CN117362913A - Thermoplastic phenolic resin and granulating process thereof - Google Patents
Thermoplastic phenolic resin and granulating process thereof Download PDFInfo
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- CN117362913A CN117362913A CN202311383326.2A CN202311383326A CN117362913A CN 117362913 A CN117362913 A CN 117362913A CN 202311383326 A CN202311383326 A CN 202311383326A CN 117362913 A CN117362913 A CN 117362913A
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- phenolic resin
- thermoplastic phenolic
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- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 105
- 239000005011 phenolic resin Substances 0.000 title claims abstract description 105
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 229920001169 thermoplastic Polymers 0.000 title claims abstract description 95
- 239000004416 thermosoftening plastic Substances 0.000 title claims abstract description 95
- 238000000034 method Methods 0.000 title claims abstract description 26
- 230000008569 process Effects 0.000 title claims abstract description 19
- 239000002048 multi walled nanotube Substances 0.000 claims abstract description 100
- 239000000654 additive Substances 0.000 claims abstract description 20
- 230000000996 additive effect Effects 0.000 claims abstract description 19
- 239000000945 filler Substances 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 239000000314 lubricant Substances 0.000 claims abstract description 9
- 239000000049 pigment Substances 0.000 claims abstract description 7
- 239000003381 stabilizer Substances 0.000 claims abstract description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 54
- 238000006243 chemical reaction Methods 0.000 claims description 37
- 238000006116 polymerization reaction Methods 0.000 claims description 34
- 230000018044 dehydration Effects 0.000 claims description 28
- 238000006297 dehydration reaction Methods 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 239000000047 product Substances 0.000 claims description 27
- 239000002994 raw material Substances 0.000 claims description 27
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 22
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 21
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 21
- 241001330002 Bambuseae Species 0.000 claims description 21
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 21
- 239000011425 bamboo Substances 0.000 claims description 21
- 239000007864 aqueous solution Substances 0.000 claims description 20
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 18
- 239000008187 granular material Substances 0.000 claims description 16
- 238000010992 reflux Methods 0.000 claims description 16
- 239000000758 substrate Substances 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 12
- 238000003860 storage Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- 238000001125 extrusion Methods 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 239000000498 cooling water Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000005469 granulation Methods 0.000 claims description 8
- 230000003179 granulation Effects 0.000 claims description 8
- 239000012760 heat stabilizer Substances 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 238000007873 sieving Methods 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 6
- -1 polytetrafluoroethylene Polymers 0.000 claims description 5
- 229910000004 White lead Inorganic materials 0.000 claims description 4
- 239000003963 antioxidant agent Substances 0.000 claims description 4
- 230000003078 antioxidant effect Effects 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 4
- 239000001023 inorganic pigment Substances 0.000 claims description 4
- RYZCLUQMCYZBJQ-UHFFFAOYSA-H lead(2+);dicarbonate;dihydroxide Chemical compound [OH-].[OH-].[Pb+2].[Pb+2].[Pb+2].[O-]C([O-])=O.[O-]C([O-])=O RYZCLUQMCYZBJQ-UHFFFAOYSA-H 0.000 claims description 4
- 239000012528 membrane Substances 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 claims description 4
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 claims description 4
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- ZQBAKBUEJOMQEX-UHFFFAOYSA-N salicylic acid phenyl ester Natural products OC1=CC=CC=C1C(=O)OC1=CC=CC=C1 ZQBAKBUEJOMQEX-UHFFFAOYSA-N 0.000 claims description 4
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 claims description 2
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003508 Dilauryl thiodipropionate Substances 0.000 claims description 2
- 239000002656 Distearyl thiodipropionate Substances 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 2
- 239000008116 calcium stearate Substances 0.000 claims description 2
- 235000013539 calcium stearate Nutrition 0.000 claims description 2
- 235000019304 dilauryl thiodipropionate Nutrition 0.000 claims description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 2
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 claims description 2
- 235000019305 distearyl thiodipropionate Nutrition 0.000 claims description 2
- SJOCPYUKFOTDAN-ZSOIEALJSA-N methyl (4z)-4-hydroxyimino-6,6-dimethyl-3-methylsulfanyl-5,7-dihydro-2-benzothiophene-1-carboxylate Chemical compound C1C(C)(C)C\C(=N\O)C=2C1=C(C(=O)OC)SC=2SC SJOCPYUKFOTDAN-ZSOIEALJSA-N 0.000 claims description 2
- 239000012860 organic pigment Substances 0.000 claims description 2
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 2
- 150000002910 rare earth metals Chemical class 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- 229940037312 stearamide Drugs 0.000 claims description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 2
- 238000005453 pelletization Methods 0.000 claims 1
- 230000001105 regulatory effect Effects 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 8
- 239000002041 carbon nanotube Substances 0.000 abstract description 8
- 229910021393 carbon nanotube Inorganic materials 0.000 abstract description 8
- 239000002270 dispersing agent Substances 0.000 abstract description 7
- 230000002776 aggregation Effects 0.000 abstract description 6
- 238000005054 agglomeration Methods 0.000 abstract description 5
- 229920005989 resin Polymers 0.000 abstract description 4
- 239000011347 resin Substances 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000011161 development Methods 0.000 abstract description 2
- 238000012545 processing Methods 0.000 abstract description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 32
- 238000012360 testing method Methods 0.000 description 29
- 230000000052 comparative effect Effects 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 5
- 150000002989 phenols Chemical class 0.000 description 4
- 230000006872 improvement Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 231100000086 high toxicity Toxicity 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 2
- 230000020477 pH reduction Effects 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- CQRYARSYNCAZFO-UHFFFAOYSA-N salicyl alcohol Chemical compound OCC1=CC=CC=C1O CQRYARSYNCAZFO-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 description 1
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 description 1
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000010891 toxic waste Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
- C08K5/42—Sulfonic acids; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
Abstract
The invention relates to the field of thermoplastic phenolic resin, in particular to thermoplastic phenolic resin and a granulating process thereof. The thermoplastic phenolic resin is prepared from 60-85 parts by weight of thermoplastic phenolic resin base material and 12-35 parts by weight of additive, wherein the additive comprises the following components in parts by weight: 0.5-2.5 parts of lubricant, 0.5-2.5 parts of stabilizer, 1-5 parts of pigment and 10-25 parts of filler, and SDS modified multi-wall carbon nano tube is used as the filler, so that the method has an enhancement effect on the performance of the thermoplastic phenolic resin, is beneficial to the dispersibility of the carbon nano tube and the resin, avoids the influence of agglomeration on the performance enhancement effect, reduces the use of the dispersing agent, is easy to realize, is suitable for mass production and processing, and meets the development direction of the current thermoplastic phenolic resin.
Description
Technical Field
The invention relates to the field of thermoplastic phenolic resin, in particular to thermoplastic phenolic resin and a granulating process thereof.
Background
Phenolic resins are resins obtained by polycondensation of phenols (phenol, cresol, xylenol, cardanol, etc.) and aldehydes (formaldehyde, acetaldehyde, furfural, etc.) under the action of a catalyst, and among them, phenolic resins obtained by polycondensation of formaldehyde and phenol are most widely used and can be classified into thermoplastic phenolic resins and thermosetting phenolic resins according to synthetic conditions and uses. The thermoplastic phenolic resin is not cured when heated, and can be cured only when added with a curing agent and heated, the chemical process for synthesizing the thermoplastic phenolic resin is that the phenol and the aldehyde are subjected to addition reaction to generate hydroxymethyl phenol, the hydroxymethyl phenol is very active in an acidic medium, and is rapidly dehydrated with another phenol molecule (ortho-para) to be connected by a methylene bridge, and the product is a mixture of three isomers. At present, phenolic resin is widely applied to advanced high and new technical fields of aviation, aerospace, electronics, automobiles, military and the like except in a resin form and also in a reinforcing material form as a matrix, and the modified phenolic resin has the advantages of high temperature resistance, high bonding strength, low smoke, low toxicity and the like.
In the common phenolic resin production technology, phenol and formaldehyde which are raw materials are substances with relatively high toxicity, and environmental pollution can be generated in the production and preparation process, which is contrary to the environment-friendly and clean production, so that the method for searching raw materials with low cost and low toxicity to replace the inherent raw materials or reduce the dosage of the inherent raw materials becomes a new way; with the continuous expansion of the application field of phenolic resin, the market pursues higher and better performances, the traditional phenolic resin cannot meet the market requirements, and the performances of the thermoplastic phenolic resin need to be improved by means of modification, additive addition and the like, although the carbon nano tube has good thermal conductivity, electrical conductivity and good chemical and mechanical stability, the carbon nano tube is easy to agglomerate and limited in the application process, and the optimal performances of the carbon nano tube are difficult to develop; meanwhile, the thermoplastic phenolic resin has higher viscosity, the addition of the additive is easy to agglomerate, the performance of the thermoplastic phenolic resin is difficult to improve to the maximum extent, and the optimization of the additive to improve the dispersibility is very important.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides the thermoplastic phenolic resin and the granulating process thereof, wherein a part of phenol is replaced by bamboo tar to participate in the polymerization reaction, so that the consumption of phenol is reduced, and the recycling of the bamboo tar is realized; the SDS modified multi-wall carbon nano tube is used as the main component of the additive, so that the performance of the thermoplastic phenolic resin is enhanced by utilizing the good mechanical property, the heat conductivity and the electric conductivity of the multi-wall carbon nano tube, and the dispersibility of the SDS modified multi-wall carbon nano tube in the thermoplastic phenolic resin is improved by modifying the multi-wall carbon nano tube with SDS (sodium dodecyl sulfate), so that agglomeration is avoided, and the excellent dispersing effect can be achieved without using an additional dispersing agent. The method is easy to realize, is suitable for large-scale production and processing, and is compatible with the current development direction of the thermoplastic phenolic resin.
According to the invention, in the preparation process of the thermoplastic phenolic resin, bamboo tar is used as a raw material to replace a part of phenol for polymerization reaction, the bamboo tar is a bamboo production byproduct and contains hundreds of organic matters, wherein phenolic compounds account for more than 40%, the ortho-para positions of the phenolic compounds have no substituent groups, and the phenolic compounds can be subjected to crosslinking reaction with formaldehyde, so that the consumption of phenol in the raw material can be reduced, the influence of toxic raw materials on the environment is reduced, and the bamboo tar can be reused. Compared with thermosetting resin, the thermoplastic resin has higher viscosity and lower specific surface free energy, and the direct mixing of the multi-wall carbon nano tube and the thermoplastic phenolic resin can lead to uneven dispersion of nano particles and agglomeration which are unfavorable for performance improvement, but the acid treatment of the multi-wall carbon nano tube only can obtain the acidified multi-wall carbon nano tube with carboxyl, hydroxyl and other functional groups, and the dispersibility of the acidified multi-wall carbon nano tube can not be improved to the greatest extent, so that the ultrasonic modification of the acidified multi-wall carbon nano tube by the surfactant is further utilized, and the ultrasonic vibration is applied in the mixing process of the multi-wall carbon nano tube and the thermoplastic phenolic resin matrix to jointly destroy the agglomeration, thereby improving the dispersibility.
A thermoplastic phenolic resin is prepared from 60-85 parts by weight of thermoplastic phenolic resin base material and 12-35 parts by weight of additive;
the thermoplastic phenolic resin substrate comprises the following raw materials in parts by weight: phenol, bamboo tar and formaldehyde aqueous solution, wherein the ratio of the dosage of the phenol, the bamboo tar and the formaldehyde aqueous solution is 0.6:0.4: 0.65-0.85; the mass fraction of the formaldehyde aqueous solution is 37%;
the additive comprises the following components in parts by weight: 0.5-2.5 parts of lubricant, 0.5-2.5 parts of stabilizer, 1-5 parts of pigment and 10-25 parts of filler;
wherein the lubricant is one of stearamide, oleamide, polytetrafluoroethylene micropowder, polyethylene wax, silane and siloxane; the stabilizer is one of an ultraviolet absorber, a heat stabilizer and an antioxidant, wherein the ultraviolet absorber is one of phenyl o-hydroxybenzoate, 2, 4-dihydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone, the heat stabilizer is one of zinc stearate, calcium stearate, basic lead carbonate, dibasic lead stearate and rare earth heat stabilizer, and the antioxidant is one of antioxidant 1010, dilauryl thiodipropionate and distearyl thiodipropionate; the pigment is an organic pigment or an inorganic pigment, and the filler is SDS modified multi-wall carbon nano-tubes.
Further, the preparation method of the thermoplastic phenolic resin substrate comprises the following steps:
s1, feeding: phenol, bamboo tar and formaldehyde aqueous solution are taken as raw materials, respectively metered by a material conveying pump and a raw material metering pump from a phenol storage tank, a bamboo tar storage tank and a formaldehyde storage tank in sequence, then enter a reaction kettle, after water is introduced into a condenser, the raw materials are stirred for 20-60 min at a stirring speed of 1200rpm, and oxalic acid is added to adjust the pH value to 0-3.0;
s2, polymerization: the outer layer of the cylinder body of the reaction kettle is provided with a steam coil pipe which can heat the reaction kettle to 55-65 ℃, and raw materials undergo polymerization reaction in the reaction kettle under normal pressure to obtain a polymerization product, wherein the polymerization reaction time is 4-8 hours; the exothermic reaction causes the polymerization product to automatically heat up to reflux, the reflux state is kept to the reaction end point, when the reaction is finished, the steam is stopped to be introduced, and the cooling water is immediately introduced into the cooling water coil pipe to cool the reaction kettle to the room temperature; after the reaction is finished, a discharge valve is opened, and the polymerization product automatically flows to a dehydration kettle;
s3, dehydration: firstly, carrying out normal-pressure dehydration, heating a polymerization product to 110-140 ℃, wherein the normal-pressure dehydration time is 0.5-1.5 h, opening a vacuum pump to carry out vacuum dehydration after the normal-pressure dehydration, continuously evaporating water in the polymerization product, wherein the vacuum dehydration time is 3.5-4.5 h, the vacuum degree is 0.09Mpa, discharging when the softening point is qualified, and the softening point is 90-160 ℃ to obtain the thermoplastic phenolic resin substrate.
Further, the SDS modified multiwall carbon nanotube is obtained by sequentially acidizing and SDS modifying multiwall carbon nanotubes with the outer diameter of 20-30 nm and the length of 10-20 mu m, and the preparation method of the SDS modified multiwall carbon nanotube is as follows:
p1, weighing multi-wall carbon nanotubes, placing the multi-wall carbon nanotubes in a three-neck flask, adding 65wt% of concentrated nitric acid or 98wt% of concentrated sulfuric acid, wherein the dosage ratio of the multi-wall carbon nanotubes to the concentrated nitric acid or the concentrated sulfuric acid is 0.01g/mL, heating the three-neck flask to 100-130 ℃, and carrying out reflux treatment for 2-6 hours to obtain the acidized multi-wall carbon nanotubes after the reflux treatment;
p2, transferring the multi-wall carbon nano tube after the back flow in the step P1 to a funnel, arranging a microporous filter membrane with the aperture of 0.45 mu m on the funnel, carrying out suction filtration by a circulating water type vacuum pump, continuously adding deionized water for washing until the pH value of filtrate obtained by the suction filtration is neutral, transferring the washed acidified multi-wall carbon nano tube to a drying container, and drying for 1-3 hours at 50-80 ℃ in an oven to obtain the acidified multi-wall carbon nano tube;
p3, dissolving the acidified multiwall carbon nanotube obtained in the step P2 in 1wt% of SDS aqueous solution, wherein the ratio of the acidified multiwall carbon nanotube to the 1wt% of SDS aqueous solution is 1mg/mL, placing the acidified multiwall carbon nanotube in an ultrasonic cleaner for treatment for 60-90 min, and centrifuging the acidified multiwall carbon nanotube in a centrifuge at 5000rpm for 2min to obtain an SDS modified acidified multiwall carbon nanotube;
and P4, washing the SDS-modified acidified multiwall carbon nanotube obtained in the step P2 by deionized water, and drying in an oven at 75 ℃ for 1-2 hours to obtain the SDS-modified multiwall carbon nanotube.
The invention also provides a granulating process of the thermoplastic phenolic resin, which comprises the following steps:
q1, mixing a thermoplastic phenolic resin base material and an additive in a high-speed stirrer according to a formula proportion, and feeding the mixture into a single-screw extrusion granulator for granulation to obtain thermoplastic phenolic resin granules, wherein the granulation is carried out at normal temperature and normal pressure, the rotation speed of a screw is 30rpm, the diameter of the screw is 25mm, and the extrusion speed is 10-30 m/min;
q2, indirectly cooling the thermoplastic phenolic resin granules obtained in the step Q1 through circulating water, wherein the cooling temperature is 20-25 ℃, and the cooling time is 20min, so as to obtain cooled thermoplastic phenolic resin granules;
and Q3, placing the cooled thermoplastic phenolic resin granules obtained in the step Q2 into a rotary vibration sieve for sieving to obtain a thermoplastic phenolic resin product, wherein the diameter of the rotary vibration sieve is 1500mm, the vibration frequency is 1500rpm, and the sieving angle is 15-30 degrees.
Preferably, in the step Q1, the thermoplastic phenolic resin base material, the lubricant, the stabilizer, the pigment and the filler are sequentially added into a high-speed stirrer, the stirring speed is 2000-3500 rpm, and the stirring time is 1-4 hours.
Further, ultrasonic waves are applied to the mixture process of the thermoplastic phenolic resin substrate and the SDS modified multi-wall carbon nano tube in the step Q1, and the frequency is 20 kHz-30 kHz.
Compared with the prior art, the invention has the following beneficial effects:
the byproduct bamboo tar produced by bamboo is used for partially replacing phenol raw materials with high toxicity and environment friendliness, so that the production cost is reduced, the bamboo tar is recycled, the consumption of toxic raw materials is reduced, the emission of toxic wastes in the production process is reduced, and the clean production and green production concepts are met; the multi-wall carbon nano tube is sequentially subjected to acidification and ultrasonic modification treatment, so that the acidified multi-wall carbon nano tube with carboxyl, hydroxyl and other functional groups is obtained, and the acidified multi-wall carbon nano tube is further modified by using sodium dodecyl sulfate serving as a surfactant in ultrasonic modification, so that the dispersibility and the surface activity of the multi-wall carbon nano tube are improved, and the self aggregation is avoided, and the strengthening effect on the performance of the thermoplastic phenolic resin is reduced; in addition, the dispersant is preloaded on the surface of the multiwall carbon nanotube and added into the thermoplastic phenolic resin along with the filler, so that the additional use of the dispersant in the additive can be avoided, and the problem that the dispersant is difficult to uniformly distribute in the thermoplastic phenolic resin with high viscosity and the effect is reduced is solved; ultrasonic waves are applied when the additive and the thermoplastic phenolic resin are mixed and stirred, and the additive is further assisted to be uniformly distributed in the thermoplastic phenolic resin through ultrasonic vibration.
Drawings
FIG. 1 is a diagram of a synthetic process for a thermoplastic phenolic resin;
FIG. 2 is a schematic diagram of a Vicat softening point tester;
FIG. 3 is a graph of tensile strength test results;
FIG. 4 is a graph of softening point test results.
Detailed Description
Example 1: the embodiment provides a thermoplastic phenolic resin, which is prepared from a thermoplastic phenolic resin substrate and an additive.
The preparation of the thermoplastic phenolic resin substrate comprises the following steps:
s1, feeding: phenol, bamboo tar and formaldehyde aqueous solution according to the weight ratio of benzene of 0.6:0.4:0.65 of the raw materials are respectively metered from a phenol storage tank, a bamboo tar storage tank and a formaldehyde storage tank through a material conveying pump and a raw material metering pump in sequence, then enter a reaction kettle, after a condenser is filled with water, raw materials are stirred for 45min at a stirring speed of 1200rpm, oxalic acid is added to adjust pH=2, wherein the mass fraction of formaldehyde aqueous solution is 37%, and the mass fraction of oxalic acid is 99.6%;
s2, polymerization: the outer layer of the cylinder body of the reaction kettle is provided with a steam coil pipe which can heat the reaction kettle to 55 ℃, and raw materials are subjected to polymerization reaction in the reaction kettle under normal pressure to obtain a polymerization product, wherein the polymerization reaction time is 7h; the exothermic reaction causes the polymerization product to automatically heat up to reflux, the reflux state is kept to the reaction end point, when the reaction is finished, the steam is stopped to be introduced, and the cooling water is immediately introduced into the cooling water coil pipe to cool the reaction kettle to the room temperature; after the reaction is finished, a discharge valve is opened, and the polymerization product automatically flows to a dehydration kettle;
s3, dehydration: firstly, carrying out normal-pressure dehydration, heating a polymerization product to 130 ℃, carrying out normal-pressure dehydration for 1h, opening a vacuum pump to carry out vacuum dehydration after the normal-pressure dehydration, continuously evaporating water in the polymerization product, carrying out vacuum dehydration for 4h, discharging when the vacuum degree is 0.09Mpa and the softening point is 143 ℃, and obtaining the thermoplastic phenolic resin substrate.
Wherein, the SDS modified multi-wall carbon nano-tube is obtained by sequentially acidizing and SDS modifying the multi-wall carbon nano-tube with the outer diameter of 25nm and the length of 15 mu m, and the preparation method of the SDS modified multi-wall carbon nano-tube is as follows:
p1, weighing multi-wall carbon nanotubes, placing the multi-wall carbon nanotubes in a three-neck flask, adding 65wt% of concentrated nitric acid or 98wt% of concentrated sulfuric acid, wherein the dosage ratio of the multi-wall carbon nanotubes to the concentrated nitric acid or the concentrated sulfuric acid is 0.01g/mL, heating the three-neck flask to 100 ℃, and carrying out reflux treatment for 3 hours to obtain the acidified multi-wall carbon nanotubes after the reflux treatment;
p2, transferring the multi-wall carbon nano tube after the back flow in the step P1 to a funnel, arranging a microporous filter membrane with the aperture of 0.45 mu m on the funnel, carrying out suction filtration by a circulating water type vacuum pump, continuously adding deionized water for washing until the pH value of the filtrate obtained by the suction filtration is neutral, transferring the washed acidified multi-wall carbon nano tube to a drying container, and drying for 1h at 70 ℃ in an oven to obtain the acidified multi-wall carbon nano tube;
p3, dissolving the acidified multiwall carbon nanotube obtained in the step P2 in 1wt% of SDS aqueous solution, wherein the ratio of the acidified multiwall carbon nanotube to the 1wt% of SDS aqueous solution is 1mg/mL, placing the acidified multiwall carbon nanotube in an ultrasonic cleaner for treatment for 90min, and centrifuging the acidified multiwall carbon nanotube in a centrifuge at 5000rpm for 2min to obtain an SDS modified acidified multiwall carbon nanotube;
and P4, washing the SDS-modified acidified multiwall carbon nano tube obtained in the step P3 by deionized water, and drying in an oven at 75 ℃ for 2 hours to obtain the SDS-modified multiwall carbon nano tube.
The embodiment also provides a granulating process of the thermoplastic phenolic resin, which comprises the following steps:
q1, sequentially adding 85 parts by weight of a thermoplastic phenolic resin substrate, 2.5 parts by weight of oleamide serving as a lubricant, 2.5 parts by weight of basic lead carbonate serving as a heat stabilizer, 5 parts by weight of ferric oxide serving as an inorganic pigment and 15 parts by weight of SDS modified multi-wall carbon nano-tubes serving as a filler into a high-speed stirrer, stirring for 2 hours at a rotating speed of 3000rpm, and applying ultrasonic waves with a frequency of 25kHz in the mixing process to improve the dispersibility; after the mixing is finished, the mixture is sent into a single screw extrusion granulator for granulation to obtain thermoplastic phenolic resin granules, the granulation is carried out at normal temperature and normal pressure, the rotation speed of the screw is 30rpm, the diameter of the screw is 25mm, and the extrusion speed is 20m/min;
q2, indirectly cooling the thermoplastic phenolic resin granules obtained in the step Q1 through circulating water, wherein the cooling temperature is 20 ℃, and the cooling time is 20 minutes, so as to obtain cooled thermoplastic phenolic resin granules;
and Q3, placing the cooled thermoplastic phenolic resin granules obtained in the step Q2 into a rotary vibration sieve for sieving to obtain a thermoplastic phenolic resin product, wherein the diameter of the rotary vibration sieve is 1500mm, the vibration frequency is 1500rpm, and the sieving angle is 15 degrees.
Example 2: the embodiment provides a thermoplastic phenolic resin, which is prepared from a thermoplastic phenolic resin substrate and an additive.
The preparation of the thermoplastic phenolic resin substrate comprises the following steps:
s1, feeding: phenol, bamboo tar and formaldehyde aqueous solution according to the weight ratio of benzene of 0.6:0.4:0.85 of raw materials are respectively metered from a phenol storage tank, a bamboo tar storage tank and a formaldehyde storage tank through a material conveying pump and a raw material metering pump in sequence and then enter a reaction kettle, after a condenser is filled with water, raw materials are stirred for 45min at a stirring speed of 1200rpm, oxalic acid is added to adjust pH=2, wherein the mass fraction of formaldehyde aqueous solution is 37%, and the mass fraction of oxalic acid is 99.6%;
s2, polymerization: the outer layer of the cylinder body of the reaction kettle is provided with a steam coil pipe which can heat the reaction kettle to 65 ℃, and raw materials are subjected to polymerization reaction in the reaction kettle under normal pressure to obtain a polymerization product, wherein the polymerization reaction time is 7h; the exothermic reaction causes the polymerization product to automatically heat up to reflux, the reflux state is kept to the reaction end point, when the reaction is finished, the steam is stopped to be introduced, and the cooling water is immediately introduced into the cooling water coil pipe to cool the reaction kettle to the room temperature; after the reaction is finished, a discharge valve is opened, and the polymerization product automatically flows to a dehydration kettle;
s3, dehydration: firstly, carrying out normal-pressure dehydration, heating a polymerization product to 130 ℃, carrying out normal-pressure dehydration for 1h, opening a vacuum pump to carry out vacuum dehydration after the normal-pressure dehydration, continuously evaporating water in the polymerization product, carrying out vacuum dehydration for 4h, discharging when the vacuum degree is 0.09Mpa and the softening point is 150 ℃, and obtaining the thermoplastic phenolic resin substrate.
Wherein, the SDS modified multi-wall carbon nano-tube is obtained by sequentially acidizing and SDS modifying the multi-wall carbon nano-tube with the outer diameter of 25nm and the length of 15 mu m, and the preparation method of the SDS modified multi-wall carbon nano-tube is as follows:
p1, weighing multi-wall carbon nanotubes, placing the multi-wall carbon nanotubes in a three-neck flask, adding 65wt% of concentrated nitric acid or 98wt% of concentrated sulfuric acid, wherein the dosage ratio of the multi-wall carbon nanotubes to the concentrated nitric acid or the concentrated sulfuric acid is 0.01g/mL, heating the three-neck flask to 100 ℃, and carrying out reflux treatment for 3 hours to obtain the acidified multi-wall carbon nanotubes after the reflux treatment;
p2, transferring the multi-wall carbon nano tube after the back flow in the step P1 to a funnel, arranging a microporous filter membrane with the aperture of 0.45 mu m on the funnel, carrying out suction filtration by a circulating water type vacuum pump, continuously adding deionized water for washing until the pH value of the filtrate obtained by the suction filtration is neutral, transferring the washed acidified multi-wall carbon nano tube to a drying container, and drying for 1h at 70 ℃ in an oven to obtain the acidified multi-wall carbon nano tube;
p3, dissolving the acidified multiwall carbon nanotube obtained in the step P2 in 1wt% of SDS aqueous solution, wherein the ratio of the acidified multiwall carbon nanotube to the 1wt% of SDS aqueous solution is 1mg/mL, placing the acidified multiwall carbon nanotube in an ultrasonic cleaner for treatment for 90min, and centrifuging the acidified multiwall carbon nanotube in a centrifuge at 5000rpm for 2min to obtain an SDS modified acidified multiwall carbon nanotube;
and P4, washing the SDS-modified acidified multiwall carbon nano tube obtained in the step P3 by deionized water, and drying in an oven at 75 ℃ for 2 hours to obtain the SDS-modified multiwall carbon nano tube.
The embodiment also provides a granulating process of the thermoplastic phenolic resin, which comprises the following steps:
q1, sequentially adding 60 parts by weight of a thermoplastic phenolic resin substrate, 2 parts by weight of oleamide serving as a lubricant, 2 parts by weight of basic lead carbonate serving as a heat stabilizer, 3 parts by weight of ferric oxide serving as an inorganic pigment and 25 parts by weight of SDS modified multiwall carbon nanotubes serving as a filler into a high-speed stirrer, stirring for 2 hours at a rotating speed of 3000rpm, and applying ultrasonic waves with a frequency of 25kHz in the mixing process to improve the dispersibility; after the mixing is finished, the mixture is sent into a single screw extrusion granulator for granulation to obtain thermoplastic phenolic resin granules, the granulation is carried out at normal temperature and normal pressure, the rotation speed of the screw is 30rpm, the diameter of the screw is 25mm, and the extrusion speed is 20m/min;
q2, indirectly cooling the thermoplastic phenolic resin granules obtained in the step Q1 through circulating water, wherein the cooling temperature is 20 ℃, and the cooling time is 20 minutes, so as to obtain cooled thermoplastic phenolic resin granules;
and Q3, placing the cooled thermoplastic phenolic resin granules obtained in the step Q2 into a rotary vibration sieve for sieving to obtain a thermoplastic phenolic resin product, wherein the diameter of the rotary vibration sieve is 1500mm, the vibration frequency is 1500rpm, and the sieving angle is 15 degrees.
Comparative example 1: this comparative example was based on example 2, except that SDS-modified multiwall carbon nanotubes were not added as a filler, ultrasound was not applied when mixing additives, and the rest of the procedure was the same as in example 2.
Comparative example 2: this comparative example is based on example 2, except that the multiwall carbon nanotubes are directly used, and are not modified, and the rest of the procedure is the same as in example 2.
Comparative example 3: this comparative example is based on example 2, except that ultrasonic vibration is not applied when the filler is mixed with the thermoplastic phenolic resin, and the rest of the procedure is the same as in example 2.
Experimental example:
1. determination of resistance (GB/T11210-2014)
(1) Test instrument:
the rated direct current open circuit voltage of the test instrument is 500V, and the test instrument is carried out by an insulation tester (ohm meter); the voltage applied to the article was 40V.
(2) Electrode and contact means:
the electrode is formed on the surface of the product through the conductive liquid, and the conductive liquid comprises the following components in parts by mass: 800 parts of anhydrous polyethylene glycol (Mr=600), 200 parts of water, 1 part of wetting agent and 10 parts of potassium chloride, wherein the contact surface of the electrode is completely wetted, and the wetting is kept until the test is finished; clean metal is adopted as a contact device and is arranged on the electrode, and the contact area is the same as the size of the electrode; the article was supported on an insulating surface having a volume resistivity of 10 during the test 10 Omega.m; the test equipment was calibrated prior to testing.
(3) Test conditions:
the test was carried out at 23℃and 50% relative humidity, with electrode sizes of 1cm. Times.1 cm.
(4) The test steps are as follows:
scrubbing the surface of the article with a slurry of diatomaceous earth and water and rinsing with distilled water, then drying at standard temperature, and not wiping or abrading the test surface;
placing electrodes on two positions on the same surface of the product, wherein each position is square with a side length of 25mm, and the distance between the opposite side lines of the two positions is 50mm;
a metal contact device was placed on the electrode, the resistance value was measured, and the resistivity was calculated, and the test results are shown in table 1.
2. Tensile Strength (GB/T1040.1-2018)
Maximum and minimum values of width and thickness are recorded within 5mm of each end of the gauge length in the middle of each sample and are ensured to be within tolerance of the corresponding standards. The average of the measured widths and thicknesses is used to calculate the cross section of the specimen.
The sample is placed in the clamp and it is necessary to align the long axis of the sample with the axis of the tester and to clamp the clamp smoothly and firmly to prevent slippage of the sample in the test and movement of the clamp. The holding force can not cause the rupture or extrusion of the sample, the sample is in an unstressed state before the test, and if the holding force generates prestress, the prestress needs to be set in advance. After setting, the calibrated extensometer is mounted on the gauge length of the sample and aligned, and a longitudinal strain gauge is mounted.
And (3) calculating: ơ =f/a, and the test results are shown in table 1 and fig. 3.
3. Vicat softening point (GB/T1633-2000)
The vicat softening point test was performed by a VST tester, as shown in fig. 2.
Two samples were used for each sample, which were round with a thickness of 5mm and a diameter of 10mm, and were flat and parallel.
The sample was placed horizontally under an unloaded presser needle, 3mm from the edge of the sample, and the surface of the sample in contact with the instrument mount was flat.
When the heating bath is used, the water silver ball of the thermometer is at the same level with the sample and is close to the sample.
After 5min, the presser head is in a rest position, and a weight is applied to the load plate to give a total thrust to the sample, for A 50 And A 120 10N for B 50 And B 120 50N. The readings of the dial gauge are then recorded.
Raising the temperature of the heating device at a constant speed of 50 ℃/h; when using a heating bath, the liquid was thoroughly stirred during the test; a ramp rate of 50 ℃/h was used for the arbitration test.
When the depth of the needle penetrating the sample exceeds 1mm from the initial position, the temperature of the oil bath measured by the sensor is recorded, and the temperature is the Vicat softening point of the sample.
The vicat softening point of the test material is expressed as the arithmetic mean of the vicat softening points of the samples, and if the range of individual test results difference exceeds 2 ℃, the individual test results are noted and one test is performed with another set of two samples rereaded.
The test results are shown in Table 1 and FIG. 4.
Analysis of results:
table 1 records the experimentally measured resistivity, tensile strength, softening point of examples 1-2 and comparative examples 1-3, and the properties of the thermoplastic phenolic resins were evaluated in terms of electrical conductivity, thermal conductivity, mechanical strength, as can be seen from the above test results: the SDS modified multi-wall carbon nano tube is used as a filler, so that the performance of the thermoplastic phenolic resin can be effectively enhanced, and the SDS modified multi-wall carbon nano tube not only shows good dispersibility when being mixed with a thermoplastic phenolic resin matrix, but also is more uniformly dispersed under the action of ultrasonic waves, so that the performance optimization is remarkable. Firstly, as can be seen from comparative example 1, the resistivity of the phenolic resin without adding SDS modified multiwall carbon nanotubes or multiwall carbon nanotubes is very high, and the phenolic resin has almost no conductivity, and the resistance performance of the phenolic resin is effectively improved by virtue of the high conductivity of the carbon nanotubes themselves; secondly, tensile strength tests (table 1, fig. 3) confirm that the addition of SDS-modified multiwall carbon nanotubes improves the mechanical properties of the thermoplastic phenolic resin, due to the interfacial interactions between the carbon nanotubes and the thermoplastic phenolic resin matrix, resulting in a greater improvement in the mechanical properties of the final thermoplastic phenolic resin; whereas the increase in service temperature of the SDS-modified multiwall carbon nanotubes over the thermoplastic phenolic resin was characterized by the softening point test (table 1, fig. 4), this improvement also results from the high thermal conductivity of the carbon nanotubes themselves.
Comparing the performance test results and the data trend of examples 1-2 and comparative examples 1-3, it can be seen that the dispersibility of the carbon nanotubes in the thermoplastic phenolic resin has an important effect on improving the performance of the thermoplastic phenolic resin, two means of acidification and ultrasonic modification are used for modifying the multi-wall carbon nanotubes, the method has a remarkable effect on improving the dispersibility of the multi-wall carbon nanotubes and avoiding agglomeration, and the use of SDS for modification also avoids the problem that the dispersing agent is difficult to uniformly disperse in a high-viscosity thermoplastic phenolic resin matrix and cannot exert the best effect when the dispersing agent is additionally added into the additive to be dispersed, and the application of ultrasonic waves in the mixing process further improves the dispersion degree and uniformity, so that the performance enhancement effect of the SDS modified multi-wall carbon nanotubes on the thermoplastic phenolic resin is best.
Table 1 results of performance testing of examples and comparative examples
The embodiments described above are some, but not all embodiments of the invention. The detailed description of the embodiments of the invention is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention, based on which one skilled in the art, without inventive effort, may derive other embodiments of the invention that fall within the scope of the invention.
Claims (6)
1. The thermoplastic phenolic resin is characterized by being prepared from 60-85 parts by weight of thermoplastic phenolic resin base material and 12-35 parts by weight of additive;
the thermoplastic phenolic resin substrate comprises the following raw materials in parts by weight: phenol, bamboo tar and formaldehyde aqueous solution, wherein the ratio of the dosage of the phenol, the bamboo tar and the formaldehyde aqueous solution is 0.6:0.4: 0.65-0.85; the mass fraction of the formaldehyde aqueous solution is 37%;
the additive comprises the following components in parts by weight: 0.5-2.5 parts of lubricant, 0.5-2.5 parts of stabilizer, 1-5 parts of pigment and 10-25 parts of filler;
the lubricant is one of stearamide, oleamide, polytetrafluoroethylene micropowder, polyethylene wax, silane and siloxane; the stabilizer is one of an ultraviolet absorber, a heat stabilizer and an antioxidant, wherein the ultraviolet absorber is one of phenyl o-hydroxybenzoate, 2, 4-dihydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone, the heat stabilizer is one of zinc stearate, calcium stearate, basic lead carbonate, dibasic lead stearate and rare earth heat stabilizer, and the antioxidant is one of antioxidant 1010, dilauryl thiodipropionate and distearyl thiodipropionate; the pigment is an organic pigment or an inorganic pigment; the filler is SDS modified multiwall carbon nano tube.
2. The thermoplastic phenolic resin of claim 1, wherein the process for preparing the thermoplastic phenolic resin substrate comprises the steps of:
s1, feeding: phenol, bamboo tar and formaldehyde aqueous solution are taken as raw materials, respectively metered by a material conveying pump and a raw material metering pump from a phenol storage tank, a bamboo tar storage tank and a formaldehyde storage tank in sequence, then enter a reaction kettle, after water is introduced into a condenser, the raw materials are stirred for 20-60 min at a stirring speed of 1200rpm, oxalic acid with the mass fraction of 99.6% is added, and the pH value is regulated to 0-3.0;
s2, polymerization: the outer layer of the cylinder body of the reaction kettle is provided with a steam coil pipe which can heat the reaction kettle to 55-65 ℃, and raw materials undergo polymerization reaction in the reaction kettle under normal pressure to obtain a polymerization product, wherein the polymerization reaction time is 4-8 hours; the exothermic reaction causes the polymerization product to automatically heat up to reflux, the reflux state is kept to the reaction end point, when the reaction is finished, the steam is stopped to be introduced, and the cooling water is immediately introduced into the cooling water coil pipe to cool the reaction kettle to the room temperature; after the reaction is finished, a discharge valve is opened, and the polymerization product automatically flows to a dehydration kettle;
s3, dehydration: firstly, carrying out normal-pressure dehydration, heating a polymerization product to 110-140 ℃, wherein the normal-pressure dehydration time is 0.5-1.5 h, opening a vacuum pump to carry out vacuum dehydration after the normal-pressure dehydration, continuously evaporating water in the polymerization product, wherein the vacuum dehydration time is 3.5-4.5 h, the vacuum degree is 0.09Mpa, discharging when the softening point is qualified, and the softening point is 90-160 ℃ to obtain the thermoplastic phenolic resin substrate.
3. The thermoplastic phenolic resin of claim 2, wherein the SDS-modified multiwall carbon nanotubes are obtained by sequentially acidizing and SDS-modifying multiwall carbon nanotubes with an outer diameter of 20-30 nm and a length of 10-20 μm, and the preparation method of the SDS-modified multiwall carbon nanotubes comprises the following steps:
p1, weighing multi-wall carbon nanotubes, placing the multi-wall carbon nanotubes in a three-neck flask, adding 65wt% of concentrated nitric acid or 98wt% of concentrated sulfuric acid, wherein the dosage ratio of the multi-wall carbon nanotubes to the concentrated nitric acid or the concentrated sulfuric acid is 0.01g/mL, heating the three-neck flask to 100-130 ℃, and carrying out reflux treatment for 2-6 hours to obtain the acidized multi-wall carbon nanotubes after the reflux treatment;
p2, transferring the multi-wall carbon nano tube after the back flow in the step P1 to a funnel, arranging a microporous filter membrane with the aperture of 0.45 mu m on the funnel, carrying out suction filtration by a circulating water type vacuum pump, continuously adding deionized water for washing until the pH value of filtrate obtained by the suction filtration is neutral, transferring the washed acidified multi-wall carbon nano tube to a drying container, and drying for 1-3 hours at 50-80 ℃ in an oven to obtain the acidified multi-wall carbon nano tube;
p3, dissolving the acidified multiwall carbon nanotube obtained in the step P2 in 1wt% of SDS aqueous solution, wherein the ratio of the acidified multiwall carbon nanotube to the 1wt% of SDS aqueous solution is 1mg/mL, placing the acidified multiwall carbon nanotube in an ultrasonic cleaner for treatment for 60-90 min, and centrifuging the acidified multiwall carbon nanotube in a centrifuge at 5000rpm for 2min to obtain an SDS modified acidified multiwall carbon nanotube;
and P4, washing the SDS-modified acidified multiwall carbon nanotube obtained in the step P3 by deionized water, and drying in an oven at 75 ℃ for 1-2 hours to obtain the SDS-modified multiwall carbon nanotube.
4. A process for the pelletisation of a thermoplastic phenolic resin according to any one of claims 1 to 3, characterised in that it comprises the following steps:
q1, mixing a thermoplastic phenolic resin base material and an additive in a high-speed stirrer according to a formula proportion, and feeding the mixture into a single-screw extrusion granulator for granulation to obtain thermoplastic phenolic resin granules, wherein the granulation is carried out at normal temperature and normal pressure, the rotation speed of a screw is 30rpm, the diameter of the screw is 25mm, and the extrusion speed is 10-30 m/min;
q2, indirectly cooling the thermoplastic phenolic resin granules obtained in the step Q1 through circulating water, wherein the cooling temperature is 20-25 ℃, and the cooling time is 20min, so as to obtain cooled thermoplastic phenolic resin granules;
and Q3, placing the cooled thermoplastic phenolic resin granules obtained in the step Q2 into a rotary vibration sieve for sieving to obtain a thermoplastic phenolic resin product, wherein the diameter of the rotary vibration sieve is 1500mm, the vibration frequency is 1500rpm, and the sieving angle is 15-30 degrees.
5. The process for granulating a thermoplastic phenolic resin according to claim 4, wherein in the step Q1, a thermoplastic phenolic resin base material, a lubricant, a stabilizer, a pigment and a filler are sequentially added into a high-speed stirrer at a stirring speed of 2000-3500 rpm for a stirring time of 1-4 hours.
6. The process for granulating a thermoplastic phenolic resin according to claim 4, wherein ultrasonic waves are applied to the thermoplastic phenolic resin substrate and the additive in the step Q1 in a mixing process, and the frequency is 20 kHz-30 kHz.
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