CN117903387A - Low-free aldehyde hot-melt boron phenolic resin and preparation method thereof - Google Patents
Low-free aldehyde hot-melt boron phenolic resin and preparation method thereof Download PDFInfo
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- CN117903387A CN117903387A CN202410070770.7A CN202410070770A CN117903387A CN 117903387 A CN117903387 A CN 117903387A CN 202410070770 A CN202410070770 A CN 202410070770A CN 117903387 A CN117903387 A CN 117903387A
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- Prior art keywords
- phenolic resin
- hot melt
- phenol
- acid
- aldehyde
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- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 91
- 239000005011 phenolic resin Substances 0.000 title claims abstract description 91
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 90
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 88
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 239000012943 hotmelt Substances 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 title abstract 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 100
- 239000003607 modifier Substances 0.000 claims abstract description 52
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 150000001639 boron compounds Chemical class 0.000 claims abstract description 46
- 239000012745 toughening agent Substances 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 30
- 238000003756 stirring Methods 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 5
- 238000005979 thermal decomposition reaction Methods 0.000 claims abstract description 5
- 238000001879 gelation Methods 0.000 claims abstract description 3
- 238000004519 manufacturing process Methods 0.000 claims abstract 2
- 150000001299 aldehydes Chemical class 0.000 claims description 112
- 238000010438 heat treatment Methods 0.000 claims description 48
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 238000002156 mixing Methods 0.000 claims description 20
- 239000003822 epoxy resin Substances 0.000 claims description 17
- 229920000647 polyepoxide Polymers 0.000 claims description 17
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 12
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 12
- 229920002866 paraformaldehyde Polymers 0.000 claims description 12
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 11
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 10
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-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
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 229920000459 Nitrile rubber Polymers 0.000 claims description 7
- 239000004327 boric acid Substances 0.000 claims description 7
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 claims description 6
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 claims description 6
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 claims description 6
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 6
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims description 6
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 6
- XIWMTQIUUWJNRP-UHFFFAOYSA-N amidol Chemical compound NC1=CC=C(O)C(N)=C1 XIWMTQIUUWJNRP-UHFFFAOYSA-N 0.000 claims description 6
- 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 6
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 6
- 229910021538 borax Inorganic materials 0.000 claims description 6
- MIHINWMALJZIBX-UHFFFAOYSA-N cyclohexa-2,4-dien-1-ol Chemical compound OC1CC=CC=C1 MIHINWMALJZIBX-UHFFFAOYSA-N 0.000 claims description 6
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 6
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical group C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 claims description 5
- JHKKTXXMAQLGJB-UHFFFAOYSA-N 2-(methylamino)phenol Chemical compound CNC1=CC=CC=C1O JHKKTXXMAQLGJB-UHFFFAOYSA-N 0.000 claims description 5
- 229920000877 Melamine resin Polymers 0.000 claims description 5
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 5
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 claims description 5
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 4
- BVJSUAQZOZWCKN-UHFFFAOYSA-N p-hydroxybenzyl alcohol Chemical compound OCC1=CC=C(O)C=C1 BVJSUAQZOZWCKN-UHFFFAOYSA-N 0.000 claims description 4
- 229920001084 poly(chloroprene) Polymers 0.000 claims description 4
- YVCYOVLYYZRNJC-UHFFFAOYSA-N (2-methoxyphenoxy)boronic acid Chemical compound COC1=CC=CC=C1OB(O)O YVCYOVLYYZRNJC-UHFFFAOYSA-N 0.000 claims description 3
- HTGQCLJTWPSFNL-UHFFFAOYSA-N (2-methylphenoxy)boronic acid Chemical compound CC1=CC=CC=C1OB(O)O HTGQCLJTWPSFNL-UHFFFAOYSA-N 0.000 claims description 3
- BODYVHJTUHHINQ-UHFFFAOYSA-N (4-boronophenyl)boronic acid Chemical compound OB(O)C1=CC=C(B(O)O)C=C1 BODYVHJTUHHINQ-UHFFFAOYSA-N 0.000 claims description 3
- 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 description 3
- 239000004471 Glycine Substances 0.000 claims description 3
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004472 Lysine Substances 0.000 claims description 3
- ONIBWKKTOPOVIA-UHFFFAOYSA-N Proline Natural products OC(=O)C1CCCN1 ONIBWKKTOPOVIA-UHFFFAOYSA-N 0.000 claims description 3
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 claims description 3
- 235000018417 cysteine Nutrition 0.000 claims description 3
- VIGVRXYWWFPORY-UHFFFAOYSA-N diphenylborinic acid Chemical compound C=1C=CC=CC=1B(O)C1=CC=CC=C1 VIGVRXYWWFPORY-UHFFFAOYSA-N 0.000 claims description 3
- 239000004328 sodium tetraborate Substances 0.000 claims description 3
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 claims description 3
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-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 2
- LEIMAOPMKTZEOV-UHFFFAOYSA-N (2-ethoxyphenoxy)boronic acid Chemical compound CCOC1=CC=CC=C1OB(O)O LEIMAOPMKTZEOV-UHFFFAOYSA-N 0.000 claims description 2
- QOCQQHJSBRCCRA-UHFFFAOYSA-N (2-ethylphenoxy)boronic acid Chemical compound CCC1=CC=CC=C1OB(O)O QOCQQHJSBRCCRA-UHFFFAOYSA-N 0.000 claims description 2
- SCWWDULYYDFWQV-UHFFFAOYSA-N (2-hydroxyphenoxy)boronic acid Chemical compound OB(O)OC1=CC=CC=C1O SCWWDULYYDFWQV-UHFFFAOYSA-N 0.000 claims description 2
- KURAGAVGYIBBFR-UHFFFAOYSA-N (2-propan-2-ylphenoxy)boronic acid Chemical compound CC(C)C1=CC=CC=C1OB(O)O KURAGAVGYIBBFR-UHFFFAOYSA-N 0.000 claims description 2
- CVISDVLTGPAQGC-UHFFFAOYSA-N (3-hydroxyphenoxy)boronic acid Chemical compound OB(O)OC1=CC=CC(O)=C1 CVISDVLTGPAQGC-UHFFFAOYSA-N 0.000 claims description 2
- VOXXGUAZBWSUSS-UHFFFAOYSA-N 2,4,6-triphenyl-1,3,5,2,4,6-trioxatriborinane Chemical compound O1B(C=2C=CC=CC=2)OB(C=2C=CC=CC=2)OB1C1=CC=CC=C1 VOXXGUAZBWSUSS-UHFFFAOYSA-N 0.000 claims description 2
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 2
- ONIBWKKTOPOVIA-BYPYZUCNSA-N L-Proline Chemical compound OC(=O)[C@@H]1CCCN1 ONIBWKKTOPOVIA-BYPYZUCNSA-N 0.000 claims description 2
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- KXLYRTSEXNEABR-UHFFFAOYSA-N [2-(hydroxymethyl)phenoxy]boronic acid Chemical compound OCC1=CC=CC=C1OB(O)O KXLYRTSEXNEABR-UHFFFAOYSA-N 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
- 239000002253 acid Substances 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims 2
- 229920005989 resin Polymers 0.000 abstract description 38
- 239000011347 resin Substances 0.000 abstract description 38
- 239000000203 mixture Substances 0.000 abstract description 26
- 230000008569 process Effects 0.000 abstract description 13
- 238000002679 ablation Methods 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 239000011819 refractory material Substances 0.000 abstract description 3
- 230000002265 prevention Effects 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 238000004821 distillation Methods 0.000 description 23
- 239000013067 intermediate product Substances 0.000 description 22
- 238000012360 testing method Methods 0.000 description 16
- 239000002131 composite material Substances 0.000 description 15
- 239000000843 powder Substances 0.000 description 13
- 239000007788 liquid Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 238000010992 reflux Methods 0.000 description 6
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 238000000518 rheometry Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- PZRPBPMLSSNFOM-UHFFFAOYSA-N [4-(hydroxymethyl)phenyl]boronic acid Chemical compound OCC1=CC=C(B(O)O)C=C1 PZRPBPMLSSNFOM-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- -1 aldehyde boron phenolic aldehyde Chemical class 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 229950011260 betanaphthol Drugs 0.000 description 2
- LYTDAPQDKKIENM-UHFFFAOYSA-N butoxy(phenyl)borinic acid Chemical compound CCCCOB(O)C1=CC=CC=C1 LYTDAPQDKKIENM-UHFFFAOYSA-N 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- ZYYANAWVBDFAHY-UHFFFAOYSA-N (2,3-dimethylphenyl)boronic acid Chemical compound CC1=CC=CC(B(O)O)=C1C ZYYANAWVBDFAHY-UHFFFAOYSA-N 0.000 description 1
- DGFCTCGCMKEILT-UHFFFAOYSA-N (2-ethoxyphenyl)boronic acid Chemical compound CCOC1=CC=CC=C1B(O)O DGFCTCGCMKEILT-UHFFFAOYSA-N 0.000 description 1
- KTZUVUWIBZMHMC-UHFFFAOYSA-N (2-propan-2-ylphenyl)boronic acid Chemical compound CC(C)C1=CC=CC=C1B(O)O KTZUVUWIBZMHMC-UHFFFAOYSA-N 0.000 description 1
- WFWQWTPAPNEOFE-UHFFFAOYSA-N (3-hydroxyphenyl)boronic acid Chemical compound OB(O)C1=CC=CC(O)=C1 WFWQWTPAPNEOFE-UHFFFAOYSA-N 0.000 description 1
- YYXFJSDMOVHLMJ-UHFFFAOYSA-N (4-hydroxyphenoxy)boronic acid Chemical compound OB(O)OC1=CC=C(O)C=C1 YYXFJSDMOVHLMJ-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001638 boron Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000000151 cysteine group Chemical group N[C@@H](CS)C(=O)* 0.000 description 1
- OFYFDTQMBRUJHN-UHFFFAOYSA-N ethoxy(phenyl)borinic acid Chemical compound CCOB(O)C1=CC=CC=C1 OFYFDTQMBRUJHN-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- LBBMOAOCCQOIAQ-UHFFFAOYSA-N methoxy(phenyl)borinic acid Chemical compound COB(O)C1=CC=CC=C1 LBBMOAOCCQOIAQ-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Landscapes
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The invention discloses a low free aldehyde hot melt boron phenolic resin and a preparation method thereof, wherein phenol is heated to be molten, boron compound is added under stirring, the mixture is uniformly mixed, the pH is regulated to 7-8, the mixture is heated to 100-180 ℃ for reaction for 3-7 h, aldehyde is added, the mixture is heated to 80-120 ℃ for polycondensation reaction for 2-9 h, modifier is added, and reduced pressure water removal is carried out after the reaction; finally adding the toughening agent, stirring uniformly, vacuum dehydrating, and performing gelation at 180+/-1 ℃ for 150-300 s. The synthesis method of the hot melt boron phenolic resin prepared by the invention is simple, the reaction is stable and controllable, the content of free aldehyde is reduced, and the initial thermal decomposition temperature of the resin cured product is improved; the hot melt boron phenolic resin has good film forming property, can keep low viscosity for a long time at the coating temperature, is suitable for the production of the process environment-friendly large-scale hot melt prepreg, and has good application prospect in the fields of ablation heat prevention, refractory materials and the like.
Description
Technical Field
The invention belongs to the technical field of phenolic resin preparation, and particularly relates to a low free aldehyde hot melt boron phenolic resin and a preparation method thereof.
Background
The boron phenolic resin has a series of excellent performances such as high temperature resistance, high carbon residue, excellent dimensional stability, low smoke toxicity and the like, is the most commonly used ablative heat-resistant composite matrix resin in the aerospace field, and is also widely applied to the fields of buildings (heat preservation and heat insulation materials), transportation (airplanes, high-speed train interior trim parts), metallurgy (refractory materials) and the like. Traditional boron phenolic resins are polymeric compounds prepared from phenol, aqueous formaldehyde and boric acid by a series of chemical reaction processes. Due to the low reactivity of boric acid, the synthesis conditions are more severe, the synthesis temperature of phenol and boric acid in patent CN 109467662a is up to 180 ℃, and the free aldehyde content of the boron phenolic resin is higher due to the conversion rate of monomers during the synthesis process. The presence of free aldehyde and unremoved aqueous solution can affect the forming process of the composite material, and can easily form air holes in the composite material, resulting in high porosity and poor composite quality of the composite material.
To solve the problem of excessive free aldehyde content in the boron phenolic resin. The most commonly used method is to add ammonia modifiers such as urea into the system in the later reaction stage, so that the content of free aldehyde in the resin can be effectively reduced, but most of the used additives are not suitable for high-temperature application, and the thermal performance of the resin is damaged after the additives are added.
Compared with the solution impregnation method (wet method), the hot-melt prepreg method (dry method) has the advantages of low volatile content, controllable resin content and good batch stability, and the prepared composite material has the advantages of low porosity, good mechanical property and good dimensional stability. The hot melt prepreg method requires that the resin has good moldability at room temperature and can be bent arbitrarily, and can maintain a low viscosity for a long period of time at a melting temperature.
The traditional boron phenolic resin has low molecular weight and high viscosity, and is not easy to form a film. At the melting temperature, the viscosity of the resin is rapidly increased, the resin is easy to gel, the film is brittle, slag is easy to fall off, and the requirements of a hot melting prepreg process are difficult to meet.
In view of this, there is a strong need for an improved method for preparing boron resins that optimizes the synthesis process, simplifies the synthesis steps, and meets the requirements of low free aldehyde content and hot melt processing process to meet the broader application of boron phenolic resins.
Disclosure of Invention
The invention aims to solve the technical problems that the free aldehyde content is high, the boron phenolic resin is high in brittleness and poor in film forming property, and the requirements of a hot melt prepreg process are difficult to meet, and the invention aims to provide a low free aldehyde hot melt boron phenolic resin and a preparation method thereof.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a preparation method of low free aldehyde hot melt boron phenolic resin comprises the following steps:
Heating phenol to be molten, adding a boron compound under stirring, uniformly mixing, adjusting the pH to 7-8, heating to 100-180 ℃ for reaction for 3-7 h, adding aldehyde, heating to 80-120 ℃ for polycondensation reaction for 2-9 h, adding a modifier, and carrying out reduced pressure water removal after reaction; finally adding a toughening agent, uniformly stirring, vacuum dehydrating, and performing gelation at 180+/-1 ℃ for 150-300 s to obtain the low free aldehyde hot melt boron phenolic resin.
Further, the molar ratio of phenol, aldehyde and boron compound is 10-200: 12-300: 1-40; the mass ratio of the phenol, the modifier and the toughening agent is 100: 5-40: 5 to 40.
Further, the molar ratio of phenol, aldehyde to boron compound is 100: 120-140: 10 to 30 percent; the mass ratio of the phenol, the modifier and the toughening agent is 100: 5-15: 5 to 10.
Further, one or more of NaOH, NH 3·H2 O and Ba (OH) 2 are adopted to adjust the pH value to 7-8.
Further, the phenol is one or two of monohydric phenol and dihydric phenol; the aldehyde is one or more of butyraldehyde, glutaraldehyde, trioxymethylene and paraformaldehyde.
Further, the monophenol is one or more of phenol, o-cresol, m-cresol, p-cresol, alpha-naphthol, beta-naphthol and 4-hydroxymethyl phenol; the dihydric phenol is one or more of catechol, resorcinol, hydroquinone, bisphenol A and bisphenol F.
Further, the boron compound is boric acid or a boric acid derivative.
Further, the boric acid derivative is one or more of phenylboric acid, hydroxymethylphenylboric acid, hydroxyphenylboric acid, biphenylboric acid, borax, sodium borate, diphenylboric acid, methylphenylboric acid, dimethylbenzeneboric acid, methoxyphenylboric acid, isopropylphenylboric acid, ethoxyphenylboric acid, 1, 4-phenyldiboronic acid, ethylphenylboric acid, butylphenylboric acid, 2,4, 6-triphenylboroxine and 3-hydroxyphenylboric acid.
Further, the modifier is one or more of aniline, o-aminophenol, melamine, urea, 2-methylaminophenol, 2, 4-diaminophenol, glycine, lysine, proline and cysteine;
the toughening agent is one or more of carboxyl-terminated nitrile rubber, amino-terminated nitrile rubber, chloroprene rubber, polyvinyl acetal, polyamide, epoxy resin E 20, epoxy resin E 44, epoxy resin E 51, epoxy resin F 44 and epoxy resin F 51.
The low free aldehyde hot-melt boron phenolic resin prepared according to the method has the free aldehyde content of 0.9-2.5%, the low viscosity window of 75-160 ℃, the carbon residue rate of 67.9-69.8% and the thermal decomposition temperature T 5％ of 398-455 ℃.
Compared with the prior art, the invention has the following beneficial effects:
According to the invention, firstly, phenolic substances and higher-activity boron compounds react under milder reaction conditions to achieve the purpose of introducing the boron-containing compounds, and then, polycondensation reaction is carried out, so that the problems of overlarge viscosity and easy-to-explode poly-gel in the later reaction period of the traditional phenolic boron-phenolic resin are overcome, and the reaction is stable and controllable; then adopting a modifier with a heat stability group to consume free aldehyde in the system; and introducing a modifier in the in-situ synthesis process of the boron phenolic resin, and then heating to reduce pressure for removing water, so that the content of free aldehyde in the boron phenolic resin is effectively reduced, and a reaction product of the modifier and the free aldehyde with an active reaction group can be well fused into a chain segment of the boron phenolic resin, the carbon residue rate of the modified resin at 800 ℃ is basically unchanged, the initial thermal decomposition temperature of a resin cured product is improved, and the forming process of the composite material is not influenced. And finally, the toughening agent is directly added under the condition of resin melting in the later stage of in-situ synthesis, so that the synthesis steps are simplified. The toughening agent is combined with low free aldehyde boron phenolic aldehyde to prepare low free aldehyde hot melt boron phenolic aldehyde suitable for ablation composite materials, the problems of poor film forming property and large brittleness of traditional boron phenolic resin are effectively solved, the obtained resin is not sticky at room temperature, does not remove slag, is bendable, can keep low viscosity for a long time at the temperature of a coating film, and is suitable for a hot melt prepreg process. The method for synthesizing the hot-melt boron phenolic resin is simple, stable and controllable in reaction, environment-friendly in process, suitable for large-scale production, and particularly has good application prospects in the fields of ablation heat prevention, refractory materials and the like.
Further, the amount of the boron compound added affects the heat resistance of the resin, so that the molar ratio of phenol, aldehyde and boron compound used in the present invention is 10 to 200: 12-300: 1 to 40.
Furthermore, the addition amount of the modifier has a larger influence, the reduction of free aldehyde is limited when a small amount of modifier is added, and the heat resistance of the resin is influenced when the modifier is excessively added, so that the mass ratio of phenol, the modifier and the toughening agent is 100: 5-40: 5 to 40.
Drawings
FIG. 1 is a TGA curve of the cured boron phenolic resin of example 8 and comparative example 1 of the present invention under nitrogen atmosphere;
Fig. 2 is a graph of the temperature change rheology of the boron phenolic resins of example 8 and comparative example 1 of the present invention at constant shear frequency (ω=1 rad·s -1) and strain (γ=1%);
Fig. 3 is a graph of mechanical data for carbon fiber composites prepared from the boron phenolic resins of example 8 and comparative example 1 of the present invention.
Detailed Description
In order that the invention may be readily understood, a more complete description of the invention will be rendered by reference to the appended drawings. The drawings illustrate preferred embodiments of the invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
The preparation method of the low free aldehyde hot melt boron phenolic resin comprises the following steps:
(1) Heating phenol to be molten, adding a boron compound under the stirring condition, uniformly mixing, adjusting the pH value to 7-8, heating to 100-180 ℃ and reacting for 3-7 h;
(2) Adding aldehyde when the temperature of the product obtained in the step (1) is reduced to 50-70 ℃, and then heating to 80-120 ℃ for polycondensation reaction for 2-9 h;
(3) When the temperature of the intermediate product obtained in the step (2) is reduced to 40-70 ℃, adding a modifier, reacting for 1h, heating to 90-110 ℃, and performing reduced pressure water removal;
(4) And (3) adding a toughening agent when the reduced pressure distillation temperature in the step (3) reaches 50-80 ℃, stirring uniformly, and then dehydrating in vacuum, wherein when the gel time at 180+/-1 ℃ reaches 150-300 s, obtaining the low free aldehyde hot melt boron phenolic resin.
The experimental methods used in the examples below are conventional methods unless otherwise specified.
Materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
Example 1
The low free aldehyde hot melt boron phenolic resin of the embodiment comprises the following components in mole ratio: 10 parts of phenol, 14 parts of aldehyde and 2 parts of boron compound; 10 parts of phenol, 1 part of modifier and 0.5 part of toughening agent.
Wherein the phenol is a monohydric phenol, and the monohydric phenol is phenol; the aldehyde is paraformaldehyde; the boron compound is p-hydroxyphenylboric acid; the modifier is aniline, and the toughening agent is E 44 epoxy resin.
The preparation method of the low free aldehyde hot melt boron phenolic resin in the embodiment is as follows:
(1) Heating phenol to be molten, adding the boron compound under the condition of stirring, uniformly mixing, adding NaOH powder to adjust the pH to 8, slowly heating to 150 ℃, and reacting for 5 hours under the temperature condition; wherein, the slow heating helps to control the reaction rate and prevent certain side reactions.
(2) Adding the aldehyde into the product obtained in the step (1) in a fractional manner when the temperature of the product is 50-70 ℃, heating the obtained mixed solution to 110 ℃ for reflux, and reacting for 1.5h at the temperature;
(3) And (3) adding the modifier into the intermediate product obtained in the step (2) when the temperature of the intermediate product is 70 ℃, reacting for 1h, heating to 100 ℃, and carrying out reduced pressure distillation to remove water generated by the reaction.
(4) And (3) when the temperature of reduced pressure distillation in the step (3) reaches 50-80 ℃, adding a toughening agent, stirring, mixing for 30min, then continuously vacuumizing and dehydrating, testing the gel time, and when the gel time of the resin at 180+/-1 ℃ reaches 200s, ending the reaction to obtain the low free aldehyde hot melt boron phenolic resin.
Example 2
The low free aldehyde hot melt boron phenolic resin of the embodiment comprises the following components in mole ratio: 100 parts of phenol, 130 parts of aldehyde and 30 parts of boron compound; 100 parts of phenol, 15 parts of modifier and 10 parts of toughening agent.
Wherein the phenol is dihydric phenol, and the dihydric phenol is resorcinol; the aldehyde is trioxymethylene; the boron compound is phenylboronic acid; the modifier is melamine; the toughening agent is neoprene.
The preparation method of the low free aldehyde hot melt boron phenolic resin in the embodiment is as follows:
(1) Heating phenol to be molten, adding the boron compound under the condition of stirring, uniformly mixing, adding Ba (OH) 2 powder to adjust the pH to 8, slowly heating to 100 ℃, and reacting for 5 hours under the temperature condition;
(2) Adding the aldehyde into the product obtained in the step (1) in a divided manner when the temperature of the product is 50-70 ℃, heating the obtained mixed solution to 105 ℃ for reflux, and reacting for 1.5h at the temperature;
(3) And (3) adding melamine into the intermediate product obtained in the step (2) when the temperature of the intermediate product is 40-70 ℃, reacting for 1h, heating to 100 ℃, and carrying out reduced pressure distillation to remove water generated by the reaction.
(4) And (3) adding chloroprene rubber when the reduced pressure distillation temperature in the step (3) reaches 50-80 ℃, stirring, mixing for 30min, then continuously vacuumizing and dehydrating, testing the gel time, and finishing the reaction when the gel time of the resin at 180+/-1 ℃ reaches 200s, thus obtaining the low free aldehyde hot melt boron phenolic resin.
Example 3
The low free aldehyde hot melt boron phenolic resin of the embodiment comprises the following components in mole ratio: 110 parts of phenol, 150 parts of aldehyde and 25 parts of boron compound; 110 parts of phenol, 15 parts of modifier and 8 parts of toughening agent.
Wherein the phenol is monohydric phenol and dihydric phenol according to the following ratio of 10:1, and mixing the components according to the molar ratio; the monohydric phenol is phenol; the dihydric phenol is resorcinol; the aldehyde is trioxymethylene powder; the boron compound is methyl phenylboronic acid, the modifier is 2-methylaminophenol, and the toughening agent is polyvinyl butyral.
The preparation method of the low free aldehyde hot melt boron phenolic resin in the embodiment is as follows:
(1) Heating phenol to be molten, adding the boron compound under the condition of stirring, uniformly mixing, adding NaOH powder to adjust the pH to 8, slowly heating to 150 ℃, and reacting for 5 hours under the temperature condition;
(2) Adding the aldehyde into the product obtained in the step (1) in a fractional manner when the temperature of the product is 50-70 ℃, heating the obtained mixed solution to 100 ℃ for reflux, and reacting for 1.5h at the temperature;
(3) And (3) adding the 2-methylaminophenol into the intermediate product obtained in the step (2) when the temperature of the intermediate product is 40-70 ℃, heating to 100 ℃ after reacting for 1h, and carrying out reduced pressure distillation to remove water generated by the reaction.
(4) And (3) when the temperature of reduced pressure distillation in the step (3) reaches 50-80 ℃, adding polyvinyl butyral, stirring, mixing for 30min, then continuously vacuumizing and dehydrating, testing the gel time, and when the gel time of the resin at 180+/-1 ℃ reaches 200s, ending the reaction to obtain the low free aldehyde hot-melt boron phenolic resin.
Example 4
The low free aldehyde hot melt boron phenolic resin of the embodiment comprises the following components in mole ratio: 100 parts of phenol, 135 parts of aldehyde and 20 parts of boron compound; the weight ratio of the modified phenolic resin is 100 parts, 7.5 parts of the modified phenolic resin and 6 parts of the toughening agent.
The phenolic resin is prepared by mixing monophenol and dihydric phenol according to the molar ratio of 1:4, wherein the monophenol is phenol, the dihydric phenol is catechol, the aldehyde is paraformaldehyde powder, the boron compound methoxyphenylboric acid, the modifier is 2, 4-diaminophenol, and the toughening agent is carboxyl-terminated nitrile rubber.
The preparation method of the low free aldehyde hot melt boron phenolic resin comprises the following steps:
(1) Taking the phenol according to the selected parts, adding a boron compound with the specified parts into the phenol, adding NaOH powder to adjust the pH to 8, slowly heating to 140 ℃, reacting for 4 hours, collecting moisture generated by the reaction in the process after the reaction, and discarding the moisture;
(2) Adding the aldehyde into the intermediate product obtained in the step (1) when the temperature of the intermediate product is reduced to below 60 ℃, heating the mixture until reflux of the system occurs, and reacting for 2 hours at the temperature;
(3) And (3) when the temperature of the intermediate product obtained in the step (2) is reduced to about 60 ℃, adding 2, 4-diaminophenol into the intermediate product, reacting for 1h, heating to 100 ℃, and distilling under reduced pressure to remove water generated by the reaction.
(4) And (3) when the temperature of reduced pressure distillation in the step (3) reaches 70 ℃, adding carboxyl-terminated nitrile rubber, stirring, mixing for 30min, then continuously vacuumizing and dehydrating, testing the gel time, and when the gel time of the resin at 180+/-1 ℃ reaches 200s, ending the reaction to obtain the low free aldehyde hot melt boron phenolic resin.
Example 5
The low free aldehyde hot melt boron phenolic resin of the embodiment comprises the following components in mole ratio: 110 parts of phenol, 140 parts of aldehyde and 30 parts of boron compound; 110 parts of phenol, 8.5 parts of modifier and 7 parts of toughening agent.
Wherein the phenol is phenol; the aldehyde is paraformaldehyde powder; the boron compound is butyl phenylboronic acid; the modifier is melamine, and the toughening agent is E 44 epoxy resin.
The preparation method of the low free aldehyde hot melt boron phenolic resin comprises the following steps:
(1) Taking the phenol according to the selected parts, adding the boron compound with the specified parts into the phenol, adding sodium hydroxide powder to adjust the pH to 7, heating to 160 ℃, and reacting for 5 hours;
(2) When the temperature of the intermediate product obtained in the step (1) is reduced to 60 ℃ or lower, adding the aldehyde thereto in two times, heating to 100 ℃, and reacting at the temperature for 1.5 hours;
(3) And (3) when the temperature of the mixture liquid obtained in the step (2) is reduced to about 70 ℃, adding a modifier into the mixture liquid, reacting for 70min, heating to 110 ℃, and carrying out reduced pressure distillation to remove water generated by the reaction.
(4) And (3) adding a toughening agent when the reduced pressure distillation temperature in the step (3) reaches 80 ℃, stirring, mixing for 30min, then continuously vacuumizing and dehydrating, testing the gel time, and finishing the reaction when the gel time of the resin at 180+/-1 ℃ reaches 150s, thus obtaining the low free aldehyde hot melt boron phenolic resin.
Example 6
The low free aldehyde hot melt boron phenolic resin of the embodiment comprises the following components: 94g of phenol; 42g of aldehyde; 24.2g of boron compound; 11g of modifier and 7g of toughening agent.
Wherein the phenol is phenol; the aldehyde is paraformaldehyde powder; the boron compound is phenylboronic acid; the modifier is 2-methylaminophenol, and the toughening agent is amino-terminated nitrile rubber.
The preparation method of the low free aldehyde hot melt boron phenolic resin comprises the following steps:
(1) Adding molten phenol into a three-neck flask, adding 24.2g of phenylboronic acid while stirring, adding sodium hydroxide to adjust the pH to 8, heating to 150 ℃ and reacting for 6 hours at the temperature, collecting moisture generated by the reaction through a water separator after 2 hours of reaction, and discarding the moisture.
(2) Cooling to 60 ℃, adding paraformaldehyde into a three-neck flask for 2 times, heating to about 100 ℃, and carrying out reflux reaction for 4 hours at the temperature;
(3) And (3) when the temperature of the intermediate product obtained in the step (2) is reduced to about 70 ℃, adding the modifier into the intermediate product, reacting for 1h, heating to 110 ℃, and distilling under reduced pressure to remove water generated by the reaction.
(4) And (3) adding a toughening agent when the reduced pressure distillation temperature in the step (3) reaches 60 ℃, stirring, mixing for 30min, then continuously vacuumizing and dehydrating, testing the gel time, and finishing the reaction when the gel time of the resin at 180+/-1 ℃ reaches 240s, thus obtaining the low free aldehyde hot melt boron phenolic resin.
Example 7
The low free aldehyde hot melt boron phenolic resin of the embodiment comprises the following components: phenol 108g; 45g of aldehyde; 20g of boron compound; 10g of modifier; 12g of toughening agent.
Wherein the phenol is o-cresol; the aldehyde is paraformaldehyde powder; the boron compound is boric acid, the modifier is aniline, and the toughening agent is oxygen resin E 51.
The preparation method of the low free aldehyde hot melt boron phenolic resin comprises the following steps:
(1) 108g of o-cresol was charged into a three-necked flask, 20g of boric acid was added at a melting temperature, pH was adjusted to 8 by adding sodium hydroxide, and the temperature was raised to 150℃and reacted at that temperature for 4 hours, and the produced moisture was collected by a water separator and discarded.
(2) Cooling to 60 ℃, adding paraformaldehyde into a three-neck flask for three times, heating to about 100 ℃, and carrying out reflux reaction for 2h at the temperature;
(3) And (3) adding the modifier into the intermediate product obtained in the step (2) when the temperature of the intermediate product is 60 ℃, reacting for 1h, heating to 100 ℃, and carrying out reduced pressure distillation to remove water generated by the reaction.
(4) And (3) adding a toughening agent when the reduced pressure distillation temperature in the step (3) reaches 80 ℃, stirring, mixing for 30min, then continuously vacuumizing and dehydrating, testing the gel time, and finishing the reaction when the gel time of the resin at 180+/-1 ℃ reaches 200s, thus obtaining the low free aldehyde hot melt boron phenolic resin.
Example 8
The low free aldehyde hot melt boron phenolic resin of the embodiment comprises the following components in mole ratio: 94g of phenol; 42g of aldehyde; 35g of boron compound; 18g of modifier; 5g of toughening agent.
Wherein the phenol is phenol; the aldehyde is paraformaldehyde powder; the boron compound is 4-hydroxymethylphenylboronic acid; the modifier is 2, 4-diaminophenol; the toughening agent is polyvinyl butyral.
The preparation method of the low free aldehyde hot melt boron phenolic resin comprises the following steps:
(1) The molten phenol was added to a three-necked flask, 35g of hydroxymethylphenylboronic acid was added while stirring, then sodium hydroxide was added to adjust the pH to 8, the temperature was slowly raised to 140℃and reacted at this temperature for 5 hours, and the water produced by the reaction was removed.
(2) When the mixed liquid in the step (1) was cooled to 60 ℃, 42g of paraformaldehyde was added to the three-necked flask in two portions, and then the temperature was slowly raised to 100 ℃ and reacted at that temperature for 8 hours.
(3) And (3) adding the modifier into the intermediate product obtained in the step (2) when the temperature of the intermediate product is 70 ℃, reacting for 1h, heating to 110 ℃, and carrying out reduced pressure distillation to remove water generated by the reaction.
(4) And (3) adding a toughening agent when the reduced pressure distillation temperature in the step (3) reaches 60 ℃, stirring, mixing for 30min, then continuously vacuumizing and dehydrating, testing the gel time, and finishing the reaction when the gel time of the resin at 180+/-1 ℃ reaches 300s, thus obtaining the low free aldehyde hot melt boron phenolic resin.
Example 9
The low free aldehyde hot melt boron phenolic resin of the embodiment comprises the following components in mole ratio: 200 parts of phenol, 120 parts of aldehyde and 1 part of boron compound; 100 parts of phenol, 5 parts of modifier and 5 parts of toughening agent.
Wherein the phenol is a mixture of paracresol and catechol in a molar ratio of 1:1; the aldehyde is paraformaldehyde; the boron compound is a mixture of biphenyl boric acid and borax in a mass ratio of 1:1; the modifier is o-aminophenol, and the toughening agent is a mixture of epoxy resin F 51 and epoxy resin E 20.
The preparation method of the low free aldehyde hot melt boron phenolic resin comprises the following steps:
(1) Taking the phenol according to the selected parts, adding the boron compound with the specified parts into the phenol, adding ammonia water to adjust the pH to 7, then heating to 160 ℃, and reacting for 5 hours;
(2) When the temperature of the intermediate product obtained in the step (1) is reduced to 60 ℃ or lower, adding the aldehyde thereto in two times, heating to 100 ℃, and reacting at the temperature for 1.5 hours;
(3) And (3) when the temperature of the mixture liquid obtained in the step (2) is reduced to about 70 ℃, adding a modifier into the mixture liquid, reacting for 70min, heating to 110 ℃, and carrying out reduced pressure distillation to remove water generated by the reaction.
(4) And (3) adding a toughening agent when the reduced pressure distillation temperature in the step (3) reaches 80 ℃, stirring, mixing for 30min, then continuously vacuumizing and dehydrating, testing the gel time, and finishing the reaction when the gel time of the resin at 180+/-1 ℃ reaches 150s, thus obtaining the low free aldehyde hot melt boron phenolic resin.
Example 10
The low free aldehyde hot melt boron phenolic resin of the embodiment comprises the following components in mole ratio: 50 parts of phenol, 140 parts of aldehyde and 40 parts of boron compound; 100 parts of phenol, 40 parts of modifier and 10 parts of toughening agent.
Wherein the phenol is a mixture of alpha-naphthol and resorcinol in a molar ratio of 1:1; the aldehyde is glutaraldehyde; the boron compound is a mixture of sodium borate, diphenyl boric acid and methyl phenylboric acid in a mass ratio of 1:1:2; the modifier is a mixture of urea and glycine in a mass ratio of 1:1, and the toughening agent is a mixture of E 44 epoxy resin and VDE in a mass ratio of 1:1.
The preparation method of the low free aldehyde hot melt boron phenolic resin comprises the following steps:
(1) Taking the phenol according to the selected parts, adding the specified parts of boron compound into the phenol, adding ammonia water to adjust the pH to 7.5, heating to 160 ℃, and reacting for 5 hours;
(2) When the temperature of the intermediate product obtained in the step (1) is reduced to 60 ℃ or lower, adding the aldehyde thereto in two times, heating to 100 ℃, and reacting at the temperature for 1.5 hours;
(3) And (3) when the temperature of the mixture liquid obtained in the step (2) is reduced to about 70 ℃, adding a modifier into the mixture liquid, reacting for 70min, heating to 110 ℃, and carrying out reduced pressure distillation to remove water generated by the reaction.
(4) And (3) adding a toughening agent when the reduced pressure distillation temperature in the step (3) reaches 80 ℃, stirring, mixing for 30min, then continuously vacuumizing and dehydrating, testing the gel time, and finishing the reaction when the gel time of the resin at 180+/-1 ℃ reaches 150s, thus obtaining the low free aldehyde hot melt boron phenolic resin.
Example 11
The low free aldehyde hot melt boron phenolic resin of the embodiment comprises the following components in mole ratio: 150 parts of phenol, 12 parts of aldehyde and 10 parts of boron compound; 100 parts of phenol, 15 parts of modifier and 40 parts of toughening agent.
Wherein the phenol is a mixture of beta-naphthol and bisphenol A in a molar ratio of 1:1; the aldehyde is butyraldehyde; the boron compound is a mixture of dimethylbenzeneboronic acid, isopropylphenyl boronic acid and ethoxyphenyl boronic acid in a mass ratio of 1:2:3; the modifier is a mixture of lysine and proline in a mass ratio of 1:1, and the toughening agent is epoxy resin F 51.
The preparation method of the low free aldehyde hot melt boron phenolic resin comprises the following steps:
(1) Taking the phenol according to the selected parts, adding the boron compound with the specified parts into the phenol, adding sodium hydroxide powder to adjust the pH to 7, heating to 160 ℃, and reacting for 5 hours;
(2) When the temperature of the intermediate product obtained in the step (1) is reduced to 60 ℃ or lower, adding the aldehyde thereto in two times, heating to 100 ℃, and reacting at the temperature for 1.5 hours;
(3) And (3) when the temperature of the mixture liquid obtained in the step (2) is reduced to about 70 ℃, adding a modifier into the mixture liquid, reacting for 70min, heating to 110 ℃, and carrying out reduced pressure distillation to remove water generated by the reaction.
(4) And (3) adding a toughening agent when the reduced pressure distillation temperature in the step (3) reaches 80 ℃, stirring, mixing for 30min, then continuously vacuumizing and dehydrating, testing the gel time, and finishing the reaction when the gel time of the resin at 180+/-1 ℃ reaches 150s, thus obtaining the low free aldehyde hot melt boron phenolic resin.
Example 12
The low free aldehyde hot melt boron phenolic resin of the embodiment comprises the following components in mole ratio: 100 parts of phenol, 300 parts of aldehyde and 30 parts of boron compound; 100 parts of phenol, 25 parts of modifier and 20 parts of toughening agent.
Wherein the phenol is in a molar ratio of 1:1 with bisphenol F; the aldehyde is a mixture of glutaraldehyde and trioxymethylene in a mass ratio of 1:1; the boron compound is a mixture of 1, 4-phenyldiboronic acid, ethylphenylboronic acid, butylphenylboronic acid, 2,4, 6-triphenylboron-oxygen alkane and 3-hydroxyphenylboronic acid in a mass ratio of 1:1:1:1:1; the modifier is cysteine, and the toughening agent is epoxy resin F 44.
The preparation method of the low free aldehyde hot melt boron phenolic resin comprises the following steps:
(1) Taking the phenol according to the selected parts, adding the boron compound with the specified parts into the phenol, adding sodium hydroxide powder to adjust the pH to 7, heating to 160 ℃, and reacting for 5 hours;
(2) When the temperature of the intermediate product obtained in the step (1) is reduced to 60 ℃ or lower, adding the aldehyde thereto in two times, heating to 100 ℃, and reacting at the temperature for 1.5 hours;
(3) And (3) when the temperature of the mixture liquid obtained in the step (2) is reduced to about 70 ℃, adding a modifier into the mixture liquid, reacting for 70min, heating to 110 ℃, and carrying out reduced pressure distillation to remove water generated by the reaction.
(4) And (3) adding a toughening agent when the reduced pressure distillation temperature in the step (3) reaches 80 ℃, stirring, mixing for 30min, then continuously vacuumizing and dehydrating, testing the gel time, and finishing the reaction when the gel time of the resin at 180+/-1 ℃ reaches 150s, thus obtaining the low free aldehyde hot melt boron phenolic resin.
Comparative example 1
The boron phenolic resin of this comparative example was identical to the ingredients in example 8 except that the modifier 2, 4-diaminophenol was not included and was prepared in the same manner as in example 8.
And (3) effect verification:
In order to verify the technical effect of the low free aldehyde content boron phenolic resin of the present invention, the boron phenolic resin prepared in examples 1 to 8 and comparative example 1 was taken, and the following experiment was performed:
and taking the boron phenolic resin to be tested, and testing the content of free formaldehyde in the resin according to GB/T-32684.
And taking the boron phenolic resin to be tested, and testing the carbon residue rate of the resin at 800 ℃ through a thermogravimetric analyzer (TG) after curing, so as to simply judge the thermal stability of the resin.
And taking the resin to be tested, and judging the processing window of the boron phenolic resin through variable temperature rheology.
And pressing the carbon fiber composite material by using the boron phenolic resin to be tested according to national standard GB/T9341-2008, and testing the bending strength and interlayer shearing strength of the prepared composite material on a universal testing machine.
The experimental results were as follows:
As can be seen from the above table, the modified boron phenolic resin has a low free aldehyde content, specifically 0.9-2.5%, a good low viscosity window, specifically 75-160 ℃, is a boron phenolic resin suitable for a hot melt prepreg method, and has a carbon residue rate of 67.9-69.8%.
The thermal stability of the resin was analyzed by thermogravimetry, and the thermogravimetric graph of the residual amount of the boron phenolic resin used in example 8 and comparative example 1 in a nitrogen atmosphere with temperature was shown in fig. 1, which revealed that the residual carbon rate of the resin at 800 ℃ was not greatly affected before and after the use of the modifier, but the thermal decomposition temperature T 5％ of the cured resin was increased.
The processing stability of the resins was judged using temperature-variable rheology, and fig. 2 is a graph of temperature-variable rheology of the boron phenolic resins of example 8 and comparative example 1 of the present invention at constant shear frequency (ω=1rad·s-1) and strain (γ=1%). The prepared boron phenolic resin has small viscosity change at 80-160 ℃ and wider processing window.
The carbon fiber composite material was pressed from the resins prepared in example 8 and comparative example 1 of the present invention, and the mechanical properties of the composite material were tested using a universal tester, and the data are shown in fig. 3. As can be seen from fig. 3, after the free aldehyde is reduced, the bending strength and the interlaminar shear strength of the composite material are both significantly improved, because the reduction of the free aldehyde reduces the pores formed in the composite material and reduces the porosity of the composite material.
Film forming properties and tackiness of examples 1-8 and comparative example 1 are shown in the following table:
As can be seen from the above table, the phenolic resin of the present invention can maintain a low viscosity for a long period of time (150 to 240 minutes) at a coating temperature (80 ℃ C.), and is a resin suitable for a hot-melt prepreg process.
The foregoing is illustrative of the preferred embodiments of the present invention and is not to be construed as limiting the claims. The present invention is not limited to the above embodiments, and the specific structure thereof is allowed to vary. It is intended that all such variations as fall within the scope of the appended claims.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
Claims (10)
1. The preparation method of the low free aldehyde hot melt boron phenolic resin is characterized by comprising the following steps of:
Heating phenol to be molten, adding a boron compound under stirring, uniformly mixing, adjusting the pH to 7-8, heating to 100-180 ℃ for reaction for 3-7 h, adding aldehyde, heating to 80-120 ℃ for polycondensation reaction for 2-9 h, adding a modifier, and carrying out reduced pressure water removal after reaction; finally adding a toughening agent, uniformly stirring, vacuum dehydrating, and performing gelation at 180+/-1 ℃ for 150-300 s to obtain the low free aldehyde hot melt boron phenolic resin.
2. The method for preparing the low free aldehyde hot melt boron phenolic resin of claim 1, wherein the molar ratio of phenol, aldehyde and boron compound is 10-200: 12-300: 1-40; the mass ratio of the phenol, the modifier and the toughening agent is 100: 5-40: 5 to 40.
3. The method for preparing the low free aldehyde hot melt boron phenolic resin of claim 1, wherein the molar ratio of phenol, aldehyde and boron compound is 100: 120-140: 10 to 30 percent; the mass ratio of the phenol, the modifier and the toughening agent is 100: 5-15: 5 to 10.
4. The method for preparing the low free aldehyde hot melt boron phenolic resin according to claim 1, wherein one or more of NaOH, NH 3·H2 O and Ba (OH) 2 are used to adjust the pH to 7-8.
5. The method for preparing low free aldehyde hot melt boron phenolic resin of claim 1, wherein said phenol is one or both of monohydric phenol and dihydric phenol; the aldehyde is one or more of butyraldehyde, glutaraldehyde, trioxymethylene and paraformaldehyde.
6. The method for preparing low free formaldehyde hot melt boron phenolic resin according to claim 5, wherein said monophenol is one or more of phenol, o-cresol, m-cresol, p-cresol, α -naphthol, β -naphthol, 4-hydroxymethylphenol; the dihydric phenol is one or more of catechol, resorcinol, hydroquinone, bisphenol A and bisphenol F.
7. The method for producing a low free aldehyde hot melt boron phenolic resin according to claim 1, wherein the boron compound is boric acid or a boric acid derivative.
8. The method for preparing a low free aldehyde hot melt boron phenolic resin according to claim 7, wherein the boric acid derivative is one or more of phenylboric acid, hydroxymethylphenylboric acid, hydroxyphenylboric acid, biphenylboric acid, borax, sodium borate, diphenylboric acid, methylphenylboric acid, dimethylbenzeneboric acid, methoxyphenylboric acid, isopropylphenylboric acid, ethoxyphenylboric acid, 1, 4-phenyldiboronic acid, ethylphenylboric acid, butylphenylboric acid, 2,4, 6-triphenylboroxine and 3-hydroxyphenylboric acid.
9. The method for preparing the low free aldehyde hot melt boron phenolic resin according to claim 1, wherein the modifier is one or more of aniline, o-aminophenol, melamine, urea, 2-methylaminophenol, 2, 4-diamino phenol, glycine, lysine, proline and cysteine;
the toughening agent is one or more of carboxyl-terminated nitrile rubber, amino-terminated nitrile rubber, chloroprene rubber, polyvinyl acetal, polyamide, epoxy resin E 20, epoxy resin E 44, epoxy resin E 51, epoxy resin F 44 and epoxy resin F 51.
10. A low free formaldehyde, hot melt boron phenolic resin prepared according to any one of claims 1 to 9, wherein said low free formaldehyde, hot melt boron phenolic resin has a free formaldehyde content of 0.9 to 2.5%, a low viscosity window of 75 to 160 ℃, a carbon residue of 67.9 to 69.8% and a thermal decomposition temperature T 5％ to 398 to 455 ℃.
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