-UHFFFAOYSA-N BrC=1C(=C(C=CC1)OB(O)O)Br Chemical compound BrC=1C(=C(C=CC1)OB(O)O)Br SIZFXIGLFOAOAD-UHFFFAOYSA-N 0.000 claims description 3
- 229920002943 EPDM rubber Polymers 0.000 claims description 3
- LEMABCWCFKCYQC-UHFFFAOYSA-N OBO.C1=CC=CC2=CC=CC=C21 Chemical class OBO.C1=CC=CC2=CC=CC=C21 LEMABCWCFKCYQC-UHFFFAOYSA-N 0.000 claims description 3
- 239000004697 Polyetherimide Substances 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- KXLYRTSEXNEABR-UHFFFAOYSA-N [2-(hydroxymethyl)phenoxy]boronic acid Chemical compound OCC1=CC=CC=C1OB(O)O KXLYRTSEXNEABR-UHFFFAOYSA-N 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- ORPDTKXFAPFHPD-UHFFFAOYSA-N anthracene;boric acid Chemical compound OB(O)O.C1=CC=CC2=CC3=CC=CC=C3C=C21 ORPDTKXFAPFHPD-UHFFFAOYSA-N 0.000 claims description 3
- 229910021538 borax Inorganic materials 0.000 claims description 3
- HVQSEKGARNNWON-UHFFFAOYSA-N boric acid pyrene Chemical compound OB(O)O.c1cc2ccc3cccc4ccc(c1)c2c34 HVQSEKGARNNWON-UHFFFAOYSA-N 0.000 claims description 3
- 239000004643 cyanate ester Substances 0.000 claims description 3
- 150000005205 dihydroxybenzenes Chemical class 0.000 claims description 3
- 239000003205 fragrance Substances 0.000 claims description 3
- SKOWZLGOFVSKLB-UHFFFAOYSA-N hypodiboric acid Chemical compound OB(O)B(O)O SKOWZLGOFVSKLB-UHFFFAOYSA-N 0.000 claims description 3
- 229920001084 poly(chloroprene) Polymers 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- 229920001601 polyetherimide Polymers 0.000 claims description 3
- 239000004328 sodium tetraborate Substances 0.000 claims description 3
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 2
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- ANQSYQOHGAJRKN-UHFFFAOYSA-N 1,1'-biphenyl;boric acid Chemical compound OB(O)O.C1=CC=CC=C1C1=CC=CC=C1 ANQSYQOHGAJRKN-UHFFFAOYSA-N 0.000 claims 1
- ZZCMLQKQCWGLCJ-UHFFFAOYSA-N 2-boronooxybenzoic acid Chemical compound OB(O)OC1=CC=CC=C1C(O)=O ZZCMLQKQCWGLCJ-UHFFFAOYSA-N 0.000 claims 1
- OLGWMYRAUTVEQE-UHFFFAOYSA-N boric acid ethoxybenzene Chemical compound B(O)(O)O.C1(=CC=CC=C1)OCC OLGWMYRAUTVEQE-UHFFFAOYSA-N 0.000 claims 1
- 150000001896 cresols Chemical class 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 7
- 238000002679 ablation Methods 0.000 abstract description 5
- 230000003628 erosive effect Effects 0.000 abstract description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract 1
- 238000000034 method Methods 0.000 description 16
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 14
- 239000002253 acid Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000004615 ingredient Substances 0.000 description 6
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 6
- 229920001568 phenolic resin Polymers 0.000 description 6
- 150000001639 boron compounds Chemical class 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000005011 phenolic resin Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 210000004243 sweat Anatomy 0.000 description 5
- 238000007598 dipping method Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- LXXWKCAIQDMAJD-UHFFFAOYSA-N phenol;toluene Chemical group CC1=CC=CC=C1.OC1=CC=CC=C1 LXXWKCAIQDMAJD-UHFFFAOYSA-N 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- XPEIJWZLPWNNOK-UHFFFAOYSA-N (4-phenylphenyl)boronic acid Chemical compound C1=CC(B(O)O)=CC=C1C1=CC=CC=C1 XPEIJWZLPWNNOK-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 229920001807 Urea-formaldehyde Polymers 0.000 description 2
- LXDRHVXMGDKBEK-UHFFFAOYSA-N [B].C1=CC=CC=C1 Chemical compound [B].C1=CC=CC=C1 LXDRHVXMGDKBEK-UHFFFAOYSA-N 0.000 description 2
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- HBGPNLPABVUVKZ-POTXQNELSA-N (1r,3as,4s,5ar,5br,7r,7ar,11ar,11br,13as,13br)-4,7-dihydroxy-3a,5a,5b,8,8,11a-hexamethyl-1-prop-1-en-2-yl-2,3,4,5,6,7,7a,10,11,11b,12,13,13a,13b-tetradecahydro-1h-cyclopenta[a]chrysen-9-one Chemical compound C([C@@]12C)CC(=O)C(C)(C)[C@@H]1[C@H](O)C[C@]([C@]1(C)C[C@@H]3O)(C)[C@@H]2CC[C@H]1[C@@H]1[C@]3(C)CC[C@H]1C(=C)C HBGPNLPABVUVKZ-POTXQNELSA-N 0.000 description 1
- SEPPVOUBHWNCAW-FNORWQNLSA-N (E)-4-oxonon-2-enal Chemical compound CCCCCC(=O)\C=C\C=O SEPPVOUBHWNCAW-FNORWQNLSA-N 0.000 description 1
- PFRGGOIBYLYVKM-UHFFFAOYSA-N 15alpha-hydroxylup-20(29)-en-3-one Natural products CC(=C)C1CCC2(C)CC(O)C3(C)C(CCC4C5(C)CCC(=O)C(C)(C)C5CCC34C)C12 PFRGGOIBYLYVKM-UHFFFAOYSA-N 0.000 description 1
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 1
- KWNPRVWFJOSGMZ-UHFFFAOYSA-N 2-boronobenzoic acid Chemical compound OB(O)C1=CC=CC=C1C(O)=O KWNPRVWFJOSGMZ-UHFFFAOYSA-N 0.000 description 1
- LLBZPESJRQGYMB-UHFFFAOYSA-N 4-one Natural products O1C(C(=O)CC)CC(C)C11C2(C)CCC(C3(C)C(C(C)(CO)C(OC4C(C(O)C(O)C(COC5C(C(O)C(O)CO5)OC5C(C(OC6C(C(O)C(O)C(CO)O6)O)C(O)C(CO)O5)OC5C(C(O)C(O)C(C)O5)O)O4)O)CC3)CC3)=C3C2(C)CC1 LLBZPESJRQGYMB-UHFFFAOYSA-N 0.000 description 1
- 229910052580 B4C Inorganic materials 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- SOKRNBGSNZXYIO-UHFFFAOYSA-N Resinone Natural products CC(=C)C1CCC2(C)C(O)CC3(C)C(CCC4C5(C)CCC(=O)C(C)(C)C5CCC34C)C12 SOKRNBGSNZXYIO-UHFFFAOYSA-N 0.000 description 1
- GMHRVOAJOPOEBP-UHFFFAOYSA-N [B].C(C)OC1=CC=CC=C1 Chemical compound [B].C(C)OC1=CC=CC=C1 GMHRVOAJOPOEBP-UHFFFAOYSA-N 0.000 description 1
- VWBNGKGHQWHQFZ-UHFFFAOYSA-N [B].C1=CC=CC=C1C1=CC=CC=C1 Chemical compound [B].C1=CC=CC=C1C1=CC=CC=C1 VWBNGKGHQWHQFZ-UHFFFAOYSA-N 0.000 description 1
- 239000011157 advanced composite material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- PGAZAORSURCSOS-UHFFFAOYSA-N benzene-1,2-diol;phenol Chemical compound OC1=CC=CC=C1.OC1=CC=CC=C1O PGAZAORSURCSOS-UHFFFAOYSA-N 0.000 description 1
- KFJXTACZTALWEB-UHFFFAOYSA-N benzoic acid;boric acid Chemical compound OB(O)O.OC(=O)C1=CC=CC=C1 KFJXTACZTALWEB-UHFFFAOYSA-N 0.000 description 1
- 150000005130 benzoxazines Chemical group 0.000 description 1
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 description 1
- KWGASIUWELSTHP-UHFFFAOYSA-N boron;phenol Chemical compound [B].OC1=CC=CC=C1 KWGASIUWELSTHP-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- WQPDQJCBHQPNCZ-UHFFFAOYSA-N cyclohexa-2,4-dien-1-one Chemical compound O=C1CC=CC=C1 WQPDQJCBHQPNCZ-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 239000006101 laboratory sample Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 210000004400 mucous membrane Anatomy 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000000088 plastic resin Substances 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C08L61/14—Modified phenol-aldehyde condensates
-
- 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
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/10—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with phenol
-
- 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
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/12—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with monohydric phenols having only one hydrocarbon substituent ortho on para to the OH group, e.g. p-tert.-butyl phenol
-
- 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
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/20—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with polyhydric phenols
-
- 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
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/20—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with polyhydric phenols
- C08G8/22—Resorcinol
-
- 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
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/24—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with mixtures of two or more phenols which are not covered by only one of the groups C08G8/10 - C08G8/20
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- 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
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08K2003/387—Borates
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Abstract
The present invention provides a kind of heat molten type boron bakelite resins, including following component: phenol, aldehyde, boron-containing compound, modifying agent, toughener.Heat molten type boron bakelite resin of the present invention has good film forming, can arbitrarily be bent, the low viscosity of a period of time can be maintained under infiltrating temperature.The present invention also provides a kind of preparation method of heat molten type boron bakelite resin, the preparation method of heat molten type boron bakelite resin of the present invention, the composite material porosity being prepared is low, interlaminar shear strength is high, resistance to ablation erosion is good.
Description
Technical field
The invention belongs to technical field of polymer materials, specifically, the present invention relates to a kind of heat molten type boron bakelite resins
And preparation method thereof.
Background technique
Phenolic resin starting material is easy to get, is cheap, is heat-resist, and it is contour to be widely used to electric and aerospace
New technical field.However, the oxidizable degradation of phenolic hydroxyl group and methylene of phenolic resin, limits it in fields such as ablation resistant materials
Large-scale application, need to be modified it thus.Boron bakelite resin be current most successful phenol-formaldehyde resin modified kind it
One, B-O bond energy is formed by much larger than C-C bond energy since the hydrogen in phenolic hydroxyl group is replaced by boron, and in resin table when high temperature pyrolysis
The boron carbide honeycomb that face is formed can prevent heat from inwardly spreading and protect internal structure, so that boron bakelite resin is with excellent
Heat resistance.
Prepreg is that resin matrix is single by the basis for impregnating complex and composite product that fiber cloth is formed
Member, therefore, the superiority and inferiority of prepreg quality are largely fixed the final performance of composite material.The production work of prepreg at present
Skill mainly has solution dipping method (wet process) and sweat connecting method (dry method).
Wherein, solution dipping method prepares prepreg there are preparation sections the deficiencies such as many and diverse, preparation efficiency is low.On the one hand, molten
Liquid infusion process introduces a large amount of solvents in matrix resin, not only easily causes environmental pollution, endangers staff's health, and solvent
Volatilization so that resin content difficulty accurately controls, prepreg lot stability is poor.On the other hand, what solution dipping method obtained is prefabricated
Part easily forms gap, bubble when forming, and seriously affects the quality and performance of product.
And the prepreg volatile content of sweat connecting method preparation is very low, resin content is controllable, lot stability is good, can have
Effect avoids environmental pollution caused by the solvent of solution dipping method, and prepared composite material porosity is low, mechanical property is good,
Dimensional accuracy is high, becomes domestic and international research hotspot in recent years.Sweat connecting method require resin to have at room temperature it is good at
Film property can be arbitrarily bent, and can maintain the low viscosity of a period of time under infiltrating temperature, and can wetting fibre preform well.
Resin matrix used by sweat connecting method is mainly epoxy resin at present, and the film forming of phenolic resin is poor,
Bulk viscosity is larger, is often stored in the form of resin solution, limits it in the use of sweat connecting technique.
Summary of the invention
The purpose of the present invention is to provide a kind of heat molten type boron bakelite resins, solve existing boron bakelite resin film forming
Difference, the problem that brittleness is big, bulk viscosity is big, and solve the problems, such as that boron phenolic composite material porosity is high, it has obtained high-quality
The heat molten type boron bakelite resin material of retention rate is measured, while improving the heat resistance and its composite product of phenolic resin
Interlaminar strength and ablation performance of flushing.
The present invention also provides a kind of preparation methods of heat molten type boron bakelite resin.
To solve the above-mentioned problems, heat molten type boron bakelite resin provided by the invention, with molar ratio computing, including such as the following group
Point:
10~200 parts of phenol；
15~300 parts of aldehyde；
4~150 parts of boron-containing compound；
The heat molten type boron bakelite resin further includes modifying agent, toughener；The modifying agent, the toughener and the phenol
Dosage relation it is as follows:
100 parts by weight of phenol；
0~60 parts by weight of modifying agent；
0~40 parts by weight of toughener.
Preferably, the heat molten type boron bakelite resin is with molar ratio computing, including following component:
100 parts of phenol；
105~150 parts of aldehyde；
4~75 parts of boron-containing compound；
The heat molten type boron bakelite resin further includes modifying agent, toughener；The modifying agent, the toughener and the phenol
Dosage relation it is as follows:
100 parts by weight of phenol；
1~30 parts by weight of modifying agent；
0.5~20 parts by weight of toughener.
Preferably, the phenol is one or both of monohydric phenol, dihydric phenol；The monohydric phenol be phenol, o-cresol,
M-cresol, p-cresol, alpha-Naphthol, betanaphthol, to one of hydroxymethylphenol or a variety of；The dihydric phenol is adjacent benzene two
One of phenol, resorcinol, hydroquinone, bisphenol-A are a variety of.
The aldehyde is one of formaldehyde, acetaldehyde, metaformaldehyde, para-acetaldehyde, paraformaldehyde, butyraldehyde or a variety of；It is described
Formaldehyde includes the formalin that mass fraction is 36~45wt%；The acetaldehyde includes that the acetaldehyde that mass fraction is 40wt% is molten
Liquid.
Preferably, the boron-containing compound is boric acid, boronic acid derivatives；
The boronic acid derivatives include phenyl boric acid, boron oxide, borax, Boratex, methylol phenyl boric acid, hydroxyl phenyl boric acid,
Biphenylboronic acid, diphenyl-borinic acids, methylphenylboronic acid, dimethylphenyl boronic acid, benzyloxyphenylboronic acid, isopropylphenylboronic acid, ethoxy
Base phenyl boric acid, 1,4- benzene hypoboric acid, ethyl phenyl boric acid, butyl phenyl boric acid, 2,4,6- triphen boroxin, 3- hydroxyl phenyl boric acid,
Carboxybenzeneboronic acid, naphthalene boronic acids, dibromo phenyl boric acid, dichloro phenyl boric acid, luxuriant and rich with fragrance boric acid, anthracene boric acid, dihydroxy benzenes boric acid, pyrene boric acid, 4-
One of (1- naphthalene) phenyl boric acid, fluorobenzoic boric acid are a variety of.
Preferably, the modifying agent is graphene oxide, aluminium hydroxide, boric acid, boron oxide, wollastonite, zinc borate, benzene boron
One of acid, titanium dioxide, boron nitride, silica, glass powder, mica, clay are a variety of.
Preferably, the toughener is one of rubber elastomer, thermoplastic resin, thermosetting resin or a variety of.
The rubber elastomer is one of nbr carboxyl terminal, neoprene, ethylene propylene diene rubber or a variety of；
The thermoplastic resin is polyamide, in polyetherimide, Pioloform, polyvinyl acetal, polyether sulfone, amine terminated polyether
It is one or more；
The thermosetting resin is epoxy resin, cyanate ester resin, monocycle benzoxazine resin, bimaleimide resin
One of or it is a variety of.
The preparation method of heat molten type boron bakelite resin of the present invention, includes the following steps:
Phenol, boron-containing compound are taken by selected number, is uniformly mixed, is reacted at 120-200 DEG C, obtain intermediate product；
The aldehyde of selected number is added into the intermediate product again, after reacting 10-120min at 60-150 DEG C, is added is modified thereto
Agent, toughener, reaction terminate to obtain heat molten type boron bakelite resin.
Preferably, the preparation method of the heat molten type boron bakelite resin, includes the following steps:
(1) phenol is taken by selected number, the boron-containing compound of selected number is added in Xiang Suoshu phenol, is warming up to
120 DEG C -160 DEG C, 1-3h is reacted, temperature is then risen to 160 DEG C -180 DEG C, is reacted 2-4 hours；Temperature is risen to 180 again
DEG C -200 DEG C, reaction obtains the intermediate product；
(2) when the temperature of the intermediate product obtained in step (1) is 60 DEG C or less, the aldehyde is added thereto,
Obtained mixed liquor is warming up to boiling again, is flowed back under the conditions of boiling, flow back 10-80min；
(3) modifying agent is added in the mixed liquor into step (2) after reflux, is then evaporated under reduced pressure, is being evaporated under reduced pressure
In the process, the modifying agent is added into mixed liquor, reaction terminates to obtain heat molten type boron bakelite resin.
It is further preferred that the preparation method of the heat molten type boron bakelite resin, includes the following steps:
(1) phenol is taken by selected number, after the phenol is heated to melting, selected number is added under agitation
The boron-containing compound, be to slowly warm up to 140 DEG C, react 1-3 hours, be then gradually heated to 164 DEG C of reactions 2-4 hours；
It is gradually heated to 181 DEG C again, reaction obtains the intermediate product；
(2) when the temperature of the intermediate product obtained in step (1) is 60 DEG C or less, thereto by several times described in addition
Obtained mixed liquor is being to slowly warm up to reaction system boiling, flowed back under the conditions of boiling, flow back 10-60min by aldehyde；
(3) modifying agent is added in the mixed liquor into step (2) after reflux, then depressurizes desolventizing；Decompression dehydration
To temperature at 55-60 DEG C, the toughener is added, continues desolventizing, in temperature is 200 ± 1 DEG C in the product of desolventizing
Under the conditions of, when gel time reaches 80-250s, reaction terminates, and obtains the heat molten type boron bakelite resin.
Compared with the prior art, the present invention has the following beneficial effects:
(1) heat molten type boron bakelite resin of the present invention, including following component: phenol, aldehyde, boron-containing compound, modifying agent,
Toughener.Heat molten type boron bakelite resin of the present invention does not use catalyst when preparation, brings there is no catalyst is indivisible
Hidden danger；
(2) heat molten type boron bakelite resin of the present invention, by the addition of modifying agent, toughener, so that resin has
The chemical bond of rigid structure group and high bond energy, so that chemical bond is difficult to be broken, small molecule is difficult to crack and release, performance
Good high temperature resistant calcination performance out.Meanwhile so that the softening point of resin reduces, thus obtained resin does not glue at room temperature
Hand, not mucous membrane, good toughness solve the problems, such as that traditional boron bakelite resin resin film forming is poor, brittleness is big.Especially to contain aldehyde radical
Benzoxazine as plasticizer, the modifying agent be boron oxide, terephthalaldehyde, phenyl boric acid with the weight ratio mixing of 1:2:2 and
Cheng Shi, in the obtained heat molten type boron bakelite resin, there are the changes of the rigid structures such as more phenyl ring group and high bond energy
It learns key (such as B-O key), high temperature resistance is optimal.
(3) heat molten type boron bakelite resin of the present invention is free of solvent, overcomes boron bakelite resin in the prior art
Solvent in solution volatilize in composite material shaping process caused by the unstable quality of stomata and prepreg cloth lack
It falls into；It can be achieved to reduce the molding porosity of boron bakelite resin based composites, improve its interlaminar shear strength, improve its resistance to ablation
The effect of erosion；Also, its moulded manufacturability is good, high temperature resistant, anti-ablation, is a kind of high-performance matrix of advanced composite material
Resin is expected to be used for the high-tech sectors such as aerospace, and before the fields such as refractory material, precoated sand have good application
Scape.
Specific embodiment
The person that is not specified actual conditions in various embodiments of the present invention, carries out according to conventional conditions or manufacturer's recommended conditions.
Reagents or instruments used without specified manufacturer, being can be with conventional products that are commercially available.It is used in each embodiment
Raw material is that market is bought, different manufacturers, model raw material have no effect on the implementation and technical effect of technical solution of the present invention
It realizes.
Embodiment 1
The heat molten type boron bakelite resin of the present embodiment, with molar ratio computing, including following component: 10 parts of phenol；15 parts of aldehyde；Boracic
4 parts of compound.
Wherein, the phenol is monohydric phenol, and the monohydric phenol is phenol；The aldehyde is formaldehyde, and the formaldehyde is mass fraction
For the formalin of 36wt%；The boron-containing compound is boric acid.
The heat molten type boron bakelite resin further includes modifying agent, toughener；The modifying agent, the toughener and the phenol
Weight fraction ratio relationship are as follows:
Phenol: modifying agent: toughener=100:1:1.
Wherein, the modifying agent is graphene oxide；The toughener is rubber elastomer, and the rubber elastomer is end
Carboxy nitrile rubber.
Preparation method is as follows:
Phenol, boron-containing compound are taken by selected number, is uniformly mixed, is reacted at 120 DEG C, obtain intermediate product；Again to
The aldehyde of selected number is added in the intermediate product, after reacting 10min at 150 DEG C, modifying agent, toughener are added thereto,
Reaction terminates to obtain heat molten type boron bakelite resin.
It alternative implementation as the present embodiment, the phenol also can be replaced other monohydric phenols, o-cresol, first
Phenol, p-cresol, alpha-Naphthol, betanaphthol, to one of hydroxymethylphenol or a variety of；The aldehyde also can be replaced acetaldehyde,
One of metaformaldehyde, para-acetaldehyde, paraformaldehyde, butyraldehyde are a variety of；The boron-containing compound also can be replaced boric acid and spread out
Biology, the boronic acid derivatives are phenyl boric acid, boron oxide, borax, Boratex, methylol phenyl boric acid, hydroxyl phenyl boric acid, biphenyl boron
Acid, diphenyl-borinic acids, methylphenylboronic acid, dimethylphenyl boronic acid, benzyloxyphenylboronic acid, isopropylphenylboronic acid, ethoxybenzene boron
Acid, 1,4- benzene hypoboric acid, ethyl phenyl boric acid, butyl phenyl boric acid, 2,4,6- triphen boroxin, 3- hydroxyl phenyl boric acid, carboxyl benzene
Boric acid, naphthalene boronic acids, dibromo phenyl boric acid, dichloro phenyl boric acid, luxuriant and rich with fragrance boric acid, anthracene boric acid, dihydroxy benzenes boric acid, pyrene boric acid, 4- (1- naphthalene
Base) phenyl boric acid, one of fluorobenzoic boric acid or a variety of.
Similarly, it alternative implementation as the present embodiment, the modifying agent also can be replaced aluminium hydroxide, boron
Acid, boron oxide, wollastonite, zinc borate, phenyl boric acid, titanium dioxide, boron nitride, silica, glass powder, mica, one in clay
Kind；The toughener also can be replaced one of other rubber elastomers, neoprene, ethylene propylene diene rubber.
Embodiment 2
The heat molten type boron bakelite resin of the present embodiment, with molar ratio computing, including following component: 120 parts of phenol；300 parts of aldehyde；Contain
50 parts of boron compound；
Wherein, the phenol is dihydric phenol, and the dihydric phenol is catechol；The aldehyde is that mass fraction is 45wt%'s
Formalin；The boron-containing compound is boronic acid derivatives；The boronic acid derivatives are boron oxide.
The heat molten type boron bakelite resin further includes modifying agent, toughener；The modifying agent, the toughener and the phenol
Weight fraction ratio relationship are as follows:
Phenol: modifying agent: toughener=100:30:20.
The modifying agent is aluminium hydroxide；The toughener is thermoplastic resin, and the thermoplastic resin is polyamide resin
Rouge.
Preparation method is as follows:
Phenol, boron-containing compound are taken by selected number, is uniformly mixed, is reacted at 160 DEG C, obtain intermediate product；Again to
The aldehyde of selected number is added in the intermediate product, after reacting 120min at 60 DEG C, modifying agent, toughener are added thereto,
Reaction terminates to obtain heat molten type boron bakelite resin.
It alternative implementation as the present embodiment, the phenol also can be replaced other dihydric phenols, resorcinol, to benzene
One of diphenol, bisphenol-A are a variety of；The aldehyde also can be replaced one of acetaldehyde, metaformaldehyde, para-acetaldehyde, butyraldehyde
Or it is a variety of.
Similarly, it alternative implementation as the present embodiment, the modifying agent also can be replaced graphene oxide, hydrogen
Aluminium oxide, boron oxide, wollastonite, zinc borate, phenyl boric acid, titanium dioxide, boron nitride, silica, glass powder, mica, glues boric acid
One of soil is a variety of；The toughener also can be replaced other thermoplastic resins, polyetherimide resin, polyvinyl alcohol contracting
One of urea formaldehyde, polyethersulfone resin, amine terminated polyether resin are a variety of.
Embodiment 3
The heat molten type boron bakelite resin of the present embodiment, with molar ratio computing, including following component: 105 parts of phenol；190 parts of aldehyde；Contain
20 parts of boron compound.
Wherein, the phenol is that monohydric phenol and dihydric phenol are mixed according to the weight ratio of 1:2；The monohydric phenol is adjacent toluene
Phenol；The dihydric phenol is resorcinol；The aldehyde is the acetaldehyde solution that mass fraction is 40wt%；The boron-containing compound is boron
Acid derivative；The boronic acid derivatives are methylphenylboronic acid.
The heat molten type boron bakelite resin further includes modifying agent, toughener；The modifying agent, the toughener and the phenol
Weight fraction ratio relationship are as follows:
Phenol: modifying agent: toughener=100:30:10.
The modifying agent is phenyl boric acid；The toughener is thermosetting resin, and the thermosetting resin is epoxy resin.
Preparation method is as follows:
Phenol, boron-containing compound are taken by selected number, is uniformly mixed, is reacted at 200 DEG C, obtain intermediate product；Again to
The aldehyde of selected number is added in the intermediate product, after reacting 65min at 100 DEG C, modifying agent, toughener are added thereto,
Reaction terminates to obtain heat molten type boron bakelite resin.
It alternative implementation as the present embodiment, the phenol also can be replaced other monohydric phenols, dihydric phenol, by unitary
The phenol of phenol, o-cresol, m-cresol, p-cresol, alpha-Naphthol, betanaphthol, to the neighbour of hydroxymethylphenol or dihydric phenol
Benzenediol, resorcinol, hydroquinone, bisphenol-A are according to any than mixing；The aldehyde also can be replaced formaldehyde, paraformaldehyde, second
Aldehyde, metaformaldehyde, para-acetaldehyde, butyraldehyde are according to any than mixing.
Similarly, it alternative implementation as the present embodiment, the toughener also can be replaced other thermosetting property trees
Rouge, one of cyanate ester resin, bimaleimide resin or a variety of.
Embodiment 4
The heat molten type boron bakelite resin of the present embodiment, with molar ratio computing, including following component: 100 parts of phenol；110 parts of aldehyde；Contain
10 parts of boron compound.
Wherein, the phenol is that monohydric phenol and dihydric phenol are mixed according to the weight ratio of 3:2；The monohydric phenol is adjacent toluene
Phenol；The dihydric phenol is resorcinol；The aldehyde is the acetaldehyde solution that mass fraction is 40wt%；The boron-containing compound is boron
Acid derivative；The boronic acid derivatives are 2,4,6- triphen boroxin.
The heat molten type boron bakelite resin further includes modifying agent, toughener；The modifying agent, the toughener and the phenol
Weight fraction ratio relationship are as follows:
Phenol: modifying agent: toughener=100:15:0.5.
The modifying agent is that boron oxide and silica are mixed according to the weight ratio of 1:3；The toughener is rubber
Elastomer, the rubber elastomer are nbr carboxyl terminal.
Preparation method is as follows:
(1) phenol is taken by selected number, after the phenol is heated to melting, selected number is added under agitation
The boron-containing compound, be to slowly warm up to 140 DEG C, react 3 hours, be then gradually heated to 164 DEG C and react 2 hours；Again by
181 DEG C are gradually warming up to, reaction obtains the intermediate product；
(2) when the temperature of the intermediate product obtained in step (1) is 60 DEG C or less, thereto by several times described in addition
Obtained mixed liquor is being to slowly warm up to reaction system boiling, flowed back under the conditions of boiling, flow back 10-60min by aldehyde；
(3) modifying agent is added in the mixed liquor into step (2) after reflux, then depressurizes desolventizing；Decompression dehydration
To temperature at 60 DEG C, the toughener is added, continues desolventizing, the condition for being 200 ± 1 DEG C in temperature in the product of desolventizing
Under, when gel time reaches 80s, reaction terminates, and obtains the heat molten type boron bakelite resin.
Embodiment 5
The heat molten type boron bakelite resin of the present embodiment, with molar ratio computing, including following component: 100 parts of phenol；130 parts of aldehyde；Contain
25 parts of boron compound.
Wherein, the phenol is that monohydric phenol and dihydric phenol are mixed according to the weight ratio of 3:2；The monohydric phenol is adjacent toluene
Phenol and alpha-Naphthol are mixed according to the weight ratio of 1:3；The dihydric phenol is bisphenol-A；The aldehyde is the formalin of 36wt%；
The boron-containing compound is boronic acid derivatives；The boronic acid derivatives be biphenylboronic acid, diphenyl-borinic acids according to 1:4 weight ratio
It is mixed into.
The heat molten type boron bakelite resin further includes modifying agent, toughener；The modifying agent, the toughener and the phenol
Weight fraction ratio relationship are as follows:
Phenol: modifying agent: toughener=100:15:10.
The modifying agent is glass powder, mica, clay are mixed according to the weight ratio of 1:3:3；The toughener is heat
Plastic resin, the thermoplastic resin are polyether sulfone.
Preparation method is as follows:
(1) phenol is taken by selected number, after the phenol is heated to melting, selected number is added under agitation
The boron-containing compound, be to slowly warm up to 140 DEG C, react 1 hour, be then gradually heated to 164 DEG C and react 4 hours；Again by
181 DEG C are gradually warming up to, reaction obtains the intermediate product；
(2) when the temperature of the intermediate product obtained in step (1) is 60 DEG C or less, thereto by several times described in addition
Obtained mixed liquor is being to slowly warm up to reaction system boiling, flowed back under the conditions of boiling, flow back 60min by aldehyde；
(3) modifying agent is added in the mixed liquor into step (2) after reflux, then depressurizes desolventizing；Decompression dehydration
To temperature at 60 DEG C, the toughener is added, continues desolventizing, the condition for being 200 ± 1 DEG C in temperature in the product of desolventizing
Under, when gel time reaches 250s, reaction terminates, and obtains the heat molten type boron bakelite resin.
Embodiment 6
The heat molten type boron bakelite resin of the present embodiment, with molar ratio computing, including following component: 100 parts of phenol；120 parts of aldehyde；Contain
30 parts of boron compound.
Wherein, the phenol is phenol；The aldehyde is paraformaldehyde；The boron-containing compound is boric acid.
The heat molten type boron bakelite resin further includes modifying agent, toughener；The modifying agent, the toughener and the phenol
Weight fraction ratio relationship are as follows:
Phenol: modifying agent: toughener=100:15:10.
The modifying agent is boron oxide；The toughener is rubber elastomer, and the rubber elastomer is carboxyl end group butyronitrile
Rubber.
Preparation method is as follows:
(1) phenol is taken by selected number, after the phenol is heated to melting, selected number is added under agitation
The boron-containing compound, be to slowly warm up to 140 DEG C, react 2 hours, be then gradually heated to 164 DEG C and react 3 hours；Again by
181 DEG C are gradually warming up to, reaction obtains the intermediate product；
(2) when the temperature of the intermediate product obtained in step (1) is 60 DEG C or less, thereto by several times described in addition
Obtained mixed liquor is being to slowly warm up to reaction system boiling, flowed back under the conditions of boiling, flow back 30min by aldehyde；
(3) modifying agent is added in the mixed liquor into step (2) after reflux, then depressurizes desolventizing；Decompression dehydration
To temperature at 60 DEG C, the toughener is added, continues desolventizing, the condition for being 200 ± 1 DEG C in temperature in the product of desolventizing
Under, when gel time reaches 150s, reaction terminates, and obtains the heat molten type boron bakelite resin.
Embodiment 7
The heat molten type boron bakelite resin of the present embodiment, including following component: phenol 956g；Aldehyde 363g；Boron-containing compound 93g；
Modifying agent 10g；The toughener 5g.
Wherein, the phenol is phenol；The aldehyde is paraformaldehyde；The boron-containing compound is boric acid；The modifying agent is
Graphene oxide；The toughener is polyvinyl butyral.
Preparation method is as follows:
First the phenol 956g of melting is added in flask, boric acid 93g is added while stirring, it is slow with the rate of 0.5 DEG C/min
Slowly 140 DEG C are warming up to, are then gradually heated to 164 DEG C with the rate of 0.2 DEG C/min, then gradually rise with the rate of 0.1 DEG C/min
For temperature to 181 DEG C, control column head temperature is no more than 98 DEG C, collects fraction, the stopping when fraction weight reaches 0.2 times of phenol weight
Heating, discards fraction.It is cooled to 60 DEG C；The total 363g of paraformaldehyde is added into flask in two times, control heating rate is 0.2
DEG C/min, 110 DEG C or more are to slowly warm up to, is flowed back until reaction system comes to life；Cool down after reflux 20-25min, is added
10g graphene oxide starts decompression dehydration, and when the temperature of desolventizing reaches 54~57 DEG C, 5g polyvinyl alcohol contracting fourth is added
Aldehyde continues to vacuumize desolventizing.Terminate when the gel time of reaction system reaches 110-120s (200 ± 1 DEG C) and then reacts, i.e.,
The heat molten type boron bakelite resin can be obtained.
Embodiment 8
The heat molten type boron bakelite resin of the present embodiment, including following component: phenol 551g；Aldehyde 363g；Boron-containing compound 61g；
Modifying agent 11g；The toughener 15g.
Wherein, the phenol is resorcinol；The aldehyde is the formalin of 37wt%；The boron-containing compound is benzene boron
Acid；The modifying agent is aluminium hydroxide；The toughener is epoxy resin E51.
Preparation method is as follows:
First resorcinol 551g is added in flask, phenyl boric acid 61g is added while stirring, it is slow with the rate of 0.5 DEG C/min
Slowly 140 DEG C are warming up to, are then gradually heated to 164 DEG C with the rate of 0.2 DEG C/min, then gradually rise with the rate of 0.1 DEG C/min
For temperature to 181 DEG C, control column head temperature is no more than 98 DEG C, collects fraction, the stopping when fraction weight reaches 0.2 times of phenol weight
Heating, discards fraction.It is cooled to 60 DEG C；The total 892g of formalin of 37wt%, control heating speed is added into flask in two times
Degree is 0.2 DEG C/min, is to slowly warm up to 110 DEG C or more, flows back until reaction system comes to life；It is dropped after reflux 10-15min
11g aluminium hydroxide is added in temperature, starts decompression dehydration, and when the temperature of desolventizing reaches 58~63 DEG C, 15g epoxy resin is added
E51 continues to vacuumize desolventizing.Terminate when the gel time of reaction system reaches 190-200s (200 ± 1 DEG C) and then reacts, i.e.,
The heat molten type boron bakelite resin can be obtained.
Embodiment 9
The present embodiment and the ingredient in embodiment 6 are completely the same, and difference is only that: by the modifying agent by boron oxide, replacing
It is changed to boron oxide, terephthalaldehyde, phenyl boric acid to mix with the weight ratio of 3:2:2, and uses method system in the same manner as in Example 6
It is standby.
Embodiment 10
The present embodiment and the ingredient in embodiment 6 are completely the same, and difference is only that: the modifying agent is replaced by boron oxide
For boron oxide: terephthalaldehyde: phenyl boric acid=1:2:2 weight ratio mixes, and uses method in the same manner as in Example 6
Preparation.
Embodiment 11
The present embodiment and the ingredient in embodiment 10 are completely the same, and difference is only that: the toughener is by carboxyl end group butyronitrile
Rubber replaces with monocycle benzoxazine resin, and the monocycle benzoxazine is benzoxazine containing aldehyde radical, and using in embodiment 6
Identical method preparation.
Comparative example 1
The benzoxazine resin of this comparative example and the ingredient in embodiment 7 are completely the same, and difference is only that: not including described
Modifying agent, toughener, and prepared using method in the same manner as in Example 7.
Comparative example 2
The benzoxazine resin of this comparative example and the ingredient in embodiment 7 are completely the same, and difference is only that: not including described
Modifying agent, and prepared using method in the same manner as in Example 7.
Comparative example 3
The benzoxazine resin of this comparative example and the ingredient in embodiment 7 are completely the same, and difference is only that: not including described
Toughener, and prepared using method in the same manner as in Example 7.
Effete test embodiment
For the technical effect for verifying heat molten type boron bakelite resin of the present invention, made in Example 1-11, comparative example 1-3
Standby obtained boron bakelite resin, is tested as follows:
Boron bakelite resin to be measured is tested by thermal weight loss (TGA), carbon yield is tested at 800 DEG C, and calculate carbon yield.
It is specific as follows: resin to be placed in air dry oven, 90 DEG C of heat preservation 1h, then 140 DEG C of heat preservation 1h, last 180 DEG C of heat preservation 4h solidification.
Phenolic resin after solidification smashes it through 100 mesh sieve in pulverizer, is collected as thermal weight loss (TGA) laboratory sample.TGA is surveyed
800 DEG C are risen to the heating rate of 10 DEG C/min when examination, nitrogen flow 35mL/min.
Boron bakelite resin to be measured is taken, using rotary viscosity design determining viscosity, and records result.
Boron bakelite resin to be measured is taken, film-forming temperature is measured using conventional method.
Boron bakelite resin to be measured is taken, is bent at room temperature with hand, and records room temperature film toughness.
Its experimental result is as follows:
It should be noted that carbon yield is higher, heat-resisting quantity is better.It can be seen that heat molten type boron phenol of the present invention
Urea formaldehyde has good heat resistance energy.Heat molten type boron bakelite resin storage stability of the present invention is good, working life is long, viscosity
It is suitable for that, especially using monocycle benzoxazine resin as plasticizer, the modifying agent is boron oxide, terephthalaldehyde, phenyl boric acid
The embodiment 11 mixed with the weight ratio of 1:2:2, effect is optimal.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or
It changes still within the protection scope of the invention.
Claims (10)
1. a kind of heat molten type boron bakelite resin, which is characterized in that with molar ratio computing, including following component:
10~200 parts of phenol；
15~300 parts of aldehyde；
4~150 parts of boron-containing compound；
The heat molten type boron bakelite resin further includes modifying agent, toughener；The use of the modifying agent, the toughener and the phenol
Magnitude relation is as follows:
100 parts by weight of phenol；
0~60 parts by weight of modifying agent；
0~40 parts by weight of toughener.
2. heat molten type boron bakelite resin according to claim 1, which is characterized in that with molar ratio computing, including following component:
100 parts of phenol；
105~150 parts of aldehyde；
4~75 parts of boron-containing compound；
The heat molten type boron bakelite resin further includes modifying agent, toughener；The use of the modifying agent, the toughener and the phenol
Magnitude relation is as follows:
100 parts by weight of phenol；
1~30 parts by weight of modifying agent；
0.5~20 parts by weight of toughener.
3. according to claim 1 or heat molten type boron bakelite resin described in 2, it is characterised in that:
The phenol is one or both of monohydric phenol, dihydric phenol；The monohydric phenol is phenol, o-cresol, m-cresol, right
Cresols, alpha-Naphthol, betanaphthol, to one of hydroxymethylphenol or a variety of；The dihydric phenol is catechol, isophthalic two
One of phenol, hydroquinone, bisphenol-A are a variety of.
4. according to claim 1 or heat molten type boron bakelite resin described in 2, it is characterised in that: the aldehyde be formaldehyde, acetaldehyde,
One of metaformaldehyde, para-acetaldehyde, paraformaldehyde, butyraldehyde are a variety of；The formaldehyde include mass fraction be 36~
The formalin of 45wt%；The acetaldehyde includes the acetaldehyde solution that mass fraction is 40wt%.
5. according to claim 1 or heat molten type boron bakelite resin described in 2, it is characterised in that:
The boron-containing compound is boric acid, boronic acid derivatives；
The boronic acid derivatives include phenyl boric acid, boron oxide, borax, Boratex, methylol phenyl boric acid, hydroxyl phenyl boric acid, biphenyl
Boric acid, diphenyl-borinic acids, methylphenylboronic acid, dimethylphenyl boronic acid, benzyloxyphenylboronic acid, isopropylphenylboronic acid, ethoxybenzene
Boric acid, 1,4- benzene hypoboric acid, ethyl phenyl boric acid, butyl phenyl boric acid, 2,4,6- triphen boroxin, 3- hydroxyl phenyl boric acid, carboxyl
Phenyl boric acid, naphthalene boronic acids, dibromo phenyl boric acid, dichloro phenyl boric acid, luxuriant and rich with fragrance boric acid, anthracene boric acid, dihydroxy benzenes boric acid, pyrene boric acid, 4- (1- naphthalene
Base) phenyl boric acid, one of fluorobenzoic boric acid or a variety of.
6. according to claim 1 or heat molten type boron bakelite resin described in 2, it is characterised in that:
The modifying agent be graphene oxide, aluminium hydroxide, boric acid, boron oxide, wollastonite, zinc borate, phenyl boric acid, titanium dioxide,
One of boron nitride, silica, glass powder, mica, clay are a variety of.
7. according to claim 1 or heat molten type boron bakelite resin described in 2, it is characterised in that:
The toughener is one of rubber elastomer, thermoplastic resin, thermosetting resin or a variety of.
8. heat molten type boron bakelite resin according to claim 7, it is characterised in that:
The rubber elastomer is one of nbr carboxyl terminal, neoprene, ethylene propylene diene rubber or a variety of；
The thermoplastic resin is one of polyamide, polyetherimide, Pioloform, polyvinyl acetal, polyether sulfone, amine terminated polyether
Or it is a variety of；
The thermosetting resin is epoxy resin, in cyanate ester resin, monocycle benzoxazine resin, bimaleimide resin
It is one or more.
9. the preparation method of heat molten type boron bakelite resin described in a kind of any one of claim 1-8, which is characterized in that packet
Include following steps:
Phenol, boron-containing compound are taken by selected number, is uniformly mixed, is reacted at 120-200 DEG C, obtain intermediate product；Again to
The aldehyde of selected number is added in the intermediate product, after reacting 10-120min at 60-150 DEG C, be added thereto modifying agent,
Toughener, reaction terminate to obtain heat molten type boron bakelite resin.
10. the preparation method of heat molten type boron bakelite resin according to claim 9, which comprises the steps of:
(1) phenol is taken by selected number, after the phenol is heated to melting, the institute of selected number is added under agitation
Boron-containing compound is stated, is to slowly warm up to 140 DEG C, reacts 1-3 hours, is then gradually heated to 164 DEG C of reactions 2-4 hours；Again by
181 DEG C are gradually warming up to, reaction obtains the intermediate product；
(2) when the temperature of the intermediate product obtained in step (1) is 60 DEG C or less, the aldehyde is added by several times thereto,
Obtained mixed liquor is being to slowly warm up to reaction system boiling, is being flowed back under the conditions of boiling, flow back 10-60min；
(3) modifying agent is added in the mixed liquor into step (2) after reflux, then depressurizes desolventizing；Decompression dehydration is to temperature
The toughener is added at 55-60 DEG C in degree, continues desolventizing, the condition for being 200 ± 1 DEG C in temperature in the product of desolventizing
Under, when gel time reaches 80-250s, reaction terminates, and obtains the heat molten type boron bakelite resin.
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Application publication date: 20190312 |